WO2024057999A1 - Coloring composition, cured film, color filter, display device and method for producing cured film - Google Patents

Coloring composition, cured film, color filter, display device and method for producing cured film Download PDF

Info

Publication number
WO2024057999A1
WO2024057999A1 PCT/JP2023/032324 JP2023032324W WO2024057999A1 WO 2024057999 A1 WO2024057999 A1 WO 2024057999A1 JP 2023032324 W JP2023032324 W JP 2023032324W WO 2024057999 A1 WO2024057999 A1 WO 2024057999A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
colored composition
mass
generator
compound
Prior art date
Application number
PCT/JP2023/032324
Other languages
French (fr)
Japanese (ja)
Inventor
啓之 山本
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2024057999A1 publication Critical patent/WO2024057999A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • 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
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

Definitions

  • the present invention relates to a colored composition containing a coloring agent.
  • the present invention also relates to a cured film, a color filter, a display device, and a cured film using the colored composition.
  • a color filter is used as key devices for displays and optical elements.
  • a color filter usually includes pixels of three primary colors, red, green, and blue, and serves to separate transmitted light into the three primary colors.
  • the colored pixels of each color of the color filter are manufactured using a colored composition containing a coloring agent.
  • Patent Document 1 describes an invention relating to a green curable resin composition for color filters containing a polyfunctional epoxy compound, an acid generator that is a diaryliodonium salt, and a green pigment.
  • Organic electroluminescent elements such as organic light emitting diodes are materials with low heat resistance, so when forming a cured film on such a material with low heat resistance, the cured film must be formed in a low temperature process of, for example, 150°C or less. It is desirable to suppress thermal damage to the support.
  • a cured film is formed by a low-temperature process, the degree of hardening of the cured film may be insufficient, and there is room for improvement in the moisture resistance of the cured film.
  • the present invention provides the following.
  • Coloring agent resin and a radically polymerizable monomer, a radical polymerization initiator, at least one generator selected from the group consisting of acid generators and base generators;
  • a colored composition comprising a compound A having a cyclic ether group with a molecular weight of 5000 or less, The content of the coloring agent in the total solid content of the coloring composition is 35% by mass or more, A colored composition in which the content of the generator in the total solid content of the colored composition is 2 to 15% by mass.
  • ⁇ 3> The colored composition according to ⁇ 1> or ⁇ 2>, wherein the compound A has four or more cyclic ether groups.
  • ⁇ 4> The colored composition according to any one of ⁇ 1> to ⁇ 3>, wherein the cyclic ether group is an epoxy group.
  • ⁇ 5> The colored composition according to any one of ⁇ 1> to ⁇ 4>, wherein the acid generator is a photoacid generator, and the base generator is a photobase generator.
  • ⁇ 6> The colored composition according to any one of ⁇ 1> to ⁇ 5>, wherein the generator is a base generator.
  • ⁇ 7> The colored composition according to any one of ⁇ 1> to ⁇ 6>, wherein the base generator includes at least one selected from the group consisting of carbamate compounds, acyloxime compounds, and onium salts.
  • the base generator includes at least one selected from the group consisting of carbamate compounds, acyloxime compounds, and onium salts.
  • the ratio of the above-mentioned generating agent and the above-mentioned compound A is described in any one of ⁇ 1> to ⁇ 7>, wherein the above-mentioned compound A is 30 to 700 parts by mass relative to 100 parts by mass of the above-mentioned generating agent. coloring composition.
  • ⁇ 9> Furthermore, it contains a surfactant, The colored composition according to any one of ⁇ 1> to ⁇ 8>, wherein the surfactant includes a silicone surfactant.
  • ⁇ 10> A cured film obtained from the colored composition according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 11> A color filter having the cured film according to ⁇ 10>.
  • ⁇ 12> A display device having the cured film according to ⁇ 10>.
  • ⁇ 13> A step of applying the colored composition according to any one of ⁇ 1> to ⁇ 9> onto a support to form a colored composition layer; a step of exposing the colored composition layer to light in a pattern; developing the colored composition layer after exposure and removing the colored composition layer in the unexposed area,
  • a method for producing a cured film the method comprising obtaining a cured film in which the colored composition layer is cured at a temperature of 150° C. or lower throughout the entire process.
  • ⁇ 14> The method for producing a cured film according to ⁇ 13>, wherein the cured film is obtained at a temperature of 100° C. or lower throughout the entire process.
  • ⁇ 15> The method for producing a cured film according to ⁇ 13>, wherein the colored composition layer after exposure is heated at a temperature of 150° C. or lower, and then the development is performed.
  • the present invention it is possible to provide a colored composition that has good storage stability and can form a cured film with excellent moisture resistance. Further, according to the present invention, it is possible to provide a cured film, a color filter, a display device, and a method for producing a cured film using a colored composition.
  • ⁇ is used to include the numerical values described before and after it as a lower limit and an upper limit.
  • the description that does not indicate substituted or unsubstituted includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the term "alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • EUV light extreme ultraviolet rays
  • (meth)acrylate” represents acrylate and/or methacrylate
  • (meth)acrylic represents both acrylic and/or methacrylic
  • (meth)acrylate” represents acrylic and/or methacrylate.
  • Acryloyl refers to either or both of acryloyl and methacryloyl.
  • Me in the structural formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
  • the total solid content refers to the total mass of all components of the composition excluding the solvent.
  • pigment means a compound that is difficult to dissolve in a solvent.
  • the term "process” is used not only to refer to an independent process, but also to include a process in which the intended effect of the process is achieved even if the process cannot be clearly distinguished from other processes. .
  • the colored composition of the present invention is colorant and resin and a radically polymerizable monomer, a radical polymerization initiator, at least one generator selected from the group consisting of acid generators and base generators;
  • a colored composition comprising a compound A having a cyclic ether group with a molecular weight of 5000 or less,
  • the content of the coloring agent in the total solid content of the coloring composition is 35% by mass or more, It is characterized in that the content of the generator in the total solid content of the coloring composition is 2 to 15% by mass.
  • the colored composition of the present invention has a cured film with excellent storage stability and moisture resistance, even though the content of the coloring agent in the total solid content of the colored composition is 35% by mass or more. can be formed.
  • a cured film having excellent moisture resistance can be formed.
  • the coloring composition of the present invention contains a compound having a cyclic ether group and a predetermined amount of the generator, it promotes the curing reaction of the compound having a cyclic ether group when forming a cured film, and is sufficiently cured even at low temperatures.
  • the molecular weight of the compound having a cyclic ether group is 5,000 or less, the increase in viscosity of the coloring composition over time can be suppressed, and as a result, the coloring composition has excellent storage stability. It is assumed that it is possible.
  • the content of the generator in the total solid content of the coloring composition is 2 to 15% by mass, there are many components that volatilize during film formation, so it is possible to make the film even thinner. It is possible to form a cured film that can further reduce the occurrence of light leakage to pixels.
  • the colored composition of the present invention is preferably used as a colored composition for color filters. More specifically, it is preferably used as a coloring composition for forming pixels of color filters. Types of pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc., and preferably red pixels, green pixels, or blue pixels, and red pixels or green pixels. More preferably, it is a red pixel, and even more preferably it is a red pixel.
  • the colored composition of the present invention can be preferably used as a colored composition for forming pixels of a color filter for a display device.
  • the type of display device is not particularly limited, but examples include display devices having an organic electroluminescent element as a light source, such as an organic electroluminescent display device.
  • the display device may have an organic electroluminescent element that displays red, blue, and green as a light source. Examples of such display devices include the display device described in Japanese Patent Application Laid-open No. 2022-066859.
  • the coloring composition of the present invention may be used to form a cured film at a temperature of 150°C or lower (preferably a temperature of 120°C or lower, more preferably a temperature of 100°C or lower) throughout the entire process. preferable.
  • forming a film at a temperature of 150° C. or lower throughout all steps means performing all steps of forming a cured film using a colored composition at a temperature of 150° C. or lower.
  • the thickness of the cured film formed by the colored composition of the present invention is preferably 0.5 to 3.0 ⁇ m.
  • the lower limit is preferably 0.8 ⁇ m or more, more preferably 1.0 ⁇ m or more, and even more preferably 1.1 ⁇ m or more.
  • the upper limit is preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, and even more preferably 1.8 ⁇ m or less.
  • the colored composition of the present invention contains a coloring agent.
  • the coloring agent include chromatic coloring agents, black coloring agents, and white coloring agents.
  • a chromatic coloring agent is used as the coloring agent.
  • the number of chromatic colorants may be one, or two or more.
  • the colorant may be a pigment or a dye.
  • the pigment may be either an inorganic pigment or an organic pigment, but organic pigments are preferable from the viewpoints of large color variations, ease of dispersion, safety, and the like.
  • the average primary particle diameter of the pigment is preferably 1 to 200 nm.
  • the lower limit is preferably 5 nm or more, more preferably 10 nm or more.
  • the upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less.
  • the primary particle diameter of a pigment can be calculated
  • the average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 pigment primary particles.
  • the primary particles of pigment refer to independent particles without agglomeration.
  • the crystallite size determined from the half-value width of the peak derived from any crystal plane in the X-ray diffraction spectrum of the pigment when CuK ⁇ rays are used as the X-ray source is preferably 0.1 to 100 nm, and 0. It is more preferably .5 to 50 nm, even more preferably 1 to 30 nm, and particularly preferably 5 to 25 nm.
  • the specific surface area of the pigment is preferably 1 to 300 m 2 /g.
  • the lower limit is preferably 10 m 2 /g or more, more preferably 30 m 2 /g or more.
  • the upper limit is preferably 250 m 2 /g or less, more preferably 200 m 2 /g or less.
  • the value of the specific surface area is determined according to DIN 66131: determination of the specific surface area of solids by gas adsorption according to the BET (Brunauer, Emmett and Teller) method. (Measurement of specific surface area of solids).
  • chromatic colorant is not particularly limited, and any known chromatic colorant can be used.
  • chromatic colorants include yellow colorants, orange colorants, red colorants, green colorants, purple colorants, and blue colorants. Specific examples of these include, for example, the following.
  • red colorants examples include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, etc. It is preferably a compound, and more preferably a diketopyrrolopyrrole compound. Moreover, it is preferable that the red colorant is a pigment.
  • red colorants include C.I. I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, Examples include red pigments such as 279, 291, 294, 295, 296, 297, and the like
  • C. I. Pigment Red 122, 177, 254, 255, 264, 269, 272 are preferred, and C.I. I. Pigment Red 254, 264, and 272 are more preferred.
  • the green coloring agent examples include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. Moreover, it is preferable that the green coloring agent is a pigment.
  • green colorants include C.I. I.
  • examples include green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66.
  • halogenated zinc phthalocyanine has an average number of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule.
  • Pigments can also be used.
  • Specific examples include compounds described in International Publication No. 2015/118720.
  • C.I. I. Pigment Green 7, 36, 58, 62, and 63 are preferred.
  • orange colorants include C.I. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. orange pigments.
  • yellow colorants examples include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds.
  • Specific examples of yellow colorants include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166
  • an azobarbituric acid nickel complex having the following structure can also be used.
  • purple colorants include C.I. I.
  • Examples include purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.
  • blue colorants include C.I. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc.
  • examples include pigments.
  • an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue colorant.
  • Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A No. 2012-247591 and paragraph number 0047 of JP-A No. 2011-157478.
  • triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP 2020-117638, and International Publication No. 2020/174991 are used.
  • a halogenated zinc phthalocyanine pigment described in Patent No. 6809649, JP 2020-180176 Isoindoline compounds described in the publication, phenothiazine compounds described in JP2021-187913A, halogenated zinc phthalocyanine described in International Publication No. 2022/004261, zinc halide described in International Publication No. 2021/250883 Phthalocyanines can be used.
  • the chromatic colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, the rod-like structure, or both structures.
  • a chromatic coloring agent As a chromatic coloring agent, a quinophthalone compound represented by formula 1 of Korean Patent Publication No. 10-2020-0030759, a polymer dye described in Korean Publication Patent No. 10-2020-0061793, and Japanese Patent Application Publication No. 2022-029701.
  • the coloring agent described in WO 2022/014635, the aluminum phthalocyanine compound described in WO 2022/024926, the compound described in JP 2022-045895, WO Compounds described in No. 2022/050051 can also be used.
  • black colorant examples include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred.
  • the black colorant described in paragraph number 0166 of International Publication No. 2022/065215, and the perylene black (Lumogen Black FK4280 etc.) described in paragraphs 0016 to 0020 of JP 2017-226821 can also be used. can.
  • White colorants include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, Examples include inorganic pigments such as zinc sulfide.
  • the white colorant described in paragraph numbers 0040 to 0043 of International Publication No. 2022/085485 can be used.
  • the content of the coloring agent in the total solid content of the coloring composition is 35% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and 50% by mass or more. It is even more preferable.
  • the upper limit is preferably 70% by mass or less, more preferably 65% by mass or less, and even more preferably 60% by mass or less.
  • the content of pigment in the colorant is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass.
  • the coloring composition of the present invention is used as a coloring composition for forming green pixels of a color filter, it is preferable to use a colorant containing a yellow colorant and a green colorant.
  • the colored composition of the present invention contains a resin.
  • the resin is blended, for example, for dispersing pigments in a coloring composition or for use as a binder.
  • a resin used mainly for dispersing pigments and the like in a coloring composition is also referred to as a dispersant.
  • this use of the resin is just an example, and the resin can also be used for purposes other than this use.
  • the weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 5000 or more.
  • (meth)acrylic resin for example, (meth)acrylic resin, (meth)acrylamide resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide.
  • examples include resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins.
  • examples of the resin include resins described in paragraph numbers 0091 to 0099 of International Publication No.
  • the resin it is preferable to use a resin having acid groups.
  • the acid group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
  • the acid value of the resin having acid groups is preferably 30 to 500 mgKOH/g.
  • the lower limit is more preferably 40 mgKOH/g or more, particularly preferably 50 mgKOH/g or more.
  • the upper limit is more preferably 400 mgKOH/g or less, even more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less.
  • the weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, more preferably 5,000 to 50,000. Further, the number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.
  • the resin having an acid group preferably contains a repeating unit having an acid group in its side chain, and more preferably contains 5 to 70 mol% of repeating units having an acid group in its side chain based on the total repeating units of the resin.
  • the upper limit of the content of repeating units having acid groups in their side chains is preferably 50 mol% or less, more preferably 30 mol% or less.
  • the lower limit of the content of repeating units having acid groups in their side chains is preferably 10 mol% or more, more preferably 20 mol% or more.
  • the colored composition of the present invention contains a resin having a basic group.
  • the resin having a basic group is preferably a resin containing a repeating unit having a basic group in its side chain, and a resin having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group.
  • a polymer is more preferable, and a block copolymer having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group is even more preferable.
  • a resin having a basic group can also be used as a dispersant.
  • the amine value of the resin having a basic group is preferably 5 to 300 mgKOH/g.
  • the lower limit is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more.
  • the upper limit is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less.
  • resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (manufactured by BYK Chemie), Solsperse 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 385 00, 39000, 53095, 56000, 7100 (all manufactured by Japan Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like.
  • the resin having a basic group is the block copolymer (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and the block copolymer (B) described in paragraphs 0046 to 0076 of JP2018-156021A. It is also possible to use block copolymer A1, a vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP-A No. 2019-184763, the contents of which are incorporated herein.
  • the colored composition of the present invention contains a resin having an acid group and a resin having a basic group. According to this aspect, the storage stability of the colored composition can be further improved.
  • the content of the resin having a basic group is preferably 20 to 500 parts by mass per 100 parts by mass of the resin having an acid group.
  • the amount is preferably 30 to 300 parts by weight, more preferably 50 to 200 parts by weight.
  • the resin it is also preferable to use a resin having an aromatic carboxy group (hereinafter also referred to as resin Ac).
  • the aromatic carboxy group may be included in the main chain of the repeating unit, or may be included in the side chain of the repeating unit.
  • the aromatic carboxy group is preferably contained in the main chain of the repeating unit.
  • an aromatic carboxy group refers to a group having a structure in which one or more carboxy groups are bonded to an aromatic ring.
  • the number of carboxy groups bonded to the aromatic ring is preferably 1 to 4, more preferably 1 to 2.
  • the resin Ac is preferably a resin containing at least one type of repeating unit selected from a repeating unit represented by formula (Ac-1) and a repeating unit represented by formula (Ac-2).
  • Ar 1 represents a group containing an aromatic carboxy group
  • L 1 represents -COO- or -CONH-
  • L 2 represents a divalent linking group
  • Ar 10 represents a group containing an aromatic carboxy group
  • L 11 represents -COO- or -CONH-
  • L 12 represents a trivalent linking group
  • P 10 represents a polymer Represents a chain.
  • Examples of the group containing an aromatic carboxy group represented by Ar 1 in formula (Ac-1) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like.
  • Examples of the aromatic tricarboxylic anhydride and aromatic tetracarboxylic anhydride include compounds having the following structures.
  • Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, represented by the following formula (Q-1). or a group represented by the following formula (Q-2).
  • the aromatic carboxy group-containing group represented by Ar 1 may have a crosslinkable group.
  • the crosslinkable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, and more preferably an ethylenically unsaturated bond-containing group.
  • Specific examples of the group containing an aromatic carboxy group represented by Ar 1 include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13). Examples include groups such as
  • n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
  • n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2.
  • n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and preferably 1. More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
  • Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, the above formula (Q- Represents a group represented by 1) or a group represented by the above formula (Q-2).
  • *1 represents the bonding position with L 1 .
  • L 1 represents -COO- or -CONH-, and preferably represents -COO-.
  • the divalent linking group represented by L 2 in formula (Ac-1) includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these. Examples include groups combining two or more of the following.
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms.
  • the alkylene group may be linear, branched, or cyclic.
  • the number of carbon atoms in the arylene group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10.
  • the alkylene group and arylene group may have a substituent.
  • the divalent linking group represented by L 2 is preferably a group represented by -L 2a -O-.
  • L 2a is an alkylene group; an arylene group; a group combining an alkylene group and an arylene group; at least one selected from an alkylene group and an arylene group, and -O-, -CO-, -COO-, -OCO-, Examples include a group combining at least one selected from -NH- and -S-, and an alkylene group is preferred.
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms.
  • the alkylene group may be linear, branched, or cyclic.
  • the alkylene group and arylene group may have a substituent. Examples of the substituent include a hydroxy group.
  • the aromatic carboxy group-containing group represented by Ar 10 in formula (Ac-2) has the same meaning as Ar 1 in formula (Ac-1), and the preferred range is also the same.
  • L 11 represents -COO- or -CONH-, preferably -COO-.
  • the trivalent linking group represented by L 12 includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these two groups. Examples include groups that combine more than one species.
  • the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic.
  • the aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • the hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group.
  • the trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2).
  • L 12b represents a trivalent linking group
  • X 1 represents S
  • *1 represents the bonding position with L 11 of formula (Ac-2)
  • *2 represents the bonding position of formula (Ac-2). It represents the bonding position of Ac-2) with P10 .
  • the trivalent linking group represented by L 12b is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-.
  • a hydrocarbon group or a group consisting of a hydrocarbon group and -O- is preferable.
  • L 12c represents a trivalent linking group
  • X 1 represents S
  • *1 represents the bonding position with L 11 of formula (Ac-2)
  • *2 represents formula ( It represents the bonding position of Ac-2) with P10 .
  • the trivalent linking group represented by L 12c is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-.
  • a hydrocarbon group is preferable.
  • P 10 represents a polymer chain.
  • the polymer chain represented by P 10 preferably has at least one repeating unit selected from poly(meth)acrylic repeating units, polyether repeating units, polyester repeating units, and polyol repeating units.
  • the weight average molecular weight of the polymer chain P 10 is preferably 500 to 20,000.
  • the lower limit is preferably 1000 or more.
  • the upper limit is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less. If the weight average molecular weight of P 10 is within the above range, the pigment will have good dispersibility in the composition.
  • the resin having an aromatic carboxy group is a resin having a repeating unit represented by formula (Ac-2), this resin is preferably used as a dispersant.
  • the polymer chain represented by P 10 may contain a crosslinkable group.
  • the crosslinkable group include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • the colored composition of the present invention preferably contains a resin as a dispersant.
  • the dispersant include acidic dispersants (acidic resins) and basic dispersants (basic resins).
  • the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups.
  • the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %.
  • the acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g.
  • the basic dispersant refers to a resin in which the amount of basic groups is greater than the amount of acid groups.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%.
  • the basic group that the basic dispersant has is preferably an amino group.
  • the resin used as a dispersant is a graft resin.
  • the descriptions in paragraphs 0025 to 0094 of JP-A No. 2012-255128 can be referred to, the contents of which are incorporated herein.
  • the resin used as the dispersant is a resin having an aromatic carboxy group (resin Ac).
  • resin Ac resin having an aromatic carboxy group
  • examples of the resin having an aromatic carboxy group include those mentioned above.
  • the resin used as a dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain.
  • the polyimine dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain.
  • the resin has The basic nitrogen atom is not particularly limited as long as it exhibits basicity.
  • the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
  • the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core portion.
  • resins include dendrimers (including star-shaped polymers).
  • specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A No. 2013-043962.
  • the resin used as a dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain.
  • the content of the repeating unit having an ethylenically unsaturated bond-containing group in its side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and more preferably 20 to 70 mol% of the total repeating units of the resin. More preferably, it is mol%.
  • resins described in JP 2018-087939, block copolymers (EB-1) to (EB-9) described in paragraph numbers 0219 to 0221 of Patent No. 6432077, and international publication Polyethyleneimine having a polyester side chain described in No. 2016/104803, block copolymer described in International Publication No. 2019/125940, block polymer having an acrylamide structural unit described in JP 2020-066687, A block polymer having an acrylamide structural unit described in JP-A No. 2020-066688, a dispersant described in International Publication No. 2016/104803, etc. can also be used.
  • Dispersants are also available as commercial products, and specific examples include the DISPERBYK series manufactured by BYK Chemie, the SOLSPERSE series manufactured by Japan Lubrizol, the Efka series manufactured by BASF, and Ajinomoto Fine Techno Co., Ltd. Examples include the Ajisper series manufactured by Manufacturer. Further, the product described in paragraph number 0129 of JP 2012-137564A and the product described in paragraph number 0235 of JP 2017-194662A can also be used as a dispersant.
  • the content of resin in the total solid content of the coloring composition is preferably 1 to 50% by mass.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the colored composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more types of resin are included, the total amount thereof is preferably within the above range.
  • the colored composition of the present invention contains a radically polymerizable monomer.
  • the radically polymerizable monomer include compounds having an ethylenically unsaturated bond-containing group.
  • examples of the ethylenically unsaturated bond-containing group include a vinyl group, (meth)allyl group, and (meth)acryloyl group.
  • the molecular weight of the radically polymerizable monomer is preferably 100 to 3,000.
  • the upper limit is preferably 2000 or less, more preferably 1500 or less.
  • the lower limit is preferably 150 or more, more preferably 250 or more.
  • the ethylenically unsaturated bond-containing group value (hereinafter referred to as C ⁇ C value) of the radically polymerizable monomer is preferably 2 to 14 mmol/g from the viewpoint of stability of the coloring composition over time.
  • the lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and even more preferably 5 mmol/g or more.
  • the upper limit is preferably 12 mmol/g or less, more preferably 10 mmol/g or less, and even more preferably 8 mmol/g or less.
  • the C ⁇ C value of a radically polymerizable monomer is a value calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the radically polymerizable monomer by the molecular weight of the radically polymerizable monomer.
  • the radically polymerizable monomer is preferably a compound containing three or more ethylenically unsaturated bond-containing groups, and more preferably a compound containing four or more ethylenically unsaturated bond-containing groups.
  • the upper limit of the ethylenically unsaturated bond-containing groups is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less from the viewpoint of the stability of the coloring composition over time.
  • the radically polymerizable monomer is preferably a trifunctional or higher functional (meth)acrylate compound, more preferably a trifunctional to 15 functional (meth)acrylate compound, and a trifunctional to 10 functional (meth)acrylate compound. More preferably, it is a tri- to hexa-functional (meth)acrylate compound.
  • Specific examples of radically polymerizable monomers include compounds described in paragraph numbers 0075 to 0083 of International Publication No. 2022/065215.
  • radically polymerizable monomers examples include dipentaerythritol tri(meth)acrylate (commercial product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercial product: KAYARAD D- 320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercial product) is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industries, Ltd.), and these (meth)acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues.
  • radical polymerizable monomers diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available product is M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., NK ester) A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) ), NK Oligo UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.),
  • the content of the radically polymerizable monomer in the total solid content of the coloring composition is preferably 1 to 35% by mass.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
  • the lower limit is preferably 2% by mass or more, more preferably 5% by mass or more.
  • the ratio of the radically polymerizable monomer to the resin is preferably 1 to 500 parts by weight based on 100 parts by weight of the resin. According to this aspect, peeling of the film during development can be suppressed.
  • the upper limit is preferably 400 parts by mass or less, more preferably 300 parts by mass or less.
  • the lower limit is preferably 10 parts by mass or more, more preferably 20 parts by mass or more.
  • the ratio of the radically polymerizable monomer to Compound A described below is preferably 5 to 1000 parts by mass per 100 parts by mass of Compound A described later. According to this aspect, when pixels are formed by patterning using photolithography, it is possible to suppress variations in line width of the resulting pixels.
  • the upper limit is preferably 500 parts by mass or less, more preferably 250 parts by mass or less.
  • the lower limit is preferably 15 parts by mass or more, more preferably 30 parts by mass or more.
  • the colored composition of the present invention may contain only one kind of radically polymerizable monomer, or may contain two or more kinds of radically polymerizable monomers. When two or more types of radically polymerizable monomers are included, it is preferable that their total amount falls within the above range.
  • the colored composition of the present invention contains a radical polymerization initiator.
  • the radical polymerization initiator include thermal radical polymerization initiators and radical photopolymerization initiators, and radical photopolymerization initiators are preferred.
  • thermal radical polymerization initiator examples include 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismarenonitrile, and dimethyl-(2,2')-azobis(2- Examples include azo compounds such as methyl propionate), tert-butyl peroxybenzoate, benzoyl peroxide, lauroyl peroxide, and organic peroxides such as potassium persulfate.
  • AIBN 2,2'-azobisisobutyronitrile
  • 3-carboxypropionitrile examples include azo compounds such as methyl propionate), tert-butyl peroxybenzoate, benzoyl peroxide, lauroyl peroxide, and organic peroxides such as potassium persulfate.
  • Examples of the photoradical polymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, Examples include thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, and the like.
  • halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
  • acylphosphine compounds for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
  • acylphosphine compounds for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
  • photoradical polymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and hexaarylene compounds.
  • rubiimidazole compounds onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds, oxime compounds, ⁇ -hydroxy A compound selected from a ketone compound, an ⁇ -aminoketone compound, and an acylphosphine compound is more preferable, and an oxime compound is even more preferable.
  • photoradical polymerization initiators compounds described in paragraphs 0065 to 0111 of JP-A No. 2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37-60p, vol.
  • hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole, etc. can be mentioned.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, and Irgacure 117. 3, Irgacure 2959, Irgacure 127 (all BASF (manufactured by a company).
  • Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, and Irgacure 36.
  • Irgacure 369E Irgacure 379EG (all manufactured by BASF) (manufactured by).
  • Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.
  • Examples of oxime compounds include the compound described in paragraph number 0142 of International Publication No. 2022/085485, the compound described in Patent No. 5430746, the compound described in Patent No. 5647738, and the general formula ( Examples include the compound represented by 1), the compound described in paragraphs 0022 to 0024, the compound represented by general formula (1) and the compound described in paragraphs 0117 to 0120 of JP-A-2021-170089.
  • oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like.
  • photopolymerization initiators include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, oxime compounds having a fluorine atom, oxime compounds having a nitro group, and benzofuran skeleton.
  • An oxime compound having a carbazole skeleton bonded with a substituent having a hydroxy group, and compounds described in paragraph numbers 0143 to 0149 of International Publication No. 2022/085485 can also be used.
  • oxime compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm.
  • the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably from 1000 to 300,000, even more preferably from 2000 to 300,000, and even more preferably from 5000 to 200,000. It is particularly preferable that there be.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
  • a difunctional, trifunctional or more functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
  • a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained.
  • the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time, thereby improving the stability of the coloring composition over time.
  • Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include compounds described in paragraph 0148 of International Publication No. 2022/065215.
  • the content of the polymerization initiator in the total solid content of the colored composition is preferably 0.1 to 30% by mass.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
  • the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
  • the polymerization initiator contained in the coloring composition contains a photopolymerization initiator.
  • the content of the photopolymerization initiator in the polymerization initiator contained in the colored composition is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and 90 to 100% by mass. It is even more preferable.
  • only one type of polymerization initiator may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
  • the colored composition of the present invention contains at least one generator selected from the group consisting of acid generators and base generators. It is preferable that the generator is substantially only an acid generator or substantially only a base generator. It is preferable that the base generator is substantially only a base generator.
  • the case where the generator is substantially only an acid generator means that the content of the acid generator in the total mass of the generator is 99% by mass or more, and 99% by mass or more. The content is preferably .9% by mass or more, and more preferably 100% by mass (consisting only of the acid generator).
  • the generator when the generator is substantially only a base generator, it means that the content of the base generator in the total mass of the generator is 99% by mass or more, and 99.9% by mass or more. It is preferably 100% by mass (consisting only of the base generator), and more preferably 100% by mass.
  • Examples of acid generators include thermal acid generators and photoacid generators.
  • the acid generator preferably includes a photoacid generator. Further, as the acid generator, a photoacid generator and a thermal acid generator may be used in combination. When a thermal acid generator and a photoacid generator are used together, the mass ratio of the thermal acid generator and the photoacid generator is 100 to 2000 parts by mass of the photoacid generator to 100 parts by mass of the thermal acid generator. Parts by mass are preferred.
  • the lower limit is preferably 150 parts by mass or more, more preferably 200 parts by mass or more.
  • the upper limit is preferably 1,500 parts by mass or less, more preferably 1,000 parts by mass or less.
  • the acid generator is substantially only a photoacid generator because it has excellent pattern formation properties in photolithography.
  • the case where the acid generator is substantially only a photoacid generator means that the content of the photoacid generator in the total mass of the acid generator is 99% by mass or more. However, it is preferably 99.9% by mass or more, and more preferably 100% by mass (consisting only of the photoacid generator).
  • an acid generator means a compound that generates an acid by applying energy such as heat or light.
  • thermal acid generator means a compound that generates an acid by thermal decomposition.
  • a photoacid generator means a compound that generates an acid upon irradiation with light.
  • the acid generator may be an ionic acid generator or a nonionic acid generator, but is preferably a nonionic acid generator.
  • the acid generator is preferably a compound that generates an acid with a pKa of 4 or less, more preferably a compound that generates an acid with a pKa of 3 or less, and a compound that generates an acid with a pKa of 2 or less. It is even more preferable. According to this aspect, it is easier to form a cured film with better moisture resistance.
  • pKa basically refers to pKa in water at 25°C. Items that cannot be measured in water are measured using a suitable solvent. Specifically, the pKa described in chemical handbooks and the like can be referred to.
  • the acid having a pKa of 3 or less is preferably a sulfonic acid or a phosphonic acid, and more preferably a sulfonic acid.
  • the molecular weight of the acid generator is preferably 200 to 1000.
  • the lower limit is preferably 230 or more.
  • the upper limit is preferably 800 or less. If the molecular weight of the acid generator is within the above range, the acid generator will easily volatilize during baking, etc. during the production of a cured film, thereby suppressing the acid generator and its decomposition products from remaining in the film. can.
  • the acid generation temperature of the thermal acid generator is preferably 80°C to 130°C, more preferably 90°C to 110°C.
  • the thermal acid generator is preferably a compound that generates a low nucleophilic acid such as sulfonic acid, carboxylic acid, or disulfonylimide upon heating.
  • the acid generated from the thermal acid generator is preferably an acid with a pKa of 4 or less, more preferably an acid with a pKa of 3 or less, and even more preferably an acid with a pKa of 2 or less.
  • sulfonic acids, alkylcarboxylic acids substituted with electron-withdrawing groups, arylcarboxylic acids, disulfonylimides, and the like are preferred.
  • the electron-withdrawing group include a halogen atom such as a fluorine atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.
  • thermal acid generator examples include diazomethane compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, phosphoric acid ester compounds, sulfonimide compounds, sulfonebenzotriazole compounds, sulfonium salts, etc. preferable.
  • the thermal acid generator is a sulfonic acid ester compound that does not substantially generate acid upon irradiation with actinic rays or radiation, but generates acid upon heat. Substantially no acid is generated by irradiation with actinic light or radiation, as determined by the absence of any change in the spectrum by measuring the infrared absorption (IR) spectrum and nuclear magnetic resonance (NMR) spectrum of the compound before and after exposure. can do.
  • the molecular weight of the sulfonic acid ester compound is preferably 230 to 1,000, more preferably 230 to 800.
  • sulfonic acid ester compound examples include tetraethylene glycol bis(p-toluenesulfonate), butyl p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenylbenzylmethylsulfonium trifluoromethanesulfonate, 4-(methoxycarbonyloxy)phenyldimethylsulfonium trifluoromethanesulfonate, Examples include benzyl-4-(methoxycarbonyloxy)phenylmethylsulfonium trifluoromethanesul
  • sulfonimide compound examples include N-(trifluoromethylsulfonyloxy)succinimide (trade name "SI-105", Midori Chemical Co., Ltd.), N-(camphorsulfonyloxy)succinimide (trade name "SI-106", Midori Chemical Co., Ltd.), N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenyl) sulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide , N-(trifluoromethylsulfonyloxy)diphenylmaleimide (trade name "PI-105",
  • Hept-5-ene-2,3-dicarboxylimide (trade name "NDI-100", Midori Kagaku Co., Ltd.), N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5 -ene-2,3-dicarboxylimide (trade name "NDI-101", Midori Kagaku Co., Ltd.), N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3- Dicarboxylimide (trade name "NDI-105", Midori Kagakusha), N-(nonafluorobutanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide (trade name "NDI-109", Midori Kagaku Co., Ltd.), N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide (trade
  • thermal acid generators include the San-Aid series manufactured by Sanshin Kagaku Kogyo Co., Ltd. (for example, SI-60, SI-80, SI-100, SI-200, SI-110, SI-145, SI -150, SI-60L, SI-80L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L, etc.), TA-100 series manufactured by San-Apro Co., Ltd., San-Apro ( Examples include the IK series manufactured by Co., Ltd.
  • the photoacid generator is preferably a compound that generates an acid in response to actinic light having a wavelength of 300 nm or more, more preferably a wavelength of 300 to 450 nm.
  • the photoacid generator is preferably a compound that generates an acid with a pKa of 4 or less when irradiated with light, more preferably a compound that generates an acid with a pKa of 3 or less, and more preferably a compound that generates an acid with a pKa of 2 or less. More preferably, it is a compound that Further, the photoacid generator is preferably a compound that does not generate acid at temperatures below 130°C.
  • photoacid generators include oxime sulfonate compounds, triazine compounds, sulfonium salts, iodonium salts, ammonium salts, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, iminosulfonic acid ester compounds, carboxylic acid ester compounds, and sulfonimide compounds.
  • the compound is preferably at least one selected from the group consisting of oxime sulfonate compounds and triazine compounds from the viewpoint of acid generation efficiency and solubility upon exposure.
  • the oxime sulfonate compound is preferably a compound containing an oxime sulfonate structure represented by formula (B1-1).
  • R 21 in formula (B1-1) represents an alkyl group or an aryl group. Wavy lines represent bonds with other groups.
  • the alkyl group represented by R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the aryl group represented by R 21 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group.
  • the aryl group of R 21 may be substituted with a fluorine atom, an alkyl group, an alkoxy group, or a halogen atom.
  • the alkyl group and aryl group represented by R 21 may have a substituent.
  • substituents include halogen atoms, aryl groups having 6 to 11 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and cyclic alkyl groups (bridged aliphatic groups such as 7,7-dimethyl-2-oxonorbornyl group). (including a cyclic group, preferably a bicycloalkyl group, etc.).
  • substituents include halogen atoms, aryl groups having 6 to 11 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and cyclic alkyl groups (bridged aliphatic groups such as 7,7-dimethyl-2-oxonorbornyl group). (including a cyclic group, preferably a bicycloalkyl group, etc.).
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.
  • Examples of the compound containing the oxime sulfonate structure represented by formula (B1-1) include the oxime sulfonate compounds described in paragraphs 0081 to 0108 of JP-A No. 2013-210616, the contents of which are not incorporated herein. It will be done.
  • oxime sulfonate compound examples include compounds having the structures described in the examples below.
  • triazine compounds examples include 2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-Methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxy- ⁇ -styryl)-bis(4,6-trichloromethyl)-s-triazine, 2 -piperonyl-bis(4,6-trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-bis(4,6-trichloromethyl)-s-triazine, 2-[2 -(5-methylfuran-2-yl)ethenyl]-bis(4,6-trichloromethyl)-s-triazine, 2-[2-(4-diethy
  • Iodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl,4-(2'-hydroxy-1 '-tetradecaoxy) phenyl iodonium trifluoromethanesulfonate, 4-(2'-hydroxy-1'-tetradecaoxy) phenyl iodonium hexafluoroantimonate, phenyl,4-(2'-hydroxy-1'-tetradeca Oxy) phenyl iodonium-p-toluenesulfonate and the like.
  • Sulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethane. Examples include sulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, and the like.
  • ammonium salts tetramethylammonium butyltris(2,6-difluorophenyl)borate, tetramethylammoniumhexyltris(p-chlorophenyl)borate, tetramethylammoniumhexyltris(3-trifluoromethylphenyl)borate, benzyldimethylphenylammonium Examples include butyltris(2,6-difluorophenyl)borate, benzyldimethylphenylammoniumhexyltris(p-chlorophenyl)borate, benzyldimethylphenylammoniumhexyltris(3-trifluoromethylphenyl)borate, and the like.
  • Diazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(4-tolylsulfonyl)diazomethane, bis(2,4-xylylsulfonyl)diazomethane, and bis(2,4-xylylsulfonyl)diazomethane.
  • sulfone compounds include ⁇ -ketosulfone compounds, ⁇ -sulfonylsulfone compounds, diaryldisulfone compounds, and the like.
  • Preferred sulfone compounds include 4-tolylphenacylsulfone, mesitylphenacylsulfone, bis(phenylsulfonyl)methane, and 4-chlorophenyl-4-tolyldisulfone compounds.
  • sulfonic acid ester compounds examples include benzoin-4-tolylsulfonate, pyrogalloltris(methylsulfonate), nitrobenzyl-9,10-diethoxyanthryl-2-sulfonate, 2,6-(dinitrobenzyl)phenylsulfonate, etc. Can be mentioned.
  • iminosulfonic acid ester compounds include benzyl monooxime-4-tolylsulfonate, benzyl monooxime-4-dodecylphenylsulfonate, benzyl monooxime hexadecylsulfonate, 4-nitroacetophenone oxime-4-tolylsulfonate, 4,4'- Dimethylbenzylmonoxime-4-tolylsulfonate, 4,4'-dimethylbenzylmonoxime-4-dodecylphenylsulfonate, dibenzylketoneoxime-4-tolylsulfonate, ⁇ -(4-tolyloxy)imino- ⁇ -cyanoacetate ethyl , furyl monooxime-4-(aminocarbonyl) phenylsulfonate, acetone oxime-4-benzoylphenyl sulfonate, 3-(benzylsulfonyloxy)
  • carboxylic acid ester compound examples include carboxylic acid 2-nitrobenzyl ester.
  • Sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(10-camphorsulfonyloxy)succinimide, N-(4-tolylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy) ) Succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(10-camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide , N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(10-camphorsulfonyloxy)dipheny
  • hept-5-ene-2,3-dicarboximide N-(10-camphorsulfonyloxy)bicyclo[2.2.1] hept-5-ene-2,3-dicarboximide, N -(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2 .1] hept-5-ene-2,3-dicarboximide, N-(4-tolylsulfonyloxy)bicyclo[2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-Tolylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2 .
  • the base generator examples include thermal base generators and photobase generators.
  • the base generator preferably includes a photobase generator. Further, as the base generator, a photobase generator and a thermal base generator may be used in combination. When a thermal base generator and a photobase generator are used together, the mass ratio of the thermal base generator and the photobase generator is 100 to 2000 parts by mass of the photobase generator to 100 parts by mass of the thermal base generator. Parts by mass are preferred.
  • the lower limit is preferably 150 parts by mass or more, more preferably 200 parts by mass or more.
  • the upper limit is preferably 1,500 parts by mass or less, more preferably 1,000 parts by mass or less.
  • the base generator is substantially only a photobase generator because it has excellent pattern formation properties in photolithography.
  • the case where the base generator is substantially only a photobase generator means that the content of the photobase generator in the total mass of the base generator is 99% by mass or more. It is preferably 99.9% by mass or more, and more preferably 100% by mass (consisting only of the photobase generator).
  • a base generator means a compound that generates a base by applying energy such as heat or light.
  • the term "thermal base generator” means a compound that generates a base by thermal decomposition.
  • a photobase generator means a compound that generates a base upon irradiation with light.
  • the base generator may be an ionic base generator or a nonionic base generator, but is preferably a nonionic base generator.
  • the base generated from the base generator may be any of primary amine, secondary amine, and tertiary amine, but from the viewpoint of pot life stability, tertiary amine is preferable.
  • the boiling point of the base generated by the base generator is preferably 80°C or higher, preferably 100°C or higher, and most preferably 140°C or higher.
  • the molecular weight of the generated base is preferably 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. Note that the molecular weight value is a theoretical value determined from the structural formula.
  • the molecular weight of the base generator is preferably 200 to 1000.
  • the lower limit is preferably 230 or more.
  • the upper limit is preferably 800 or less. If the molecular weight of the base generator is within the above range, the base generator will easily volatilize during baking, etc. during the production of a cured film, thereby suppressing the base generator and its decomposition products from remaining in the film. can.
  • the base generation temperature of the thermal base generator is preferably 80°C to 130°C, more preferably 90°C to 110°C.
  • thermal base generators examples include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole compounds, amine imide compounds, and pyridine compounds. , ⁇ -aminoacetophenone compounds, ammonium salts, pyridinium salts, ⁇ -lactone ring derivative compounds, amine imide compounds, phthalimide compounds, acyloxyimino compounds, and the like.
  • an acidic compound that generates a base when heated to 40° C. or higher, and an ammonium salt having an anion having a pKa1 of 0 to 4 and an ammonium cation can also be used.
  • these compounds include the compounds described in paragraph numbers 0045 to 0066 of International Publication No. 2017/141723, the contents of which are incorporated herein.
  • thermal base generators include the U-CAT series manufactured by San-Apro Co., Ltd. (eg, SA1, SA102, SA603, SA810, SA831, SA841, SA851, SA838A, etc.).
  • the photobase generator is preferably a compound that generates a base in response to actinic light having a wavelength of 300 nm or more, more preferably from 300 to 450 nm. Further, the photobase generator is preferably a compound that does not generate a base at temperatures below 130°C.
  • Examples of the photobase generator include carbamate compounds, sulfonamide compounds, acyloxime compounds, and onium salts, and preferably contains at least one selected from the group consisting of carbamate compounds, acyloxime compounds, and onium salts. More preferably, it contains a carbamate compound.
  • Carbamate compounds include N-(2-nitrobenzyloxy)carbonyl-N-methylamine, N-(2-nitrobenzyloxy)carbonyl-Nn-propylamine, N-(2-nitrobenzyloxy)carbonyl- N-n-hexylamine, N-(2-nitrobenzyloxy)carbonyl-N-cyclohexylamine, N-(2-nitrobenzyloxy)carbonylaniline, N-(2-nitrobenzyloxy)carbonylpiperidine, N,N '-bis[(2-nitrobenzyloxy)carbonyl]-1,6-hexamethylenediamine, N,N'-bis[(2-nitrobenzyloxy)carbonyl]-1,4-phenylenediamine, N,N' -bis[(2-nitrobenzyloxy)carbonyl]-2,4-tolylenediamine, N,N'-bis[(2-nitrobenzyloxy)carbonyl]-4,4'-diaminodiphenylme
  • the carbamate compound is also preferably a compound represented by formula (PBG-1).
  • R a and R b each independently represent a hydrogen atom or a monovalent organic group, and even if R a and R b combine with each other to form a cyclic amino group, Often R c represents a hydrogen atom or a methyl group and Ar a represents an aromatic group.
  • the monovalent organic group represented by R a and R b includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group consisting of a combination thereof.
  • the aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic.
  • the cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and the like.
  • the aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • the aromatic hydrocarbon group is preferably a monocyclic or fused ring aromatic hydrocarbon group having 2 to 4 condensed rings.
  • An example of the aromatic hydrocarbon group is an aryl group.
  • the aliphatic hydrocarbon group and aromatic hydrocarbon group may have a substituent. Examples of the substituent include the groups listed below for substituent T.
  • R a and R b are each independently preferably an aliphatic hydrocarbon group, more preferably an alkyl group, even more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. , a linear or branched alkyl group having 1 to 5 carbon atoms is even more preferable, and a methyl group, ethyl group or isopropyl group is particularly preferable.
  • R a and R b may be bonded to each other to form a cyclic amino group.
  • the cyclic amino groups formed include 1-aziridinyl group, 1-azetidinyl group, 1-pyrrolidinyl group, 1-piperidinyl group, 1-hexamethyleneimino group, 1-heptamethyleneimino group, 1-octamethyleneimino group, 1-nonamethyleneimino group, 1-1-imidazolyl group, 4,5-dihydro-1-imidazolyl group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolidinyl group, 1-piperazinyl group, morpholino group, etc. can be mentioned.
  • the cyclic amino group formed by bonding R a and R b to each other may have a substituent. Examples of the substituent include the groups listed below for substituent T.
  • the aromatic group represented by Ar a includes an aromatic hydrocarbon group and an aromatic heterocyclic group.
  • the aromatic group represented by Ar a may be a monocyclic aromatic group, but is preferably a condensed ring aromatic group having 2 to 4 condensed rings.
  • Examples of the aromatic hydrocarbon group include a benzene ring group, a naphthalene ring group, an anthracene ring group, and a fluorene ring group.
  • aromatic heterocyclic groups include pyrrole ring group, furan ring group, thiophene ring group, pyridine ring group, imidazole ring group, pyrazole ring group, oxazole ring group, thiazole ring group, pyridazine ring group, pyrimidine ring group, Pyrazine ring group, indole ring group, isoindole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, benzotriazole ring group, quinoline ring group, isoquinoline ring group, quinazoline ring group, quinoxaline ring group, anthraquinone Examples include ring groups.
  • the aromatic group represented by Ar a may have a substituent. Examples of the substituent include the groups listed below for substituent T.
  • Halogen atom e.g. fluorine atom, chlorine atom, bromine atom, iodine atom
  • alkyl group preferably an alkyl group having 1 to 30 carbon atoms
  • alkenyl group preferably an alkenyl group having 2 to 30 carbon atoms
  • alkynyl group preferably an alkynyl group having 2 to 30 carbon atoms
  • an aryl group preferably an aryl group having 6 to 30 carbon atoms
  • a heterocyclic group preferably a heterocyclic group having 1 to 30 carbon atoms
  • an amino group preferably an amino group having 0 to 30 carbon atoms
  • an alkoxy group preferably an alkoxy group having 1 to 30 carbon atoms
  • an aryloxy group preferably an aryloxy group having 6 to 30 carbon atoms
  • a heterocyclic oxy group preferably a carbon Heterocyclic oxy group having 1 to 30 carbon atoms
  • acyl group e.g. flu
  • Acyloxime compounds include acetophenone-O-propanoyloxime, benzophenone-O-propanoyloxime, acetone-O-propanoyloxime, acetophenone-O-butanoyloxime, benzophenone-O-butanoyloxime, acetone-O- Butanoyloxime, bis(acetophenone)-O,O'-hexane-1,6-dioyloxime, bis(benzophenone)-O,O'-hexane-1,6-dioyloxime, bis(acetone)-O , O'-hexane-1,6-dioyloxime, acetophenone-O-acryloyloxime, benzophenone-O-acryloyloxime, acetone-O-acryloyloxime, and the like.
  • onium salts include compounds having the structures described in the examples below.
  • WPBG series for example, WPBG-018, WPBG-027, WPBG-082, WPBG-140, WPBG-165, WPBG-167, WPBG-
  • WPBG-140 for example, a photobase generator manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. 168, WPBG-140, etc.
  • the content of the generator in the total solid content of the coloring composition is 2 to 15% by mass.
  • the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.
  • the upper limit is preferably 12% by mass or less, more preferably 10% by mass or less.
  • the content of the acid generator (preferably the content of the photoacid generator) in the total solid content of the colored composition is preferably 2 to 15% by mass.
  • the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.
  • the upper limit is preferably 12% by mass or less, more preferably 10% by mass or less.
  • the content of the base generator (preferably the content of the photobase generator) in the total solid content of the colored composition is preferably 2 to 15% by mass.
  • the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.
  • the upper limit is preferably 12% by mass or less, more preferably 10% by mass or less.
  • the coloring composition of the present invention contains a compound A having a cyclic ether group having a molecular weight of 5000 or less (hereinafter also referred to as compound A).
  • the molecular weight of Compound A is preferably 1,500 or less, more preferably 1,000 or less, and even more preferably 500 or less.
  • the molecular weight of Compound A is the value calculated from the structural formula.
  • the weight average molecular weight in terms of polystyrene measured by GPC gel permeation chromatography
  • Examples of the cyclic ether group that Compound A has include an epoxy group and an oxetanyl group, and an epoxy group is preferred.
  • Compound A preferably has two or more cyclic ether groups, more preferably three or more, and even more preferably four or more.
  • the upper limit of the number of cyclic ether groups is preferably 8 or less, more preferably 6 or less.
  • Compound A preferably has two or more epoxy groups, more preferably three or more, and even more preferably four or more.
  • the upper limit of the number of epoxy groups is preferably 8 or less, more preferably 6 or less.
  • Compound A is preferably a compound having a group represented by formula (EP-1).
  • the number of groups represented by formula (EP-1) in compound A is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more.
  • the upper limit is preferably 8 or less, more preferably 6 or less.
  • Compound A may further have a hydroxy group in addition to the cyclic ether group.
  • Compound A When Compound A further has a hydroxy group, it can increase its affinity with radically polymerizable monomers and the like.
  • the number of hydroxy groups contained in compound A is preferably 1 to 4, more preferably 1 to 2.
  • compound A examples include the compounds described in the Examples below.
  • commercially available products of Compound A include the Denacol series (EX-121, EX-314, EX-321L, EX-421, EX-614, etc.) manufactured by Nagase ChemteX Co., Ltd., BATG (Showa Denko K.K. )), etc.
  • the content of compound A in the total solid content of the coloring composition is preferably 1 to 30% by mass.
  • the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.
  • the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
  • the ratio of the above-mentioned generator to Compound A is preferably 30 to 700 parts by mass of Compound A to 100 parts by mass of the above-mentioned generator. According to this aspect, a dense cured film can be formed.
  • the upper limit is preferably 500 parts by mass or less, more preferably 350 parts by mass or less.
  • the lower limit is preferably 50 parts by mass or more, more preferably 70 parts by mass or more.
  • the colored composition of the present invention may contain only one type of compound A, or may contain two or more types of compound A. When two or more types of compound A are included, it is preferable that the total amount thereof falls within the above range.
  • the colored composition of the present invention contains a solvent.
  • the solvent include organic solvents.
  • the type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition.
  • the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
  • paragraph number 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein.
  • Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used.
  • organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N
  • aromatic hydrocarbons benzene, toluene, xylene, ethylbenzene, etc.
  • organic solvents for environmental reasons (for example, 50 mass ppm (parts) based on the total amount of organic solvents). per million), 10 mass ppm or less, and 1 mass ppm or less).
  • an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content. It is preferable that the metal content of the organic solvent is, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by Toyo Gosei Co., Ltd. (Kagaku Kogyo Nippo, November 13, 2015). .
  • Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.
  • the organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one type of isomer may be included, or multiple types may be included.
  • the content of peroxide in the organic solvent is 0.8 mmol/L or less, and it is more preferable that the organic solvent contains substantially no peroxide.
  • the content of the solvent in the coloring composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.
  • the colored composition of the present invention does not substantially contain environmentally regulated substances.
  • "not substantially containing environmentally controlled substances” means that the content of environmentally controlled substances in the coloring composition is 50 mass ppm or less, preferably 30 mass ppm or less. , more preferably 10 mass ppm or less, particularly preferably 1 mass ppm or less.
  • environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • REACH Registration Evaluation Authorization and Restriction of CHemicals
  • PRTR Policy Release and It is registered as an environmentally regulated substance under the Transfer Register Act
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • the method is strictly regulated.
  • These compounds may be used as a solvent when producing each component used in the coloring composition, and may be mixed into the coloring composition as a residual solvent. From the viewpoint of human safety and environmental considerations, it is preferable to reduce the amount of these substances as much as possible.
  • methods for reducing environmentally controlled substances include a method of heating or reducing pressure in the system to raise the temperature above the boiling point of the environmentally controlled substance to distill off the environmentally controlled substances from the system.
  • distillation methods can be used at the stage of raw materials, at the stage of products obtained by reacting raw materials (for example, resin solution or polyfunctional monomer solution after polymerization), or at the stage of colored compositions prepared by mixing these compounds. This is possible at any stage.
  • the colored composition of the present invention can contain a pigment derivative.
  • the pigment derivative include compounds having at least one structure selected from the group consisting of a pigment structure and a triazine structure, and an acid group or a basic group.
  • the above dye structures include quinoline dye structure, benzimidazolone dye structure, benzisoindole dye structure, benzothiazole dye structure, iminium dye structure, squarylium dye structure, croconium dye structure, oxonol dye structure, pyrrolopyrrole dye structure, diketo Pyrrolopyrrole dye structure, azo dye structure, azomethine dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, anthraquinone dye structure, quinacridone dye structure, dioxazine dye structure, perinone dye structure, perylene dye structure, thiazine indigo dye structure, thioindigo dye structure, isoindoline dye structure, isoindolinone dye structure, quinophthalone dye structure, dithiol dye structure, triarylmethane dye structure, pyrromethene dye structure, etc.
  • Examples of the acid group that the pigment derivative has include a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, an imide acid group, and salts thereof.
  • Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + , etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ , etc.), ammonium ions, imidazolium ions, pyridinium ions, Examples include phosphonium ions.
  • the imide acid group is preferably a group represented by -SO 2 NHSO 2 R X1 , -CONHSO 2 R X2 , -CONHCOR X3 or -SO 2 NHCOR , or -SO 2 NHCOR X4 is more preferred, and -SO 2 NHSO 2 R X1 or -CONHSO 2 R X2 is even more preferred.
  • R X1 to R X4 each independently represent an alkyl group or an aryl group.
  • the alkyl group and aryl group represented by R X1 to R X4 may have a substituent.
  • the substituent is preferably a halogen atom, more preferably a fluorine atom.
  • R X1 to R X4 are each independently preferably an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and more preferably an alkyl group containing a fluorine atom.
  • the number of carbon atoms in the alkyl group containing a fluorine atom is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
  • the number of carbon atoms in the aryl group containing a fluorine atom is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6.
  • Examples of the basic group that the pigment derivative has include an amino group, a pyridinyl group and its salts, an ammonium group salt, and a phthalimidomethyl group.
  • Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
  • a pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative) can be used.
  • the maximum molar extinction coefficient ( ⁇ max) of the transparent pigment derivative in the wavelength range of 400 to 700 nm is preferably 3000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less, and preferably 1000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less. is more preferable, and even more preferably 100 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less.
  • the lower limit of ⁇ max is, for example, 1 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more, and may be 10 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more.
  • pigment derivatives include the compounds described in paragraph 0124 of International Publication No. 2022/085485, and the benzimidazolone compounds or salts thereof described in JP-A-2018-168244.
  • the content of the pigment derivative is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the pigment.
  • the lower limit of this range is more preferably 0.25 parts by mass or more, even more preferably 0.5 parts by mass or more, particularly preferably 0.75 parts by mass or more, and 1 part by mass or more. It is more preferable that there be.
  • the upper limit of this range is more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less.
  • the storage stability of the colored composition can be further improved. Only one type of pigment derivative may be used, or two or more types may be used in combination. When two or more types are used together, it is preferable that the total amount thereof falls within the above range.
  • the colored composition of the present invention can also contain polyalkyleneimine.
  • Polyalkyleneimines are used, for example, as dispersion aids.
  • Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine.
  • the polyalkyleneimine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group, respectively.
  • the alkylene imine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
  • the molecular weight of the polyalkylene imine is preferably 200 or more, more preferably 250 or more.
  • the upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less.
  • the molecular weight of the polyalkylene imine if the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkylene imine is the value calculated from the structural formula.
  • the molecular weight of a specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used.
  • the value of the number average molecular weight measured by the viscosity method is used. If the viscosity method cannot be used or it is difficult to measure, the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) is used.
  • the amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
  • alkyleneimine examples include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, etc. Ethyleneimine or propyleneimine is preferable, and ethyleneimine is more preferable. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. Further, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more of primary amino groups based on the total of primary amino groups, secondary amino groups, and tertiary amino groups. , more preferably 30 mol% or more.
  • Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).
  • the content of polyalkyleneimine in the total solid content of the coloring composition is preferably 0.1 to 5% by mass.
  • the lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
  • the upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
  • the content of polyalkyleneimine is preferably 0.5 to 20 parts by weight per 100 parts by weight of the pigment.
  • the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more.
  • the upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. Only one type of polyalkylene imine may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.
  • the colored composition of the present invention may also contain a curing accelerator.
  • the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds, and the like.
  • Specific examples of the curing accelerator include the compound described in paragraph 0164 of International Publication No. 2022/085485, the compound described in JP 2021-181406, and the like.
  • the content of the curing accelerator in the total solid content of the colored composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
  • the colored composition of the present invention can contain a silane coupling agent.
  • the silane coupling agent is preferably a silane compound having a hydrolyzable group, more preferably a silane compound having a hydrolyzable group and other functional groups.
  • the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkoxy group is preferred.
  • Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, and isocyanate groups. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferable.
  • the silane coupling agent is preferably a compound having an alkoxysilyl group. Specific examples of the silane coupling agent include compounds described in paragraph 0177 of International Publication No. 2022/085485.
  • the content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and even more preferably 0.1% to 5% by mass. preferable.
  • the colored composition of the present invention may contain only one kind of silane coupling agent, or may contain two or more kinds of silane coupling agents. When two or more types are included, it is preferable that their total amount falls within the above range.
  • the colored composition of the present invention can contain a polymerization inhibitor.
  • Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-t-butylphenol), Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.).
  • the content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5% by mass.
  • the colored composition of the present invention may contain only one kind of polymerization inhibitor, or may contain two or more kinds of polymerization inhibitors. When two or more types are included, it is preferable that their total amount falls within the above range.
  • the colored composition of the present invention can contain an ultraviolet absorber.
  • an ultraviolet absorber a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, etc.
  • Specific examples of such compounds include the compound described in paragraph number 0179 of International Publication No. 2022/085485.
  • the content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 3% by mass.
  • the colored composition of the present invention may contain only one kind of ultraviolet absorber, or may contain two or more kinds of ultraviolet absorbers. When two or more types are included, it is preferable that their total amount falls within the above range.
  • the colored composition of the present invention can contain a surfactant.
  • a surfactant various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.
  • the surfactant is preferably a fluorosurfactant or a silicone surfactant, more preferably a silicone surfactant.
  • examples of the surfactant include the surfactants described in paragraph numbers 0238 to 0245 of International Publication No. 2015/166779, the contents of which are incorporated herein.
  • fluorine-based surfactant examples include compounds described in paragraph numbers 0167 to 0173 of International Publication No. 2022/085485.
  • nonionic surfactants examples include compounds described in paragraph 0174 of International Publication No. 2022/085485.
  • silicone -based surfactants include DOWSIL SH8400, SH8400 FLUID, FZ -1222, 67 ADDITIVE, 74 ADDITIVE, SF 8419 OIL (more than Dow Toray Co., Ltd.), TSF -430.
  • TSF -4445, TSF-4460, TSF-4452 manufactured by Momentive Performance Materials
  • KP-341, KF-6000, KF-6001, KF-6002, KF-6003 manufactured by Shin-Etsu Chemical Co., Ltd.
  • BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 manufactured by BYK Chemie
  • a compound having the following structure can also be used as the silicone surfactant.
  • the content of the surfactant in the total solid content of the coloring composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% to 3.0% by mass.
  • the colored composition of the present invention may contain only one kind of surfactant, or may contain two or more kinds of surfactants. When two or more types are included, it is preferable that their total amount falls within the above range.
  • the colored composition of the present invention can contain an antioxidant.
  • antioxidants include phenol compounds, phosphite compounds, thioether compounds, and the like.
  • the phenol compound any phenol compound known as a phenolic antioxidant can be used.
  • Preferred phenol compounds include hindered phenol compounds.
  • a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred.
  • the above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms.
  • a compound having a phenol group and a phosphorous acid ester group in the same molecule is also preferable.
  • phosphorus-based antioxidants can also be suitably used.
  • a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl )oxy]ethyl]amine, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
  • antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Co., Ltd.).
  • antioxidants include compounds described in paragraph numbers 0023 to 0048 of Patent No. 6268967, compounds described in International Publication No. 2017/006600, compounds described in International Publication No. 2017/164024, Compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used.
  • the content of the antioxidant in the total solid content of the coloring composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.
  • the coloring composition of the present invention may optionally contain sensitizers, plasticizers, and other auxiliary agents (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances). , surface tension regulator, chain transfer agent, latent antioxidant, etc.).
  • sensitizers plasticizers
  • other auxiliary agents e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances.
  • surface tension regulator e.g., surface tension regulator, chain transfer agent, latent antioxidant, etc.
  • the colored composition of the present invention may also contain a lightfastness improver.
  • a lightfastness improver examples include compounds described in paragraph number 0183 of International Publication No. 2022/085485.
  • the colored composition of the present invention is substantially free of terephthalic acid ester.
  • substantially not containing means that the content of terephthalic acid ester is 1000 mass ppb or less in the total amount of the coloring composition, more preferably 100 mass ppb or less, Particularly preferred is zero.
  • the colored composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less. Further, the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Examples of methods for reducing free metals and halogens in the colored composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification using ion-exchange resins.
  • perfluoroalkyl sulfonic acids and their salts may be regulated.
  • perfluoroalkylsulfonic acids particularly perfluoroalkylsulfonic acids whose perfluoroalkyl group has 6 to 8 carbon atoms
  • salts thereof and perfluoroalkylsulfonic acids
  • the content of fluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid whose perfluoroalkyl group has 6 to 8 carbon atoms) and its salt is 0.01 ppb to 1,000 ppb based on the total solid content of the coloring composition.
  • the coloring composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt.
  • a coloring composition that is substantially free of and salts thereof.
  • Compounds that can be substituted for regulated compounds include, for example, compounds that are excluded from regulated targets due to differences in the number of carbon atoms in perfluoroalkyl groups.
  • the colored compositions of the present invention may include perfluoroalkyl sulfonic acids and salts thereof, and perfluoroalkyl carboxylic acids and salts thereof, to the maximum extent permissible.
  • the container for storing the coloring composition is not particularly limited, and any known container can be used. Further, as the storage container, the container described in paragraph 0187 of International Publication No. 2022/085485 can be used.
  • the colored composition of the present invention can be produced by mixing the above-mentioned components.
  • the colored composition may be produced by dissolving and/or dispersing all components in a solvent at the same time, or, if necessary, each component may be suitably prepared as two or more solutions or dispersions.
  • the colored composition may be manufactured by mixing these at the time of use (at the time of application).
  • the production of the colored composition may include a process of dispersing pigments.
  • mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like.
  • Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like.
  • pulverizing pigments in a sand mill (bead mill) it is preferable to use small-diameter beads or increase the filling rate of the beads, thereby increasing the pulverizing efficiency.
  • the process and dispersion machine for dispersing pigments are described in ⁇ Complete Works of Dispersion Technology, Published by Information Technology Corporation, July 15, 2005'' and ⁇ Dispersion technology centered on suspension (solid/liquid dispersion system) and industrial
  • the process and dispersion machine described in Paragraph No. 0022 of JP 2015-157893 A, "Practical Application Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be suitably used.
  • the particles may be made finer in a salt milling step.
  • the descriptions in JP-A No. 2015-194521 and JP-A No. 2012-046629 can be referred to, for example.
  • the colored composition In preparing the colored composition, it is preferable to filter the colored composition with a filter for the purpose of removing foreign substances and reducing defects.
  • a filter for the purpose of removing foreign substances and reducing defects.
  • Examples of the type of filter and filtration method used for filtration include the filters and filtration methods described in paragraph numbers 0196 to 0199 of International Publication No. 2022/085485.
  • the cured film of the present invention is a cured film obtained from the colored composition of the present invention described above.
  • the cured film of the present invention can be used for optical filters such as color filters.
  • the thickness of the cured film of the present invention can be adjusted as appropriate depending on the purpose.
  • the film thickness is preferably 0.5 to 3.0 ⁇ m.
  • the lower limit is preferably 0.8 ⁇ m or more, more preferably 1.0 ⁇ m or more, and even more preferably 1.1 ⁇ m or more.
  • the upper limit is preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, and even more preferably 1.8 ⁇ m or less.
  • the line width (pattern size) of the cured film is preferably 2.0 to 10.0 ⁇ m.
  • the upper limit is preferably 7.5 ⁇ m or less, more preferably 5.0 ⁇ m or less, and even more preferably 4.0 ⁇ m or less.
  • the lower limit is preferably 2.25 ⁇ m or more, more preferably 2.5 ⁇ m or more, and even more preferably 2.75 ⁇ m or more.
  • the color filter of the present invention has the cured film of the present invention described above. It is preferable to have the cured film of the present invention as a pixel (preferably a colored pixel) of a color filter.
  • the color filter of the present invention can be used in solid-state imaging devices and display devices.
  • the pixel line width is preferably 2.0 to 10.0 ⁇ m.
  • the upper limit is preferably 7.5 ⁇ m or less, more preferably 5.0 ⁇ m or less, and even more preferably 4.0 ⁇ m or less.
  • the lower limit is preferably 2.25 ⁇ m or more, more preferably 2.5 ⁇ m or more, and even more preferably 2.75 ⁇ m or more.
  • a preferred embodiment of the color filter of the present invention includes an embodiment having a red pixel, a blue pixel, and a green pixel. It is preferable that at least one selected from a red pixel, a blue pixel, and a green pixel is formed using the colored composition of the present invention.
  • the color filter may have a structure in which each colored pixel is embedded in a space partitioned into, for example, a lattice shape by partition walls.
  • the partition wall preferably has a lower refractive index than each colored pixel.
  • the partition wall may be formed with the configuration described in US Patent Application Publication No. 2018/0040656.
  • a protective layer may be provided on the surface of the cured film of the present invention.
  • various functions such as oxygen blocking, low reflection, hydrophilic and hydrophobic properties, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted.
  • the thickness of the protective layer is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m. Examples of methods for forming the protective layer include a method of coating a resin composition dissolved in an organic solvent, a chemical vapor deposition method, and a method of pasting a molded resin with an adhesive.
  • Components constituting the protective layer include (meth)acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide.
  • Resin polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Examples include resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al 2 O 3 , Mo, SiO 2 , Si 2 N 4 and the like, and two or more of these components may be contained.
  • the protective layer preferably contains a polyol resin, SiO 2 and Si 2 N 4 .
  • the protective layer preferably contains a (meth)acrylic resin and a fluororesin.
  • a protective layer by applying a resin composition known methods such as a spin coating method, a casting method, a screen printing method, an inkjet method, etc. can be used as a method for applying the resin composition.
  • organic solvent contained in the resin composition known organic solvents (eg, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used.
  • chemical vapor deposition methods thermal chemical vapor deposition, plasma enhanced chemical vapor deposition, photochemical vapor deposition
  • photochemical vapor deposition can be used as the chemical vapor deposition method.
  • the protective layer may contain organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants, and other additives, as necessary. It may contain.
  • organic/inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like.
  • the absorber for light of a specific wavelength a known absorber can be used.
  • the content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, based on the total weight of the protective layer.
  • the protective layers described in paragraph numbers 0073 to 0092 of JP 2017-151176 A can also be used.
  • the method for producing a cured film of the present invention includes a step of applying the above-described colored composition of the present invention onto a support to form a colored composition layer; a step of exposing the colored composition layer to light in a pattern; The method includes a step of developing the colored composition layer after exposure and removing the colored composition layer in the unexposed area. Then, a cured film in which the colored composition layer is cured is obtained at a temperature of 150° C. or lower (preferably 120° C. or lower, more preferably 100° C. or lower) throughout the entire process.
  • all steps are performed at a temperature of 150° C. or lower means that all steps of forming a cured film using a colored composition are performed at a temperature of 150° C. or lower.
  • this heating step is also performed at a temperature of 150° C. or lower. The details of each process will be described below.
  • a colored composition is applied onto a support to form a colored composition layer.
  • the support include a glass substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, and the like.
  • An organic light emitting layer may be formed on these substrates.
  • an undercoat layer may be provided on the substrate to improve adhesion with the upper layer, prevent substance diffusion, or flatten the surface.
  • the surface contact angle of the undercoat layer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferable that the angle is 30 to 80° when measured with water.
  • a known method can be used to apply the coloring composition.
  • dropping method drop casting
  • slit coating method spray method
  • roll coating method spin coating method
  • casting coating method slit and spin method
  • Various methods such as inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Examples include printing method; transfer method using a mold etc.; nanoimprint method.
  • the application method for inkjet is not particularly limited, and for example, the method shown in "Expanding and Usable Inkjet - Infinite Possibilities Seen in Patents," Published February 2005, Sumibe Techno Research (especially from page 115).
  • the colored composition layer formed on the support may be dried (prebaked).
  • the prebaking temperature is preferably 80°C or lower, more preferably 70°C or lower, even more preferably 60°C or lower, and particularly preferably 50°C or lower.
  • the lower limit can be, for example, 40°C or higher.
  • the pre-bake time is preferably 10 to 3600 seconds. Prebaking can be performed on a hot plate, oven, or the like.
  • the colored composition layer is exposed in a pattern.
  • the colored composition layer can be exposed in a pattern by exposing it to light through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. This allows the exposed portion to be cured.
  • Radiation (light) that can be used during exposure includes g-line, i-line, etc. Furthermore, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm). Furthermore, a long-wave light source of 300 nm or more can also be used.
  • pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the millisecond level or less).
  • the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less.
  • the lower limit of the pulse width is not particularly limited, but can be 1 femtosecond (fs) or more, and can also be 10 femtoseconds or more.
  • the frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and even more preferably 4 kHz or more.
  • the upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and even more preferably 10 kHz or less.
  • the maximum instantaneous illuminance is preferably 500000000 W/m 2 or more, more preferably 100000000 W/m 2 or more, and even more preferably 200000000 W/m 2 or more. Further, the upper limit of the maximum instantaneous illuminance is preferably 1000000000 W/m 2 or less, more preferably 800000000 W/m 2 or less, and even more preferably 500000000 W/m 2 or less.
  • the pulse width refers to the time during which light is irradiated in a pulse period.
  • frequency refers to the number of pulse periods per second.
  • the maximum instantaneous illuminance is the average illuminance within the time period during which light is irradiated in the pulse period.
  • the pulse period is a period in which one cycle includes light irradiation and a pause in pulse exposure.
  • the irradiation amount (exposure amount) is preferably 30 to 2500 mJ/cm 2 .
  • the lower limit is preferably 50 mJ/cm 2 or more, more preferably 100 mJ/cm 2 or more, even more preferably 500 mJ/cm 2 or more, even more preferably 800 mJ/cm 2 or more. , 1000 mJ/cm 2 or more is even more preferable.
  • the upper limit is preferably 2000 mJ/cm 2 or less, more preferably 1500 mJ/cm 2 or less.
  • the exposure illuminance can be set as appropriate, and is preferably, for example, 50 mW/cm 2 to 10 W/cm 2 .
  • the lower limit of the exposure illuminance is preferably 500 mW/cm 2 or more, more preferably 800 mW/cm 2 or more, and even more preferably 1000 mW/cm 2 or more.
  • the upper limit of the exposure illuminance is preferably 10 W/cm 2 or less, more preferably 7 W/cm 2 or less, and even more preferably 5 W/cm 2 or less.
  • the oxygen concentration at the time of exposure can be appropriately selected, and in addition to being carried out in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially
  • the exposure may be performed in an oxygen-free environment (in the absence of oxygen), or in a high oxygen atmosphere with an oxygen concentration of more than 21 volume % (for example, 22 volume %, 30 volume %, or 50 volume %).
  • the oxygen concentration and the exposure illuminance may be appropriately combined.
  • the illumination intensity may be 1 W/cm 2 at an oxygen concentration of 10% by volume, or 2 W/cm 2 at an oxygen concentration of 35% by volume.
  • the colored composition layer is preferably exposed to light with a wavelength of more than 250 nm and less than 380 nm at an exposure dose of 100 mJ/cm 2 or more.
  • the colored composition layer after exposure is developed to remove the colored composition layer in the unexposed areas.
  • the unexposed areas of the colored composition layer can be removed using a developer.
  • the unexposed portions of the colored composition layer are eluted into the developer, leaving only the photocured portions.
  • the temperature of the developer is preferably, for example, 20 to 30°C.
  • the development time is preferably 20 to 180 seconds. Furthermore, in order to improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
  • Examples of the developer include organic solvents and alkaline developers, and alkaline developers are preferred.
  • the developer and cleaning method after development the developer and cleaning method described in paragraph number 0214 of International Publication No. 2022/085485 can be used.
  • the exposed colored composition layer it is also preferable to heat the exposed colored composition layer at a temperature of 150° C. or lower, and then perform the development described above.
  • the upper limit of the heating temperature in the heat treatment before development is preferably 120°C or less, more preferably 100°C or less.
  • the lower limit of the heating temperature is preferably 50°C or higher, more preferably 75°C or higher.
  • the heating time is preferably 1 minute or more, more preferably 5 minutes or more, and even more preferably 10 minutes or more.
  • the upper limit is not particularly limited, but from the viewpoint of productivity, it is preferably 20 minutes or less.
  • Additional exposure processing and post-bake are post-development curing processing to complete curing.
  • the heating temperature is preferably 150°C or less.
  • the upper limit of the heating temperature is preferably 120°C or lower, more preferably 100°C or lower.
  • the lower limit of the heating temperature is preferably 50°C or higher, more preferably 75°C or higher.
  • the heating time is preferably 1 minute or more, more preferably 5 minutes or more, and even more preferably 10 minutes or more.
  • the upper limit is not particularly limited, but from the viewpoint of productivity, it is preferably 20 minutes or less. It is also preferable that post-baking is performed under an inert gas atmosphere. According to this aspect, thermal polymerization can proceed with extremely high efficiency without being inhibited by oxygen, and even when pixels are manufactured at a temperature of 150° C.
  • the inert gas include nitrogen gas, argon gas, helium gas, etc., and nitrogen gas is preferred.
  • the oxygen concentration during post-baking is preferably 100 ppm or less.
  • the step of exposing the colored composition layer to light in a pattern involves exposing the colored composition layer to light with a wavelength of more than 350 nm and less than or equal to 380 nm (preferably light with a wavelength of 355 to 370 nm
  • the additional exposure treatment is performed by exposing the colored composition layer to light with a wavelength of 254 to 350 nm (preferably light with a wavelength of 254 nm). ) is preferably used for exposure.
  • the colored composition layer can be moderately cured with the first exposure (exposure before development), and the entire colored composition layer can be almost completely cured with the next exposure (exposure after development).
  • the colored composition layer can be sufficiently cured even under low temperature conditions, and pixels with excellent properties such as moisture resistance, adhesion, and rectangularity can be formed.
  • the colored composition contains, as a photopolymerization initiator, a photopolymerization initiator A1 having an extinction coefficient of 1.0 ⁇ 10 3 mL/g cm or more at a wavelength of 365 nm in methanol.
  • the extinction coefficient at a wavelength of 365 nm in methanol is 1.0 ⁇ 10 2 mL/g cm or less and the extinction coefficient at a wavelength of 254 nm is 1.0 ⁇ 10 3 mL/g cm or more. It is preferable to use one containing Agent A2.
  • Exposure after development can be performed using, for example, an ultraviolet photoresist curing device.
  • the ultraviolet photoresist curing device may emit light having a wavelength of 254 to 350 nm, as well as other light (for example, i-line).
  • the exposure source spectrum in the case of performing additional exposure processing is preferably a continuous spectrum, and more preferably has a different spectral distribution from the exposure before development.
  • the following radiations (a) to (c) can be mentioned.
  • the upper limit of the peak intensity at a wavelength of 313 nm is not particularly limited, it is preferably smaller than the peak intensity at a wavelength of 365 nm, and more preferably 3/4 or less.
  • the intensity is 1/4 or less, preferably 1/10 or less, more preferably 1/20 of the smaller peak intensity of the peak intensity at a wavelength of 405 nm (h line) and the peak intensity at a wavelength of 436 nm (g line). radiation.
  • the lower limit of the peak intensity at a wavelength of 313 nm (J-line) and a wavelength of 365 nm (i-line) is not particularly limited.
  • the exposure before development is radiation including a wavelength of 365 nm (i-line), a wavelength of 405 nm (h-line), and a wavelength of 436 nm (g-line), and the peak intensity at a wavelength of 313 nm (j-line) is 365 nm ( Radiation having a peak intensity of less than 1/6 with respect to the peak intensity in i-line) is preferred.
  • Radiation exhibiting such spectral characteristics can be obtained, for example, by using a light source exhibiting spectral characteristics as described above, or by passing radiation emitted from a high-pressure mercury lamp through an ultraviolet cut filter or a bandpass filter.
  • the irradiation amount (exposure amount) in the exposure after development is preferably 30 to 4000 mJ/cm 2 , more preferably 50 to 3500 mJ/cm 2 .
  • the difference between the wavelength of light used for exposure before development and the wavelength of light used for exposure after development is preferably 200 nm or less, more preferably 100 to 150 nm.
  • the display device of the present invention has the film of the present invention described above.
  • Examples of the display device include a liquid crystal display device and an organic electroluminescence display device.
  • a display device and details of each display device see, for example, “Electronic Display Devices (written by Akio Sasaki, Kogyo Chosenkai Co., Ltd., published in 1990)” and “Display Devices (written by Junaki Ibuki, published by Sangyo Tosho Co., Ltd.)". (published in 1989).
  • liquid crystal display devices are described, for example, in “Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994)".
  • the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology.”
  • the organic electroluminescent display device may be a microdisplay.
  • the diagonal length of the display surface of the microdisplay can be, for example, 4 inches or less, 2 inches or less, 1 inch or less, and 0.2 inches or less. You can also do it.
  • Applications of microdisplays include, but are not limited to, electronic viewfinders, smart glasses, head-mounted displays, and the like.
  • the organic electroluminescent display device may have a light source made of a white organic electroluminescent element.
  • the white organic electroluminescent device preferably has a tandem structure.
  • Regarding the tandem structure of organic electroluminescent elements see Japanese Patent Application Laid-open No. 2003-045676, supervised by Akiyoshi Mikami, "The forefront of organic EL technology development - High brightness, high precision, long life, collection of know-how", Technical Information Association. , pp. 326-328, 2008.
  • the spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430 nm to 485 nm), green region (530 nm to 580 nm), and yellow region (580 nm to 620 nm). In addition to these emission peaks, it is more preferable to have a maximum emission peak in the red region (650 nm to 700 nm).
  • the organic electroluminescent display device may have a color filter.
  • the color filter may be provided on the base layer.
  • transparent pixels may be provided and the white light may be used as it is for light emission. By doing so, the brightness of the display device can also be increased.
  • the organic electroluminescent display device may have a lens on the color filter.
  • the shape of the lens can take various shapes derived from optical system design, such as a convex shape and a concave shape. For example, by having a concave shape (concave lens), it is easy to improve the light condensing property.
  • the lens may be in direct contact with the color filter, or other layers such as an adhesion layer or a flattening layer may be provided between the lens and the color filter. Further, the lenses can also be used by being arranged in the manner described in International Publication No. 2018/135189.
  • An organic electroluminescent display device is an organic electroluminescent display device that has an organic electroluminescent element that displays at least red, green, and blue on a substrate, and a colored layer having the same color as the organic electroluminescent element above the organic electroluminescent element. There may be. Examples of such an organic electroluminescent display device include the organic electroluminescent display device described in JP-A No. 2022-066859.
  • the colored composition and cured film of the present invention can also be used in solid-state imaging devices.
  • the configuration of the solid-state image sensor is not particularly limited as long as it functions as a solid-state image sensor, but examples include the following configurations.
  • the substrate has a plurality of photodiodes that constitute the light receiving area of a solid-state image sensor (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon or the like.
  • a device protective film made of silicon nitride or the like is formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a configuration in which a color filter is provided on the device protective film.
  • a configuration in which a light condensing means (for example, a microlens, etc., the same applies hereinafter) is provided on the device protective film and below the color filter (on the side closer to the substrate), or a configuration in which the condensing means is provided on the color filter, etc.
  • the pixels of the color filter may be embedded in a space partitioned, for example, in a grid pattern by partition walls.
  • the refractive index of the partition wall is preferably lower than that of the pixel. Examples of imaging devices having such a structure are described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, International Publication No. 2018/043654, and US Patent Application Publication No.
  • An imaging device including a solid-state imaging device can be used not only as a digital camera or an electronic device having an imaging function (such as a mobile phone), but also as an in-vehicle camera or a surveillance camera.
  • Pigment derivative 1 Compound with the following structure
  • Dispersant 1 Resin with the following structure (The number in parentheses of the main chain represents the molar ratio of each repeating unit, and the number in parentheses of the side chain represents the number of repeating units. The weight average molecular weight is 20,000.)
  • PR254 C. I. pigment red 254 PR177: C. I. pigment red 177 PR264: C. I. pigment red 264 PR269: C. I. pigment red 269 PR291: C. I. pigment red 291 PY139: C. I. pigment yellow 139 PY150: C. I. pigment yellow 150 PY185: C. I. pigment yellow 185 PG7: C. I. pigment green 7 PG36: C. I. pigment green 36 PG58: C. I. pigment green 58 PB15:4: C. I. pigment blue 15:4 PB15:6: C. I. pigment blue 15:6 PV23: C. I. pigment violet 23
  • A1 Irgacure OXE02 (manufactured by BASF, photoradical polymerization initiator, oxime compound)
  • A2 KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd., photoradical polymerization initiator, compound with the following structure)
  • A3 Irgacure OXE01 (manufactured by BASF, photoradical polymerization initiator, oxime compound)
  • A4 Omnirad 2959 (manufactured by IGM Resins B.V., photoradical polymerization initiator, ⁇ -hydroxyketone compound)
  • PAG1 IRGACURE PAG-103 (manufactured by BASF, compound with the following structure, oxime sulfonate compound, photoacid generator)
  • PAG2 MOP-triazine (manufactured by Sanwa Chemical Co., Ltd., compound with the following structure, triazine compound, photoacid generator)
  • TAG1 Sunaid SI-60 (manufactured by Sanshin Chemical Industry Co., Ltd., sulfonium salt, thermal acid generator)
  • PBG1 WPBG-018 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., compound with the following structure, carbamate compound, photobase generator)
  • PBG2 WPBG-226 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., compound with the following structure, onium salt, photobase generator)
  • PBG3 Compound with the following structure (onium salt, photobase generator)
  • PBG4 Acetophenone-O-propanoyloxime (photobase generator, acyloxime compound)
  • TBG1 U-CAT SA1 (manufactured by San-Apro Co., Ltd., thermal base generator)
  • (resin) B1 40% by mass propylene glycol monomethyl ether acetate solution of resin with the following structure (the numbers appended to the main chain are molar ratios; weight average molecular weight 11000, acid value 69 mgKOH/g)
  • B2 Resin synthesized by the following method 196 parts by mass of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80 ° C.
  • E1 Compound with the following structure (molecular weight 406)
  • E2 Compound with the following structure (molecular weight 452)
  • E3 Mixture of compounds with the following structure (molecular weight of the compound with the structure on the left: 204, molecular weight of the compound with the structure on the right: 260)
  • E4 Mixture of compounds with the following structure (molecular weight of the compound with the structure on the left: 304, molecular weight of the compound with the structure on the right: 246)
  • E5 Compound with the following structure (molecular weight 334)
  • E6 Compound with the following structure (molecular weight 186)
  • cE1 Epoxy polymer with the following structure (the number appended to the main chain is
  • surfactant G1 KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone surfactant)
  • G2 DOWSIL SH8400 FLUID (manufactured by Dow Toray Industries, Inc., silicone surfactant)
  • Viscosity increase rate (%) [(viscosity (V2) - viscosity (V1)) / viscosity (V1)] x 100 5: The viscosity increase rate is less than 0.25% 4: The viscosity increase rate is 0.25% or more and less than 1% 3: The viscosity increase rate is 1% or more and less than 2.5% 2: The viscosity increase rate is 2.5% or more and less than 5% 1: Thickening rate is 5% or more
  • the colored composition obtained above was applied onto a glass substrate using a spin coater so that the finished film thickness after drying was 1.5 ⁇ m, and dried on a hot plate at 80° C. for 2 minutes. Thereafter, exposure was performed using an ultra-high pressure mercury lamp under conditions of an exposure illuminance of 20 mW/cm 2 and an exposure amount of 1000 mJ/cm 2 . Next, it was heated on a hot plate at 100° C. for 20 minutes and allowed to cool to form a cured film. A humidity resistance test was carried out in which the obtained cured film was exposed to white light emitting diode light for 1000 hours at a temperature of 85° C. and a humidity of 85%.
  • the spectral transmittance of the cured film before and after the moisture resistance test was measured. In the wavelength range of 400 to 1100 nm, the rate of change in transmittance was calculated for each measured wavelength, and the moisture resistance was evaluated as follows using the maximum value of these rates of change as an index. Note that a surface emitting light source (LEDVH390-W, manufactured by Misumi) was used as a light source for white light emitting diode light. 5: The rate of change serving as an index is 1% or less. 4: The indicator change rate is greater than 1% and 2% or less. 3: The indicator change rate is greater than 2% and 3% or less. 2: The indicator change rate is greater than 3% and 4% or less. Yes 1: The indicator change rate is greater than 4%
  • the content of the coloring agent in the total solid content of the coloring composition is recorded in the column of colorant content, and the content of the coloring agent (acid generator or base generator) in the total solid content of the coloring composition is recorded. Record the content in the generator content column.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)

Abstract

This coloring composition contains a coloring agent, a resin, a radically polymerizable monomer, a radical polymerization initiator, at least one generator which is selected from the group consisting of an acid generator and a base generator, and a compound A which has a cyclic ether group, while having a molecular weight of 5,000 or less. With respect to this coloring composition, the content of the coloring agent relative to the total solid content of this coloring composition is 35% by mass or more, and the content of the generator relative to the total solid content of this coloring composition is 2 to 15% by mass. The present invention also provides a cured film, a color filter, a display device and a method for producing a cured film, each of which uses this coloring composition.

Description

着色組成物、硬化膜、カラーフィルタ、表示装置及び硬化膜の製造方法Colored composition, cured film, color filter, display device, and method for producing cured film
　本発明は、着色剤を含む着色組成物に関する。また、本発明は、着色組成物を用いた硬化膜、カラーフィルタ、表示装置及び硬化膜に関する。 The present invention relates to a colored composition containing a coloring agent. The present invention also relates to a cured film, a color filter, a display device, and a cured film using the colored composition.
　近年、デジタルカメラ、カメラ付き携帯電話等の普及から、電荷結合素子（ＣＣＤ）イメージセンサなどの固体撮像素子の需要が大きく伸びている。ディスプレイや光学素子のキーデバイスとしてカラーフィルタが使用されている。カラーフィルタは、通常、赤、緑及び青の３原色の画素を備えており、透過光を３原色へ分解する役割を果たしている。 In recent years, with the spread of digital cameras, camera-equipped mobile phones, etc., demand for solid-state image sensors such as charge-coupled device (CCD) image sensors has increased significantly. Color filters are used as key devices for displays and optical elements. A color filter usually includes pixels of three primary colors, red, green, and blue, and serves to separate transmitted light into the three primary colors.
　カラーフィルタの各色の着色画素は、着色剤を含む着色組成物を用いて製造されている。 The colored pixels of each color of the color filter are manufactured using a colored composition containing a coloring agent.
　特許文献１には、多官能エポキシ化合物と、ジアリールヨードニウム塩である酸発生剤と、緑色顔料とを含むカラーフィルター用緑色硬化性樹脂組成物に関する発明が記載されている。 Patent Document 1 describes an invention relating to a green curable resin composition for color filters containing a polyfunctional epoxy compound, an acid generator that is a diaryliodonium salt, and a green pigment.
特開２０１０－０８５７６８号公報Japanese Patent Application Publication No. 2010-085768
　近年においては、耐熱性の低い部材上に、硬化膜を形成する試みが行われている。例えば、近年の表示装置は有機エレクトロルミネッセンス（ＥＬ）化が進んでいる。有機発光ダイオードなどの有機エレクトロルミネッセンス素子は、耐熱性が低い部材であるため、このような耐熱性の低い部材上に硬化膜を形成する場合には、例えば１５０℃以下の低温プロセスで硬化膜を形成して、支持体への熱的ダメージを抑制することが望ましい。しかしながら、低温プロセスで硬化膜を形成した場合、硬化膜の硬化度合が不十分なことがあり、硬化膜の耐湿性について改善の余地があった。 In recent years, attempts have been made to form cured films on members with low heat resistance. For example, display devices in recent years are increasingly using organic electroluminescence (EL). Organic electroluminescent elements such as organic light emitting diodes are materials with low heat resistance, so when forming a cured film on such a material with low heat resistance, the cured film must be formed in a low temperature process of, for example, 150°C or less. It is desirable to suppress thermal damage to the support. However, when a cured film is formed by a low-temperature process, the degree of hardening of the cured film may be insufficient, and there is room for improvement in the moisture resistance of the cured film.
　また、近年においては、カラーフィルタなどに用いられる硬化膜について、更なる薄膜化が望まれている。所望の分光性能を維持しつつ薄膜化を達成するためには、着色組成物中の全固形分中における着色剤濃度を高めることが必要である。しかしながら、着色組成物中の全固形分中における着色剤濃度が高くなるに伴い、相対的に着色剤以外の成分の割合が少なくなるので、硬化膜の耐湿性がより低下し易い傾向にあった。 Additionally, in recent years, it has been desired to further reduce the thickness of cured films used in color filters and the like. In order to achieve a thin film while maintaining desired spectral performance, it is necessary to increase the colorant concentration in the total solid content of the coloring composition. However, as the concentration of the colorant in the total solid content of the coloring composition increases, the proportion of components other than the colorant decreases, so the moisture resistance of the cured film tends to decrease more easily. .
　よって、本発明の目的は、保存安定性が良好で、耐湿性に優れた硬化膜を形成することができる着色組成物を提供することにある。また、本発明の目的は、着色組成物を用いた硬化膜、カラーフィルタ、表示装置及び硬化膜の製造方法を提供することにある。 Therefore, an object of the present invention is to provide a colored composition that has good storage stability and can form a cured film with excellent moisture resistance. Another object of the present invention is to provide a cured film, a color filter, a display device, and a method for producing a cured film using a colored composition.
　本発明者の検討によれば、後述する着色組成物により上記目的を達成できることを見出し、本発明を完成するに至った。よって、本発明は以下を提供する。 According to the studies of the present inventors, it was discovered that the above object can be achieved by the coloring composition described below, and the present invention was completed. Accordingly, the present invention provides the following.
　＜１＞　着色剤と、
　樹脂と、
　ラジカル重合性モノマーと、
　ラジカル重合開始剤と、
　酸発生剤および塩基発生剤からなる群より選択される少なくとも１種の発生剤と、
　分子量が５０００以下の環状エーテル基を有する化合物Ａと、を含む着色組成物であって、
　上記着色組成物の全固形分中における上記着色剤の含有量が３５質量％以上であり、
　上記着色組成物の全固形分中における上記発生剤の含有量が２～１５質量％である、着色組成物。
　＜２＞　上記化合物Ａの分子量が１５００以下である、＜１＞に記載の着色組成物。
　＜３＞　上記化合物Ａは環状エーテル基を４個以上有する、＜１＞または＜２＞に記載の着色組成物。
　＜４＞　上記環状エーテル基はエポキシ基である、＜１＞～＜３＞のいずれか１つに記載の着色組成物。
　＜５＞　上記酸発生剤は光酸発生剤であり、上記塩基発生剤は光塩基発生剤である、＜１＞～＜４＞のいずれか１つに記載の着色組成物。
　＜６＞　上記発生剤は塩基発生剤である、＜１＞～＜５＞のいずれか１つに記載の着色組成物。
　＜７＞　上記塩基発生剤は、カルバメート化合物、アシルオキシム化合物およびオニウム塩からなる群より選択される少なくとも１種を含む、＜１＞～＜６＞のいずれか１つに記載の着色組成物。
　＜８＞　上記発生剤と上記化合物Ａとの割合は、上記発生剤１００質量部に対して上記化合物Ａが３０～７００質量部である、＜１＞～＜７＞のいずれか１つに記載の着色組成物。
　＜９＞　更に、界面活性剤を含み、
　上記界面活性剤はシリコーン系界面活性剤を含む、＜１＞～＜８＞のいずれか１つに記載の着色組成物。
　＜１０＞　＜１＞～＜９＞のいずれか１つに記載の着色組成物から得られる硬化膜。
　＜１１＞　＜１０＞に記載の硬化膜を有するカラーフィルタ。
　＜１２＞　＜１０＞に記載の硬化膜を有する表示装置。
　＜１３＞　＜１＞～＜９＞のいずれか１つに記載の着色組成物を支持体上に塗布して着色組成物層を形成する工程と、
　上記着色組成物層をパターン状に露光する工程と、
　露光後の着色組成物層を現像して未露光部の着色組成物層を除去する工程とを含み、
　全工程を通じて１５０℃以下の温度下で、上記着色組成物層が硬化した膜である硬化膜を得る、硬化膜の製造方法。
　＜１４＞　全工程を通じて１００℃以下の温度下で上記硬化膜を得る、＜１３＞に記載の硬化膜の製造方法。
　＜１５＞　露光後の上記着色組成物層を１５０℃以下の温度で加熱した後、上記現像を行う、＜１３＞に記載の硬化膜の製造方法。 <1> Coloring agent,
resin and
a radically polymerizable monomer,
a radical polymerization initiator,
at least one generator selected from the group consisting of acid generators and base generators;
A colored composition comprising a compound A having a cyclic ether group with a molecular weight of 5000 or less,
The content of the coloring agent in the total solid content of the coloring composition is 35% by mass or more,
A colored composition in which the content of the generator in the total solid content of the colored composition is 2 to 15% by mass.
<2> The colored composition according to <1>, wherein the compound A has a molecular weight of 1500 or less.
<3> The colored composition according to <1> or <2>, wherein the compound A has four or more cyclic ether groups.
<4> The colored composition according to any one of <1> to <3>, wherein the cyclic ether group is an epoxy group.
<5> The colored composition according to any one of <1> to <4>, wherein the acid generator is a photoacid generator, and the base generator is a photobase generator.
<6> The colored composition according to any one of <1> to <5>, wherein the generator is a base generator.
<7> The colored composition according to any one of <1> to <6>, wherein the base generator includes at least one selected from the group consisting of carbamate compounds, acyloxime compounds, and onium salts.
<8> The ratio of the above-mentioned generating agent and the above-mentioned compound A is described in any one of <1> to <7>, wherein the above-mentioned compound A is 30 to 700 parts by mass relative to 100 parts by mass of the above-mentioned generating agent. coloring composition.
<9> Furthermore, it contains a surfactant,
The colored composition according to any one of <1> to <8>, wherein the surfactant includes a silicone surfactant.
<10> A cured film obtained from the colored composition according to any one of <1> to <9>.
<11> A color filter having the cured film according to <10>.
<12> A display device having the cured film according to <10>.
<13> A step of applying the colored composition according to any one of <1> to <9> onto a support to form a colored composition layer;
a step of exposing the colored composition layer to light in a pattern;
developing the colored composition layer after exposure and removing the colored composition layer in the unexposed area,
A method for producing a cured film, the method comprising obtaining a cured film in which the colored composition layer is cured at a temperature of 150° C. or lower throughout the entire process.
<14> The method for producing a cured film according to <13>, wherein the cured film is obtained at a temperature of 100° C. or lower throughout the entire process.
<15> The method for producing a cured film according to <13>, wherein the colored composition layer after exposure is heated at a temperature of 150° C. or lower, and then the development is performed.
　本発明によれば、保存安定性が良好で、耐湿性に優れた硬化膜を形成することができる着色組成物を提供することができる。また、本発明によれば、着色組成物を用いた硬化膜、カラーフィルタ、表示装置及び硬化膜の製造方法を提供することができる。 According to the present invention, it is possible to provide a colored composition that has good storage stability and can form a cured film with excellent moisture resistance. Further, according to the present invention, it is possible to provide a cured film, a color filter, a display device, and a method for producing a cured film using a colored composition.
　以下において、本発明の内容について詳細に説明する。
　本明細書において、「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において、「（メタ）アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「（メタ）アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「（メタ）アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
　本明細書において、構造式中のＭｅはメチル基を表し、Ｅｔはエチル基を表し、Ｂｕはブチル基を表し、Ｐｈはフェニル基を表す。
　本明細書において、重量平均分子量および数平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）法により測定したポリスチレン換算値である。
　本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。
　本明細書において、顔料とは、溶剤に対して溶解しにくい化合物を意味する。
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。 The content of the present invention will be explained in detail below.
In this specification, "~" is used to include the numerical values described before and after it as a lower limit and an upper limit.
In the description of a group (atomic group) in this specification, the description that does not indicate substituted or unsubstituted includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents acrylate and/or methacrylate, "(meth)acrylic" represents both acrylic and/or methacrylic, and "(meth)acrylate" represents acrylic and/or methacrylate. ) "Acryloyl" refers to either or both of acryloyl and methacryloyl.
In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent.
In this specification, pigment means a compound that is difficult to dissolve in a solvent.
In this specification, the term "process" is used not only to refer to an independent process, but also to include a process in which the intended effect of the process is achieved even if the process cannot be clearly distinguished from other processes. .
＜着色組成物＞
　本発明の着色組成物は、
　着色剤と、
　樹脂と、
　ラジカル重合性モノマーと、
　ラジカル重合開始剤と、
　酸発生剤および塩基発生剤からなる群より選択される少なくとも１種の発生剤と、
　分子量が５０００以下の環状エーテル基を有する化合物Ａと、を含む着色組成物であって、
　上記着色組成物の全固形分中における上記着色剤の含有量が３５質量％以上であり、
　上記着色組成物の全固形分中における上記発生剤の含有量が２～１５質量％であることを特徴とする。 <Colored composition>
The colored composition of the present invention is
colorant and
resin and
a radically polymerizable monomer,
a radical polymerization initiator,
at least one generator selected from the group consisting of acid generators and base generators;
A colored composition comprising a compound A having a cyclic ether group with a molecular weight of 5000 or less,
The content of the coloring agent in the total solid content of the coloring composition is 35% by mass or more,
It is characterized in that the content of the generator in the total solid content of the coloring composition is 2 to 15% by mass.
　本発明の着色組成物は、着色組成物の全固形分中における着色剤の含有量が３５質量％以上であるにもかかわらず、保存安定性に優れ、かつ、耐湿性に優れた硬化膜を形成することができる。特に、１５０℃以下（好ましくは１２０℃以下）の低温で硬化膜を形成した場合であっても、優れた耐湿性を有する硬化膜を形成することができる。このような効果が得られる理由は、以下によるものであると推測される。本発明の着色組成物は、環状エーテル基を有する化合物と、上記発生剤を所定量含むので、硬化膜の形成時において、環状エーテル基を有する化合物の硬化反応を促進して低温でも十分に硬化させることができ、耐湿性に優れた硬化膜を形成することができると推測される。また、上記環状エーテル基を有する化合物の分子量が５０００以下であることにより、着色組成物の経時的な粘度の増加を抑制することができ、その結果、保存安定性に優れた着色組成物とすることができると推測される。 The colored composition of the present invention has a cured film with excellent storage stability and moisture resistance, even though the content of the coloring agent in the total solid content of the colored composition is 35% by mass or more. can be formed. In particular, even when the cured film is formed at a low temperature of 150° C. or lower (preferably 120° C. or lower), a cured film having excellent moisture resistance can be formed. The reason why such an effect is obtained is presumed to be due to the following. Since the coloring composition of the present invention contains a compound having a cyclic ether group and a predetermined amount of the generator, it promotes the curing reaction of the compound having a cyclic ether group when forming a cured film, and is sufficiently cured even at low temperatures. It is presumed that it is possible to form a cured film with excellent moisture resistance. Furthermore, since the molecular weight of the compound having a cyclic ether group is 5,000 or less, the increase in viscosity of the coloring composition over time can be suppressed, and as a result, the coloring composition has excellent storage stability. It is assumed that it is possible.
　また、着色組成物の全固形分中における上記発生剤の含有量が２～１５質量％であるので、製膜時に揮発する成分が多いので、更なる薄膜化が可能であり、それによって、隣接する画素への光漏れの発生をより低減することのできる硬化膜を形成することができる。 In addition, since the content of the generator in the total solid content of the coloring composition is 2 to 15% by mass, there are many components that volatilize during film formation, so it is possible to make the film even thinner. It is possible to form a cured film that can further reduce the occurrence of light leakage to pixels.
　本発明の着色組成物は、カラーフィルタ用の着色組成物として好ましく用いられる。より詳しくは、カラーフィルタの画素形成用の着色組成物として好ましく用いられる。画素の種類としては、赤色画素、緑色画素、青色画素、マゼンタ色画素、シアン色画素、黄色画素などが挙げられ、赤色画素、緑色画素または青色画素であることが好ましく、赤色画素または緑色画素であることがより好ましく、赤色画素であることが更に好ましい。 The colored composition of the present invention is preferably used as a colored composition for color filters. More specifically, it is preferably used as a coloring composition for forming pixels of color filters. Types of pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc., and preferably red pixels, green pixels, or blue pixels, and red pixels or green pixels. More preferably, it is a red pixel, and even more preferably it is a red pixel.
　本発明の着色組成物は、表示装置用のカラーフィルタの画素形成用の着色組成物として好ましく用いることができる。表示装置の種類としては特に限定はないが、有機エレクトロルミネッセンス表示装置などの有機エレクトロルミネッセンス素子を光源として有する表示装置などが挙げられる。表示装置は、赤色、青色および緑色を表示する有機エレクトロルミネッセンス素子を光源として有するものであってもよい。このような表示装置としては、特開２０２２－０６６８５９号公報に記載されている表示装置などが挙げられる。 The colored composition of the present invention can be preferably used as a colored composition for forming pixels of a color filter for a display device. The type of display device is not particularly limited, but examples include display devices having an organic electroluminescent element as a light source, such as an organic electroluminescent display device. The display device may have an organic electroluminescent element that displays red, blue, and green as a light source. Examples of such display devices include the display device described in Japanese Patent Application Laid-open No. 2022-066859.
　本発明の着色組成物は、全工程を通じて１５０℃以下の温度（好ましくは、１２０℃以下の温度、より好ましくは１００℃以下の温度）で硬化膜を形成するために用いられるものであることも好ましい。なお、本明細書において全工程を通じて１５０℃以下の温度で膜を形成するとは、着色組成物を用いて硬化膜を形成する工程の全てを１５０℃以下の温度で行うことを意味する。 The coloring composition of the present invention may be used to form a cured film at a temperature of 150°C or lower (preferably a temperature of 120°C or lower, more preferably a temperature of 100°C or lower) throughout the entire process. preferable. Note that in this specification, forming a film at a temperature of 150° C. or lower throughout all steps means performing all steps of forming a cured film using a colored composition at a temperature of 150° C. or lower.
　本発明の着色組成物によって形成される硬化膜の厚さは、０．５～３．０μｍであることが好ましい。下限は０．８μｍ以上が好ましく、１．０μｍ以上がより好ましく、１．１μｍ以上がさらに好ましい。上限は２．５μｍ以下が好ましく、２．０μｍ以下がより好ましく、１．８μｍ以下がさらに好ましい。 The thickness of the cured film formed by the colored composition of the present invention is preferably 0.5 to 3.0 μm. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, and even more preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, and even more preferably 1.8 μm or less.
　以下、本発明の着色組成物について詳細に説明する。 Hereinafter, the colored composition of the present invention will be explained in detail.
＜＜着色剤＞＞
　本発明の着色組成物は着色剤を含有する。着色剤としては、有彩色着色剤、黒色着色剤および白色着色剤などが挙げられる。着色組成物をカラーフィルタ用として用いる場合には、着色剤として有彩色着色剤が用いられる。有彩色着色剤は１種のみであってもよく、２種以上含んでいてもよい。 <<Colorant>>
The colored composition of the present invention contains a coloring agent. Examples of the coloring agent include chromatic coloring agents, black coloring agents, and white coloring agents. When the colored composition is used for a color filter, a chromatic coloring agent is used as the coloring agent. The number of chromatic colorants may be one, or two or more.
　着色剤は、顔料であってもよく、染料であってもよい。顔料は、無機顔料、有機顔料のいずれでもよいが、カラーバリエーションの多さ、分散の容易性、安全性等の観点から有機顔料であることが好ましい。 The colorant may be a pigment or a dye. The pigment may be either an inorganic pigment or an organic pigment, but organic pigments are preferable from the viewpoints of large color variations, ease of dispersion, safety, and the like.
　顔料の平均一次粒子径は、１～２００ｎｍが好ましい。下限は５ｎｍ以上が好ましく、１０ｎｍ以上がより好ましい。上限は、１８０ｎｍ以下が好ましく、１５０ｎｍ以下がより好ましく、１００ｎｍ以下が更に好ましい。なお、本明細書において、顔料の一次粒子径は、顔料の一次粒子を透過型電子顕微鏡により観察し、得られた写真から求めることができる。具体的には、顔料の一次粒子の投影面積を求め、それに対応する円相当径を顔料の一次粒子径として算出する。また、本発明における平均一次粒子径は、４００個の顔料の一次粒子についての一次粒子径の算術平均値とする。また、顔料の一次粒子とは、凝集のない独立した粒子をいう。 The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. In addition, in this specification, the primary particle diameter of a pigment can be calculated|required from the photograph obtained by observing the primary particle of a pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circular equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 pigment primary particles. Moreover, the primary particles of pigment refer to independent particles without agglomeration.
　顔料の、ＣｕＫα線をＸ線源としたときのＸ線回折スペクトルにおけるいずれかの結晶面に由来するピークの半値幅より求めた結晶子サイズは、０．１～１００ｎｍであることが好ましく、０．５～５０ｎｍであることがより好ましく、１～３０ｎｍであることが更に好ましく、５～２５ｎｍであることが特に好ましい。 The crystallite size determined from the half-value width of the peak derived from any crystal plane in the X-ray diffraction spectrum of the pigment when CuKα rays are used as the X-ray source is preferably 0.1 to 100 nm, and 0. It is more preferably .5 to 50 nm, even more preferably 1 to 30 nm, and particularly preferably 5 to 25 nm.
　顔料の比表面積は１～３００ｍ２／ｇであることが好ましい。下限は１０ｍ２／ｇ以上であることが好ましく、３０ｍ２／ｇ以上であることがより好ましい。上限は、２５０ｍ２／ｇ以下であることが好ましく、２００ｍ２／ｇ以下であることがより好ましい。比表面積の値は、ＢＥＴ（Ｂｒｕｎａｕｅｒ、ＥｍｍｅｔｔおよびＴｅｌｌｅｒ）法に準じてＤＩＮ　６６１３１：ｄｅｔｅｒｍｉｎａｔｉｏｎ　ｏｆ　ｔｈｅ　ｓｐｅｃｉｆｉｃ　ｓｕｒｆａｃｅ　ａｒｅａ　　ｏｆ　ｓｏｌｉｄｓ　ｂｙ　ｇａｓ　ａｄｓｏｒｐｔｉｏｎ（ガス吸着による固体の比表面積の測定）に従って測定することができる。 The specific surface area of the pigment is preferably 1 to 300 m 2 /g. The lower limit is preferably 10 m 2 /g or more, more preferably 30 m 2 /g or more. The upper limit is preferably 250 m 2 /g or less, more preferably 200 m 2 /g or less. The value of the specific surface area is determined according to DIN 66131: determination of the specific surface area of solids by gas adsorption according to the BET (Brunauer, Emmett and Teller) method. (Measurement of specific surface area of solids).
（有彩色着色剤）
　有彩色着色剤としては、特に限定されず、公知の有彩色着色剤を用いることができる。有彩色着色剤としては、黄色着色剤、オレンジ色着色剤、赤色着色剤、緑色着色剤、紫色着色剤および青色着色剤などが挙げられる。これらの具体例としては、例えば、以下が挙げられる。 (Chromatic colorant)
The chromatic colorant is not particularly limited, and any known chromatic colorant can be used. Examples of chromatic colorants include yellow colorants, orange colorants, red colorants, green colorants, purple colorants, and blue colorants. Specific examples of these include, for example, the following.
　赤色着色剤としては、ジケトピロロピロール化合物、アントラキノン化合物、アゾ化合物、ナフトール化合物、アゾメチン化合物、キサンテン化合物、キナクリドン化合物、ペリレン化合物、チオインジゴ化合物などが挙げられ、ジケトピロロピロール化合物、アントラキノン化合物、アゾ化合物であることが好ましく、ジケトピロロピロール化合物であることがより好ましい。また、赤色着色剤は顔料であることが好ましい。 Examples of red colorants include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, etc. It is preferably a compound, and more preferably a diketopyrrolopyrrole compound. Moreover, it is preferable that the red colorant is a pigment.
　赤色着色剤の具体例としては、Ｃ．Ｉ．（カラーインデックス）ピグメントレッド１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２６９，２７０，２７２，２７９，２９１，２９４，２９５，２９６，２９７等の赤色顔料が挙げられる。また、赤色着色剤として、国際公開第２０２２／０８５４８５号の段落番号００３４に記載の化合物、特開２０２０－０８５９４７号公報に記載の臭素化ジケトピロロピロール化合物を用いることもできる。 Specific examples of red colorants include C.I. I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, Examples include red pigments such as 279, 291, 294, 295, 296, 297, and the like. Further, as a red colorant, a compound described in paragraph number 0034 of International Publication No. 2022/085485 and a brominated diketopyrrolopyrrole compound described in JP 2020-085947 can also be used.
　赤色着色剤としては、Ｃ．Ｉ．ピグメントレッド１２２，１７７，２５４，２５５，２６４，２６９，２７２が好ましく、Ｃ．Ｉ．ピグメントレッド２５４，２６４，２７２がより好ましい。 As the red colorant, C. I. Pigment Red 122, 177, 254, 255, 264, 269, 272 are preferred, and C.I. I. Pigment Red 254, 264, and 272 are more preferred.
　緑色着色剤としては、フタロシアニン化合物、スクアリリウム化合物などが挙げられ、フタロシアニン化合物であることが好ましい。また、緑色着色剤は顔料であることが好ましい。 Examples of the green coloring agent include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. Moreover, it is preferable that the green coloring agent is a pigment.
　緑色着色剤の具体例としては、Ｃ．Ｉ．ピグメントグリーン７，１０，３６，３７，５８，５９，６２，６３，６４，６５，６６等の緑色顔料が挙げられる。また、緑色着色剤として、１分子中のハロゲン原子数が平均１０～１４個であり、臭素原子数が平均８～１２個であり、塩素原子数が平均２～５個であるハロゲン化亜鉛フタロシアニン顔料を用いることもできる。具体例としては、国際公開第２０１５／１１８７２０号に記載の化合物が挙げられる。また、緑色着色剤として国際公開第２０２２／０８５４８５号の段落番号００２９に記載の化合物、特開２０２０－０７０４２６号公報に記載のアルミニウムフタロシアニン化合物、特表２０２０－５０４７５８号公報に記載のジアリールメタン化合物などを用いることもできる。 Specific examples of green colorants include C.I. I. Examples include green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. In addition, as a green coloring agent, halogenated zinc phthalocyanine has an average number of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule. Pigments can also be used. Specific examples include compounds described in International Publication No. 2015/118720. In addition, as green colorants, compounds described in paragraph number 0029 of International Publication No. 2022/085485, aluminum phthalocyanine compounds described in JP-A-2020-070426, diarylmethane compounds described in Japanese Patent Publication No. 2020-504758, etc. You can also use
　緑色着色剤としては、Ｃ．Ｉ．ピグメントグリーン７，３６，５８，６２，６３が好ましい。 As the green colorant, C.I. I. Pigment Green 7, 36, 58, 62, and 63 are preferred.
　オレンジ色着色剤の具体例としては、Ｃ．Ｉ．ピグメントオレンジ２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等のオレンジ色顔料が挙げられる。 Specific examples of orange colorants include C.I. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. orange pigments.
　黄色着色剤としては、アゾ化合物、アゾメチン化合物、イソインドリン化合物、プテリジン化合物、キノフタロン化合物およびペリレン化合物が挙げられる。黄色着色剤の具体例としては、Ｃ．Ｉ．ピグメントイエロー１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４，２１５，２２８，２３１，２３２，２３３，２３４，２３５，２３６等が挙げられる。 Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. Specific examples of yellow colorants include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236 and the like.
　黄色着色剤としては、下記構造のアゾバルビツール酸ニッケル錯体を用いることもできる。
 As the yellow coloring agent, an azobarbituric acid nickel complex having the following structure can also be used.
　また、黄色着色剤として、国際公開第２０２２／０８５４８５号の段落番号００３１～００３３に記載の化合物、特開２０１９－０７３６９５号公報に記載のメチン染料、特開２０１９－０７３６９６号公報に記載のメチン染料を用いることができる。 In addition, as a yellow coloring agent, compounds described in paragraph numbers 0031 to 0033 of International Publication No. 2022/085485, methine dyes described in JP 2019-073695, methine dyes described in JP 2019-073696, can be used.
　紫色着色剤の具体例としては、Ｃ．Ｉ．ピグメントバイオレット１，１９，２３，２７，３２，３７，４２，６０，６１等の紫色顔料が挙げられる。 Specific examples of purple colorants include C.I. I. Examples include purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.
　青色着色剤の具体例としては、Ｃ．Ｉ．ピグメントブルー１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，２９，６０，６４，６６，７９，８０，８７，８８等の青色顔料が挙げられる。また、青色着色剤として、リン原子を有するアルミニウムフタロシアニン化合物を用いることもできる。具体例としては、特開２０１２－２４７５９１号公報の段落番号００２２～００３０、特開２０１１－１５７４７８号公報の段落番号００４７に記載の化合物が挙げられる。 Specific examples of blue colorants include C.I. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc. Examples include pigments. Moreover, an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue colorant. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A No. 2012-247591 and paragraph number 0047 of JP-A No. 2011-157478.
　有彩色着色剤として、韓国公開特許第１０－２０２０－００２８１６０号公報に記載されたトリアリールメタン染料ポリマー、特開２０２０－１１７６３８号公報に記載のキサンテン化合物、国際公開第２０２０／１７４９９１号に記載のフタロシアニン化合物、特開２０２０－１６０２７９号公報に記載のイソインドリン化合物又はそれらの塩、韓国公開特許第１０－２０２０－００６９４４２号公報に記載の式１で表される化合物、韓国公開特許第１０－２０２０－００６９７３０号公報に記載の式１で表される化合物、韓国公開特許第１０－２０２０－００６９０７０号公報に記載の式１で表される化合物、韓国公開特許第１０－２０２０－００６９０６７号公報に記載の式１で表される化合物、韓国公開特許第１０－２０２０－００６９０６２号公報に記載の式１で表される化合物、特許第６８０９６４９号に記載のハロゲン化亜鉛フタロシアニン顔料、特開２０２０－１８０１７６号公報に記載のイソインドリン化合物、特開２０２１－１８７９１３号公報に記載のフェノチアジン系化合物、国際公開第２０２２／００４２６１号に記載のハロゲン化亜鉛フタロシアニン、国際公開第２０２１／２５０８８３号に記載のハロゲン化亜鉛フタロシアニンを用いることができる。有彩色着色剤は、ロタキサンであってもよく、色素骨格はロタキサンの環状構造に使用されていてもよく、棒状構造に使用されていてもよく、両方の構造に使用されていてもよい。有彩色着色剤として、韓国公開特許第１０－２０２０－００３０７５９号公報の式１で表されるキノフタロン化合物、韓国公開特許第１０－２０２０－００６１７９３号公報に記載の高分子染料、特開２０２２－０２９７０１号公報に記載の着色剤、国際公開第２０２２／０１４６３５号に記載のイソインドリン化合物、国際公開第２０２２／０２４９２６号に記載のアルミニウムフタロシアニン化合物、特開２０２２－０４５８９５号公報に記載の化合物、国際公開第２０２２／０５００５１号に記載の化合物を用いることもできる。 As chromatic colorants, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP 2020-117638, and International Publication No. 2020/174991 are used. Phthalocyanine compounds, isoindoline compounds or their salts described in JP-A No. 2020-160279, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069442, Korean Publication Patent No. 10-2020 Compounds represented by formula 1 described in -0069730, compounds represented by formula 1 described in Korean published patent No. 10-2020-0069070, and described in Korean published patent No. 10-2020-0069067 A compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069062, a halogenated zinc phthalocyanine pigment described in Patent No. 6809649, JP 2020-180176 Isoindoline compounds described in the publication, phenothiazine compounds described in JP2021-187913A, halogenated zinc phthalocyanine described in International Publication No. 2022/004261, zinc halide described in International Publication No. 2021/250883 Phthalocyanines can be used. The chromatic colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, the rod-like structure, or both structures. As a chromatic coloring agent, a quinophthalone compound represented by formula 1 of Korean Patent Publication No. 10-2020-0030759, a polymer dye described in Korean Publication Patent No. 10-2020-0061793, and Japanese Patent Application Publication No. 2022-029701. The coloring agent described in WO 2022/014635, the aluminum phthalocyanine compound described in WO 2022/024926, the compound described in JP 2022-045895, WO Compounds described in No. 2022/050051 can also be used.
（黒色着色剤）
　黒色着色剤としては、ビスベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物、アゾ化合物などが挙げられ、ビスベンゾフラノン化合物、ペリレン化合物が好ましい。黒色着色剤は、国際公開第２０２２／０６５２１５号の段落番号０１６６に記載の黒色着色剤、特開２０１７－２２６８２１号公報の段落００１６～００２０に記載のペリレンブラック（Ｌｕｍｏｇｅｎ　Ｂｌａｃｋ　ＦＫ４２８０等）を用いることもできる。 (black colorant)
Examples of the black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. As the black colorant, the black colorant described in paragraph number 0166 of International Publication No. 2022/065215, and the perylene black (Lumogen Black FK4280 etc.) described in paragraphs 0016 to 0020 of JP 2017-226821 can also be used. can.
（白色着色剤）
　白色着色剤としては、酸化チタン、チタン酸ストロンチウム、チタン酸バリウム、酸化亜鉛、酸化マグネシウム、酸化ジルコニウム、酸化アルミニウム、硫酸バリウム、シリカ、タルク、マイカ、水酸化アルミニウム、ケイ酸カルシウム、ケイ酸アルミニウム、硫化亜鉛などの無機顔料が挙げられる。白色着色剤は、国際公開第２０２２／０８５４８５号の段落番号００４０～００４３に記載の白色着色剤を用いることができる。 (white colorant)
White colorants include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, Examples include inorganic pigments such as zinc sulfide. As the white colorant, the white colorant described in paragraph numbers 0040 to 0043 of International Publication No. 2022/085485 can be used.
　着色組成物の全固形分中における着色剤の含有量は、３５質量％以上であり、４０質量％以上であることが好ましく、４５質量％以上であることがより好ましく、５０質量％以上であることが更に好ましい。上限は、７０質量％以下であることが好ましく、６５質量％以下であることがより好ましく、６０質量％以下であることが更に好ましい。 The content of the coloring agent in the total solid content of the coloring composition is 35% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and 50% by mass or more. It is even more preferable. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less, and even more preferably 60% by mass or less.
　着色剤中における顔料の含有量は、２０～１００質量％であることが好ましく、５０～１００質量％であることがより好ましく、７０～１００質量％であることが更に好ましい。 The content of pigment in the colorant is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass.
　本発明の着色組成物をカラーフィルタの赤色画素形成用の着色組成物として用いる場合、着色剤には黄色着色剤と赤色着色剤を含むものを用いることが好ましい。また、黄色着色剤と赤色着色剤との質量比は、黄色着色剤：赤色着色剤＝１０：９０～７０：３０であることが好ましく、２０：８０～６０：４０であることがより好ましく、３０：７０～５０：５０であることが更に好ましい。 When using the coloring composition of the present invention as a coloring composition for forming red pixels of a color filter, it is preferable to use a colorant containing a yellow colorant and a red colorant. Further, the mass ratio of the yellow colorant to the red colorant is preferably yellow colorant:red colorant = 10:90 to 70:30, more preferably 20:80 to 60:40, More preferably, the ratio is 30:70 to 50:50.
　本発明の着色組成物をカラーフィルタの緑色画素形成用の着色組成物として用いる場合、着色剤には黄色着色剤と緑色着色剤を含むものを用いることが好ましい。また、黄色着色剤と緑色着色剤との質量比は、黄色着色剤：緑色着色剤＝３０：７０～７０：３０であることが好ましく、３０：７０～６０：４０であることがより好ましく、３０：７０～５０：５０であることが更に好ましい。 When the coloring composition of the present invention is used as a coloring composition for forming green pixels of a color filter, it is preferable to use a colorant containing a yellow colorant and a green colorant. Further, the mass ratio of the yellow colorant to the green colorant is preferably yellow colorant:green colorant = 30:70 to 70:30, more preferably 30:70 to 60:40, More preferably, the ratio is 30:70 to 50:50.
＜＜樹脂＞＞
　本発明の着色組成物は樹脂を含む。樹脂は、例えば、顔料などを着色組成物中で分散させる用途や、バインダーの用途で配合される。なお、主に顔料などを着色組成物中で分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外を目的として樹脂を使用することもできる。 <<Resin>>
The colored composition of the present invention contains a resin. The resin is blended, for example, for dispersing pigments in a coloring composition or for use as a binder. Note that a resin used mainly for dispersing pigments and the like in a coloring composition is also referred to as a dispersant. However, this use of the resin is just an example, and the resin can also be used for purposes other than this use.
　樹脂の重量平均分子量（Ｍｗ）は、３０００～２００００００が好ましい。上限は、１００００００以下が好ましく、５０００００以下がより好ましい。下限は、４０００以上が好ましく、５０００以上がより好ましい。 The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.
　樹脂としては、例えば、（メタ）アクリル樹脂、（メタ）アクリルアミド樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂、シロキサン樹脂などが挙げられる。また、樹脂としては、国際公開第２０２２／０６５２１５号の段落番号００９１～００９９に記載の樹脂、特開２０１６－２２２８９１号公報に記載されたブロックポリイソシアネート樹脂、特開２０２０－１２２０５２号公報に記載された樹脂、特開２０２０－１１１６５６号公報に記載された樹脂、特開２０２０－１３９０２１号公報に記載された樹脂、特開２０１７－１３８５０３号公報に記載の主鎖に環構造を有する構成単位と側鎖にビフェニル基を有する構成単位とを含む樹脂、特開２０２０－１８６３７３号公報の段落０１９９～０２３３に記載の樹脂、特開２０２０－１８６３２５号公報に記載のアルカリ可溶性樹脂、韓国公開特許第１０－２０２０－００７８３３９号公報に記載の式１で表される樹脂を用いることもできる。 As the resin, for example, (meth)acrylic resin, (meth)acrylamide resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide. Examples include resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins. In addition, examples of the resin include resins described in paragraph numbers 0091 to 0099 of International Publication No. 2022/065215, block polyisocyanate resins described in JP2016-222891A, and resins described in JP2020-122052A. Resin described in JP 2020-111656, resin described in JP 2020-139021, structural unit having a ring structure in the main chain and side described in JP 2017-138503 Resin containing a structural unit having a biphenyl group in the chain, resin described in paragraphs 0199 to 0233 of JP 2020-186373, alkali-soluble resin described in JP 2020-186325, Korean Published Patent No. 10- A resin represented by formula 1 described in JP 2020-0078339 can also be used.
　樹脂としては、酸基を有する樹脂を用いることが好ましい。酸基としては、例えば、カルボキシ基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられる。 As the resin, it is preferable to use a resin having acid groups. Examples of the acid group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
　酸基を有する樹脂の酸価は、３０～５００ｍｇＫＯＨ／ｇが好ましい。下限は、４０ｍｇＫＯＨ／ｇ以上がより好ましく、５０ｍｇＫＯＨ／ｇ以上が特に好ましい。上限は、４００ｍｇＫＯＨ／ｇ以下がより好ましく、３００ｍｇＫＯＨ／ｇ以下が更に好ましく、２００ｍｇＫＯＨ／ｇ以下が特に好ましい。酸基を有する樹脂の重量平均分子量（Ｍｗ）は、５０００～１０００００が好ましく、５０００～５００００がより好ましい。また、酸基を有する樹脂の数平均分子量（Ｍｎ）は、１０００～２００００が好ましい。 The acid value of the resin having acid groups is preferably 30 to 500 mgKOH/g. The lower limit is more preferably 40 mgKOH/g or more, particularly preferably 50 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, even more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less. The weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, more preferably 5,000 to 50,000. Further, the number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.
　酸基を有する樹脂は、酸基を側鎖に有する繰り返し単位を含むことが好ましく、酸基を側鎖に有する繰り返し単位を樹脂の全繰り返し単位中５～７０モル％含むことがより好ましい。酸基を側鎖に有する繰り返し単位の含有量の上限は、５０モル％以下であることが好ましく、３０モル％以下であることがより好ましい。酸基を側鎖に有する繰り返し単位の含有量の下限は、１０モル％以上であることが好ましく、２０モル％以上であることがより好ましい。 The resin having an acid group preferably contains a repeating unit having an acid group in its side chain, and more preferably contains 5 to 70 mol% of repeating units having an acid group in its side chain based on the total repeating units of the resin. The upper limit of the content of repeating units having acid groups in their side chains is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of repeating units having acid groups in their side chains is preferably 10 mol% or more, more preferably 20 mol% or more.
　酸基を有する樹脂については、特開２０１２－２０８４９４号公報の段落番号０５５８～０５７１（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の段落番号０６８５～０７００）の記載、特開２０１２－１９８４０８号公報の段落番号００７６～００９９の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、酸基を有する樹脂は市販品を用いることもできる。また、樹脂への酸基の導入方法としては、特に制限はないが、例えば、特許第６３４９６２９号公報に記載の方法が挙げられる。更に、樹脂への酸基の導入方法としては、エポキシ基の開環反応で生じたヒドロキシ基に酸無水物を反応させて酸基を導入する方法も挙げられる。 Regarding resins having acid groups, the descriptions in paragraph numbers 0558 to 0571 of JP 2012-208494 (corresponding paragraph numbers 0685 to 0700 of US Patent Application Publication No. 2012/0235099), JP 2012-198408 The descriptions in paragraph numbers 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated into the present specification. Furthermore, commercially available resins having acid groups can also be used. Furthermore, there are no particular limitations on the method for introducing acid groups into the resin, but examples include the method described in Japanese Patent No. 6,349,629. Furthermore, as a method for introducing acid groups into the resin, there is also a method of reacting an acid anhydride with a hydroxy group generated by a ring-opening reaction of an epoxy group to introduce an acid group.
　本発明の着色組成物は、塩基性基を有する樹脂を含むことも好ましい。塩基性基を有する樹脂は、塩基性基を側鎖に有する繰り返し単位を含む樹脂であることが好ましく、塩基性基を側鎖に有する繰り返し単位と塩基性基を含まない繰り返し単位とを有する共重合体であることがより好ましく、塩基性基を側鎖に有する繰り返し単位と、塩基性基を含まない繰り返し単位とを有するブロック共重合体であることが更に好ましい。塩基性基を有する樹脂は分散剤として用いることもできる。塩基性基を有する樹脂のアミン価は、５～３００ｍｇＫＯＨ／ｇが好ましい。下限は、１０ｍｇＫＯＨ／ｇ以上が好ましく、２０ｍｇＫＯＨ／ｇ以上がより好ましい。上限は、２００ｍｇＫＯＨ／ｇ以下が好ましく、１００ｍｇＫＯＨ／ｇ以下がより好ましい。 It is also preferable that the colored composition of the present invention contains a resin having a basic group. The resin having a basic group is preferably a resin containing a repeating unit having a basic group in its side chain, and a resin having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group. A polymer is more preferable, and a block copolymer having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group is even more preferable. A resin having a basic group can also be used as a dispersant. The amine value of the resin having a basic group is preferably 5 to 300 mgKOH/g. The lower limit is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more. The upper limit is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less.
　塩基性基を有する樹脂の市販品としては、ＤＩＳＰＥＲＢＹＫ－１６１、１６２、１６３、１６４、１６６、１６７、１６８、１７４、１８２、１８３、１８４、１８５、２０００、２００１、２０５０、２１５０、２１６３、２１６４、ＢＹＫ－ＬＰＮ６９１９（以上、ビックケミー社製）、ソルスパース１１２００、１３２４０、１３６５０、１３９４０、２４０００、２６０００、２８０００、３２０００、３２５００、３２５５０、３２６００、３３０００、３４７５０、３５１００、３５２００、３７５００、３８５００、３９０００、５３０９５、５６０００、７１００（以上、日本ルーブリゾール社製）、Ｅｆｋａ　ＰＸ　４３００、４３３０、４０４６、４０６０、４０８０（以上、ＢＡＳＦ社製）等が挙げられる。また、塩基性基を有する樹脂は、特開２０１４－２１９６６５号公報の段落番号００６３～０１１２に記載されたブロック共重合体（Ｂ）、特開２０１８－１５６０２１号公報の段落番号００４６～００７６に記載されたブロック共重合体Ａ１、特開２０１９－１８４７６３号公報の段落番号０１５０～０１５３に記載された塩基性基を有するビニル樹脂を用いることもでき、これらの内容は本明細書に組み込まれる。 Commercially available resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (manufactured by BYK Chemie), Solsperse 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 385 00, 39000, 53095, 56000, 7100 (all manufactured by Japan Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like. In addition, the resin having a basic group is the block copolymer (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and the block copolymer (B) described in paragraphs 0046 to 0076 of JP2018-156021A. It is also possible to use block copolymer A1, a vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP-A No. 2019-184763, the contents of which are incorporated herein.
　本発明の着色組成物は、酸基を有する樹脂と塩基性基を有する樹脂とをそれぞれ含むことも好ましい。この態様によれば、着色組成物の保存安定性をより向上できる。酸基を有する樹脂と塩基性基を有する樹脂とを併用する場合、塩基性基を有する樹脂の含有量は、酸基を有する樹脂の１００質量部に対して２０～５００質量部であることが好ましく、３０～３００質量部であることがより好ましく、５０～２００質量部であることが更に好ましい。 It is also preferable that the colored composition of the present invention contains a resin having an acid group and a resin having a basic group. According to this aspect, the storage stability of the colored composition can be further improved. When a resin having an acid group and a resin having a basic group are used together, the content of the resin having a basic group is preferably 20 to 500 parts by mass per 100 parts by mass of the resin having an acid group. The amount is preferably 30 to 300 parts by weight, more preferably 50 to 200 parts by weight.
　樹脂としては、芳香族カルボキシ基を有する樹脂（以下、樹脂Ａｃともいう）を用いることも好ましい。樹脂Ａｃにおいて、芳香族カルボキシ基は繰り返し単位の主鎖に含まれていてもよく、繰り返し単位の側鎖に含まれていてもよい。芳香族カルボキシ基は繰り返し単位の主鎖に含まれていることが好ましい。なお、本明細書において、芳香族カルボキシ基とは、芳香族環にカルボキシ基が１個以上結合した構造の基のことである。芳香族カルボキシ基において、芳香族環に結合したカルボキシ基の数は、１～４個であることが好ましく、１～２個であることがより好ましい。 As the resin, it is also preferable to use a resin having an aromatic carboxy group (hereinafter also referred to as resin Ac). In the resin Ac, the aromatic carboxy group may be included in the main chain of the repeating unit, or may be included in the side chain of the repeating unit. The aromatic carboxy group is preferably contained in the main chain of the repeating unit. In addition, in this specification, an aromatic carboxy group refers to a group having a structure in which one or more carboxy groups are bonded to an aromatic ring. In the aromatic carboxy group, the number of carboxy groups bonded to the aromatic ring is preferably 1 to 4, more preferably 1 to 2.
　樹脂Ａｃは、式（Ａｃ－１）で表される繰り返し単位および式（Ａｃ－２）で表される繰り返し単位から選ばれる少なくとも１種の繰り返し単位を含む樹脂であることが好ましい。
　式（Ａｃ－１）中、Ａｒ１は芳香族カルボキシ基を含む基を表し、Ｌ１は、－ＣＯＯ－または－ＣＯＮＨ－を表し、Ｌ２は、２価の連結基を表す。
　式（Ａｃ－２）中、Ａｒ１０は芳香族カルボキシ基を含む基を表し、Ｌ１１は、－ＣＯＯ－または－ＣＯＮＨ－を表し、Ｌ１２は３価の連結基を表し、Ｐ１０はポリマー鎖を表す。 The resin Ac is preferably a resin containing at least one type of repeating unit selected from a repeating unit represented by formula (Ac-1) and a repeating unit represented by formula (Ac-2).
In formula (Ac-1), Ar 1 represents a group containing an aromatic carboxy group, L 1 represents -COO- or -CONH-, and L 2 represents a divalent linking group.
In formula (Ac-2), Ar 10 represents a group containing an aromatic carboxy group, L 11 represents -COO- or -CONH-, L 12 represents a trivalent linking group, and P 10 represents a polymer Represents a chain.
　式（Ａｃ－１）においてＡｒ１が表す芳香族カルボキシ基を含む基としては、芳香族トリカルボン酸無水物から由来する構造、芳香族テトラカルボン酸無水物から由来する構造などが挙げられる。芳香族トリカルボン酸無水物および芳香族テトラカルボン酸無水物としては、下記構造の化合物が挙げられる。
 Examples of the group containing an aromatic carboxy group represented by Ar 1 in formula (Ac-1) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like. Examples of the aromatic tricarboxylic anhydride and aromatic tetracarboxylic anhydride include compounds having the following structures.
　上記式中、Ｑ１は、単結合、－Ｏ－、－ＣＯ－、－ＣＯＯＣＨ２ＣＨ２ＯＣＯ－、－ＳＯ２－、－Ｃ（ＣＦ３）２－、下記式（Ｑ－１）で表される基または下記式（Ｑ－２）で表される基を表す。
 In the above formula, Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, represented by the following formula (Q-1). or a group represented by the following formula (Q-2).
　Ａｒ１が表す芳香族カルボキシ基を含む基は、架橋性基を有していてもよい。架橋性基は、エチレン性不飽和結合含有基および環状エーテル基であることが好ましく、エチレン性不飽和結合含有基であることがより好ましい。Ａｒ１が表す芳香族カルボキシ基を含む基の具体例としては、式（Ａｒ－１１）で表される基、式（Ａｒ－１２）で表される基、式（Ａｒ－１３）で表される基などが挙げられる。
 The aromatic carboxy group-containing group represented by Ar 1 may have a crosslinkable group. The crosslinkable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, and more preferably an ethylenically unsaturated bond-containing group. Specific examples of the group containing an aromatic carboxy group represented by Ar 1 include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13). Examples include groups such as
　式（Ａｒ－１１）中、ｎ１は１～４の整数を表し、１または２であることが好ましく、２であることがより好ましい。
　式（Ａｒ－１２）中、ｎ２は１～８の整数を表し、１～４の整数であることが好ましく、１または２であることがより好ましく、２であることが更に好ましい。
　式（Ａｒ－１３）中、ｎ３およびｎ４はそれぞれ独立して０～４の整数を表し、０～２の整数であることが好ましく、１または２であることがより好ましく、１であることが更に好ましい。ただし、ｎ３およびｎ４の少なくとも一方は１以上の整数である。
　式（Ａｒ－１３）中、Ｑ１は、単結合、－Ｏ－、－ＣＯ－、－ＣＯＯＣＨ２ＣＨ２ＯＣＯ－、－ＳＯ２－、－Ｃ（ＣＦ３）２－、上記式（Ｑ－１）で表される基または上記式（Ｑ－２）で表される基を表す。
　式（Ａｒ－１１）～（Ａｒ－１３）中、＊１はＬ１との結合位置を表す。 In formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
In formula (Ar-12), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2.
In formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and preferably 1. More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
In formula (Ar-13), Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, the above formula (Q- Represents a group represented by 1) or a group represented by the above formula (Q-2).
In formulas (Ar-11) to (Ar-13), *1 represents the bonding position with L 1 .
　式（Ａｃ－１）においてＬ１は、－ＣＯＯ－または－ＣＯＮＨ－を表し、－ＣＯＯ－を表すことが好ましい。 In formula (Ac-1), L 1 represents -COO- or -CONH-, and preferably represents -COO-.
　式（Ａｃ－１）においてＬ２が表す２価の連結基としては、アルキレン基、アリーレン基、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－Ｓ－およびこれらの２種以上を組み合わせた基が挙げられる。アルキレン基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。アルキレン基は、直鎖、分岐、環状のいずれでもよい。アリーレン基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１０が更に好ましい。アルキレン基およびアリーレン基は置換基を有していてもよい。置換基としては、ヒドロキシ基などが挙げられる。Ｌ２が表す２価の連結基は、－Ｌ２ａ－Ｏ－で表される基であることが好ましい。Ｌ２ａは、アルキレン基；アリーレン基；アルキレン基とアリーレン基とを組み合わせた基；アルキレン基およびアリーレン基から選ばれる少なくとも１種と、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－および－Ｓ－から選ばれる少なくとも１種とを組み合わせた基などが挙げられ、アルキレン基であることが好ましい。アルキレン基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。アルキレン基は、直鎖、分岐、環状のいずれでもよい。アルキレン基およびアリーレン基は置換基を有していてもよい。置換基としては、ヒドロキシ基などが挙げられる。 The divalent linking group represented by L 2 in formula (Ac-1) includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these. Examples include groups combining two or more of the following. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms. The alkylene group may be linear, branched, or cyclic. The number of carbon atoms in the arylene group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The alkylene group and arylene group may have a substituent. Examples of the substituent include a hydroxy group. The divalent linking group represented by L 2 is preferably a group represented by -L 2a -O-. L 2a is an alkylene group; an arylene group; a group combining an alkylene group and an arylene group; at least one selected from an alkylene group and an arylene group, and -O-, -CO-, -COO-, -OCO-, Examples include a group combining at least one selected from -NH- and -S-, and an alkylene group is preferred. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms. The alkylene group may be linear, branched, or cyclic. The alkylene group and arylene group may have a substituent. Examples of the substituent include a hydroxy group.
　式（Ａｃ－２）においてＡｒ１０が表す芳香族カルボキシ基を含む基としては、式（Ａｃ－１）のＡｒ１と同義であり、好ましい範囲も同様である。 The aromatic carboxy group-containing group represented by Ar 10 in formula (Ac-2) has the same meaning as Ar 1 in formula (Ac-1), and the preferred range is also the same.
　式（Ａｃ－２）においてＬ１１は、－ＣＯＯ－または－ＣＯＮＨ－を表し、－ＣＯＯ－を表すことが好ましい。 In formula (Ac-2), L 11 represents -COO- or -CONH-, preferably -COO-.
　式（Ａｃ－２）においてＬ１２が表す３価の連結基としては、炭化水素基、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－Ｓ－およびこれらの２種以上を組み合わせた基が挙げられる。炭化水素基は、脂肪族炭化水素基、芳香族炭化水素基が挙げられる。脂肪族炭化水素基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。脂肪族炭化水素基は、直鎖、分岐、環状のいずれでもよい。芳香族炭化水素基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１０が更に好ましい。炭化水素基は置換基を有していてもよい。置換基としては、ヒドロキシ基などが挙げられる。Ｌ１２が表す３価の連結基は、式（Ｌ１２－１）で表される基であることが好ましく、式（Ｌ１２－２）で表される基であることがより好ましい。
 In formula (Ac-2), the trivalent linking group represented by L 12 includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these two groups. Examples include groups that combine more than one species. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group. The trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2).
　式（Ｌ１２－１）中、Ｌ１２ｂは３価の連結基を表し、Ｘ１はＳを表し、＊１は式（Ａｃ－２）のＬ１１との結合位置を表し、＊２は式（Ａｃ－２）のＰ１０との結合位置を表す。Ｌ１２ｂが表す３価の連結基としては、炭化水素基；炭化水素基と、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－および－Ｓ－から選ばれる少なくとも１種とを組み合わせた基などが挙げられ、炭化水素基または炭化水素基と－Ｏ－とを組み合わせた基であることが好ましい。 In formula (L12-1), L 12b represents a trivalent linking group, X 1 represents S, *1 represents the bonding position with L 11 of formula (Ac-2), and *2 represents the bonding position of formula (Ac-2). It represents the bonding position of Ac-2) with P10 . The trivalent linking group represented by L 12b is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. A hydrocarbon group or a group consisting of a hydrocarbon group and -O- is preferable.
　式（Ｌ１２－２）中、Ｌ１２ｃは３価の連結基を表し、Ｘ１はＳを表し、＊１は式（Ａｃ－２）のＬ１１との結合位置を表し、＊２は式（Ａｃ－２）のＰ１０との結合位置を表す。Ｌ１２ｃが表す３価の連結基としては、炭化水素基；炭化水素基と、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－および－Ｓ－から選ばれる少なくとも１種とを組み合わせた基などが挙げられ、炭化水素基であることが好ましい。 In formula (L12-2), L 12c represents a trivalent linking group, X 1 represents S, *1 represents the bonding position with L 11 of formula (Ac-2), and *2 represents formula ( It represents the bonding position of Ac-2) with P10 . The trivalent linking group represented by L 12c is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. A hydrocarbon group is preferable.
　式（Ａｃ－２）においてＰ１０はポリマー鎖を表す。Ｐ１０が表すポリマー鎖は、ポリ（メタ）アクリル繰り返し単位、ポリエーテル繰り返し単位、ポリエステル繰り返し単位およびポリオール繰り返し単位から選ばれる少なくとも１種の繰り返し単位を有することが好ましい。ポリマー鎖Ｐ１０の重量平均分子量は５００～２００００が好ましい。下限は１０００以上が好ましい。上限は１００００以下が好ましく、５０００以下がより好ましく、３０００以下が更に好ましい。Ｐ１０の重量平均分子量が上記範囲であれば組成物中における顔料の分散性が良好である。芳香族カルボキシ基を有する樹脂が式（Ａｃ－２）で表される繰り返し単位を有する樹脂である場合は、この樹脂は分散剤として好ましく用いられる。 In formula (Ac-2), P 10 represents a polymer chain. The polymer chain represented by P 10 preferably has at least one repeating unit selected from poly(meth)acrylic repeating units, polyether repeating units, polyester repeating units, and polyol repeating units. The weight average molecular weight of the polymer chain P 10 is preferably 500 to 20,000. The lower limit is preferably 1000 or more. The upper limit is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less. If the weight average molecular weight of P 10 is within the above range, the pigment will have good dispersibility in the composition. When the resin having an aromatic carboxy group is a resin having a repeating unit represented by formula (Ac-2), this resin is preferably used as a dispersant.
　Ｐ１０が表すポリマー鎖は、架橋性基を含んでいてもよい。架橋性基としては、エチレン性不飽和結合含有基および環状エーテル基が挙げられる。 The polymer chain represented by P 10 may contain a crosslinkable group. Examples of the crosslinkable group include ethylenically unsaturated bond-containing groups and cyclic ether groups.
　本発明の着色組成物は、分散剤としての樹脂を含有することが好ましい。分散剤としては、酸性分散剤（酸性樹脂）、塩基性分散剤（塩基性樹脂）が挙げられる。ここで、酸性分散剤（酸性樹脂）とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤（酸性樹脂）としては、酸基の量と塩基性基の量の合計量を１００モル％としたときに、酸基の量が７０モル％以上である樹脂が好ましい。酸性分散剤（酸性樹脂）が有する酸基は、カルボキシ基が好ましい。酸性分散剤（酸性樹脂）の酸価は、１０～１０５ｍｇＫＯＨ／ｇが好ましい。また、塩基性分散剤（塩基性樹脂）とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤（塩基性樹脂）としては、酸基の量と塩基性基の量の合計量を１００モル％としたときに、塩基性基の量が５０モル％を超える樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミノ基が好ましい。 The colored composition of the present invention preferably contains a resin as a dispersant. Examples of the dispersant include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %. The acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. Moreover, the basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%. The basic group that the basic dispersant has is preferably an amino group.
　分散剤として用いる樹脂は、グラフト樹脂であることも好ましい。グラフト樹脂の詳細については、特開２０１２－２５５１２８号公報の段落番号００２５～００９４の記載を参酌でき、この内容は本明細書に組み込まれる。 It is also preferable that the resin used as a dispersant is a graft resin. For details of the graft resin, the descriptions in paragraphs 0025 to 0094 of JP-A No. 2012-255128 can be referred to, the contents of which are incorporated herein.
　分散剤として用いる樹脂は、芳香族カルボキシ基を有する樹脂（樹脂Ａｃ）であることも好ましい。芳香族カルボキシ基を有する樹脂としては上述したものが挙げられる。 It is also preferable that the resin used as the dispersant is a resin having an aromatic carboxy group (resin Ac). Examples of the resin having an aromatic carboxy group include those mentioned above.
　分散剤として用いる樹脂は、主鎖及び側鎖の少なくとも一方に窒素原子を含むポリイミン系分散剤であることも好ましい。ポリイミン系分散剤としては、ｐＫａ１４以下の官能基を有する部分構造を有する主鎖と、原子数４０～１００００の側鎖とを有し、かつ主鎖及び側鎖の少なくとも一方に塩基性窒素原子を有する樹脂が好ましい。塩基性窒素原子は、塩基性を呈する窒素原子であれば特に制限はない。ポリイミン系分散剤については、特開２０１２－２５５１２８号公報の段落番号０１０２～０１６６の記載を参酌でき、この内容は本明細書に組み込まれる。 It is also preferable that the resin used as a dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain. Preferably, the resin has The basic nitrogen atom is not particularly limited as long as it exhibits basicity. Regarding the polyimine dispersant, the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
　分散剤として用いる樹脂は、コア部に複数個のポリマー鎖が結合した構造の樹脂であることも好ましい。このような樹脂としては、例えば、デンドリマー（星型ポリマーを含む）が挙げられる。また、デンドリマーの具体例としては、特開２０１３－０４３９６２号公報の段落番号０１９６～０２０９に記載された高分子化合物Ｃ－１～Ｃ－３１などが挙げられる。 It is also preferable that the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such resins include dendrimers (including star-shaped polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A No. 2013-043962.
　分散剤として用いる樹脂は、エチレン性不飽和結合含有基を側鎖に有する繰り返し単位を含む樹脂であることも好ましい。エチレン性不飽和結合含有基を側鎖に有する繰り返し単位の含有量は、樹脂の全繰り返し単位中１０モル％以上であることが好ましく、１０～８０モル％であることがより好ましく、２０～７０モル％であることが更に好ましい。 The resin used as a dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in its side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and more preferably 20 to 70 mol% of the total repeating units of the resin. More preferably, it is mol%.
　分散剤として、特開２０１８－０８７９３９号公報に記載された樹脂、特許第６４３２０７７号公報の段落番号０２１９～０２２１に記載されたブロック共重合体（ＥＢ－１）～（ＥＢ－９）、国際公開第２０１６／１０４８０３号に記載のポリエステル側鎖を有するポリエチレンイミン、国際公開第２０１９／１２５９４０号に記載のブロック共重合体、特開２０２０－０６６６８７号公報に記載のアクリルアミド構造単位を有するブロックポリマー、特開２０２０－０６６６８８号公報に記載のアクリルアミド構造単位を有するブロックポリマー、国際公開第２０１６／１０４８０３号に記載の分散剤などを用いることもできる。 As a dispersant, resins described in JP 2018-087939, block copolymers (EB-1) to (EB-9) described in paragraph numbers 0219 to 0221 of Patent No. 6432077, and international publication Polyethyleneimine having a polyester side chain described in No. 2016/104803, block copolymer described in International Publication No. 2019/125940, block polymer having an acrylamide structural unit described in JP 2020-066687, A block polymer having an acrylamide structural unit described in JP-A No. 2020-066688, a dispersant described in International Publication No. 2016/104803, etc. can also be used.
　分散剤は、市販品としても入手可能であり、そのような具体例としては、ＢＹＫＣｈｅｍｉｅ社製のＤＩＳＰＥＲＢＹＫシリーズ、日本ルーブリゾール社製のＳＯＬＳＰＥＲＳＥシリーズ、ＢＡＳＦ社製のＥｆｋａシリーズ、味の素ファインテクノ（株）製のアジスパーシリーズ等が挙げられる。また、特開２０１２－１３７５６４号公報の段落番号０１２９に記載された製品、特開２０１７－１９４６６２号公報の段落番号０２３５に記載された製品を分散剤として用いることもできる。 Dispersants are also available as commercial products, and specific examples include the DISPERBYK series manufactured by BYK Chemie, the SOLSPERSE series manufactured by Japan Lubrizol, the Efka series manufactured by BASF, and Ajinomoto Fine Techno Co., Ltd. Examples include the Ajisper series manufactured by Manufacturer. Further, the product described in paragraph number 0129 of JP 2012-137564A and the product described in paragraph number 0235 of JP 2017-194662A can also be used as a dispersant.
　着色組成物の全固形分中における樹脂の含有量は１～５０質量％であることが好ましい。上限は、４０質量％以下であることが好ましく、３０質量％以下であることがより好ましい。下限は、５質量％以上であることが好ましく、１０質量％以上であることがより好ましい。本発明の着色組成物は、樹脂を１種のみ含んでいてもよいし、２種以上含んでいてもよい。樹脂を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of resin in the total solid content of the coloring composition is preferably 1 to 50% by mass. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. The colored composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more types of resin are included, the total amount thereof is preferably within the above range.
＜＜ラジカル重合性モノマー＞＞
　本発明の着色組成物は、ラジカル重合性モノマーを含有する。ラジカル重合性モノマーとしては、エチレン性不飽和結合含有基を有する化合物などが挙げられる。エチレン性不飽和結合含有基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基などが挙げられる。 <<Radical polymerizable monomer>>
The colored composition of the present invention contains a radically polymerizable monomer. Examples of the radically polymerizable monomer include compounds having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, (meth)allyl group, and (meth)acryloyl group.
　ラジカル重合性モノマーの分子量は、１００～３０００が好ましい。上限は、２０００以下が好ましく、１５００以下がより好ましい。下限は、１５０以上が好ましく、２５０以上がより好ましい。 The molecular weight of the radically polymerizable monomer is preferably 100 to 3,000. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, more preferably 250 or more.
　ラジカル重合性モノマーのエチレン性不飽和結合含有基価（以下、Ｃ＝Ｃ価という）は、着色組成物の経時安定性の観点から２～１４ｍｍｏｌ／ｇであることが好ましい。下限は、３ｍｍｏｌ／ｇ以上であることが好ましく、４ｍｍｏｌ／ｇ以上であることがより好ましく、５ｍｍｏｌ／ｇ以上であることが更に好ましい。上限は１２ｍｍｏｌ／ｇ以下であることが好ましく、１０ｍｍｏｌ／ｇ以下であることがより好ましく、８ｍｍｏｌ／ｇ以下であることが更に好ましい。ラジカル重合性モノマーのＣ＝Ｃ価は、ラジカル重合性モノマーの１分子中に含まれるエチレン性不飽和結合含有基の数をラジカル重合性モノマーの分子量で割ることで算出した値である。 The ethylenically unsaturated bond-containing group value (hereinafter referred to as C═C value) of the radically polymerizable monomer is preferably 2 to 14 mmol/g from the viewpoint of stability of the coloring composition over time. The lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and even more preferably 5 mmol/g or more. The upper limit is preferably 12 mmol/g or less, more preferably 10 mmol/g or less, and even more preferably 8 mmol/g or less. The C═C value of a radically polymerizable monomer is a value calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the radically polymerizable monomer by the molecular weight of the radically polymerizable monomer.
　ラジカル重合性モノマーは、エチレン性不飽和結合含有基を３個以上含む化合物であることが好ましく、エチレン性不飽和結合含有基を４個以上含む化合物であることがより好ましい。エチレン性不飽和結合含有基の上限は、着色組成物の経時安定性の観点から１５個以下であることが好ましく、１０個以下であることがより好ましく、６個以下であることが更に好ましい。また、ラジカル重合性モノマーは、３官能以上の（メタ）アクリレート化合物であることが好ましく、３～１５官能の（メタ）アクリレート化合物であることがより好ましく、３～１０官能の（メタ）アクリレート化合物であることが更に好ましく、３～６官能の（メタ）アクリレート化合物であることが特に好ましい。ラジカル重合性モノマーの具体例としては、国際公開第２０２２／０６５２１５号の段落番号００７５～００８３に記載の化合物が挙げられる。 The radically polymerizable monomer is preferably a compound containing three or more ethylenically unsaturated bond-containing groups, and more preferably a compound containing four or more ethylenically unsaturated bond-containing groups. The upper limit of the ethylenically unsaturated bond-containing groups is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less from the viewpoint of the stability of the coloring composition over time. Further, the radically polymerizable monomer is preferably a trifunctional or higher functional (meth)acrylate compound, more preferably a trifunctional to 15 functional (meth)acrylate compound, and a trifunctional to 10 functional (meth)acrylate compound. More preferably, it is a tri- to hexa-functional (meth)acrylate compound. Specific examples of radically polymerizable monomers include compounds described in paragraph numbers 0075 to 0083 of International Publication No. 2022/065215.
　ラジカル重合性モノマーとしては、ジペンタエリスリトールトリ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、ＮＫエステルＡ－ＤＰＨ－１２Ｅ；新中村化学工業（株）製）、およびこれらの（メタ）アクリロイル基がエチレングリコールおよび／またはプロピレングリコール残基を介して結合している構造の化合物（例えば、サートマー社から市販されている、ＳＲ４５４、ＳＲ４９９）が好ましい。また、ラジカル重合性モノマーとしては、ジグリセリンＥＯ（エチレンオキシド）変性（メタ）アクリレート（市販品としてはＭ－４６０；東亞合成製）、ペンタエリスリトールテトラアクリレート（新中村化学工業（株）製、ＮＫエステルＡ－ＴＭＭＴ）、１，６－ヘキサンジオールジアクリレート（日本化薬（株）製、ＫＡＹＡＲＡＤ　ＨＤＤＡ）、ＲＰ－１０４０（日本化薬（株）製）、アロニックスＴＯ－２３４９（東亞合成（株）製）、ＮＫオリゴＵＡ－７２００（新中村化学工業（株）製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００、ＬＩＮＣ－２０２ＵＡ（共栄社化学（株）製）、８ＵＨ－１００６、８ＵＨ－１０１２（以上、大成ファインケミカル（株）製）、ライトアクリレートＰＯＢ－Ａ０（共栄社化学（株）製）などを用いることもできる。 Examples of radically polymerizable monomers include dipentaerythritol tri(meth)acrylate (commercial product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercial product: KAYARAD D- 320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercial product) is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industries, Ltd.), and these (meth)acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues. Compounds having a structure in which the conjugates are bonded together (for example, SR454 and SR499, commercially available from Sartomer) are preferred. In addition, as radical polymerizable monomers, diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available product is M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., NK ester) A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) ), NK Oligo UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600 , AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. It can also be used.
　着色組成物の全固形分中におけるラジカル重合性モノマーの含有量は、１～３５質量％であることが好ましい。上限は、３０質量％以下であることが好ましく、２５質量％以下であることがより好ましい。下限は、２質量％以上であることが好ましく、５質量％以上であることがより好ましい。
　ラジカル重合性モノマーと樹脂との割合は、樹脂１００質量部に対してラジカル重合性モノマーが１～５００質量部であることが好ましい。この態様によれば、現像時の膜の剥がれを抑制することができる。上限は、４００質量部以下であることが好ましく、３００質量部以下であることがより好ましい。下限は、１０質量部以上であることが好ましく、２０質量部以上であることがより好ましい。
　ラジカル重合性モノマーと後述する化合物Ａとの割合は、後述する化合物Ａの１００質量部に対してラジカル重合性モノマーが５～１０００質量部であることが好ましい。この態様によれば、フォトリソグラフィ法でパターン形成して画素を形成した際に、得られる画素の線幅のばらつきを抑制できる。上限は、５００質量部以下であることが好ましく、２５０質量部以下であることがより好ましい。下限は、１５質量部以上であることが好ましく、３０質量部以上であることがより好ましい。
　本発明の着色組成物は、ラジカル重合性モノマーを１種のみ含んでいてもよいし、２種以上含んでいてもよい。ラジカル重合性モノマーを２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the radically polymerizable monomer in the total solid content of the coloring composition is preferably 1 to 35% by mass. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more.
The ratio of the radically polymerizable monomer to the resin is preferably 1 to 500 parts by weight based on 100 parts by weight of the resin. According to this aspect, peeling of the film during development can be suppressed. The upper limit is preferably 400 parts by mass or less, more preferably 300 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 20 parts by mass or more.
The ratio of the radically polymerizable monomer to Compound A described below is preferably 5 to 1000 parts by mass per 100 parts by mass of Compound A described later. According to this aspect, when pixels are formed by patterning using photolithography, it is possible to suppress variations in line width of the resulting pixels. The upper limit is preferably 500 parts by mass or less, more preferably 250 parts by mass or less. The lower limit is preferably 15 parts by mass or more, more preferably 30 parts by mass or more.
The colored composition of the present invention may contain only one kind of radically polymerizable monomer, or may contain two or more kinds of radically polymerizable monomers. When two or more types of radically polymerizable monomers are included, it is preferable that their total amount falls within the above range.
＜＜ラジカル重合開始剤＞＞
　本発明の着色組成物はラジカル重合開始剤を含有する。ラジカル重合開始剤としては、熱ラジカル重合開始剤および光ラジカル重合開始剤が挙げられ、光ラジカル重合開始剤であることが好ましい。 <<Radical polymerization initiator>>
The colored composition of the present invention contains a radical polymerization initiator. Examples of the radical polymerization initiator include thermal radical polymerization initiators and radical photopolymerization initiators, and radical photopolymerization initiators are preferred.
　熱ラジカル重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル（ＡＩＢＮ）、３－カルボキシプロピオニトリル、アゾビスマレノニトリル、ジメチル－（２，２’）－アゾビス（２－メチルプロピオネート）等のアゾ化合物、ｔｅｒｔ－ブチルパーオキシベンゾエート、過酸化ベンゾイル、過酸化ラウロイル、及び、過硫酸カリウム等の有機過酸化物が挙げられる。 Examples of the thermal radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismarenonitrile, and dimethyl-(2,2')-azobis(2- Examples include azo compounds such as methyl propionate), tert-butyl peroxybenzoate, benzoyl peroxide, lauroyl peroxide, and organic peroxides such as potassium persulfate.
　光ラジカル重合開始剤としては、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物など）、アシルホスフィン化合物、ヘキサアリールビイミダゾール化合物、オキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、α－ヒドロキシケトン化合物、α－アミノケトン化合物などが挙げられる。光ラジカル重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、ヘキサアリールビイミダゾール化合物、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン－ベンゼン－鉄錯体、ハロメチルオキサジアゾール化合物および３－アリール置換クマリン化合物であることが好ましく、オキシム化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、および、アシルホスフィン化合物から選ばれる化合物であることがより好ましく、オキシム化合物であることが更に好ましい。また、光ラジカル重合開始剤としては、特開２０１４－１３０１７３号公報の段落００６５～０１１１に記載された化合物、特許第６３０１４８９号公報に記載された化合物、ＭＡＴＥＲＩＡＬ　ＳＴＡＧＥ　３７～６０ｐ，ｖｏｌ．１９，Ｎｏ．３，２０１９に記載されたパーオキサイド系光重合開始剤、国際公開第２０１８／２２１１７７号に記載の光重合開始剤、国際公開第２０１８／１１０１７９号に記載の光重合開始剤、特開２０１９－０４３８６４号公報に記載の光重合開始剤、特開２０１９－０４４０３０号公報に記載の光重合開始剤、特開２０１９－１６７３１３号公報に記載の過酸化物系開始剤、特開２０２０－０５５９９２号公報に記載のオキサゾリジン基を有するアミノアセトフェノン系開始剤、特開２０１３－１９０４５９号公報に記載のオキシム系光重合開始剤、特開２０２０－１７２６１９号公報に記載の重合体、国際公開第２０２０／１５２１２０号に記載の式１で表される化合物、特開２０２１－１８１４０６号公報に記載の化合物、特開２０２２－０１３３７９号公報に記載の光重合開始剤、特開２０２２－０１５７４７号公報に記載の式（１）で表される化合物、特表２０２１－５０７０５８号公報に記載のフッ素含有フルオレンオキシムエステル系光開始剤、中国特許出願公開第１１０７６４３６７号明細書に記載の開始剤、特表２０２２－５１８５３５号公報に記載の開始剤、国際公開第２０２１／１７５８５５号に記載の開始剤などが挙げられる。 Examples of the photoradical polymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, Examples include thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, photoradical polymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and hexaarylene compounds. Preferred are rubiimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds, oxime compounds, α-hydroxy A compound selected from a ketone compound, an α-aminoketone compound, and an acylphosphine compound is more preferable, and an oxime compound is even more preferable. In addition, as photoradical polymerization initiators, compounds described in paragraphs 0065 to 0111 of JP-A No. 2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3,2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiator described in JP-A No. 2019-044030, the peroxide-based initiator described in JP-A No. 2019-167313, the photopolymerization initiator described in JP-A No. 2020-055992 The aminoacetophenone initiator having an oxazolidine group as described, the oxime photopolymerization initiator described in JP 2013-190459, the polymer described in JP 2020-172619, the WO 2020/152120 The compound represented by the formula 1 described in JP-A No. 2021-181406, the photopolymerization initiator described in JP-A No. 2022-013379, the formula (1) described in JP-A No. 2022-015747 ), the fluorine-containing fluorene oxime ester photoinitiator described in Japanese Patent Publication No. 2021-507058, the initiator described in China Patent Application Publication No. 110764367, the initiator described in Japanese Patent Publication No. 2022-518535 Examples include the initiator described in WO 2021/175855, and the like.
　ヘキサアリールビイミダゾール化合物の具体例としては、２，２’，４－トリス（２－クロロフェニル）－５－（３，４－ジメトキシフェニル）－４，５－ジフェニル－１，１’－ビイミダゾールなどが挙げられる。 Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole, etc. can be mentioned.
　α－ヒドロキシケトン化合物の市販品としては、Ｏｍｎｉｒａｄ　１８４、Ｏｍｎｉｒａｄ　１１７３、Ｏｍｎｉｒａｄ　２９５９、Ｏｍｎｉｒａｄ　１２７（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、Ｉｒｇａｃｕｒｅ　１８４、Ｉｒｇａｃｕｒｅ　１１７３、Ｉｒｇａｃｕｒｅ　２９５９、Ｉｒｇａｃｕｒｅ　１２７（以上、ＢＡＳＦ社製）などが挙げられる。α－アミノケトン化合物の市販品としては、Ｏｍｎｉｒａｄ　９０７、Ｏｍｎｉｒａｄ　３６９、Ｏｍｎｉｒａｄ　３６９Ｅ、Ｏｍｎｉｒａｄ　３７９ＥＧ（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、Ｉｒｇａｃｕｒｅ　９０７、Ｉｒｇａｃｕｒｅ　３６９、Ｉｒｇａｃｕｒｅ　３６９Ｅ、Ｉｒｇａｃｕｒｅ　３７９ＥＧ（以上、ＢＡＳＦ社製）などが挙げられる。アシルホスフィン化合物の市販品としては、Ｏｍｎｉｒａｄ　８１９、Ｏｍｎｉｒａｄ　ＴＰＯ（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、Ｉｒｇａｃｕｒｅ　８１９、Ｉｒｇａｃｕｒｅ　ＴＰＯ（以上、ＢＡＳＦ社製）などが挙げられる。 Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, and Irgacure 117. 3, Irgacure 2959, Irgacure 127 (all BASF (manufactured by a company). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, and Irgacure 36. 9, Irgacure 369E, Irgacure 379EG (all manufactured by BASF) (manufactured by). Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.
　オキシム化合物としては、国際公開第２０２２／０８５４８５号の段落番号０１４２に記載の化合物、特許第５４３０７４６号に記載の化合物、特許第５６４７７３８号に記載の化合物、特開２０２１－１７３８５８号公報の一般式（１）で表される化合物や段落００２２から００２４に記載の化合物、特開２０２１－１７００８９号公報の一般式（１）で表される化合物や段落０１１７から０１２０に記載の化合物などが挙げられる。オキシム化合物の具体例としては、３－ベンゾイルオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オン、１－［４－（フェニルチオ）フェニル］－３－シクロヘキシル－プロパン－１，２－ジオン－２－（Ｏ－アセチルオキシム）などが挙げられる。市販品としては、Ｉｒｇａｃｕｒｅ　ＯＸＥ０１、Ｉｒｇａｃｕｒｅ　ＯＸＥ０２、Ｉｒｇａｃｕｒｅ　ＯＸＥ０３、Ｉｒｇａｃｕｒｅ　ＯＸＥ０４（以上、ＢＡＳＦ社製）、ＴＲ－ＰＢＧ－３０１、ＴＲ－ＰＢＧ－３０４、ＴＲ－ＰＢＧ－３２７（ＴＲＯＮＬＹ社製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－０１４０５２号公報に記載の光重合開始剤２）が挙げられる。また、オキシム化合物としては、着色性が無い化合物や、透明性が高く変色し難い化合物を用いることも好ましい。市販品としては、アデカアークルズＮＣＩ－７３０、ＮＣＩ－８３１、ＮＣＩ－９３０（以上、（株）ＡＤＥＫＡ製）などが挙げられる。 Examples of oxime compounds include the compound described in paragraph number 0142 of International Publication No. 2022/085485, the compound described in Patent No. 5430746, the compound described in Patent No. 5647738, and the general formula ( Examples include the compound represented by 1), the compound described in paragraphs 0022 to 0024, the compound represented by general formula (1) and the compound described in paragraphs 0117 to 0120 of JP-A-2021-170089. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-327 (manufactured by TRONLY). ), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., photopolymerization initiator 2) described in JP-A-2012-014052 can be mentioned. Further, as the oxime compound, it is also preferable to use a compound without coloring property or a compound with high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Co., Ltd.).
　光重合開始剤としては、フルオレン環を有するオキシム化合物、カルバゾール環の少なくとも１つのベンゼン環がナフタレン環となった骨格を有するオキシム化合物、フッ素原子を有するオキシム化合物、ニトロ基を有するオキシム化合物、ベンゾフラン骨格を有するオキシム化合物、カルバゾール骨格にヒドロキシ基を有する置換基が結合したオキシム化合物、国際公開第２０２２／０８５４８５号の段落番号０１４３～０１４９に記載の化合物を用いることもできる。 Examples of photopolymerization initiators include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, oxime compounds having a fluorine atom, oxime compounds having a nitro group, and benzofuran skeleton. An oxime compound having a carbazole skeleton bonded with a substituent having a hydroxy group, and compounds described in paragraph numbers 0143 to 0149 of International Publication No. 2022/085485 can also be used.
　本発明において好ましく使用されるオキシム化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of oxime compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.
　オキシム化合物は、波長３５０～５００ｎｍの範囲に極大吸収波長を有する化合物が好ましく、波長３６０～４８０ｎｍの範囲に極大吸収波長を有する化合物がより好ましい。また、オキシム化合物の波長３６５ｎｍ又は波長４０５ｎｍにおけるモル吸光係数は、感度の観点から、高いことが好ましく、１０００～３０００００であることがより好ましく、２０００～３０００００であることが更に好ましく、５０００～２０００００であることが特に好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm. In addition, from the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably from 1000 to 300,000, even more preferably from 2000 to 300,000, and even more preferably from 5000 to 200,000. It is particularly preferable that there be. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
　光ラジカル重合開始剤としては、２官能あるいは３官能以上の光ラジカル重合開始剤を用いてもよい。そのような光ラジカル重合開始剤を用いることにより、光ラジカル重合開始剤の１分子から２つ以上のラジカルが発生するため、良好な感度が得られる。また、非対称構造の化合物を用いた場合においては、結晶性が低下して溶剤などへの溶解性が向上して、経時で析出しにくくなり、着色組成物の経時安定性を向上させることができる。２官能あるいは３官能以上の光ラジカル重合開始剤の具体例としては、国際公開第２０２２／０６５２１５号の段落０１４８に記載の化合物が挙げられる。 As the photoradical polymerization initiator, a difunctional, trifunctional or more functional photoradical polymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time, thereby improving the stability of the coloring composition over time. . Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include compounds described in paragraph 0148 of International Publication No. 2022/065215.
　着色組成物の全固形分中における重合開始剤の含有量は０．１～３０質量％が好ましい。下限は、０．５質量％以上が好ましく、１質量％以上がより好ましい。上限は、２０質量％以下が好ましく、１５質量％以下がより好ましい。
　また、着色組成物に含まれる重合開始剤は、光重合開始剤を含むものであることが好ましい。着色組成物に含まれる重合開始剤中における光重合開始剤の含有量は、５０～１００質量％であることが好ましく、８０～１００質量％であることがより好ましく、９０～１００質量％であることが更に好ましい。
　本発明の着色組成物において、重合開始剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、それらの合計量が上記範囲となることが好ましい。 The content of the polymerization initiator in the total solid content of the colored composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
Moreover, it is preferable that the polymerization initiator contained in the coloring composition contains a photopolymerization initiator. The content of the photopolymerization initiator in the polymerization initiator contained in the colored composition is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and 90 to 100% by mass. It is even more preferable.
In the colored composition of the present invention, only one type of polymerization initiator may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
＜＜発生剤＞＞
　本発明の着色組成物は、酸発生剤および塩基発生剤からなる群より選択される少なくとも１種の発生剤を含む。発生剤は、実質的に酸発生剤のみであるか、または、実質的に塩基発生剤のみであることが好ましく、膜へのダメージ抑制や、金属部材などの腐食抑制などの観点から、発生剤は実質的に塩基発生剤のみであることが好ましい。
　なお、本明細書において、発生剤が、実質的に酸発生剤のみである場合とは、発生剤の全質量中における酸発生剤の含有量が９９質量％以上であることを意味し、９９．９質量％以上であることが好ましく、１００質量％（酸発生剤のみからなる）であることがより好ましい。また、発生剤が、実質的に塩基発生剤のみである場合とは、発生剤の全質量中における塩基発生剤の含有量が９９質量％以上であることを意味し、９９．９質量％以上であることが好ましく、１００質量％（塩基発生剤のみからなる）であることがより好ましい。 ＜＜Generator＞＞
The colored composition of the present invention contains at least one generator selected from the group consisting of acid generators and base generators. It is preferable that the generator is substantially only an acid generator or substantially only a base generator. It is preferable that the base generator is substantially only a base generator.
In addition, in this specification, the case where the generator is substantially only an acid generator means that the content of the acid generator in the total mass of the generator is 99% by mass or more, and 99% by mass or more. The content is preferably .9% by mass or more, and more preferably 100% by mass (consisting only of the acid generator). In addition, when the generator is substantially only a base generator, it means that the content of the base generator in the total mass of the generator is 99% by mass or more, and 99.9% by mass or more. It is preferably 100% by mass (consisting only of the base generator), and more preferably 100% by mass.
（酸発生剤）
　酸発生剤としては、熱酸発生剤および光酸発生剤が挙げられる。酸発生剤は、光酸発生剤を含むものであることが好ましい。また、酸発生剤は、光酸発生剤と熱酸発生剤とを併用してもよい。熱酸発生剤と光酸発生剤とを併用する場合は、熱酸発生剤と光酸発生剤との質量比は、熱酸発生剤の１００質量部に対して光酸発生剤が１００～２０００質量部であることが好ましい。下限は、１５０質量部以上であることが好ましく、２００質量部以上であることがより好ましい。上限は１５００質量部以下であることが好ましく、１０００質量部以下であることがより好ましい。なかでも、プロセス温度のより低温化が可能で、１５０℃以下（好ましくは１２０℃以下）の低温で硬化膜を形成した場合であっても、より耐湿性に優れた硬化膜を形成することができ、更には、フォトリソグラフィ法でのパターン形成性に優れるという理由から酸発生剤は、実質的に光酸発生剤のみであることが特に好ましい。なお、本明細書において、酸発生剤が実質的に光酸発生剤のみである場合とは、酸発生剤の全質量中における光酸発生剤の含有量が９９質量％以上であることを意味し、９９．９質量％以上であることが好ましく、１００質量％（光酸発生剤のみからなる）であることがより好ましい。
　なお、本明細書において、酸発生剤とは、熱や光などのエネルギーを加えることで酸を発生する化合物のことを意味する。また、熱酸発生剤とは、熱分解により酸を発生する化合物のことを意味する。また、光酸発生剤とは、光照射により酸を発生する化合物のことを意味する。 (acid generator)
Examples of acid generators include thermal acid generators and photoacid generators. The acid generator preferably includes a photoacid generator. Further, as the acid generator, a photoacid generator and a thermal acid generator may be used in combination. When a thermal acid generator and a photoacid generator are used together, the mass ratio of the thermal acid generator and the photoacid generator is 100 to 2000 parts by mass of the photoacid generator to 100 parts by mass of the thermal acid generator. Parts by mass are preferred. The lower limit is preferably 150 parts by mass or more, more preferably 200 parts by mass or more. The upper limit is preferably 1,500 parts by mass or less, more preferably 1,000 parts by mass or less. Among these, it is possible to lower the process temperature, and even when forming a cured film at a low temperature of 150°C or less (preferably 120°C or less), it is possible to form a cured film with better moisture resistance. Furthermore, it is particularly preferable that the acid generator is substantially only a photoacid generator because it has excellent pattern formation properties in photolithography. In this specification, the case where the acid generator is substantially only a photoacid generator means that the content of the photoacid generator in the total mass of the acid generator is 99% by mass or more. However, it is preferably 99.9% by mass or more, and more preferably 100% by mass (consisting only of the photoacid generator).
In addition, in this specification, an acid generator means a compound that generates an acid by applying energy such as heat or light. Further, the term "thermal acid generator" means a compound that generates an acid by thermal decomposition. Moreover, a photoacid generator means a compound that generates an acid upon irradiation with light.
　酸発生剤は、イオン型酸発生剤でもよく、非イオン型酸発生剤でもよいが、非イオン型酸発生剤であることが好ましい。 The acid generator may be an ionic acid generator or a nonionic acid generator, but is preferably a nonionic acid generator.
　酸発生剤は、ｐＫａが４以下の酸を発生する化合物であることが好ましく、ｐＫａが３以下の酸を発生する化合物であることがより好ましく、ｐＫａが２以下の酸を発生する化合物であることが更に好ましい。この態様によれば、より耐湿性に優れた硬化膜を形成しやすい。なお、本明細書において、ｐＫａは、基本的に２５℃の水中におけるｐＫａを指す。水中で測定できないものは、測定に適する溶剤に変更し測定したものを指す。具体的には、化学便覧等に記載のｐＫａが参考にできる。ｐＫａが３以下の酸としては、スルホン酸またはホスホン酸であることが好ましく、スルホン酸であることがより好ましい。 The acid generator is preferably a compound that generates an acid with a pKa of 4 or less, more preferably a compound that generates an acid with a pKa of 3 or less, and a compound that generates an acid with a pKa of 2 or less. It is even more preferable. According to this aspect, it is easier to form a cured film with better moisture resistance. Note that in this specification, pKa basically refers to pKa in water at 25°C. Items that cannot be measured in water are measured using a suitable solvent. Specifically, the pKa described in chemical handbooks and the like can be referred to. The acid having a pKa of 3 or less is preferably a sulfonic acid or a phosphonic acid, and more preferably a sulfonic acid.
　酸発生剤の分子量は、２００～１０００が好ましい。下限は、２３０以上が好ましい。上限は、８００以下が好ましい。酸発生剤の分子量が上記範囲であれば、硬化膜の製造時におけるベーク等の際に、酸発生剤が揮発しやすくでき、膜中に酸発生剤やその分解物などが残留することを抑制できる。 The molecular weight of the acid generator is preferably 200 to 1000. The lower limit is preferably 230 or more. The upper limit is preferably 800 or less. If the molecular weight of the acid generator is within the above range, the acid generator will easily volatilize during baking, etc. during the production of a cured film, thereby suppressing the acid generator and its decomposition products from remaining in the film. can.
－熱酸発生剤－
　熱酸発生剤の酸発生温度は８０℃～１３０℃であることが好ましく、９０℃～１１０℃であることがより好ましい。 -Thermal acid generator-
The acid generation temperature of the thermal acid generator is preferably 80°C to 130°C, more preferably 90°C to 110°C.
　熱酸発生剤は、加熱によりスルホン酸、カルボン酸、ジスルホニルイミドなどの低求核性の酸を発生する化合物であることが好ましい。熱酸発生剤から発生する酸としては、ｐＫａが４以下の酸が好ましく、ｐＫａが３以下の酸がより好ましく、ｐＫａが２以下の酸が更に好ましい。例えば、スルホン酸や電子求引基で置換されたアルキルカルボン酸、アリールカルボン酸、ジスルホニルイミドなどが好ましい。電子求引基としてはフッ素原子などのハロゲン原子、トリフルオロメチル基等のハロアルキル基、ニトロ基、シアノ基を挙げることができる。 The thermal acid generator is preferably a compound that generates a low nucleophilic acid such as sulfonic acid, carboxylic acid, or disulfonylimide upon heating. The acid generated from the thermal acid generator is preferably an acid with a pKa of 4 or less, more preferably an acid with a pKa of 3 or less, and even more preferably an acid with a pKa of 2 or less. For example, sulfonic acids, alkylcarboxylic acids substituted with electron-withdrawing groups, arylcarboxylic acids, disulfonylimides, and the like are preferred. Examples of the electron-withdrawing group include a halogen atom such as a fluorine atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.
　熱酸発生剤としては、ジアゾメタン化合物、スルホン酸エステル化合物、カルボン酸エステル化合物、リン酸エステル化合物、スルホンイミド化合物、スルホンベンゾトリアゾール化合物、スルホニウム塩等が挙げられ、スルホン酸エステル化合物およびスルホンイミド化合物が好ましい。 Examples of the thermal acid generator include diazomethane compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, phosphoric acid ester compounds, sulfonimide compounds, sulfonebenzotriazole compounds, sulfonium salts, etc. preferable.
　熱酸発生剤は、活性光線又は放射線の照射によって実質的に酸を発生せず、熱によって酸を発生するスルホン酸エステル化合物であることも好ましい。活性光線又は放射線の照射によって実質的に酸を発生していないことは、化合物の露光前後での赤外線吸収（ＩＲ）スペクトル、核磁気共鳴（ＮＭＲ）スペクトル測定により、スペクトルに変化がないことで判定することができる。上記スルホン酸エステル化合物の分子量は、２３０～１，０００が好ましく、２３０～８００がより好ましい。 It is also preferable that the thermal acid generator is a sulfonic acid ester compound that does not substantially generate acid upon irradiation with actinic rays or radiation, but generates acid upon heat. Substantially no acid is generated by irradiation with actinic light or radiation, as determined by the absence of any change in the spectrum by measuring the infrared absorption (IR) spectrum and nuclear magnetic resonance (NMR) spectrum of the compound before and after exposure. can do. The molecular weight of the sulfonic acid ester compound is preferably 230 to 1,000, more preferably 230 to 800.
　スルホン酸エステル化合物としては、例えば、テトラエチレングリコールビス（ｐ－トルエンスルホナート）、ｐ－トルエンスルホン酸ブチル、４－ヒドロキシフェニルジメチルスルホニウムトリフルオロメタンスルホネート、ベンジル－４－ヒドロキシフェニルメチルスルホニウムトリフルオロメタンスルホネート、２－メチルベンジル－４－ヒドロキシフェニルメチルスルホニウムトリフルオロメタンスルホネート、４－アセトキシフェニルジメチルスルホニウムトリフルオロメタンスルホネート、４－アセトキシフェニルベンジルメチルスルホニウムトリフルオロメタンスルホネート、４－（メトキシカルボニルオキシ）フェニルジメチルスルホニウムトリフルオロメタンスルホネート、ベンジル－４－（メトキシカルボニルオキシ）フェニルメチルスルホニウムトリフルオロメタンスルホネートなどが挙げられる。 Examples of the sulfonic acid ester compound include tetraethylene glycol bis(p-toluenesulfonate), butyl p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenylbenzylmethylsulfonium trifluoromethanesulfonate, 4-(methoxycarbonyloxy)phenyldimethylsulfonium trifluoromethanesulfonate, Examples include benzyl-4-(methoxycarbonyloxy)phenylmethylsulfonium trifluoromethanesulfonate.
　スルホンイミド化合物としては、例えば、Ｎ－（トリフルオロメチルスルホニルオキシ）スクシンイミド（商品名「ＳＩ－１０５」、みどり化学社）、Ｎ－（カンファスルホニルオキシ）スクシンイミド（商品名「ＳＩ－１０６」、みどり化学社）、Ｎ－（４－メチルフェニルスルホニルオキシ）スクシンイミド（商品名「ＳＩ－１０１」、みどり化学社）、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）スクシンイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）スクシンイミド、Ｎ－（トリフルオロメチルスルホニルオキシ）フタルイミド、Ｎ－（カンファスルホニルオキシ）フタルイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）フタルイミド、Ｎ－（２－フルオロフェニルスルホニルオキシ）フタルイミド、Ｎ－（トリフルオロメチルスルホニルオキシ）ジフェニルマレイミド（商品名「ＰＩ－１０５」、みどり化学社）、Ｎ－（カンファスルホニルオキシ）ジフェニルマレイミド、４－メチルフェニルスルホニルオキシ）ジフェニルマレイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）ジフェニルマレイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）ジフェニルマレイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）ジフェニルマレイミド、Ｎ－（フェニルスルホニルオキシ）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシルイミド（商品名「ＮＤＩ－１００」、みどり化学社）、Ｎ－（４－メチルフェニルスルホニルオキシ）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシルイミド（商品名「ＮＤＩ－１０１」、みどり化学社）、Ｎ－（トリフルオロメタンスルホニルオキシ）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシルイミド（商品名「ＮＤＩ－１０５」、みどり化学社）、Ｎ－（ノナフルオロブタンスルホニルオキシ）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシルイミド（商品名「ＮＤＩ－１０９」、みどり化学社）、Ｎ－（カンファスルホニルオキシ）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシルイミド（商品名「ＮＤＩ－１０６」、みどり化学社）、Ｎ－（カンファスルホニルオキシ）－７－オキサビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシルイミド、Ｎ－（トリフルオロメチルスルホニルオキシ）－７－オキサビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシルイミド、Ｎ－（４－メチルフェニルスルホニルオキシ）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシルイミド、Ｎ－（４－メチルフェニルスルホニルオキシ）－７－オキサビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシルイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシルイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）－７－オキサビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシルイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシルイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）－７－オキサビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシルイミド、Ｎ－（トリフルオロメチルスルホニルオキシ）ビシクロ［２．２．１］ヘプタン－５，６－オキシ－２，３－ジカルボキシルイミド、Ｎ－（カンファスルホニルオキシ）ビシクロ［２．２．１］ヘプタン－５，６－オキシ－２，３－ジカルボキシルイミド、Ｎ－（４－メチルフェニルスルホニルオキシ）ビシクロ［２．２．１］ヘプタン－５，６－オキシ－２，３－ジカルボキシルイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）ビシクロ［２．２．１］ヘプタン－５，６－オキシ－２，３－ジカルボキシルイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）ビシクロ［２．２．１］ヘプタン－５，６－オキシ－２，３－ジカルボキシルイミド、Ｎ－（トリフルオロメチルスルホニルオキシ）ナフチルジカルボキシルイミド（商品名「ＮＡＩ－１０５」、みどり化学社）、Ｎ－（カンファスルホニルオキシ）ナフチルジカルボキシルイミド（商品名「ＮＡＩ－１０６」、みどり化学社）、Ｎ－（４－メチルフェニルスルホニルオキシ）ナフチルジカルボキシルイミド（商品名「ＮＡＩ－１０１」、みどり化学社）、Ｎ－（フェニルスルホニルオキシ）ナフチルジカルボキシルイミド（商品名「ＮＡＩ－１００」、みどり化学社）、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）ナフチルジカルボキシルイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）ナフチルジカルボキシルイミド、Ｎ－（ペンタフルオロエチルスルホニルオキシ）ナフチルジカルボキシルイミド、Ｎ－（ヘプタフルオロプロピルスルホニルオキシ）ナフチルジカルボキシルイミド、Ｎ－（ノナフルオロブチルスルホニルオキシ）ナフチルジカルボキシルイミド（商品名「ＮＡＩ－１０９」、みどり化学社）、Ｎ－（エチルスルホニルオキシ）ナフチルジカルボキシルイミド、Ｎ－（プロピルスルホニルオキシ）ナフチルジカルボキシルイミド、Ｎ－（ブチルスルホニルオキシ）ナフチルジカルボキシルイミド（商品名「ＮＡＩ－１００４」、みどり化学社）、Ｎ－（ペンチルスルホニルオキシ）ナフチルジカルボキシルイミド、Ｎ－（ヘキシルスルホニルオキシ）ナフチルジカルボキシルイミド、Ｎ－（ヘプチルスルホニルオキシ）ナフチルジカルボキシルイミド、Ｎ－（オクチルスルホニルオキシ）ナフチルジカルボキシルイミド、Ｎ－（ノニルスルホニルオキシ）ナフチルジカルボキシルイミド等が挙げられる。 Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)succinimide (trade name "SI-105", Midori Chemical Co., Ltd.), N-(camphorsulfonyloxy)succinimide (trade name "SI-106", Midori Chemical Co., Ltd.), N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenyl) sulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide , N-(trifluoromethylsulfonyloxy)diphenylmaleimide (trade name "PI-105", Midori Kagakusha), N-(camphorsulfonyloxy)diphenylmaleimide, 4-methylphenylsulfonyloxy)diphenylmaleimide, N-(2 -trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(phenylsulfonyloxy)bicyclo[2.2. 1] Hept-5-ene-2,3-dicarboxylimide (trade name "NDI-100", Midori Kagaku Co., Ltd.), N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5 -ene-2,3-dicarboxylimide (trade name "NDI-101", Midori Kagaku Co., Ltd.), N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3- Dicarboxylimide (trade name "NDI-105", Midori Kagakusha), N-(nonafluorobutanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide (trade name "NDI-109", Midori Kagaku Co., Ltd.), N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide (trade name "NDI-106", Midori Kagaku Co., Ltd.) ), N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1] Hept-5-ene-2,3-dicarboxylimide Carboxylimide, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide, N-(2-trifluoromethylphenylsulfonyloxy) ) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5 -ene-2,3-dicarboxylimide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide, N-(4-fluorophenyl sulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5, 6-oxy-2,3-dicarboxylimide, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimide, N-(4-methylphenyl sulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5 ,6-oxy-2,3-dicarboxylimide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimide, N-( Trifluoromethylsulfonyloxy) naphthyl dicarboxylimide (trade name "NAI-105", Midori Kagaku Co., Ltd.), N-(camphorsulfonyloxy) naphthyl dicarboxylimide (trade name "NAI-106", Midori Kagaku Co., Ltd.), N -(4-Methylphenylsulfonyloxy)naphthyldicarboxylimide (trade name "NAI-101", Midori Chemical Co., Ltd.), N-(phenylsulfonyloxy)naphthyldicarboxylimide (trade name "NAI-100", Midori Chemical Co., Ltd.) ), N-(2-trifluoromethylphenylsulfonyloxy)naphthyldicarboxylimide, N-(4-fluorophenylsulfonyloxy)naphthyldicarboxylimide, N-(pentafluoroethylsulfonyloxy)naphthyldicarboxylimide, N- (Heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N-(nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide (trade name "NAI-109", Midori Kagaku Co., Ltd.), N-(ethylsulfonyloxy) naphthyl dicarboxylimide , N-(propylsulfonyloxy) naphthyl dicarboxylimide, N-(butylsulfonyloxy) naphthyl dicarboxylimide (trade name "NAI-1004", Midori Kagaku Co., Ltd.), N-(pentylsulfonyloxy) naphthyl dicarboxylimide, N-(hexylsulfonyloxy)naphthyldicarboxylimide, N-(heptylsulfonyloxy)naphthyldicarboxylimide, N-(octylsulfonyloxy)naphthyldicarboxylimide, N-(nonylsulfonyloxy)naphthyldicarboxylimide, etc. It will be done.
　熱酸発生剤の市販品としては、三新化学工業（株）製のサンエイドシリーズ（例えば、ＳＩ－６０、ＳＩ－８０、ＳＩ－１００、ＳＩ－２００、ＳＩ－１１０、ＳＩ－１４５、ＳＩ－１５０、ＳＩ－６０Ｌ、ＳＩ－８０Ｌ、ＳＩ－１００Ｌ、ＳＩ－１１０Ｌ、ＳＩ－１４５Ｌ、ＳＩ－１５０Ｌ、ＳＩ－１６０Ｌ、ＳＩ－１８０Ｌなど）、サンアプロ（株）製のＴＡ－１００シリーズ、サンアプロ（株）製のＩＫシリーズなどが挙げられる。 Commercially available thermal acid generators include the San-Aid series manufactured by Sanshin Kagaku Kogyo Co., Ltd. (for example, SI-60, SI-80, SI-100, SI-200, SI-110, SI-145, SI -150, SI-60L, SI-80L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L, etc.), TA-100 series manufactured by San-Apro Co., Ltd., San-Apro ( Examples include the IK series manufactured by Co., Ltd.
－光酸発生剤－
　光酸発生剤は、波長３００ｎｍ以上、より好ましくは波長３００～４５０ｎｍの活性光線に感応し、酸を発生する化合物が好ましい。光酸発生剤は、光照射によってｐＫａが４以下の酸を発生する化合物であることが好ましく、ｐＫａが３以下の酸を発生する化合物であることがより好ましく、ｐＫａが２以下の酸を発生する化合物であることが更に好ましい。また、光酸発生剤は、１３０℃以下では酸を発生しない化合物であることが好ましい。 -Photoacid generator-
The photoacid generator is preferably a compound that generates an acid in response to actinic light having a wavelength of 300 nm or more, more preferably a wavelength of 300 to 450 nm. The photoacid generator is preferably a compound that generates an acid with a pKa of 4 or less when irradiated with light, more preferably a compound that generates an acid with a pKa of 3 or less, and more preferably a compound that generates an acid with a pKa of 2 or less. More preferably, it is a compound that Further, the photoacid generator is preferably a compound that does not generate acid at temperatures below 130°C.
　光酸発生剤としては、オキシムスルホネート化合物、トリアジン化合物、スルホニウム塩、ヨードニウム塩、アンモニウム塩、ジアゾメタン化合物、スルホン化合物、スルホン酸エステル化合物、イミノスルホン酸エステル化合物、カルボン酸エステル化合物およびスルホンイミド化合物が挙げられ、露光による酸の発生効率、溶解性の観点からオキシムスルホネート化合物およびトリアジン化合物からなる群より選択される少なくとも１種であることが好ましい。 Examples of photoacid generators include oxime sulfonate compounds, triazine compounds, sulfonium salts, iodonium salts, ammonium salts, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, iminosulfonic acid ester compounds, carboxylic acid ester compounds, and sulfonimide compounds. The compound is preferably at least one selected from the group consisting of oxime sulfonate compounds and triazine compounds from the viewpoint of acid generation efficiency and solubility upon exposure.
　オキシムスルホネート化合としては、式（Ｂ１－１）で表されるオキシムスルホネート構造を含有する化合物であることが好ましい。 The oxime sulfonate compound is preferably a compound containing an oxime sulfonate structure represented by formula (B1-1).
式（Ｂ１－１）
　式（Ｂ１－１）のＲ２１は、アルキル基またはアリール基を表す。波線は他の基との結合を表す。 Formula (B1-1)
R 21 in formula (B1-1) represents an alkyl group or an aryl group. Wavy lines represent bonds with other groups.
　Ｒ２１が表すアルキル基は、炭素数１～１０の、直鎖または分岐のアルキル基であることが好ましい。
　Ｒ２１が表すアリール基としては、炭素数６～１１のアリール基が好ましく、フェニル基またはナフチル基がより好ましい。Ｒ２１のアリール基は、フッ素原子、アルキル基、アルコキシ基あるいはハロゲン原子で置換されてもよい。
Ｒ２１が表すアルキル基およびアリール基は、置換基を有していてもよい。置換基としては、ハロゲン原子、炭素数６～１１のアリール基、炭素数１～１０のアルコキシ基、環状のアルキル基（７，７－ジメチル－２－オキソノルボルニル基などの有橋式脂環基を含む、好ましくはビシクロアルキル基等）などが挙げられる。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子およびヨウ素原子が挙げられ、フッ素原子であることが好ましい。 The alkyl group represented by R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
The aryl group represented by R 21 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of R 21 may be substituted with a fluorine atom, an alkyl group, an alkoxy group, or a halogen atom.
The alkyl group and aryl group represented by R 21 may have a substituent. Examples of substituents include halogen atoms, aryl groups having 6 to 11 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and cyclic alkyl groups (bridged aliphatic groups such as 7,7-dimethyl-2-oxonorbornyl group). (including a cyclic group, preferably a bicycloalkyl group, etc.). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.
　式（Ｂ１－１）で表されるオキシムスルホネート構造を含有する化合物は、特開２０１３－２１０６１６号公報の段落番号００８１～０１０８に記載のオキシムスルホネート化合物が挙げられ、この内容は本明細書に組み込まれる。 Examples of the compound containing the oxime sulfonate structure represented by formula (B1-1) include the oxime sulfonate compounds described in paragraphs 0081 to 0108 of JP-A No. 2013-210616, the contents of which are not incorporated herein. It will be done.
　オキシムスルホネート化合物の具体例としては、後述する実施例に記載の構造の化合物などが挙げられる。 Specific examples of the oxime sulfonate compound include compounds having the structures described in the examples below.
　トリアジン化合物としては、２－（３－クロロフェニル）－ビス（４，６－トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシフェニル）－ビス（４，６－トリクロロメチル）－ｓ－トリアジン、２－（４－メチルチオフェニル）－ビス（４，６－トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシ－β－スチリル）－ビス（４，６－トリクロロメチル）－ｓ－トリアジン、２－ピペロニル－ビス（４，６－トリクロロメチル）－ｓ－トリアジン、２－［２－（フラン－２－イル）エテニル］－ビス（４，６－トリクロロメチル）－ｓ－トリアジン、２－［２－（５－メチルフラン－２－イル）エテニル］－ビス（４，６－トリクロロメチル）－ｓ－トリアジン、２－［２－（４－ジエチルアミノ－２－メチルフェニル）エテニル］－ビス（４，６－トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシナフチル）－ビス（４，６－トリクロロメチル）－ｓ－トリアジンなどが挙げられる。 Examples of triazine compounds include 2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-Methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxy-β-styryl)-bis(4,6-trichloromethyl)-s-triazine, 2 -piperonyl-bis(4,6-trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-bis(4,6-trichloromethyl)-s-triazine, 2-[2 -(5-methylfuran-2-yl)ethenyl]-bis(4,6-trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-bis(4, Examples include 6-trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine, and the like.
　ヨードニウム塩としては、ジフェニルヨードニウムトリフルオロアセテート、ジフェニルヨードニウムトリフルオロメタンスルホナート、４－メトキシフェニルフェニルヨードニウムトリフルオロメタンスルホナート、４－メトキシフェニルフェニルヨードニウムトリフルオロアセテート、フェニル，４－（２’－ヒドロキシ－１’－テトラデカオキシ）フェニルヨードニウムトリフルオロメタンスルホナート、４－（２’－ヒドロキシ－１’－テトラデカオキシ）フェニルヨードニウムヘキサフルオロアンチモナート、フェニル，４－（２’－ヒドロキシ－１’－テトラデカオキシ）フェニルヨードニウム－ｐ－トルエンスルホナートなどが挙げられる。 Iodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl,4-(2'-hydroxy-1 '-tetradecaoxy) phenyl iodonium trifluoromethanesulfonate, 4-(2'-hydroxy-1'-tetradecaoxy) phenyl iodonium hexafluoroantimonate, phenyl,4-(2'-hydroxy-1'-tetradeca Oxy) phenyl iodonium-p-toluenesulfonate and the like.
　スルホニウム塩としては、トリフェニルスルホニウムトリフルオロメタンスルホナート、トリフェニルスルホニウムトリフルオロアセテート、４－メトキシフェニルジフェニルスルホニウムトリフルオロメタンスルホナート、４－メトキシフェニルジフェニルスルホニウムトリフルオロアセテート、４－フェニルチオフェニルジフェニルスルホニウムトリフルオロメタンスルホナート、４－フェニルチオフェニルジフェニルスルホニウムトリフルオロアセテートなどが挙げられる。 Sulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethane. Examples include sulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, and the like.
　アンモニウム塩として、テトラメチルアンモニウムブチルトリス（２，６－ジフルオロフェニル）ボレート、テトラメチルアンモニウムヘキシルトリス（ｐ－クロロフェニル）ボレート、テトラメチルアンモニウムヘキシルトリス（３－トリフルオロメチルフェニル）ボレート、ベンジルジメチルフェニルアンモニウムブチルトリス（２，６－ジフルオロフェニル）ボレート、ベンジルジメチルフェニルアンモニウムヘキシルトリス（ｐ－クロロフェニル）ボレート、ベンジルジメチルフェニルアンモニウムヘキシルトリス（３－トリフルオロメチルフェニル）ボレート等が挙げられる。 As ammonium salts, tetramethylammonium butyltris(2,6-difluorophenyl)borate, tetramethylammoniumhexyltris(p-chlorophenyl)borate, tetramethylammoniumhexyltris(3-trifluoromethylphenyl)borate, benzyldimethylphenylammonium Examples include butyltris(2,6-difluorophenyl)borate, benzyldimethylphenylammoniumhexyltris(p-chlorophenyl)borate, benzyldimethylphenylammoniumhexyltris(3-trifluoromethylphenyl)borate, and the like.
　ジアゾメタン化合物としては、ビス（トリフルオロメチルスルホニル）ジアゾメタン、ビス（シクロヘキシルスルホニル）ジアゾメタン、ビス（フェニルスルホニル）ジアゾメタン、ビス（４－トリルスルホニル）ジアゾメタン、ビス（２，４－キシリルスルホニル）ジアゾメタン、ビス（４－クロロフェニルスルホニル）ジアゾメタン、メチルスルホニル－４－トリルスルホニルジアゾメタン、シクロヘキシルスルホニル（１，１－ジメチルエチルスルホニル）ジアゾメタン、ビス（１，１－ジメチルエチルスルホニル）ジアゾメタン、フェニルスルホニル（ベンゾイル）ジアゾメタンなどが挙げられる。 Diazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(4-tolylsulfonyl)diazomethane, bis(2,4-xylylsulfonyl)diazomethane, and bis(2,4-xylylsulfonyl)diazomethane. (4-chlorophenylsulfonyl)diazomethane, methylsulfonyl-4-tolylsulfonyldiazomethane, cyclohexylsulfonyl(1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, phenylsulfonyl(benzoyl)diazomethane, etc. Can be mentioned.
　スルホン化合物としては、β－ケトスルホン化合物、β－スルホニルスルホン化合物、ジアリールジスルホン化合物などが挙げられる。好ましいスルホン化合物としては、４－トリルフェナシルスルホン、メシチルフェナシルスルホン、ビス（フェニルスルホニル）メタン、４－クロロフェニル－４－トリルジスルホン化合物などが挙げられる。 Examples of sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryldisulfone compounds, and the like. Preferred sulfone compounds include 4-tolylphenacylsulfone, mesitylphenacylsulfone, bis(phenylsulfonyl)methane, and 4-chlorophenyl-4-tolyldisulfone compounds.
　スルホン酸エステル化合物としては、ベンゾイン－４－トリルスルホネート、ピロガロールトリス（メチルスルホネート）、ニトロベンジル－９，１０－ジエトキシアンスリル－２－スルホネート、２，６－（ジニトロベンジル）フェニルルホネートなどが挙げられる。 Examples of sulfonic acid ester compounds include benzoin-4-tolylsulfonate, pyrogalloltris(methylsulfonate), nitrobenzyl-9,10-diethoxyanthryl-2-sulfonate, 2,6-(dinitrobenzyl)phenylsulfonate, etc. Can be mentioned.
　イミノスルホン酸エステル化合物としては、ベンジルモノオキシム－４－トリルスルホネート、ベンジルモノオキシム－４－ドデシルフェニルスルホネート、ベンジルモノオキシムヘキサデシルスルホネート、４－ニトロアセトフェノンオキシム－４－トリルスルホネート、４，４’－ジメチルベンジルモノオキシム－４－トリルスルホネート、４，４’－ジメチルベンジルモノオキシム－４－ドデシルフェニルスルホネート、ジベンジルケトンオキシム－４－トリルスルホネート、α－（４－トリルオキシ）イミノ－α－シアノ酢酸エチル、フリルモノオキシム－４－（アミノカルボニル）フェニルスルホネート、アセトンオキシム－４－ベンゾイルフェニルスルホネート、３－（ベンジルスルホニルオキシ）イミノアセチルアセトン、ビス（ベンジルモノオキサイド）ジオクチルナフチルジスルホネート、α－（４－トリルスルホニルオキシ）イミノベンジルシアニド、α－（４－トリルスルホニルオキシ）イミノ－４－メトキシベンジルシアニド（「ＰＡＩ－１０１」、商品名、みどり化学（株）製）、α－（１０－カンファースルホニルオキシ）イミノ－４－メトキシベンジルシアニド（「ＰＡＩ－１０６」、商品名、みどり化学（株）製）、５－（４－トリルスルホニルオキシ）イミノ－５Ｈ－チオフェン－２－イリデン－（２－メチルフェニル）アセトニトリル（「ＣＧＩ－１３１１」、商品名、ＢＡＳＦ製）などが挙げられる。 Examples of iminosulfonic acid ester compounds include benzyl monooxime-4-tolylsulfonate, benzyl monooxime-4-dodecylphenylsulfonate, benzyl monooxime hexadecylsulfonate, 4-nitroacetophenone oxime-4-tolylsulfonate, 4,4'- Dimethylbenzylmonoxime-4-tolylsulfonate, 4,4'-dimethylbenzylmonoxime-4-dodecylphenylsulfonate, dibenzylketoneoxime-4-tolylsulfonate, α-(4-tolyloxy)imino-α-cyanoacetate ethyl , furyl monooxime-4-(aminocarbonyl) phenylsulfonate, acetone oxime-4-benzoylphenyl sulfonate, 3-(benzylsulfonyloxy)iminoacetylacetone, bis(benzyl monooxide) dioctylnaphthyl disulfonate, α-(4-tolyl) Sulfonyloxy)iminobenzyl cyanide, α-(4-tolylsulfonyloxy)imino-4-methoxybenzyl cyanide (“PAI-101”, trade name, manufactured by Midori Kagaku Co., Ltd.), α-(10-camphorsulfonyl) oxy)imino-4-methoxybenzyl cyanide (“PAI-106”, trade name, manufactured by Midori Kagaku Co., Ltd.), 5-(4-tolylsulfonyloxy)imino-5H-thiophene-2-ylidene-(2- Examples include methylphenyl)acetonitrile (“CGI-1311”, trade name, manufactured by BASF).
　カルボン酸エステル化合物としては、カルボン酸２－ニトロベンジルエステルなどが挙げられる。 Examples of the carboxylic acid ester compound include carboxylic acid 2-nitrobenzyl ester.
　スルホンイミド化合物としては、Ｎ－（トリフルオロメチルスルホニルオキシ）スクシンイミド、Ｎ－（１０－カンファースルホニルオキシ）スクシンイミド、Ｎ－（４－トリルスルホニルオキシ）スクシンイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）スクシンイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）スクシンイミド、Ｎ－（トリフルオロメチルスルホニルオキシ）フタルイミド、Ｎ－（１０－カンファースルホニルオキシ）フタルイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）フタルイミド、Ｎ－（２－フルオロフェニルスルホニルオキシ）フタルイミド、Ｎ－（トリフルオロメチルスルホニルオキシ）ジフェニルマレイミド、Ｎ－（１０－カンファースルホニルオキシ）ジフェニルマレイミド、４－トリルスルホニルオキシ）ジフェニルマレイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）ジフェニルマレイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）ジフェニルマレイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）ジフェニルマレイミド、Ｎ－（トリフルオロメチルスルホニルオキシ）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１０－カンファースルホニルオキシ）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（カンファースルホニルオキシ）－７－オキサビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（トリフルオロメチルスルホニルオキシ）－７－オキサビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（４－トリルスルホニルオキシ）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（４－トリルスルホニルオキシ）－７－オキサビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）－７－オキサビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）－７－オキサビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（トリフルオロメチルスルホニルオキシ）ビシクロ［２．２．１］ヘプタン－５，６－オキシ－２，３－ジカルボキシイミド、Ｎ－（１０－カンファースルホニルオキシ）ビシクロ［２．２．１］ヘプタン－５，６－オキシ－２，３－ジカルボキシイミド、Ｎ－（４－トリルスルホニルオキシ）ビシクロ［２．２．１］ヘプタン－５，６－オキシ－２，３－ジカルボキシイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）ビシクロ［２．２．１］ヘプタン－５，６－オキシ－２，３－ジカルボキシイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）ビシクロ［２．２．１］ヘプタン－５，６－オキシ－２，３－ジカルボキシイミド、Ｎ－（トリフルオロメチルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（１０－カンファースルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（４－トリルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（ペンタフルオロエチルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（ヘプタフルオロプロピルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（ノナフルオロブチルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（エチルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（プロピルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（ブチルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（ペンチルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（ヘキシルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（ヘプチルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（オクチルスルホニルオキシ）ナフチルジカルボキシイミド、Ｎ－（ノニルスルホニルオキシ）ナフチルジカルボキシイミドなどが挙げられる。 Sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(10-camphorsulfonyloxy)succinimide, N-(4-tolylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy) ) Succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(10-camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide , N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(10-camphorsulfonyloxy)diphenylmaleimide, 4-tolylsulfonyloxy)diphenylmaleimide, N-(2 -trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2. 2.1] hept-5-ene-2,3-dicarboximide, N-(10-camphorsulfonyloxy)bicyclo[2.2.1] hept-5-ene-2,3-dicarboximide, N -(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2 .1] hept-5-ene-2,3-dicarboximide, N-(4-tolylsulfonyloxy)bicyclo[2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-Tolylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2 .1] hept-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3 -dicarboximide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)-7- oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2, 3-dicarboximide, N-(10-camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboximide, N-(4-tolylsulfonyloxy)bicyclo[ 2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy- 2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy) ) Naphthyldicarboximide, N-(10-camphorsulfonyloxy)naphthyldicarboximide, N-(4-tolylsulfonyloxy)naphthyldicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)naphthyldicarboximide , N-(4-fluorophenylsulfonyloxy)naphthyldicarboximide, N-(pentafluoroethylsulfonyloxy)naphthyldicarboximide, N-(heptafluoropropylsulfonyloxy)naphthyldicarboximide, N-(nonafluorobutyl) Sulfonyloxy)naphthyldicarboximide, N-(ethylsulfonyloxy)naphthyldicarboximide, N-(propylsulfonyloxy)naphthyldicarboximide, N-(butylsulfonyloxy)naphthyldicarboximide, N-(pentylsulfonyloxy) ) Naphthyldicarboximide, N-(hexylsulfonyloxy)naphthyldicarboximide, N-(heptylsulfonyloxy)naphthyldicarboximide, N-(octylsulfonyloxy)naphthyldicarboximide, N-(nonylsulfonyloxy)naphthyl Examples include dicarboximide.
（塩基発生剤）
　塩基発生剤としては、熱塩基発生剤および光塩基発生剤が挙げられる。塩基発生剤は、光塩基発生剤を含むものであることが好ましい。また、塩基発生剤は、光塩基発生剤と熱塩基発生剤とを併用してもよい。熱塩基発生剤と光塩基発生剤とを併用する場合は、熱塩基発生剤と光塩基発生剤との質量比は、熱塩基発生剤の１００質量部に対して光塩基発生剤が１００～２０００質量部であることが好ましい。下限は、１５０質量部以上であることが好ましく、２００質量部以上であることがより好ましい。上限は１５００質量部以下であることが好ましく、１０００質量部以下であることがより好ましい。なかでも、プロセス温度のより低温化が可能で、１５０℃以下（好ましくは１２０℃以下）の低温で硬化膜を形成した場合であっても、より耐湿性に優れた硬化膜を形成することができ、更には、フォトリソグラフィ法でのパターン形成性に優れるという理由から塩基発生剤は、実質的に光塩基発生剤のみであることが特に好ましい。なお、本明細書において、塩基発生剤が、実質的に光塩基発生剤のみである場合とは、塩基発生剤の全質量中における光塩基発生剤の含有量が９９質量％以上であることを意味し、９９．９質量％以上であることが好ましく、１００質量％（光塩基発生剤のみからなる）であることがより好ましい。
　なお、本明細書において、塩基発生剤とは、熱や光などのエネルギーを加えることで塩基を発生する化合物のことを意味する。また、熱塩基発生剤とは、熱分解により塩基を発生する化合物のことを意味する。また、光塩基発生剤とは、光照射により塩基を発生する化合物のことを意味する。 (base generator)
Examples of the base generator include thermal base generators and photobase generators. The base generator preferably includes a photobase generator. Further, as the base generator, a photobase generator and a thermal base generator may be used in combination. When a thermal base generator and a photobase generator are used together, the mass ratio of the thermal base generator and the photobase generator is 100 to 2000 parts by mass of the photobase generator to 100 parts by mass of the thermal base generator. Parts by mass are preferred. The lower limit is preferably 150 parts by mass or more, more preferably 200 parts by mass or more. The upper limit is preferably 1,500 parts by mass or less, more preferably 1,000 parts by mass or less. Among these, it is possible to lower the process temperature, and even when forming a cured film at a low temperature of 150°C or less (preferably 120°C or less), it is possible to form a cured film with better moisture resistance. Furthermore, it is particularly preferable that the base generator is substantially only a photobase generator because it has excellent pattern formation properties in photolithography. In this specification, the case where the base generator is substantially only a photobase generator means that the content of the photobase generator in the total mass of the base generator is 99% by mass or more. It is preferably 99.9% by mass or more, and more preferably 100% by mass (consisting only of the photobase generator).
Note that in this specification, a base generator means a compound that generates a base by applying energy such as heat or light. Further, the term "thermal base generator" means a compound that generates a base by thermal decomposition. Moreover, a photobase generator means a compound that generates a base upon irradiation with light.
　塩基発生剤は、イオン型塩基発生剤でもよく、非イオン型塩基発生剤でもよいが、非イオン型塩基発生剤であることが好ましい。 The base generator may be an ionic base generator or a nonionic base generator, but is preferably a nonionic base generator.
　塩基発生剤から発生する塩基は、１級アミン、２級アミンおよび３級アミンのいずれでもよいが、ポットライフの安定性の観点から、３級アミンであることが好ましい。また、塩基発生剤により発生する塩基の沸点は、８０℃以上であることが好ましく、１００℃以上であることが好ましく、１４０℃以上であることが最も好ましい。また、発生する塩基の分子量は、８０～２０００が好ましい。下限は１００以上がより好ましい。上限は５００以下がより好ましい。なお、分子量の値は、構造式から求めた理論値である。 The base generated from the base generator may be any of primary amine, secondary amine, and tertiary amine, but from the viewpoint of pot life stability, tertiary amine is preferable. Further, the boiling point of the base generated by the base generator is preferably 80°C or higher, preferably 100°C or higher, and most preferably 140°C or higher. Further, the molecular weight of the generated base is preferably 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. Note that the molecular weight value is a theoretical value determined from the structural formula.
　塩基発生剤の分子量は、２００～１０００が好ましい。下限は、２３０以上が好ましい。上限は、８００以下が好ましい。塩基発生剤の分子量が上記範囲であれば、硬化膜の製造時におけるベーク等の際に、塩基発生剤が揮発しやすくでき、膜中に塩基発生剤やその分解物などが残留することを抑制できる。 The molecular weight of the base generator is preferably 200 to 1000. The lower limit is preferably 230 or more. The upper limit is preferably 800 or less. If the molecular weight of the base generator is within the above range, the base generator will easily volatilize during baking, etc. during the production of a cured film, thereby suppressing the base generator and its decomposition products from remaining in the film. can.
－熱塩基発生剤－
　熱塩基発生剤の塩基発生温度は８０℃～１３０℃であることが好ましく、９０℃～１１０℃であることがより好ましい。 -Thermal base generator-
The base generation temperature of the thermal base generator is preferably 80°C to 130°C, more preferably 90°C to 110°C.
　熱塩基発生剤としては、カルバモイルオキシム化合物、カルバモイルヒドロキシルアミン化合物、カルバミン酸化合物、ホルムアミド化合物、アセトアミド化合物、カルバメート化合物、ベンジルカルバメート化合物、ニトロベンジルカルバメート化合物、スルホンアミド化合物、イミダゾール化合物、アミンイミド化合物、ピリジン化合物、α－アミノアセトフェノン化合物、アンモニウム塩、ピリジニウム塩、α－ラクトン環誘導体化合物、アミンイミド化合物、フタルイミド化合物、アシルオキシイミノ化合物などが挙げられる。 Examples of thermal base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole compounds, amine imide compounds, and pyridine compounds. , α-aminoacetophenone compounds, ammonium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide compounds, acyloxyimino compounds, and the like.
　また、熱塩基発生剤には、４０℃以上に加熱すると塩基を発生する酸性化合物、および、ｐＫａ１が０～４のアニオンとアンモニウムカチオンとを有するアンモニウム塩を用いることもできる。これらの化合物については、国際公開第２０１７／１４１７２３号の段落番号００４５～００６６に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。
　なお、本明細書において、酸性化合物とは、化合物を容器に１ｇ採取し、イオン交換水とテトラヒドロフランとの混合液（質量比は水／テトラヒドロフラン＝１／４）を５０ｍＬ加えて、室温で１時間攪拌する。その溶液をｐＨメーターを用いて、２０℃にて測定した値が７未満である化合物を意味する。 Further, as the thermal base generator, an acidic compound that generates a base when heated to 40° C. or higher, and an ammonium salt having an anion having a pKa1 of 0 to 4 and an ammonium cation can also be used. Examples of these compounds include the compounds described in paragraph numbers 0045 to 0066 of International Publication No. 2017/141723, the contents of which are incorporated herein.
In this specification, the term "acidic compound" refers to 1 g of the compound taken in a container, 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio: water/tetrahydrofuran = 1/4), and the mixture was incubated at room temperature for 1 hour. Stir. It means a compound whose value is less than 7 when the solution is measured at 20°C using a pH meter.
　熱塩基発生剤の市販品としては、サンアプロ（株）製のＵ－ＣＡＴシリーズ（例えば、ＳＡ１、ＳＡ１０２、ＳＡ６０３、ＳＡ８１０、ＳＡ８３１、ＳＡ８４１、ＳＡ８５１、ＳＡ８３８Ａなど）が挙げられる。 Commercially available thermal base generators include the U-CAT series manufactured by San-Apro Co., Ltd. (eg, SA1, SA102, SA603, SA810, SA831, SA841, SA851, SA838A, etc.).
－光塩基発生剤－
　光塩基発生剤は、波長３００ｎｍ以上、より好ましくは波長３００～４５０ｎｍの活性光線に感応し、塩基を発生する化合物が好ましい。
　また、光塩基発生剤は、１３０℃以下では塩基を発生しない化合物であることが好ましい。 -Photobase generator-
The photobase generator is preferably a compound that generates a base in response to actinic light having a wavelength of 300 nm or more, more preferably from 300 to 450 nm.
Further, the photobase generator is preferably a compound that does not generate a base at temperatures below 130°C.
　光塩基発生剤としては、カルバメート化合物、スルホンアミド化合物、アシルオキシム化合物およびオニウム塩が挙げられ、カルバメート化合物、アシルオキシム化合物およびオニウム塩からなる群より選択される少なくとも１種を含むものであることが好ましく、カルバメート化合物を含むものであることがより好ましい。 Examples of the photobase generator include carbamate compounds, sulfonamide compounds, acyloxime compounds, and onium salts, and preferably contains at least one selected from the group consisting of carbamate compounds, acyloxime compounds, and onium salts. More preferably, it contains a carbamate compound.
　カルバメート化合物としては、Ｎ－（２－ニトロベンジルオキシ）カルボニル－Ｎ－メチルアミン、Ｎ－（２－ニトロベンジルオキシ）カルボニル－Ｎ－ｎ－プロピルアミン、Ｎ－（２－ニトロベンジルオキシ）カルボニル－Ｎ－ｎ－ヘキシルアミン、Ｎ－（２－ニトロベンジルオキシ）カルボニル－Ｎ－シクロヘキシルアミン、Ｎ－（２－ニトロベンジルオキシ）カルボニルアニリン、Ｎ－（２－ニトロベンジルオキシ）カルボニルピペリジン、Ｎ，Ｎ’－ビス［（２－ニトロベンジルオキシ）カルボニル］－１，６－ヘキサメチレンジアミン、Ｎ，Ｎ’－ビス［（２－ニトロベンジルオキシ）カルボニル］－１，４－フェニレンジアミン、Ｎ，Ｎ’－ビス［（２－ニトロベンジルオキシ）カルボニル］－２，４－トリレンジアミン、Ｎ，Ｎ’－ビス［（２－ニトロベンジルオキシ）カルボニル］－４，４’－ジアミノジフェニルメタン、Ｎ，Ｎ’－ビス［（２－ニトロベンジルオキシ）カルボニル］ピペラジン、Ｎ－（２，６－ジニトロベンジルオキシ）カルボニル－Ｎ－メチルアミン、Ｎ－（２，６－ジニトロベンジルオキシ）カルボニル－Ｎ－ｎ－プロピルアミン、Ｎ－（２，６－ジニトロベンジルオキシ）カルボニル－Ｎ－ｎ－ヘキシルアミン、Ｎ－（２，６－ジニトロベンジルオキシ）カルボニル－Ｎ－シクロヘキシルアミン、Ｎ－（２，６－ジニトロベンジルオキシ）カルボニルアニリン、Ｎ－（２，６－ジニトロベンジルオキシ）カルボニルピペリジン、Ｎ，Ｎ’－ビス［（２，６－ジニトロベンジルオキシ）カルボニル］－１，６－ヘキサメチレンジアミン、Ｎ，Ｎ’－ビス［（２，６－ジニトロベンジルオキシ）カルボニル］－１，４－フェニレンジアミン、Ｎ，Ｎ’－ビス［（２，６－ジニトロベンジルオキシ）カルボニル］－２，４－トリレンジアミン、Ｎ，Ｎ’－ビス［（２，６－ジニトロベンジルオキシ）カルボニル］－４，４－ジアミノジフェニルメタン、Ｎ，Ｎ’－ビス［（２，６－ジニトロベンジルオキシ）カルボニル］ピペラジン、Ｎ－（α，α－ジメチル－３，５－ジメトキシベンジルオキシ）カルボニル－Ｎ－メチルアミン、Ｎ－（α，α－ジメチル－３，５－ジメトキシベンジルオキシ）カルボニル－Ｎ－ｎ－プロピルアミン、Ｎ－（α，α－ジメチル－３，５－ジメトキシベンジルオキシ）カルボニル－Ｎ－ｎ－ヘキシルアミン、Ｎ－（α，α－ジメチル－３，５－ジメトキシベンジルオキシ）カルボニル－Ｎ－シクロヘキシルアミン、Ｎ－（α，α－ジメチル－３，５－ジメトキシベンジルオキシ）カルボニルアニリン、Ｎ－（α，α－ジメチル－３，５－ジメトキシベンジルオキシ）カルボニルピペリジン、Ｎ，Ｎ’－ビス［（α，α－ジメチル－３，５－ジメトキシベンジルオキシ）カルボニル］－１，６－ヘキサメチレンジアミン、Ｎ，Ｎ’－ビス［（α，α－ジメチル－３，５－ジメトキシベンジルオキシ）カルボニル］－１，４－フェニレンジアミン、Ｎ，Ｎ’－ビス［（α，α－ジメチル－３，５－ジメトキシベンジルオキシ）カルボニル］－２，４－トリレンジアミン、Ｎ，Ｎ’－ビス［（α，α－ジメチル－３，５－ジメトキシベンジルオキシ）カルボニル］－４，４’－ジアミノジフェニルメタン、Ｎ，Ｎ’－ビス［（α，α－ジメチル－３，５－ジメトキシベンジルオキシ）カルボニル］ピペラジンなどが挙げられる。 Carbamate compounds include N-(2-nitrobenzyloxy)carbonyl-N-methylamine, N-(2-nitrobenzyloxy)carbonyl-Nn-propylamine, N-(2-nitrobenzyloxy)carbonyl- N-n-hexylamine, N-(2-nitrobenzyloxy)carbonyl-N-cyclohexylamine, N-(2-nitrobenzyloxy)carbonylaniline, N-(2-nitrobenzyloxy)carbonylpiperidine, N,N '-bis[(2-nitrobenzyloxy)carbonyl]-1,6-hexamethylenediamine, N,N'-bis[(2-nitrobenzyloxy)carbonyl]-1,4-phenylenediamine, N,N' -bis[(2-nitrobenzyloxy)carbonyl]-2,4-tolylenediamine, N,N'-bis[(2-nitrobenzyloxy)carbonyl]-4,4'-diaminodiphenylmethane, N,N' -bis[(2-nitrobenzyloxy)carbonyl]piperazine, N-(2,6-dinitrobenzyloxy)carbonyl-N-methylamine, N-(2,6-dinitrobenzyloxy)carbonyl-Nn-propyl Amine, N-(2,6-dinitrobenzyloxy)carbonyl-Nn-hexylamine, N-(2,6-dinitrobenzyloxy)carbonyl-N-cyclohexylamine, N-(2,6-dinitrobenzyloxy) ) carbonylaniline, N-(2,6-dinitrobenzyloxy)carbonylpiperidine, N,N'-bis[(2,6-dinitrobenzyloxy)carbonyl]-1,6-hexamethylenediamine, N,N'- Bis[(2,6-dinitrobenzyloxy)carbonyl]-1,4-phenylenediamine, N,N'-bis[(2,6-dinitrobenzyloxy)carbonyl]-2,4-tolylenediamine, N, N'-bis[(2,6-dinitrobenzyloxy)carbonyl]-4,4-diaminodiphenylmethane, N,N'-bis[(2,6-dinitrobenzyloxy)carbonyl]piperazine, N-(α,α -dimethyl-3,5-dimethoxybenzyloxy)carbonyl-N-methylamine, N-(α,α-dimethyl-3,5-dimethoxybenzyloxy)carbonyl-Nn-propylamine, N-(α,α -dimethyl-3,5-dimethoxybenzyloxy)carbonyl-Nn-hexylamine, N-(α,α-dimethyl-3,5-dimethoxybenzyloxy)carbonyl-N-cyclohexylamine, N-(α,α -dimethyl-3,5-dimethoxybenzyloxy)carbonylaniline, N-(α,α-dimethyl-3,5-dimethoxybenzyloxy)carbonylpiperidine, N,N'-bis[(α,α-dimethyl-3, 5-dimethoxybenzyloxy)carbonyl]-1,6-hexamethylenediamine, N,N'-bis[(α,α-dimethyl-3,5-dimethoxybenzyloxy)carbonyl]-1,4-phenylenediamine, N , N'-bis[(α,α-dimethyl-3,5-dimethoxybenzyloxy)carbonyl]-2,4-tolylenediamine, N,N'-bis[(α,α-dimethyl-3,5- Examples include dimethoxybenzyloxy)carbonyl]-4,4'-diaminodiphenylmethane, N,N'-bis[(α,α-dimethyl-3,5-dimethoxybenzyloxy)carbonyl]piperazine, and the like.
　カルバメート化合物は、式（ＰＢＧ－１）で表される化合物であることも好ましい。
 The carbamate compound is also preferably a compound represented by formula (PBG-1).
　式（ＰＥＧ－１）中、ＲａおよびＲｂはそれぞれ独立して、水素原子または１価の有機基を表し、ＲａとＲｂは互いに結合して環状のアミノ基を形成していてもよく、Ｒｃは水素原子またはメチル基を表し、Ａｒａは芳香族基を表す。 In formula (PEG-1), R a and R b each independently represent a hydrogen atom or a monovalent organic group, and even if R a and R b combine with each other to form a cyclic amino group, Often R c represents a hydrogen atom or a methyl group and Ar a represents an aromatic group.
　ＲａおよびＲｂが表す１価の有機基としては、脂肪族炭化水素基、芳香族炭化水素基、または、これらの組み合わせからなる基が挙げられる。
　脂肪族炭化水素基の炭素数は、１～２０が好ましく、１～１０がさらに好ましく、１～５が特に好ましい。脂肪族炭化水素基は、直鎖、分岐、環状のいずれであってもよい。また、環状の脂肪族炭化水素基は、単環、多環のいずれであってもよい。脂肪族炭化水素基としては、アルキル基、アルケニル基、アルキニル基などが挙げられる。
　芳香族炭化水素基の炭素数は、６～１８が好ましく、６～１４がより好ましく、６～１０がさらに好ましい。芳香族炭化水素基は、単環または縮合数が２～４の縮合環の芳香族炭化水素基であることが好ましい。芳香族炭化水素基としてはアリール基が挙げられる。
　脂肪族炭化水素基および芳香族炭化水素基は置換基を有していてもよい。置換基としては後述する置換基Ｔで挙げた基が挙げられる。 The monovalent organic group represented by R a and R b includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group consisting of a combination thereof.
The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Furthermore, the cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and the like.
The aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group is preferably a monocyclic or fused ring aromatic hydrocarbon group having 2 to 4 condensed rings. An example of the aromatic hydrocarbon group is an aryl group.
The aliphatic hydrocarbon group and aromatic hydrocarbon group may have a substituent. Examples of the substituent include the groups listed below for substituent T.
　ＲａおよびＲｂは、それぞれ独立して脂肪族炭化水素基であることが好ましく、アルキル基であることがより好ましく、炭素数１～１０の直鎖または分岐のアルキル基であることが更に好ましく、炭素数１～５の直鎖または分岐のアルキル基であることがより一層好ましく、メチル基、エチル基またはイソプロピル基であることが特に好ましい。 R a and R b are each independently preferably an aliphatic hydrocarbon group, more preferably an alkyl group, even more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. , a linear or branched alkyl group having 1 to 5 carbon atoms is even more preferable, and a methyl group, ethyl group or isopropyl group is particularly preferable.
　ＲａとＲｂは互いに結合して環状のアミノ基を形成していてもよい。形成される環状アミノ基としては、１－アジリジニル基、１－アゼチジニル基、１－ピロリジニル基、１－ピペリジニル基、１－ヘキサメチレンイミノ基、１－ヘプタメチレンイミノ基、１－オクタメチレンイミノ基、１－ノナメチレンイミノ基、１－１－イミダゾリル基、４，５－ジヒドロ－１－イミダゾリル基、１－ピロリル基、１－ピラゾリル基、１－イミダゾリジニル基、１－ピペラジニル基、および、モルホリノ基などが挙げられる。
　ＲａとＲｂが互いに結合して形成される環状のアミノ基は、置換基を有していてもよい。置換基としては、置換基としては後述する置換基Ｔで挙げた基が挙げられる。 R a and R b may be bonded to each other to form a cyclic amino group. The cyclic amino groups formed include 1-aziridinyl group, 1-azetidinyl group, 1-pyrrolidinyl group, 1-piperidinyl group, 1-hexamethyleneimino group, 1-heptamethyleneimino group, 1-octamethyleneimino group, 1-nonamethyleneimino group, 1-1-imidazolyl group, 4,5-dihydro-1-imidazolyl group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolidinyl group, 1-piperazinyl group, morpholino group, etc. can be mentioned.
The cyclic amino group formed by bonding R a and R b to each other may have a substituent. Examples of the substituent include the groups listed below for substituent T.
　Ａｒａが表す芳香族基としては、芳香族炭化水素基および芳香族複素環基が挙げられる。Ａｒａが表す芳香族基は、単環の芳香族基であってもよいが、縮合数が２～４の縮合環の芳香族基であることが好ましい。
　芳香族炭化水素基としては、ベンゼン環基、ナフタレン環基、アントラセン環基、フルオレン環基などが挙げられる。
　芳香族複素環基としては、ピロール環基、フラン環基、チオフェン環基、ピリジン環基、イミダゾール環基、ピラゾ―ル環基、オキサゾール環基、チアゾール環基、ピリダジン環基、ピリミジン環基、ピラジン環基、インドール環基、イソインドール環基、ベンゾイミダゾール環基、ベンゾオキサゾール環基、ベンゾチアゾール環基、ベンゾトリアゾール環基、キノリン環基、イソキノリン環基、キナゾリン環基、キノキサリン環基、アントラキノン環基などが挙げられる。
　Ａｒａが表す芳香族基は置換基を有していてもよい。置換基としては後述する置換基Ｔで挙げた基が挙げられる。 The aromatic group represented by Ar a includes an aromatic hydrocarbon group and an aromatic heterocyclic group. The aromatic group represented by Ar a may be a monocyclic aromatic group, but is preferably a condensed ring aromatic group having 2 to 4 condensed rings.
Examples of the aromatic hydrocarbon group include a benzene ring group, a naphthalene ring group, an anthracene ring group, and a fluorene ring group.
Examples of aromatic heterocyclic groups include pyrrole ring group, furan ring group, thiophene ring group, pyridine ring group, imidazole ring group, pyrazole ring group, oxazole ring group, thiazole ring group, pyridazine ring group, pyrimidine ring group, Pyrazine ring group, indole ring group, isoindole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, benzotriazole ring group, quinoline ring group, isoquinoline ring group, quinazoline ring group, quinoxaline ring group, anthraquinone Examples include ring groups.
The aromatic group represented by Ar a may have a substituent. Examples of the substituent include the groups listed below for substituent T.
　上述した置換基Ｔとして、次の基が挙げられる。ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子）、アルキル基（好ましくは炭素数１～３０のアルキル基）、アルケニル基（好ましくは炭素数２～３０のアルケニル基）、アルキニル基（好ましくは炭素数２～３０のアルキニル基）、アリール基（好ましくは炭素数６～３０のアリール基）、複素環基（好ましくは炭素数１～３０の複素環基）、アミノ基（好ましくは炭素数０～３０のアミノ基）、アルコキシ基（好ましくは炭素数１～３０のアルコキシ基）、アリールオキシ基（好ましくは炭素数６～３０のアリールオキシ基）、複素環オキシ基（好ましくは炭素数１～３０の複素環オキシ基）、アシル基（好ましくは炭素数２～３０のアシル基）、アルコキシカルボニル基（好ましくは炭素数２～３０のアルコキシカルボニル基）、アリールオキシカルボニル基（好ましくは炭素数７～３０のアリールオキシカルボニル基）、複素環オキシカルボニル基（好ましくは炭素数２～３０の複素環オキシカルボニル基）、アシルオキシ基（好ましくは炭素数２～３０のアシルオキシ基）、アシルアミノ基（好ましくは炭素数２～３０のアシルアミノ基）、アミノカルボニルアミノ基（好ましくは炭素数２～３０のアミノカルボニルアミノ基）、アルコキシカルボニルアミノ基（好ましくは炭素数２～３０のアルコキシカルボニルアミノ基）、アリールオキシカルボニルアミノ基（好ましくは炭素数７～３０のアリールオキシカルボニルアミノ基）、スルファモイル基（好ましくは炭素数０～３０のスルファモイル基）、スルファモイルアミノ基（好ましくは炭素数０～３０のスルファモイルアミノ基）、カルバモイル基（好ましくは炭素数１～３０のカルバモイル基）、アルキルチオ基（好ましくは炭素数１～３０のアルキルチオ基）、アリールチオ基（好ましくは炭素数６～３０のアリールチオ基）、複素環チオ基（好ましくは炭素数１～３０の複素環チオ基）、アルキルスルホニル基（好ましくは炭素数１～３０のアルキルスルホニル基）、アルキルスルホニルアミノ基（好ましくは炭素数１～３０のアルキルスルホニルアミノ基）、アリールスルホニル基（好ましくは炭素数６～３０のアリールスルホニル基）、アリールスルホニルアミノ基（好ましくは炭素数６～３０のアリールスルホニルアミノ基）、複素環スルホニル基（好ましくは炭素数１～３０の複素環スルホニル基）、複素環スルホニルアミノ基（好ましくは炭素数１～３０の複素環スルホニルアミノ基）、アルキルスルフィニル基（好ましくは炭素数１～３０のアルキルスルフィニル基）、アリールスルフィニル基（好ましくは炭素数６～３０のアリールスルフィニル基）、複素環スルフィニル基（好ましくは炭素数１～３０の複素環スルフィニル基）、ウレイド基（好ましくは炭素数１～３０のウレイド基）、ヒドロキシ基、ニトロ基、カルボキシ基、スルホ基、リン酸基、カルボン酸アミド基、スルホン酸アミド基、イミド基、ホスフィノ基、メルカプト基、シアノ基、アルキルスルフィノ基、アリールスルフィノ基、アリールアゾ基、複素環アゾ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、シリル基、ヒドラジノ基、イミノ基、ビニル基、スチレン基、（メタ）アリル基、（メタ）アクリロイル基、（メタ）アクリロイルオキシ基。これらの基は、更に置換可能な基である場合、更に置換基を有してもよい。 Examples of the above-mentioned substituent T include the following groups. Halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms), a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms), an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), a heterocyclic oxy group (preferably a carbon Heterocyclic oxy group having 1 to 30 carbon atoms), acyl group (preferably acyl group having 2 to 30 carbon atoms), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably aryloxycarbonyl group having 7 to 30 carbon atoms), heterocyclic oxycarbonyl group (preferably heterocyclic oxycarbonyl group having 2 to 30 carbon atoms), acyloxy group (preferably acyloxy group having 2 to 30 carbon atoms), acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an aminocarbonylamino group (preferably an aminocarbonylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms) , an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), a sulfamoylamino group (preferably a sulfamoyl group having 0 to 30 carbon atoms) sulfamoylamino group), carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms) group), heterocyclic thio group (preferably heterocyclic thio group having 1 to 30 carbon atoms), alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), alkylsulfonylamino group (preferably 1 to 30 carbon atoms), 30 alkylsulfonylamino group), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 30 carbon atoms), an arylsulfonylamino group (preferably an arylsulfonylamino group having 6 to 30 carbon atoms), a heterocyclic sulfonyl group (preferably an arylsulfonylamino group having 6 to 30 carbon atoms), is a heterocyclic sulfonyl group having 1 to 30 carbon atoms), a heterocyclic sulfonylamino group (preferably a heterocyclic sulfonylamino group having 1 to 30 carbon atoms), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 30 carbon atoms) , an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 30 carbon atoms), a heterocyclic sulfinyl group (preferably a heterocyclic sulfinyl group having 1 to 30 carbon atoms), a ureido group (preferably a ureido group having 1 to 30 carbon atoms) ), hydroxy group, nitro group, carboxy group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imide group, phosphino group, mercapto group, cyano group, alkylsulfino group, arylsulfino group, Arylazo group, heterocyclic azo group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, hydrazino group, imino group, vinyl group, styrene group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group. These groups may further have a substituent when the group is a substitutable group.
　式（ＰＢＧ－１）で表される化合物の具体例としては、後述する実施例に記載の構造の化合物が挙げられる。 Specific examples of the compound represented by formula (PBG-1) include compounds having the structures described in the Examples below.
　アシルオキシム化合物としては、アセトフェノン－Ｏ－プロパノイルオキシム、ベンゾフェノン－Ｏ－プロパノイルオキシム、アセトン－Ｏ－プロパノイルオキシム、アセトフェノン－Ｏ－ブタノイルオキシム、ベンゾフェノン－Ｏ－ブタノイルオキシム、アセトン－Ｏ－ブタノイルオキシム、ビス（アセトフェノン）－Ｏ，Ｏ’－ヘキサン－１，６－ジオイルオキシム、ビス（ベンゾフェノン）－Ｏ，Ｏ’－ヘキサン－１，６－ジオイルオキシム、ビス（アセトン）－Ｏ，Ｏ’－ヘキサン－１，６－ジオイルオキシム、アセトフェノン－Ｏ－アクリロイルオキシム、ベンゾフェノン－Ｏ－アクリロイルオキシム、アセトン－Ｏ－アクリロイルオキシムなどが挙げられる。 Acyloxime compounds include acetophenone-O-propanoyloxime, benzophenone-O-propanoyloxime, acetone-O-propanoyloxime, acetophenone-O-butanoyloxime, benzophenone-O-butanoyloxime, acetone-O- Butanoyloxime, bis(acetophenone)-O,O'-hexane-1,6-dioyloxime, bis(benzophenone)-O,O'-hexane-1,6-dioyloxime, bis(acetone)-O , O'-hexane-1,6-dioyloxime, acetophenone-O-acryloyloxime, benzophenone-O-acryloyloxime, acetone-O-acryloyloxime, and the like.
　オニウム塩としては、後述する実施例に記載の構造の化合物が挙げられる。 Examples of onium salts include compounds having the structures described in the examples below.
　光塩基発生剤の市販品としては、富士フイルム和光純薬（株）のＷＰＢＧシリーズ（例えば、ＷＰＢＧ－０１８、ＷＰＢＧ－０２７、ＷＰＢＧ－０８２、ＷＰＢＧ－１４０、ＷＰＢＧ－１６５、ＷＰＢＧ－１６７、ＷＰＢＧ－１６８、ＷＰＢＧ－１４０など）などが挙げられる。 Commercially available photobase generators include the WPBG series (for example, WPBG-018, WPBG-027, WPBG-082, WPBG-140, WPBG-165, WPBG-167, WPBG-) manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. 168, WPBG-140, etc.).
　着色組成物の全固形分中における発生剤の含有量は２～１５質量％である。下限は３質量％以上であることが好ましく、５質量％以上であることがより好ましい。上限は、１２質量％以下であることが好ましく、１０質量％以下であることがより好ましい。 The content of the generator in the total solid content of the coloring composition is 2 to 15% by mass. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 12% by mass or less, more preferably 10% by mass or less.
　発生剤として酸発生剤を用いる場合には、着色組成物の全固形分中における酸発生剤の含有量（好ましくは光酸発生剤の含有量）は２～１５質量％であることが好ましい。下限は３質量％以上であることが好ましく、５質量％以上であることがより好ましい。上限は、１２質量％以下であることが好ましく、１０質量％以下であることがより好ましい。 When using an acid generator as the generator, the content of the acid generator (preferably the content of the photoacid generator) in the total solid content of the colored composition is preferably 2 to 15% by mass. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 12% by mass or less, more preferably 10% by mass or less.
　発生剤として塩基発生剤を用いる場合には、着色組成物の全固形分中における塩基発生剤の含有量（好ましくは光塩基発生剤の含有量）は２～１５質量％であることが好ましい。下限は３質量％以上であることが好ましく、５質量％以上であることがより好ましい。上限は、１２質量％以下であることが好ましく、１０質量％以下であることがより好ましい。 When a base generator is used as the generator, the content of the base generator (preferably the content of the photobase generator) in the total solid content of the colored composition is preferably 2 to 15% by mass. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 12% by mass or less, more preferably 10% by mass or less.
＜＜環状エーテル基を有する化合物Ａ＞＞
　本発明の着色組成物は、分子量が５０００以下の環状エーテル基を有する化合物Ａ（以下、化合物Ａともいう）を含む。 <<Compound A having a cyclic ether group>>
The coloring composition of the present invention contains a compound A having a cyclic ether group having a molecular weight of 5000 or less (hereinafter also referred to as compound A).
　化合物Ａの分子量は、１５００以下であることが好ましく、１０００以下であることがより好ましく、５００以下であることが更に好ましい。なお、化合物Ａの分子量の値について、構造式から分子量が計算できる場合は、化合物Ａの分子量は構造式から計算した値である。一方、化合物Ａの分子量が構造式から計算できない、あるいは、計算が困難な場合には、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）法により測定したポリスチレン換算値での重量平均分子量の値を用いる。 The molecular weight of Compound A is preferably 1,500 or less, more preferably 1,000 or less, and even more preferably 500 or less. Regarding the value of the molecular weight of Compound A, if the molecular weight can be calculated from the structural formula, the molecular weight of Compound A is the value calculated from the structural formula. On the other hand, when the molecular weight of Compound A cannot be calculated from the structural formula or is difficult to calculate, the weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) is used.
　化合物Ａが有する環状エーテル基としては、エポキシ基およびオキセタニル基が挙げられ、エポキシ基であることが好ましい。 Examples of the cyclic ether group that Compound A has include an epoxy group and an oxetanyl group, and an epoxy group is preferred.
　化合物Ａは、環状エーテル基を２個以上有する化合物であることが好ましく、３個以上有する化合物であることがより好ましく、４個以上有する化合物であることが更に好ましい。環状エーテル基の個数の上限は、８個以下であることが好ましく、６個以下であることがより好ましい。
　化合物Ａは、エポキシ基を２個以上有する化合物であることが好ましく、３個以上有する化合物であることがより好ましく、４個以上有する化合物であることが更に好ましい。エポキシ基の個数の上限は、８個以下であることが好ましく、６個以下であることがより好ましい。 Compound A preferably has two or more cyclic ether groups, more preferably three or more, and even more preferably four or more. The upper limit of the number of cyclic ether groups is preferably 8 or less, more preferably 6 or less.
Compound A preferably has two or more epoxy groups, more preferably three or more, and even more preferably four or more. The upper limit of the number of epoxy groups is preferably 8 or less, more preferably 6 or less.
　化合物Ａは、式（ＥＰ－１）で表される基を有する化合物であることが好ましい。化合物Ａが有する式（ＥＰ－１）で表される基の個数は、基を２個以上であることが好ましく、３個以上であることがより好ましく、４個以上であることが更に好ましい。上限は、８個以下であることが好ましく、６個以下であることがより好ましい。
 Compound A is preferably a compound having a group represented by formula (EP-1). The number of groups represented by formula (EP-1) in compound A is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more. The upper limit is preferably 8 or less, more preferably 6 or less.
　化合物Ａは、環状エーテル基の他に、更にヒドロキシ基を有していてもよい。化合物Ａが更にヒドロキシ基を有している場合には、ラジカル重合性モノマーなどとの親和性を高めることができる。 Compound A may further have a hydroxy group in addition to the cyclic ether group. When Compound A further has a hydroxy group, it can increase its affinity with radically polymerizable monomers and the like.
　化合物Ａがヒドロキシ基を有する場合、化合物Ａが有するヒドロキシ基の個数は、１～４個であることが好ましく、１～２個であることがより好ましい。 When compound A has a hydroxy group, the number of hydroxy groups contained in compound A is preferably 1 to 4, more preferably 1 to 2.
　化合物Ａの具体例としては、後述する実施例に記載の化合物が挙げられる。また、化合物Ａの市販品としては、ナガセケムテックス（株）製のデナコールシリーズ（ＥＸ－１２１、ＥＸ－３１４、ＥＸ－３２１Ｌ、ＥＸ－４２１、ＥＸ－６１４など）、ＢＡＴＧ（昭和電工（株）製）などが挙げられる。 Specific examples of compound A include the compounds described in the Examples below. In addition, commercially available products of Compound A include the Denacol series (EX-121, EX-314, EX-321L, EX-421, EX-614, etc.) manufactured by Nagase ChemteX Co., Ltd., BATG (Showa Denko K.K. )), etc.
　着色組成物の全固形分中における化合物Ａの含有量は、１～３０質量％であることが好ましい。下限は、３質量％以上であることが好ましく、５質量％以上であることがより好ましい。上限は２０質量％以下であることが好ましく、１５質量％以下であることがより好ましい。 The content of compound A in the total solid content of the coloring composition is preferably 1 to 30% by mass. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
　上述した発生剤と化合物Ａとの割合は、上述した発生剤１００質量部に対して化合物Ａが３０～７００質量部であることが好ましい。この態様によれば、緻密な硬化膜を形成することができる。上限は、５００質量部以下であることが好ましく、３５０質量部以下であることがより好ましい。下限は、５０質量部以上であることが好ましく、７０質量部以上であることがより好ましい。 The ratio of the above-mentioned generator to Compound A is preferably 30 to 700 parts by mass of Compound A to 100 parts by mass of the above-mentioned generator. According to this aspect, a dense cured film can be formed. The upper limit is preferably 500 parts by mass or less, more preferably 350 parts by mass or less. The lower limit is preferably 50 parts by mass or more, more preferably 70 parts by mass or more.
　本発明の着色組成物は、化合物Ａを１種のみ含んでいてもよいし、２種以上含んでいてもよい。化合物Ａを２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The colored composition of the present invention may contain only one type of compound A, or may contain two or more types of compound A. When two or more types of compound A are included, it is preferable that the total amount thereof falls within the above range.
＜＜溶剤＞＞
　本発明の着色組成物は、溶剤を含有することが好ましい。溶剤としては、有機溶剤が挙げられる。溶剤の種類は、各成分の溶解性や組成物の塗布性を満足すれば基本的には特に制限はない。有機溶剤としては、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤などが挙げられる。これらの詳細については、国際公開第２０１５／１６６７７９号の段落番号０２２３を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤も好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、ジクロロメタン、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、２－ペンタノン、３－ペンタノン、４－ヘプタノン、シクロヘキサノン、２－メチルシクロヘキサノン、３－メチルシクロヘキサノン、４－メチルシクロヘキサノン、シクロヘプタノン、シクロオクタノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、プロピレングリコールジアセテート、３－メトキシブタノール、メチルエチルケトン、ガンマブチロラクトン、スルホラン、アニソール、１，４－ジアセトキシブタン、ジエチレングリコールモノエチルエーテルアセタート、二酢酸ブタン－１，３－ジイル、ジプロピレングリコールメチルエーテルアセタート、ジアセトンアルコール（別名としてダイアセトンアルコール、４－ヒドロキシ－４－メチル－２－ペンタノン）、２－メトキシプロピルアセテート、２－メトキシ－１－プロパノール、イソプロピルアルコールなどが挙げられる。ただし有機溶剤としての芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン等）は、環境面等の理由により低減したほうがよい場合がある（例えば、有機溶剤全量に対して、５０質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）以下とすることもでき、１０質量ｐｐｍ以下とすることもでき、１質量ｐｐｍ以下とすることもできる）。 <<Solvent>>
It is preferable that the colored composition of the present invention contains a solvent. Examples of the solvent include organic solvents. The type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For these details, paragraph number 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein. Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxy Butanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as Examples include diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol. However, it may be better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, 50 mass ppm (parts) based on the total amount of organic solvents). per million), 10 mass ppm or less, and 1 mass ppm or less).
　本発明においては、金属含有量の少ない有機溶剤を用いることが好ましい。有機溶剤の金属含有量は、例えば、１０質量ｐｐｂ（ｐａｒｔｓ　ｐｅｒ　ｂｉｌｌｉｏｎ）以下であることが好ましい。必要に応じて質量ｐｐｔ（ｐａｒｔｓ　ｐｅｒ　ｔｒｉｌｌｉｏｎ）レベルの有機溶剤を用いてもよく、そのような有機溶剤は，例えば、東洋合成社が提供している（化学工業日報、２０１５年１１月１３日）。 In the present invention, it is preferable to use an organic solvent with a low metal content. It is preferable that the metal content of the organic solvent is, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by Toyo Gosei Co., Ltd. (Kagaku Kogyo Nippo, November 13, 2015). .
　有機溶剤から金属等の不純物を除去する方法としては、例えば、蒸留（分子蒸留や薄膜蒸留等）やフィルタを用いたろ過を挙げることができる。ろ過に用いるフィルタのフィルタ孔径としては、１０μｍ以下が好ましく、５μｍ以下がより好ましく、３μｍ以下が更に好ましい。フィルタの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。 Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.
　有機溶剤は、異性体（原子数が同じであるが構造が異なる化合物）が含まれていてもよい。また、異性体は、１種のみが含まれていてもよいし、複数種含まれていてもよい。 The organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one type of isomer may be included, or multiple types may be included.
　有機溶剤中の過酸化物の含有率が０．８ｍｍｏｌ／Ｌ以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。 It is preferable that the content of peroxide in the organic solvent is 0.8 mmol/L or less, and it is more preferable that the organic solvent contains substantially no peroxide.
　着色組成物中における溶剤の含有量は、１０～９５質量％であることが好ましく、２０～９０質量％であることがより好ましく、３０～９０質量％であることが更に好ましい。 The content of the solvent in the coloring composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.
　また、本発明の着色組成物は、環境規制の観点から環境規制物質を実質的に含有しないことが好ましい。なお、本発明において、環境規制物質を実質的に含有しないとは、着色組成物中における環境規制物質の含有量が５０質量ｐｐｍ以下であることを意味し、３０質量ｐｐｍ以下であることが好ましく、１０質量ｐｐｍ以下であることが更に好ましく、１質量ｐｐｍ以下であることが特に好ましい。環境規制物質は、例えば、ベンゼン；トルエン、キシレン等のアルキルベンゼン類；クロロベンゼン等のハロゲン化ベンゼン類等が挙げられる。これらは、ＲＥＡＣＨ（Ｒｅｇｉｓｔｒａｔｉｏｎ　Ｅｖａｌｕａｔｉｏｎ　Ａｕｔｈｏｒｉｚａｔｉｏｎ　ａｎｄ　Ｒｅｓｔｒｉｃｔｉｏｎ　ｏｆ　ＣＨｅｍｉｃａｌｓ）規則、ＰＲＴＲ（Ｐｏｌｌｕｔａｎｔ　Ｒｅｌｅａｓｅ　ａｎｄ　Ｔｒａｎｓｆｅｒ　Ｒｅｇｉｓｔｅｒ）法、ＶＯＣ（Ｖｏｌａｔｉｌｅ　Ｏｒｇａｎｉｃ　Ｃｏｍｐｏｕｎｄｓ）規制等のもとに環境規制物質として登録されており、使用量や取り扱い方法が厳しく規制されている。これらの化合物は、着色組成物に用いられる各成分などを製造する際に溶媒として用いられることがあり、残留溶媒として着色組成物中に混入することがある。人への安全性、環境への配慮の観点よりこれらの物質は可能な限り低減することが好ましい。環境規制物質を低減する方法としては、系中を加熱や減圧して環境規制物質の沸点以上にして系中から環境規制物質を留去して低減する方法が挙げられる。また、少量の環境規制物質を留去する場合においては、効率を上げる為に該当溶媒と同等の沸点を有する溶媒と共沸させることも有用である。また、ラジカル重合性を有する化合物を含有する場合、減圧留去中にラジカル重合反応が進行して分子間で架橋してしまうことを抑制するために重合禁止剤等を添加して減圧留去してもよい。これらの留去方法は、原料の段階、原料を反応させた生成物（例えば、重合した後の樹脂溶液や多官能モノマー溶液）の段階、またはこれらの化合物を混ぜて作製した着色組成物の段階などのいずれの段階でも可能である。 Furthermore, from the viewpoint of environmental regulations, it is preferable that the colored composition of the present invention does not substantially contain environmentally regulated substances. In the present invention, "not substantially containing environmentally controlled substances" means that the content of environmentally controlled substances in the coloring composition is 50 mass ppm or less, preferably 30 mass ppm or less. , more preferably 10 mass ppm or less, particularly preferably 1 mass ppm or less. Examples of environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are REACH (Registration Evaluation Authorization and Restriction of CHemicals) rules, PRTR (Pollutant Release and It is registered as an environmentally regulated substance under the Transfer Register Act, VOC (Volatile Organic Compounds) regulations, etc., and its usage and handling are The method is strictly regulated. These compounds may be used as a solvent when producing each component used in the coloring composition, and may be mixed into the coloring composition as a residual solvent. From the viewpoint of human safety and environmental considerations, it is preferable to reduce the amount of these substances as much as possible. Examples of methods for reducing environmentally controlled substances include a method of heating or reducing pressure in the system to raise the temperature above the boiling point of the environmentally controlled substance to distill off the environmentally controlled substances from the system. Furthermore, when distilling off a small amount of environmentally regulated substances, it is also useful to carry out azeotropy with a solvent having the same boiling point as the relevant solvent in order to increase efficiency. In addition, if a compound that has radical polymerizability is contained, a polymerization inhibitor or the like may be added to prevent the radical polymerization reaction from proceeding during vacuum distillation and crosslinking between molecules. You can. These distillation methods can be used at the stage of raw materials, at the stage of products obtained by reacting raw materials (for example, resin solution or polyfunctional monomer solution after polymerization), or at the stage of colored compositions prepared by mixing these compounds. This is possible at any stage.
＜＜顔料誘導体＞＞
　本発明の着色組成物は、顔料誘導体を含有することができる。顔料誘導体としては、色素構造およびトリアジン構造からなる群より選ばれる少なくとも１種の構造と、酸基または塩基性基とを有する化合物が挙げられる。 <<Pigment derivative>>
The colored composition of the present invention can contain a pigment derivative. Examples of the pigment derivative include compounds having at least one structure selected from the group consisting of a pigment structure and a triazine structure, and an acid group or a basic group.
　上記色素構造としては、キノリン色素構造、ベンゾイミダゾロン色素構造、ベンゾイソインドール色素構造、ベンゾチアゾール色素構造、イミニウム色素構造、スクアリリウム色素構造、クロコニウム色素構造、オキソノール色素構造、ピロロピロール色素構造、ジケトピロロピロール色素構造、アゾ色素構造、アゾメチン色素構造、フタロシアニン色素構造、ナフタロシアニン色素構造、アントラキノン色素構造、キナクリドン色素構造、ジオキサジン色素構造、ペリノン色素構造、ペリレン色素構造、チアジンインジゴ色素構造、チオインジゴ色素構造、イソインドリン色素構造、イソインドリノン色素構造、キノフタロン色素構造、ジチオール色素構造、トリアリールメタン色素構造、ピロメテン色素構造等が挙げられる。 The above dye structures include quinoline dye structure, benzimidazolone dye structure, benzisoindole dye structure, benzothiazole dye structure, iminium dye structure, squarylium dye structure, croconium dye structure, oxonol dye structure, pyrrolopyrrole dye structure, diketo Pyrrolopyrrole dye structure, azo dye structure, azomethine dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, anthraquinone dye structure, quinacridone dye structure, dioxazine dye structure, perinone dye structure, perylene dye structure, thiazine indigo dye structure, thioindigo dye structure, isoindoline dye structure, isoindolinone dye structure, quinophthalone dye structure, dithiol dye structure, triarylmethane dye structure, pyrromethene dye structure, etc.
　顔料誘導体が有する酸基としては、カルボキシ基、スルホ基、リン酸基、ボロン酸基、イミド酸基及びこれらの塩等が挙げられる。塩を構成する原子または原子団としては、アルカリ金属イオン（Ｌｉ＋、Ｎａ＋、Ｋ＋など）、アルカリ土類金属イオン（Ｃａ２＋、Ｍｇ２＋など）、アンモニウムイオン、イミダゾリウムイオン、ピリジニウムイオン、ホスホニウムイオンなどが挙げられる。イミド酸基としては、－ＳＯ２ＮＨＳＯ２ＲＸ１、－ＣＯＮＨＳＯ２ＲＸ２、－ＣＯＮＨＣＯＲＸ３または－ＳＯ２ＮＨＣＯＲＸ４で表される基が好ましく、－ＳＯ２ＮＨＳＯ２ＲＸ１、－ＣＯＮＨＳＯ２ＲＸ２、または－ＳＯ２ＮＨＣＯＲＸ４で表される基がより好ましく、－ＳＯ２ＮＨＳＯ２ＲＸ１または－ＣＯＮＨＳＯ２ＲＸ２が更に好ましい。ＲＸ１～ＲＸ４は、それぞれ独立に、アルキル基またはアリール基を表す。ＲＸ１～ＲＸ４が表すアルキル基及びアリール基は、置換基を有してもよい。置換基としてはハロゲン原子であることが好ましく、フッ素原子であることがより好ましい。ＲＸ１～ＲＸ４は、それぞれ独立に、フッ素原子を含むアルキル基またはフッ素原子を含むアリール基であることが好ましく、フッ素原子を含むアルキル基であることがより好ましい。フッ素原子を含むアルキル基の炭素数は１～１０が好ましく、１～５がより好ましく、１～３が更に好ましい。フッ素原子を含むアリール基の炭素数は６～２０が好ましく、６～１２がより好ましく、６が更に好ましい。 Examples of the acid group that the pigment derivative has include a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, an imide acid group, and salts thereof. Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + , etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ , etc.), ammonium ions, imidazolium ions, pyridinium ions, Examples include phosphonium ions. The imide acid group is preferably a group represented by -SO 2 NHSO 2 R X1 , -CONHSO 2 R X2 , -CONHCOR X3 or -SO 2 NHCOR , or -SO 2 NHCOR X4 is more preferred, and -SO 2 NHSO 2 R X1 or -CONHSO 2 R X2 is even more preferred. R X1 to R X4 each independently represent an alkyl group or an aryl group. The alkyl group and aryl group represented by R X1 to R X4 may have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom. R X1 to R X4 are each independently preferably an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and more preferably an alkyl group containing a fluorine atom. The number of carbon atoms in the alkyl group containing a fluorine atom is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The number of carbon atoms in the aryl group containing a fluorine atom is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6.
　顔料誘導体が有する塩基性基としては、アミノ基、ピリジニル基およびその塩、アンモニウム基の塩、並びにフタルイミドメチル基が挙げられる。塩を構成する原子または原子団としては、水酸化物イオン、ハロゲンイオン、カルボン酸イオン、スルホン酸イオン、フェノキシドイオンなどが挙げられる。 Examples of the basic group that the pigment derivative has include an amino group, a pyridinyl group and its salts, an ammonium group salt, and a phthalimidomethyl group. Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
　顔料誘導体は、可視透明性に優れた顔料誘導体（以下、透明顔料誘導体ともいう）を用いることもできる。透明顔料誘導体の４００～７００ｎｍの波長領域におけるモル吸光係数の最大値（εｍａｘ）は３０００Ｌ・ｍｏｌ－１・ｃｍ－１以下であることが好ましく、１０００Ｌ・ｍｏｌ－１・ｃｍ－１以下であることがより好ましく、１００Ｌ・ｍｏｌ－１・ｃｍ－１以下であることがさらに好ましい。εｍａｘの下限は、例えば１Ｌ・ｍｏｌ－１・ｃｍ－１以上であり、１０Ｌ・ｍｏｌ－１・ｃｍ－１以上でもよい。 As the pigment derivative, a pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative) can be used. The maximum molar extinction coefficient (εmax) of the transparent pigment derivative in the wavelength range of 400 to 700 nm is preferably 3000 L·mol −1 ·cm −1 or less, and preferably 1000 L·mol −1 ·cm −1 or less. is more preferable, and even more preferably 100 L·mol −1 ·cm −1 or less. The lower limit of εmax is, for example, 1 L·mol −1 ·cm −1 or more, and may be 10 L·mol −1 ·cm −1 or more.
　顔料誘導体の具体例としては、国際公開第２０２２／０８５４８５号の段落０１２４に記載の化合物、特開２０１８－１６８２４４号公報に記載のベンゾイミダゾロン化合物又はそれらの塩が挙げられる。 Specific examples of pigment derivatives include the compounds described in paragraph 0124 of International Publication No. 2022/085485, and the benzimidazolone compounds or salts thereof described in JP-A-2018-168244.
　顔料誘導体の含有量は、顔料１００質量部に対し、０．１～３０質量部が好ましい。この範囲の下限は、０．２５質量部以上であることがより好ましく、０．５質量部以上であることがさらに好ましく、０．７５質量部以上であることが特に好ましく、１質量部以上であることが一層好ましい。また、この範囲の上限は、２５質量部以下であることがより好ましく、２０質量部以下であることがさらに好ましく、１５質量部以下であることが特に好ましい。顔料誘導体の含有量が上記範囲内であることにより、着色組成物の保存安定性をより向上させることができる。顔料誘導体は、１種のみを用いてもよいし、２種以上を併用してもよい。２種以上を併用する場合は、それらの合計量が上記範囲となることが好ましい。 The content of the pigment derivative is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the pigment. The lower limit of this range is more preferably 0.25 parts by mass or more, even more preferably 0.5 parts by mass or more, particularly preferably 0.75 parts by mass or more, and 1 part by mass or more. It is more preferable that there be. Further, the upper limit of this range is more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less. When the content of the pigment derivative is within the above range, the storage stability of the colored composition can be further improved. Only one type of pigment derivative may be used, or two or more types may be used in combination. When two or more types are used together, it is preferable that the total amount thereof falls within the above range.
＜＜ポリアルキレンイミン＞＞
　本発明の着色組成物は、ポリアルキレンイミンを含有することもできる。ポリアルキレンイミンは例えば分散助剤として用いられる。ポリアルキレンイミンとは、アルキレンイミンを開環重合したポリマーのことである。ポリアルキレンイミンは、１級アミノ基と、２級アミノ基と、３級アミノ基とをそれぞれ含む分岐構造を有するポリマーであることが好ましい。アルキレンイミンの炭素数は２～６が好ましく、２～４がより好ましく、２または３であることが更に好ましく、２であることが特に好ましい。 <<Polyalkyleneimine>>
The colored composition of the present invention can also contain polyalkyleneimine. Polyalkyleneimines are used, for example, as dispersion aids. Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine. The polyalkyleneimine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group, respectively. The alkylene imine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
　ポリアルキレンイミンの分子量は、２００以上であることが好ましく、２５０以上であることがより好ましい。上限は、１０００００以下であることが好ましく、５００００以下であることがより好ましく、１００００以下であることが更に好ましく、２０００以下であることが特に好ましい。なお、ポリアルキレンイミンの分子量の値について、構造式から分子量が計算できる場合は、ポリアルキレンイミンの分子量は構造式から計算した値である。一方、特定アミン化合物の分子量が構造式から計算できない、あるいは、計算が困難な場合には、沸点上昇法で測定した数平均分子量の値を用いる。また、沸点上昇法でも測定できない、あるいは、測定が困難な場合は、粘度法で測定した数平均分子量の値を用いる。また、粘度法でも測定できない、あるいは、粘度法での測定が困難な場合は、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）法により測定したポリスチレン換算値での数平均分子量の値を用いる。 The molecular weight of the polyalkylene imine is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less. Regarding the value of the molecular weight of polyalkylene imine, if the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkylene imine is the value calculated from the structural formula. On the other hand, if the molecular weight of a specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used. In addition, if measurement cannot be performed by the boiling point elevation method or is difficult to measure, the value of the number average molecular weight measured by the viscosity method is used. If the viscosity method cannot be used or it is difficult to measure, the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) is used.
　ポリアルキレンイミンのアミン価は５ｍｍｏｌ／ｇ以上であることが好ましく、１０ｍｍｏｌ／ｇ以上であることがより好ましく、１５ｍｍｏｌ／ｇ以上であることが更に好ましい。 The amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
　アルキレンイミンの具体例としては、エチレンイミン、プロピレンイミン、１，２－ブチレンイミン、２，３－ブチレンイミンなどが挙げられ、エチレンイミンまたはプロピレンイミンであることが好ましく、エチレンイミンであることがより好ましい。ポリアルキレンイミンは、ポリエチレンイミンであることが特に好ましい。また、ポリエチレンイミンは、１級アミノ基を、１級アミノ基と２級アミノ基と３級アミノ基との合計に対して１０モル％以上含むことが好ましく、２０モル％以上含むことがより好ましく、３０モル％以上含むことが更に好ましい。ポリエチレンイミンの市販品としては、エポミンＳＰ－００３、ＳＰ－００６、ＳＰ－０１２、ＳＰ－０１８、ＳＰ－２００、Ｐ－１０００（以上、（株）日本触媒製）などが挙げられる。 Specific examples of alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, etc. Ethyleneimine or propyleneimine is preferable, and ethyleneimine is more preferable. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. Further, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more of primary amino groups based on the total of primary amino groups, secondary amino groups, and tertiary amino groups. , more preferably 30 mol% or more. Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).
　着色組成物の全固形分中におけるポリアルキレンイミンの含有量は０．１～５質量％であることが好ましい。下限は０．２質量％以上であることが好ましく、０．５質量％以上であることがより好ましく、１質量％以上であることが更に好ましい。上限は４．５質量％以下であることが好ましく、４質量％以下であることがより好ましく、３質量％以下であることが更に好ましい。また、ポリアルキレンイミンの含有量は、顔料１００質量部に対して０．５～２０質量部であることが好ましい。下限は０．６質量部以上であることが好ましく、１質量部以上であることがより好ましく、２質量部以上であることが更に好ましい。上限は１０質量部以下であることが好ましく、８質量部以下であることがより好ましい。ポリアルキレンイミンは、１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合はそれらの合計量が上記範囲であることが好ましい。 The content of polyalkyleneimine in the total solid content of the coloring composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. Further, the content of polyalkyleneimine is preferably 0.5 to 20 parts by weight per 100 parts by weight of the pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. Only one type of polyalkylene imine may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.
＜＜硬化促進剤＞＞
　本発明の着色組成物は、硬化促進剤を含んでもよい。硬化促進剤としては、チオール化合物、メチロール化合物、アミン化合物、ホスホニウム塩化合物、アミジン塩化合物、アミド化合物、塩基発生剤、イソシアネート化合物、アルコキシシラン化合物、オニウム塩化合物などが挙げられる。硬化促進剤の具体例としては、国際公開第２０２２／０８５４８５号の段落０１６４に記載の化合物、特開２０２１－１８１４０６号公報に記載の化合物などが挙げられる。着色組成物の全固形分中における硬化促進剤の含有量は０．３～８．９質量％が好ましく、０．８～６．４質量％がより好ましい。 <<Curing accelerator>>
The colored composition of the present invention may also contain a curing accelerator. Examples of the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds, and the like. Specific examples of the curing accelerator include the compound described in paragraph 0164 of International Publication No. 2022/085485, the compound described in JP 2021-181406, and the like. The content of the curing accelerator in the total solid content of the colored composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
＜＜シランカップリング剤＞＞
　本発明の着色組成物は、シランカップリング剤を含有することができる。シランカップリング剤としては、加水分解性基を有するシラン化合物であることが好ましく、加水分解性基とそれ以外の官能基とを有するシラン化合物であることがより好ましい。加水分解性基とは、ケイ素原子に直結し、加水分解反応及び縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。また、加水分解性基以外の官能基としては、例えば、ビニル基、（メタ）アリル基、（メタ）アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基、フェニル基などが挙げられ、アミノ基、（メタ）アクリロイル基およびエポキシ基が好ましい。シランカップリング剤は、アルコキシシリル基を有する化合物であることが好ましい。シランカップリング剤の具体例としては、国際公開第２０２２／０８５４８５号の段落０１７７に記載の化合物が挙げられる。着色組成物の全固形分中におけるシランカップリング剤の含有量は、０．００１～２０質量％が好ましく、０．０１～１０質量％がより好ましく、０．１質量％～５質量％が更に好ましい。本発明の着色組成物は、シランカップリング剤を１種のみを含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 <<Silane coupling agent>>
The colored composition of the present invention can contain a silane coupling agent. The silane coupling agent is preferably a silane compound having a hydrolyzable group, more preferably a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkoxy group is preferred. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, and isocyanate groups. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferable. The silane coupling agent is preferably a compound having an alkoxysilyl group. Specific examples of the silane coupling agent include compounds described in paragraph 0177 of International Publication No. 2022/085485. The content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and even more preferably 0.1% to 5% by mass. preferable. The colored composition of the present invention may contain only one kind of silane coupling agent, or may contain two or more kinds of silane coupling agents. When two or more types are included, it is preferable that their total amount falls within the above range.
＜＜重合禁止剤＞＞
　本発明の着色組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔ－ブチルカテコール、ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシアミン塩（アンモニウム塩、第一セリウム塩等）等が挙げられる。着色組成物の全固形分中における重合禁止剤の含有量は、０．０００１～５質量％が好ましい。本発明の着色組成物は、重合禁止剤を１種のみを含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 <<Polymerization inhibitor>>
The colored composition of the present invention can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-t-butylphenol), Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). The content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5% by mass. The colored composition of the present invention may contain only one kind of polymerization inhibitor, or may contain two or more kinds of polymerization inhibitors. When two or more types are included, it is preferable that their total amount falls within the above range.
＜＜紫外線吸収剤＞＞
　本発明の着色組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤は、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物などを用いることができる。このような化合物の具体例としては、国際公開第２０２２／０８５４８５号の段落番号０１７９に記載の化合物が挙げられる。また、紫外線吸収剤は、特開２０２１－１７８９１８号公報に記載の反応性トリアジン紫外線吸収剤、特 開２０２２－００７８８４号公報に記載の紫外線吸収剤を用いることもできる。着色組成物の全固形分中における紫外線吸収剤の含有量は、０．１～１０質量％が好ましく、０．１～５質量％がより好ましく、０．１～３質量％が特に好ましい。本発明の着色組成物は、紫外線吸収剤を１種のみを含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 <<Ultraviolet absorber>>
The colored composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, etc. can be used. Specific examples of such compounds include the compound described in paragraph number 0179 of International Publication No. 2022/085485. Further, as the ultraviolet absorber, a reactive triazine ultraviolet absorber described in JP-A No. 2021-178918 and an ultraviolet absorber described in JP-A No. 2022-007884 can also be used. The content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 3% by mass. The colored composition of the present invention may contain only one kind of ultraviolet absorber, or may contain two or more kinds of ultraviolet absorbers. When two or more types are included, it is preferable that their total amount falls within the above range.
＜＜界面活性剤＞＞
　本発明の着色組成物は、界面活性剤を含有することができる。界面活性剤としては、フッ素系界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、アニオン性界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用することができる。界面活性剤はフッ素系界面活性剤またはシリコーン系界面活性剤であることが好ましく、シリコーン系界面活性剤であることがより好ましい。界面活性剤については、国際公開第２０１５／１６６７７９号の段落番号０２３８～０２４５に記載された界面活性剤が挙げられ、この内容は本明細書に組み込まれる。 <<Surfactant>>
The colored composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. The surfactant is preferably a fluorosurfactant or a silicone surfactant, more preferably a silicone surfactant. Examples of the surfactant include the surfactants described in paragraph numbers 0238 to 0245 of International Publication No. 2015/166779, the contents of which are incorporated herein.
　フッ素系界面活性剤としては、国際公開第２０２２／０８５４８５号の段落番号０１６７～０１７３に記載の化合物が挙げられる。 Examples of the fluorine-based surfactant include compounds described in paragraph numbers 0167 to 0173 of International Publication No. 2022/085485.
　ノニオン性界面活性剤としては、国際公開第２０２２／０８５４８５号の段落０１７４に記載の化合物が挙げられる。 Examples of nonionic surfactants include compounds described in paragraph 0174 of International Publication No. 2022/085485.
　シリコーン系界面活性剤としては、ＤＯＷＳＩＬ　ＳＨ８４００、ＳＨ８４００　ＦＬＵＩＤ、ＦＺ－２１２２、６７　Ａｄｄｉｔｉｖｅ、７４　Ａｄｄｉｔｉｖｅ、Ｍ　Ａｄｄｉｔｉｖｅ、ＳＦ　８４１９　ＯＩＬ（以上、ダウ・東レ（株）製）、ＴＳＦ－４３００、ＴＳＦ－４４４５、ＴＳＦ－４４６０、ＴＳＦ－４４５２（以上、モメンティブ・パフォーマンス・マテリアルズ社製）、ＫＰ－３４１、ＫＦ－６０００、ＫＦ－６００１、ＫＦ－６００２、ＫＦ－６００３（以上、信越化学工業（株）製）、ＢＹＫ－３０７、ＢＹＫ－３２２、ＢＹＫ－３２３、ＢＹＫ－３３０、ＢＹＫ－３３３、ＢＹＫ－３７６０、ＢＹＫ－ＵＶ３５１０（以上、ビックケミー社製）等が挙げられる。また、シリコーン系界面活性剤には下記構造の化合物を用いることもできる。
 As silicone -based surfactants include DOWSIL SH8400, SH8400 FLUID, FZ -1222, 67 ADDITIVE, 74 ADDITIVE, SF 8419 OIL (more than Dow Toray Co., Ltd.), TSF -430. 0, TSF -4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) , BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by BYK Chemie), and the like. Moreover, a compound having the following structure can also be used as the silicone surfactant.
　着色組成物の全固形分中における界面活性剤の含有量は、０．００１質量％～５．０質量％が好ましく、０．００５～３．０質量％がより好ましい。本発明の着色組成物は、界面活性剤を１種のみを含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the surfactant in the total solid content of the coloring composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% to 3.0% by mass. The colored composition of the present invention may contain only one kind of surfactant, or may contain two or more kinds of surfactants. When two or more types are included, it is preferable that their total amount falls within the above range.
＜＜酸化防止剤＞＞
　本発明の着色組成物は、酸化防止剤を含有することができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位（オルト位）に置換基を有する化合物が好ましい。前述の置換基としては炭素数１～２２の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス［２－［［２，４，８，１０－テトラキス（１，１－ジメチルエチル）ジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－６－イル］オキシ］エチル］アミン、トリス［２－［（４，６，９，１１－テトラ－ｔｅｒｔ－ブチルジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－２－イル）オキシ］エチル］アミン、亜リン酸エチルビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ　ＡＯ－２０、アデカスタブ　ＡＯ－３０、アデカスタブ　ＡＯ－４０、アデカスタブ　ＡＯ－５０、アデカスタブ　ＡＯ－５０Ｆ、アデカスタブ　ＡＯ－６０、アデカスタブ　ＡＯ－６０Ｇ、アデカスタブ　ＡＯ－８０、アデカスタブ　ＡＯ－３３０（以上、（株）ＡＤＥＫＡ製）などが挙げられる。また、酸化防止剤は、特許第６２６８９６７号公報の段落番号００２３～００４８に記載された化合物、国際公開第２０１７／００６６００号に記載された化合物、国際公開第２０１７／１６４０２４号に記載された化合物、韓国公開特許第１０－２０１９－００５９３７１号公報に記載された化合物を使用することもできる。着色組成物の全固形分中における酸化防止剤の含有量は、０．０１～２０質量％であることが好ましく、０．３～１５質量％であることがより好ましい。酸化防止剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、合計量が上記範囲となることが好ましい。 <<Antioxidant>>
The colored composition of the present invention can contain an antioxidant. Examples of antioxidants include phenol compounds, phosphite compounds, thioether compounds, and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenol compounds include hindered phenol compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. The above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Further, as the antioxidant, a compound having a phenol group and a phosphorous acid ester group in the same molecule is also preferable. Further, as the antioxidant, phosphorus-based antioxidants can also be suitably used. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl )oxy]ethyl]amine, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Co., Ltd.). In addition, antioxidants include compounds described in paragraph numbers 0023 to 0048 of Patent No. 6268967, compounds described in International Publication No. 2017/006600, compounds described in International Publication No. 2017/164024, Compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used. The content of the antioxidant in the total solid content of the coloring composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.
＜＜その他成分＞＞
　本発明の着色組成物は、必要に応じて、増感剤、可塑剤及びその他の助剤類（例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、香料、表面張力調整剤、連鎖移動剤。潜在酸化防止剤など）を含有してもよい。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、国際公開第２０２２／０８５４８５号の段落０１８２に記載の化合物を用いることができる。 ＜＜Other ingredients＞＞
The coloring composition of the present invention may optionally contain sensitizers, plasticizers, and other auxiliary agents (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances). , surface tension regulator, chain transfer agent, latent antioxidant, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. As these components, the compounds described in paragraph 0182 of International Publication No. 2022/085485 can be used.
　本発明の着色組成物は、耐光性改良剤を含んでもよい。耐光性改良剤としては、国際公開第２０２２／０８５４８５号の段落番号０１８３に記載の化合物が挙げられる。 The colored composition of the present invention may also contain a lightfastness improver. Examples of the light resistance improver include compounds described in paragraph number 0183 of International Publication No. 2022/085485.
　本発明の着色組成物は、テレフタル酸エステルを実質的に含まないことも好ましい。ここで、「実質的に含まない」とは、テレフタル酸エステルの含有量が、着色組成物の全量中、１０００質量ｐｐｂ以下であることを意味し、１００質量ｐｐｂ以下であることがより好ましく、ゼロであることが特に好ましい。 It is also preferable that the colored composition of the present invention is substantially free of terephthalic acid ester. Here, "substantially not containing" means that the content of terephthalic acid ester is 1000 mass ppb or less in the total amount of the coloring composition, more preferably 100 mass ppb or less, Particularly preferred is zero.
　本発明の着色組成物は、遊離の金属含有量が１００ｐｐｍ以下であることが好ましく、５０ｐｐｍ以下であることがより好ましい。また、遊離のハロゲン含有量は１００ｐｐｍ以下であることが好ましく、５０ｐｐｍ以下であることがより好ましい。着色組成物中の遊離の金属やハロゲンの低減方法としては、イオン交換水による洗浄、ろ過、限外ろ過、イオン交換樹脂による精製等の方法が挙げられる。 The colored composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less. Further, the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Examples of methods for reducing free metals and halogens in the colored composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification using ion-exchange resins.
　環境規制の観点から、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩の使用が規制されることがある。本発明の着色組成物において、上記した化合物の含有率を小さくする場合、パーフルオロアルキルスルホン酸（特にパーフルオロアルキル基の炭素数が６～８のパーフルオロアルキルスルホン酸）及びその塩、並びにパーフルオロアルキルカルボン酸（特にパーフルオロアルキル基の炭素数が６～８のパーフルオロアルキルカルボン酸）及びその塩の含有率は、着色組成物の全固形分に対して、０．０１ｐｐｂ～１，０００ｐｐｂの範囲であることが好ましく、０．０５ｐｐｂ～５００ｐｐｂの範囲であることがより好ましく、０．１ｐｐｂ～３００ｐｐｂの範囲であることが更に好ましい。本発明の着色組成物は、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩を実質的に含まなくてもよい。例えば、パーフルオロアルキルスルホン酸及びその塩の代替となりうる化合物、並びにパーフルオロアルキルカルボン酸及びその塩の代替となりうる化合物を用いることで、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩を実質的に含まない着色組成物を選択してもよい。規制化合物の代替となりうる化合物としては、例えば、パーフルオロアルキル基の炭素数の違いによって規制対象から除外された化合物が挙げられる。ただし、上記した内容は、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩の使用を妨げるものではない。本発明の着色組成物は、許容される最大の範囲内で、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩を含んでもよい。 From the perspective of environmental regulations, the use of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts may be regulated. In the coloring composition of the present invention, when reducing the content of the above-mentioned compounds, perfluoroalkylsulfonic acids (particularly perfluoroalkylsulfonic acids whose perfluoroalkyl group has 6 to 8 carbon atoms), salts thereof, and perfluoroalkylsulfonic acids, The content of fluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid whose perfluoroalkyl group has 6 to 8 carbon atoms) and its salt is 0.01 ppb to 1,000 ppb based on the total solid content of the coloring composition. It is preferably in the range of , more preferably in the range of 0.05 ppb to 500 ppb, even more preferably in the range of 0.1 ppb to 300 ppb. The coloring composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt. For example, by using a compound that can be substituted for perfluoroalkylsulfonic acid and its salt, and a compound that can be substituted for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid You may select a coloring composition that is substantially free of and salts thereof. Compounds that can be substituted for regulated compounds include, for example, compounds that are excluded from regulated targets due to differences in the number of carbon atoms in perfluoroalkyl groups. However, the above content does not preclude the use of perfluoroalkylsulfonic acids and salts thereof, and perfluoroalkylcarboxylic acids and salts thereof. The colored compositions of the present invention may include perfluoroalkyl sulfonic acids and salts thereof, and perfluoroalkyl carboxylic acids and salts thereof, to the maximum extent permissible.
＜＜収容容器＞＞
　着色組成物の収容容器としては、特に限定はなく、公知の収容容器を用いることができる。また、収容容器として、国際公開第２０２２／０８５４８５号の段落０１８７に記載の容器を用いることができる。 <<Storage container>>
The container for storing the coloring composition is not particularly limited, and any known container can be used. Further, as the storage container, the container described in paragraph 0187 of International Publication No. 2022/085485 can be used.
＜着色組成物の製造方法＞
　本発明の着色組成物は、前述の成分を混合して製造できる。着色組成物の製造に際しては、全成分を同時に溶剤に溶解および／または分散して着色組成物を製造してもよいし、必要に応じて、各成分を適宜２つ以上の溶液または分散液としておいて、使用時（塗布時）にこれらを混合して着色組成物を製造してもよい。 <Method for producing colored composition>
The colored composition of the present invention can be produced by mixing the above-mentioned components. When producing a colored composition, the colored composition may be produced by dissolving and/or dispersing all components in a solvent at the same time, or, if necessary, each component may be suitably prepared as two or more solutions or dispersions. The colored composition may be manufactured by mixing these at the time of use (at the time of application).
　着色組成物の製造に際して、顔料を分散させるプロセスを含んでいてもよい。顔料を分散させるプロセスにおいて、顔料の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断、キャビテーションなどが挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、ボールミル、ペイントシェーカー、マイクロフルイダイザー、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化、超音波分散などが挙げられる。またサンドミル（ビーズミル）における顔料の粉砕においては、径の小さいビーズを使用する、ビーズの充填率を大きくする事等により粉砕効率を高めた条件で処理することが好ましい。また、粉砕処理後にろ過、遠心分離などで粗粒子を除去することが好ましい。また、顔料を分散させるプロセスおよび分散機は、「分散技術大全集、株式会社情報機構発行、２００５年７月１５日」や「サスペンション（固／液分散系）を中心とした分散技術と工業的応用の実際　総合資料集、経営開発センター出版部発行、１９７８年１０月１０日」、特開２０１５－１５７８９３号公報の段落番号００２２に記載のプロセス及び分散機を好適に使用出来る。また顔料を分散させるプロセスにおいては、ソルトミリング工程にて粒子の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器、処理条件等は、例えば特開２０１５－１９４５２１号公報、特開２０１２－０４６６２９号公報の記載を参酌できる。 The production of the colored composition may include a process of dispersing pigments. In the process of dispersing pigments, mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like. In addition, when pulverizing pigments in a sand mill (bead mill), it is preferable to use small-diameter beads or increase the filling rate of the beads, thereby increasing the pulverizing efficiency. Further, it is preferable to remove coarse particles by filtration, centrifugation, etc. after the pulverization treatment. In addition, the process and dispersion machine for dispersing pigments are described in ``Complete Works of Dispersion Technology, Published by Information Technology Corporation, July 15, 2005'' and ``Dispersion technology centered on suspension (solid/liquid dispersion system) and industrial The process and dispersion machine described in Paragraph No. 0022 of JP 2015-157893 A, "Practical Application Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be suitably used. Further, in the process of dispersing the pigment, the particles may be made finer in a salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling process, the descriptions in JP-A No. 2015-194521 and JP-A No. 2012-046629 can be referred to, for example.
　着色組成物の調製にあたり、異物の除去や欠陥の低減などの目的で、着色組成物をフィルタでろ過することが好ましい。ろ過に用いるフィルタの種類およびろ過方法としては、国際公開第２０２２／０８５４８５号の段落番号０１９６～０１９９に記載のフィルタおよびろ過方法が挙げられる。 In preparing the colored composition, it is preferable to filter the colored composition with a filter for the purpose of removing foreign substances and reducing defects. Examples of the type of filter and filtration method used for filtration include the filters and filtration methods described in paragraph numbers 0196 to 0199 of International Publication No. 2022/085485.
＜硬化膜＞
　本発明の硬化膜は、上述した本発明の着色組成物から得られる硬化膜である。本発明の硬化膜は、カラーフィルタなどの光学フィルタに用いることができる。 <Cured film>
The cured film of the present invention is a cured film obtained from the colored composition of the present invention described above. The cured film of the present invention can be used for optical filters such as color filters.
　本発明の硬化膜の膜厚は、目的に応じて適宜調整できる。例えば、膜厚は０．５～３．０μｍであることが好ましい。下限は０．８μｍ以上が好ましく、１．０μｍ以上がより好ましく、１．１μｍ以上がさらに好ましい。上限は２．５μｍ以下が好ましく、２．０μｍ以下がより好ましく、１．８μｍ以下がさらに好ましい。 The thickness of the cured film of the present invention can be adjusted as appropriate depending on the purpose. For example, the film thickness is preferably 0.5 to 3.0 μm. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, and even more preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, and even more preferably 1.8 μm or less.
　また、硬化膜の線幅（パターンサイズ）は、２．０～１０．０μｍであることが好ましい。上限は７．５μｍ以下が好ましく、５．０μｍ以下がより好ましく、４．０μｍ以下がさらに好ましい。下限は２．２５μｍ以上が好ましく、２．５μｍ以上がより好ましく、２．７５μｍ以上がさらに好ましい。 Furthermore, the line width (pattern size) of the cured film is preferably 2.0 to 10.0 μm. The upper limit is preferably 7.5 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. The lower limit is preferably 2.25 μm or more, more preferably 2.5 μm or more, and even more preferably 2.75 μm or more.
＜カラーフィルタ＞
　本発明のカラーフィルタについて説明する。本発明のカラーフィルタは、上述した本発明の硬化膜を有する。カラーフィルタの画素（好ましくは着色画素）として、本発明の硬化膜を有することが好ましい。本発明のカラーフィルタは、固体撮像素子や表示装置に用いることができる。 <Color filter>
The color filter of the present invention will be explained. The color filter of the present invention has the cured film of the present invention described above. It is preferable to have the cured film of the present invention as a pixel (preferably a colored pixel) of a color filter. The color filter of the present invention can be used in solid-state imaging devices and display devices.
　カラーフィルタにおいて、画素の線幅（パターンサイズ）は、２．０～１０．０μｍであることが好ましい。上限は７．５μｍ以下が好ましく、５．０μｍ以下がより好ましく、４．０μｍ以下がさらに好ましい。下限は２．２５μｍ以上が好ましく、２．５μｍ以上がより好ましく、２．７５μｍ以上がさらに好ましい。 In the color filter, the pixel line width (pattern size) is preferably 2.0 to 10.0 μm. The upper limit is preferably 7.5 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. The lower limit is preferably 2.25 μm or more, more preferably 2.5 μm or more, and even more preferably 2.75 μm or more.
　本発明のカラーフィルタの好ましい態様として、赤色画素と、青色画素と、緑色画素と、を有する態様が挙げられる。赤色画素、青色画素および緑色画素から選ばれる少なくとも１種が、本発明の着色組成物を用いて形成されたものであることが好ましい。カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各着色画素が埋め込まれた構造を有していてもよい。この場合の隔壁は各着色画素よりも低屈折率であることが好ましい。また、米国特許出願公開第２０１８／００４０６５６号明細書に記載の構成で隔壁を形成しても良い。 A preferred embodiment of the color filter of the present invention includes an embodiment having a red pixel, a blue pixel, and a green pixel. It is preferable that at least one selected from a red pixel, a blue pixel, and a green pixel is formed using the colored composition of the present invention. The color filter may have a structure in which each colored pixel is embedded in a space partitioned into, for example, a lattice shape by partition walls. In this case, the partition wall preferably has a lower refractive index than each colored pixel. Alternatively, the partition wall may be formed with the configuration described in US Patent Application Publication No. 2018/0040656.
　カラーフィルタは、本発明の硬化膜の表面に保護層が設けられていてもよい。保護層を設けることで、酸素遮断化、低反射化、親疎水化、特定波長の光（紫外線、近赤外線等）の遮蔽等の種々の機能を付与することができる。保護層の厚さとしては、０．０１～１０μｍが好ましく、０．１～５μｍがより好ましい。保護層の形成方法としては、有機溶剤に溶解した樹脂組成物を塗布して形成する方法、化学気相蒸着法、成型した樹脂を接着剤で貼りつける方法等が挙げられる。保護層を構成する成分としては、（メタ）アクリル樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂、ポリオール樹脂、ポリ塩化ビニリデン樹脂、メラミン樹脂、ウレタン樹脂、アラミド樹脂、ポリアミド樹脂、アルキド樹脂、エポキシ樹脂、変性シリコーン樹脂、フッ素樹脂、ポリアクリロニトリル樹脂、セルロース樹脂、Ｓｉ、Ｃ、Ｗ、Ａｌ２Ｏ３、Ｍｏ、ＳｉＯ２、Ｓｉ２Ｎ４などが挙げられ、これらの成分を二種以上含有しても良い。例えば、酸素遮断化を目的とした保護層の場合、保護層はポリオール樹脂と、ＳｉＯ２と、Ｓｉ２Ｎ４を含むことが好ましい。また、低反射化を目的とした保護層の場合、保護層は（メタ）アクリル樹脂とフッ素樹脂を含むことが好ましい。 In the color filter, a protective layer may be provided on the surface of the cured film of the present invention. By providing a protective layer, various functions such as oxygen blocking, low reflection, hydrophilic and hydrophobic properties, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Examples of methods for forming the protective layer include a method of coating a resin composition dissolved in an organic solvent, a chemical vapor deposition method, and a method of pasting a molded resin with an adhesive. Components constituting the protective layer include (meth)acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide. Resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Examples include resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al 2 O 3 , Mo, SiO 2 , Si 2 N 4 and the like, and two or more of these components may be contained. For example, in the case of a protective layer intended for oxygen blocking, the protective layer preferably contains a polyol resin, SiO 2 and Si 2 N 4 . Furthermore, in the case of a protective layer intended for low reflection, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.
　樹脂組成物を塗布して保護層を形成する場合、樹脂組成物の塗布方法としては、スピンコート法、キャスト法、スクリーン印刷法、インクジェット法等の公知の方法を用いることができる。樹脂組成物に含まれる有機溶剤は、公知の有機溶剤（例えば、プロピレングリコール１－モノメチルエーテル２－アセテート、シクロペンタノン、乳酸エチル等）を用いることが出来る。保護層を化学気相蒸着法にて形成する場合、化学気相蒸着法としては、公知の化学気相蒸着法（熱化学気相蒸着法、プラズマ化学気相蒸着法、光化学気相蒸着法）を用いることができる。 When forming a protective layer by applying a resin composition, known methods such as a spin coating method, a casting method, a screen printing method, an inkjet method, etc. can be used as a method for applying the resin composition. As the organic solvent contained in the resin composition, known organic solvents (eg, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used. When forming the protective layer by chemical vapor deposition, known chemical vapor deposition methods (thermal chemical vapor deposition, plasma enhanced chemical vapor deposition, photochemical vapor deposition) can be used as the chemical vapor deposition method. can be used.
　保護層は、必要に応じて、有機・無機微粒子、特定波長の光（例えば、紫外線、近赤外線等）の吸収剤、屈折率調整剤、酸化防止剤、密着剤、界面活性剤等の添加剤を含有しても良い。有機・無機微粒子の例としては、例えば、高分子微粒子（例えば、シリコーン樹脂微粒子、ポリスチレン微粒子、メラミン樹脂微粒子）、酸化チタン、酸化亜鉛、酸化ジルコニウム、酸化インジウム、酸化アルミニウム、窒化チタン、酸窒化チタン、フッ化マグネシウム、中空シリカ、シリカ、炭酸カルシウム、硫酸バリウム等が挙げられる。特定波長の光の吸収剤は公知の吸収剤を用いることができる。これらの添加剤の含有量は適宜調整できるが、保護層の全質量に対して０．１～７０質量％が好ましく、１～６０質量％がさらに好ましい。 The protective layer may contain organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants, and other additives, as necessary. It may contain. Examples of organic/inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like. As the absorber for light of a specific wavelength, a known absorber can be used. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, based on the total weight of the protective layer.
　保護層としては、特開２０１７－１５１１７６号公報の段落番号００７３～００９２に記載の保護層を用いることもできる。 As the protective layer, the protective layers described in paragraph numbers 0073 to 0092 of JP 2017-151176 A can also be used.
＜硬化膜の製造方法＞
　次に、本発明の着色組成物を用いた硬化膜の形成方法について説明する。
　本発明の硬化膜の製造方法は、上述した本発明の着色組成物を支持体上に塗布して着色組成物層を形成する工程と、
　上記着色組成物層をパターン状に露光する工程と、
　露光後の着色組成物層を現像して未露光部の着色組成物層を除去する工程とを含む。そして、全工程を通じて１５０℃以下（好ましくは１２０℃以下、より好ましくは１００℃以下）の温度下で、上記着色組成物層が硬化した膜である硬化膜を得る。なお、本明細書において、「全工程を通じて１５０℃以下の温度で行う」とは、着色組成物を用いて硬化膜を形成する工程の全てを、１５０℃以下の温度で行うことを意味する。露光後の着色組成物層を現像した後、さらに加熱する工程を設ける場合は、この加熱する工程も１５０℃以下の温度で行うことを意味する。以下、各工程について詳細を述べる。 <Method for manufacturing cured film>
Next, a method for forming a cured film using the colored composition of the present invention will be explained.
The method for producing a cured film of the present invention includes a step of applying the above-described colored composition of the present invention onto a support to form a colored composition layer;
a step of exposing the colored composition layer to light in a pattern;
The method includes a step of developing the colored composition layer after exposure and removing the colored composition layer in the unexposed area. Then, a cured film in which the colored composition layer is cured is obtained at a temperature of 150° C. or lower (preferably 120° C. or lower, more preferably 100° C. or lower) throughout the entire process. In addition, in this specification, "all steps are performed at a temperature of 150° C. or lower" means that all steps of forming a cured film using a colored composition are performed at a temperature of 150° C. or lower. When a further heating step is provided after developing the exposed colored composition layer, this heating step is also performed at a temperature of 150° C. or lower. The details of each process will be described below.
　着色組成物層を形成する工程では、支持体上に着色組成物を塗布して着色組成物層を形成する。支持体としては、ガラス基板、ポリカーボネート基板、ポリエステル基板、芳香族ポリアミド基板、ポリアミドイミド基板、ポリイミド基板等が挙げられる。これらの基板上には有機発光層が形成されていてもよい。また、基板上には、上部の層との密着性改良、物質の拡散防止或いは表面の平坦化のために下塗り層が設けられていてもよい。下塗り層の表面接触角は、ジヨードメタンで測定した際に２０～７０°であることが好ましい。また、水で測定した際に３０～８０°であることが好ましい。 In the step of forming a colored composition layer, a colored composition is applied onto a support to form a colored composition layer. Examples of the support include a glass substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, and the like. An organic light emitting layer may be formed on these substrates. Furthermore, an undercoat layer may be provided on the substrate to improve adhesion with the upper layer, prevent substance diffusion, or flatten the surface. The surface contact angle of the undercoat layer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferable that the angle is 30 to 80° when measured with water.
　着色組成物の塗布方法としては、公知の方法を用いることができる。例えば、滴下法（ドロップキャスト）；スリットコート法；スプレー法；ロールコート法；回転塗布法（スピンコーティング）；流延塗布法；スリットアンドスピン法；プリウェット法（たとえば、特開２００９－１４５３９５号公報に記載されている方法）；インクジェット（例えばオンデマンド方式、ピエゾ方式、サーマル方式）、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷などの各種印刷法；金型等を用いた転写法；ナノインプリント法などが挙げられる。インクジェットでの適用方法としては、特に限定されず、例えば「広がる・使えるインクジェット－特許に見る無限の可能性－、２００５年２月発行、住ベテクノリサーチ」に示された方法（特に１１５ページ～１３３ページ）や、特開２００３－２６２７１６号公報、特開２００３－１８５８３１号公報、特開２００３－２６１８２７号公報、特開２０１２－１２６８３０号公報、特開２００６－１６９３２５号公報などに記載の方法が挙げられる。また、着色組成物の塗布方法については、国際公開第２０１７／０３０１７４号、国際公開第２０１７／０１８４１９号の記載を参酌でき、これらの内容は本明細書に組み込まれる。 A known method can be used to apply the coloring composition. For example, dropping method (drop casting); slit coating method; spray method; roll coating method; spin coating method; casting coating method; slit and spin method; Various methods such as inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Examples include printing method; transfer method using a mold etc.; nanoimprint method. The application method for inkjet is not particularly limited, and for example, the method shown in "Expanding and Usable Inkjet - Infinite Possibilities Seen in Patents," Published February 2005, Sumibe Techno Research (especially from page 115). 133 pages), and methods described in JP-A No. 2003-262716, JP-A No. 2003-185831, JP-A No. 2003-261827, JP-A No. 2012-126830, JP-A No. 2006-169325, etc. Can be mentioned. Further, regarding the method of applying the coloring composition, the descriptions in International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and the contents of these are incorporated herein.
　支持体上に形成した着色組成物層は、乾燥（プリベーク）してもよい。プリベークを行う場合、プリベーク温度は、８０℃以下が好ましく、７０℃以下がより好ましく、６０℃以下が更に好ましく、５０℃以下が特に好ましい。下限は、例えば、４０℃以上とすることができる。プリベーク時間は、１０～３６００秒が好ましい。プリベークは、ホットプレート、オーブン等で行うことができる。 The colored composition layer formed on the support may be dried (prebaked). When prebaking is performed, the prebaking temperature is preferably 80°C or lower, more preferably 70°C or lower, even more preferably 60°C or lower, and particularly preferably 50°C or lower. The lower limit can be, for example, 40°C or higher. The pre-bake time is preferably 10 to 3600 seconds. Prebaking can be performed on a hot plate, oven, or the like.
　次に、着色組成物層をパターン状に露光する。例えば、着色組成物層に対し、ステッパー露光機やスキャナ露光機などを用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン状に露光することができる。これにより、露光部分を硬化することができる。 Next, the colored composition layer is exposed in a pattern. For example, the colored composition layer can be exposed in a pattern by exposing it to light through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. This allows the exposed portion to be cured.
　露光に際して用いることができる放射線（光）としては、ｇ線、ｉ線等が挙げられる。また、波長３００ｎｍ以下の光（好ましくは波長１８０～３００ｎｍの光）を用いることもできる。波長３００ｎｍ以下の光としては、ＫｒＦ線（波長２４８ｎｍ）、ＡｒＦ線（波長１９３ｎｍ）などが挙げられ、ＫｒＦ線（波長２４８ｎｍ）が好ましい。また、３００ｎｍ以上の長波な光源も利用できる。 Radiation (light) that can be used during exposure includes g-line, i-line, etc. Furthermore, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm). Furthermore, a long-wave light source of 300 nm or more can also be used.
　また、露光に際して、光を連続的に照射して露光してもよく、パルス的に照射して露光（パルス露光）してもよい。なお、パルス露光とは、短時間（例えば、ミリ秒レベル以下）のサイクルで光の照射と休止を繰り返して露光する方式の露光方法のことである。パルス露光の場合、パルス幅は、１００ナノ秒（ｎｓ）以下であることが好ましく、５０ナノ秒以下であることがより好ましく、３０ナノ秒以下であることが更に好ましい。パルス幅の下限は、特に限定はないが、１フェムト秒（ｆｓ）以上とすることができ、１０フェムト秒以上とすることもできる。周波数は、１ｋＨｚ以上であることが好ましく、２ｋＨｚ以上であることがより好ましく、４ｋＨｚ以上であることが更に好ましい。周波数の上限は５０ｋＨｚ以下であることが好ましく、２０ｋＨｚ以下であることがより好ましく、１０ｋＨｚ以下であることが更に好ましい。最大瞬間照度は、５０００００００Ｗ／ｍ２以上であることが好ましく、１００００００００Ｗ／ｍ２以上であることがより好ましく、２００００００００Ｗ／ｍ２以上であることが更に好ましい。また、最大瞬間照度の上限は、１０００００００００Ｗ／ｍ２以下であることが好ましく、８００００００００Ｗ／ｍ２以下であることがより好ましく、５００００００００Ｗ／ｍ２以下であることが更に好ましい。なお、パルス幅とは、パルス周期における光が照射されている時間のことである。また、周波数とは、１秒あたりのパルス周期の回数のことである。また、最大瞬間照度とは、パルス周期における光が照射されている時間内での平均照度のことである。また、パルス周期とは、パルス露光における光の照射と休止を１サイクルとする周期のことである。 Moreover, upon exposure, exposure may be performed by continuously irradiating light, or may be performed by irradiating light in a pulsed manner (pulse exposure). Note that pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the millisecond level or less). In the case of pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, but can be 1 femtosecond (fs) or more, and can also be 10 femtoseconds or more. The frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and even more preferably 4 kHz or more. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and even more preferably 10 kHz or less. The maximum instantaneous illuminance is preferably 500000000 W/m 2 or more, more preferably 100000000 W/m 2 or more, and even more preferably 200000000 W/m 2 or more. Further, the upper limit of the maximum instantaneous illuminance is preferably 1000000000 W/m 2 or less, more preferably 800000000 W/m 2 or less, and even more preferably 500000000 W/m 2 or less. Note that the pulse width refers to the time during which light is irradiated in a pulse period. Furthermore, frequency refers to the number of pulse periods per second. Further, the maximum instantaneous illuminance is the average illuminance within the time period during which light is irradiated in the pulse period. Further, the pulse period is a period in which one cycle includes light irradiation and a pause in pulse exposure.
　照射量（露光量）は、３０～２５００ｍＪ／ｃｍ２が好ましい。下限は、５０ｍＪ／ｃｍ２以上であることが好ましく、１００ｍＪ／ｃｍ２以上であることがより好ましく、５００ｍＪ／ｃｍ２以上であることが更に好ましく、８００ｍＪ／ｃｍ２以上であることがより一層好ましく、１０００ｍＪ／ｃｍ２以上であることが更に一層好ましい。上限は、２０００ｍＪ／ｃｍ２以下であることが好ましく、１５００ｍＪ／ｃｍ２以下であることがより好ましい。また、露光照度は、適宜設定することが可能であり、例えば、５０ｍＷ／ｃｍ２～１０Ｗ／ｃｍ２であることが好ましい。露光照度の下限は、５００ｍＷ／ｃｍ２以上であることが好ましく、８００ｍＷ／ｃｍ２以上であることがより好ましく、１０００ｍＷ／ｃｍ２以上であることが更に好ましい。露光照度の上限は、１０Ｗ／ｃｍ２以下であることが好ましく、７Ｗ／ｃｍ２以下であることがより好ましく、５Ｗ／ｃｍ２以下であることが更に好ましい。 The irradiation amount (exposure amount) is preferably 30 to 2500 mJ/cm 2 . The lower limit is preferably 50 mJ/cm 2 or more, more preferably 100 mJ/cm 2 or more, even more preferably 500 mJ/cm 2 or more, even more preferably 800 mJ/cm 2 or more. , 1000 mJ/cm 2 or more is even more preferable. The upper limit is preferably 2000 mJ/cm 2 or less, more preferably 1500 mJ/cm 2 or less. Further, the exposure illuminance can be set as appropriate, and is preferably, for example, 50 mW/cm 2 to 10 W/cm 2 . The lower limit of the exposure illuminance is preferably 500 mW/cm 2 or more, more preferably 800 mW/cm 2 or more, and even more preferably 1000 mW/cm 2 or more. The upper limit of the exposure illuminance is preferably 10 W/cm 2 or less, more preferably 7 W/cm 2 or less, and even more preferably 5 W/cm 2 or less.
　露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば酸素濃度が１９体積％以下の低酸素雰囲気下（例えば、１５体積％、５体積％、または、実質的に無酸素）で露光してもよく、酸素濃度が２１体積％を超える高酸素雰囲気下（例えば、２２体積％、３０体積％、または、５０体積％）で露光してもよい。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度１０体積％で照度１Ｗ／ｃｍ２、酸素濃度３５体積％で照度２Ｗ／ｃｍ２などとすることができる。 The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being carried out in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially The exposure may be performed in an oxygen-free environment (in the absence of oxygen), or in a high oxygen atmosphere with an oxygen concentration of more than 21 volume % (for example, 22 volume %, 30 volume %, or 50 volume %). The oxygen concentration and the exposure illuminance may be appropriately combined. For example, the illumination intensity may be 1 W/cm 2 at an oxygen concentration of 10% by volume, or 2 W/cm 2 at an oxygen concentration of 35% by volume.
　着色組成物層の露光は、２５０ｎｍ超３８０ｎｍ以下の波長の光を１００ｍＪ／ｃｍ２以上の露光量で照射して行うことが好ましい。 The colored composition layer is preferably exposed to light with a wavelength of more than 250 nm and less than 380 nm at an exposure dose of 100 mJ/cm 2 or more.
　次に、露光後の着色組成物層を現像して未露光部の着色組成物層を除去する。着色組成物層の未露光部の除去は、現像液を用いて行うことができる。これにより、未露光部の着色組成物層が現像液に溶出し、光硬化した部分だけが残る。現像液の温度は、例えば、２０～３０℃が好ましい。現像時間は、２０～１８０秒が好ましい。また、残渣除去性を向上するため、現像液を６０秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返してもよい。 Next, the colored composition layer after exposure is developed to remove the colored composition layer in the unexposed areas. The unexposed areas of the colored composition layer can be removed using a developer. As a result, the unexposed portions of the colored composition layer are eluted into the developer, leaving only the photocured portions. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. Furthermore, in order to improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
　現像液としては、有機溶剤、アルカリ現像液などが挙げられ、アルカリ現像液であることが好ましい。現像液、および、現像後の洗浄（リンス）方法については、国際公開第２０２２／０８５４８５号の段落番号０２１４に記載の現像液や洗浄方法を用いることができる。 Examples of the developer include organic solvents and alkaline developers, and alkaline developers are preferred. Regarding the developer and the cleaning (rinsing) method after development, the developer and cleaning method described in paragraph number 0214 of International Publication No. 2022/085485 can be used.
　硬化膜の製造方法においては、露光後の着色組成物層を１５０℃以下の温度で加熱した後、上記現像を行うことも好ましい。上記現像前の加熱処理における加熱温度の上限は、１２０℃以下が好ましく、１００℃以下がより好ましい。加熱温度の下限は、５０℃以上が好ましく、７５℃以上がより好ましい。加熱時間は１分以上が好ましく、５分以上がより好ましく、１０分以上が更に好ましい。上限は特に限定はないが、生産性の観点から２０分以下が好ましい。 In the method for producing a cured film, it is also preferable to heat the exposed colored composition layer at a temperature of 150° C. or lower, and then perform the development described above. The upper limit of the heating temperature in the heat treatment before development is preferably 120°C or less, more preferably 100°C or less. The lower limit of the heating temperature is preferably 50°C or higher, more preferably 75°C or higher. The heating time is preferably 1 minute or more, more preferably 5 minutes or more, and even more preferably 10 minutes or more. The upper limit is not particularly limited, but from the viewpoint of productivity, it is preferably 20 minutes or less.
　現像後、乾燥を施した後に追加露光処理や加熱処理（ポストベーク）を行うことも好ましい。追加露光処理やポストベークは、硬化を完全なものとするための現像後の硬化処理である。 It is also preferable to perform additional exposure treatment or heat treatment (post-bake) after drying after development. Additional exposure processing and post-bake are post-development curing processing to complete curing.
　ポストベークを行う場合、加熱温度は１５０℃以下が好ましい。加熱温度の上限は、１２０℃以下が好ましく、１００℃以下がより好ましい。加熱温度の下限は、５０℃以上が好ましく、７５℃以上がより好ましい。加熱時間は１分以上が好ましく、５分以上がより好ましく、１０分以上が更に好ましい。上限は特に限定はないが、生産性の観点から２０分以下が好ましい。ポストベークは、不活性ガスの雰囲気下で行うことも好ましい。この態様によれば、熱重合を、酸素に阻害されることなく、非常に高い効率で進行させることができ、全工程を通じて１５０℃以下の温度で画素を製造した場合であっても、平坦性が良好で、耐湿性などの特性に優れた画素を製造することができる。不活性ガスとしては、窒素ガス、アルゴンガス、ヘリウムガス等が挙げられ、窒素ガスであることが好ましい。ポストベーク時の酸素濃度は、１００ｐｐｍ以下であることが好ましい。 When post-baking is performed, the heating temperature is preferably 150°C or less. The upper limit of the heating temperature is preferably 120°C or lower, more preferably 100°C or lower. The lower limit of the heating temperature is preferably 50°C or higher, more preferably 75°C or higher. The heating time is preferably 1 minute or more, more preferably 5 minutes or more, and even more preferably 10 minutes or more. The upper limit is not particularly limited, but from the viewpoint of productivity, it is preferably 20 minutes or less. It is also preferable that post-baking is performed under an inert gas atmosphere. According to this aspect, thermal polymerization can proceed with extremely high efficiency without being inhibited by oxygen, and even when pixels are manufactured at a temperature of 150° C. or lower throughout the entire process, flatness can be maintained. It is possible to manufacture pixels with excellent properties such as moisture resistance and moisture resistance. Examples of the inert gas include nitrogen gas, argon gas, helium gas, etc., and nitrogen gas is preferred. The oxygen concentration during post-baking is preferably 100 ppm or less.
　追加露光処理を行う場合、波長２５４～３５０ｎｍの光を照射して露光することが好ましい。より好ましい態様としては、着色組成物層をパターン状に露光する工程（現像前の露光）は、着色組成物層に対して波長３５０ｎｍを超え３８０ｎｍ以下の光（好ましくは波長３５５～３７０ｎｍの光、より好ましくはｉ線）を照射して露光して行い、追加露光処理（現像後の露光）は、現像後の着色組成物層に対して、波長２５４～３５０ｎｍの光（好ましくは波長２５４ｎｍの光）を照射して露光することが好ましい。この態様によれば、最初の露光（現像前の露光）で着色組成物層を適度に硬化させることができ、次の露光（現像後の露光）で着色組成物層全体をほぼ完全に硬化させることができるので、結果として、低温条件でも、着色組成物層を充分に硬化させて、耐湿性、密着性および矩形性などの特性に優れた画素を形成することができる。このように２段階で露光を行う場合、着色組成物は、光重合開始剤として、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０３ｍＬ／ｇ・ｃｍ以上の光重合開始剤Ａ１と、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０２ｍＬ／ｇ・ｃｍ以下で、かつ、波長２５４ｎｍの吸光係数が１．０×１０３ｍＬ／ｇ・ｃｍ以上の光重合開始剤Ａ２とを含むものを用いることが好ましい。 When additional exposure processing is performed, it is preferable to perform the exposure by irradiating light with a wavelength of 254 to 350 nm. In a more preferred embodiment, the step of exposing the colored composition layer to light in a pattern (exposure before development) involves exposing the colored composition layer to light with a wavelength of more than 350 nm and less than or equal to 380 nm (preferably light with a wavelength of 355 to 370 nm, The additional exposure treatment (exposure after development) is performed by exposing the colored composition layer to light with a wavelength of 254 to 350 nm (preferably light with a wavelength of 254 nm). ) is preferably used for exposure. According to this aspect, the colored composition layer can be moderately cured with the first exposure (exposure before development), and the entire colored composition layer can be almost completely cured with the next exposure (exposure after development). As a result, the colored composition layer can be sufficiently cured even under low temperature conditions, and pixels with excellent properties such as moisture resistance, adhesion, and rectangularity can be formed. When the exposure is performed in two stages in this way, the colored composition contains, as a photopolymerization initiator, a photopolymerization initiator A1 having an extinction coefficient of 1.0×10 3 mL/g cm or more at a wavelength of 365 nm in methanol. and photopolymerization initiation in which the extinction coefficient at a wavelength of 365 nm in methanol is 1.0 × 10 2 mL/g cm or less and the extinction coefficient at a wavelength of 254 nm is 1.0 × 10 3 mL/g cm or more. It is preferable to use one containing Agent A2.
　現像後の露光は、例えば紫外線フォトレジスト硬化装置を用いて行うことができる。紫外線フォトレジスト硬化装置からは、例えば波長２５４～３５０ｎｍの光とともに、これ以外の光（例えばｉ線）が照射されてもよい。 Exposure after development can be performed using, for example, an ultraviolet photoresist curing device. The ultraviolet photoresist curing device may emit light having a wavelength of 254 to 350 nm, as well as other light (for example, i-line).
　また、追加露光処理を行う場合の露光源スペクトルとしては、連続スペクトルが好ましく、現像前の露光と異なる分光スペクトル分布を有することがより好ましい。例えば、下記の（ａ）～（ｃ）の放射線を挙げることができる。
　（ａ）現像前の露光と異なる分光スペクトル分布を有する放射線であって、波長３１３ｎｍ（ｊ線）におけるピーク強度が、波長３６５ｎｍ（ｉ線）におけるピーク強度に対して、１／６以上１／３未満である放射線。
　（ｂ）現像前の露光と異なる分光スペクトル分布を有する放射線であって、波長３１３ｎｍ（ｊ線）におけるピーク強度が、波長３６５ｎｍ（ｉ線）におけるピーク強度に対して、１／３以上である放射線。なお、かかる波長３１３ｎｍにおけるピーク強度の上限は特に制限されないが、波長３６５ｎｍにおけるピーク強度より小さいことが好ましく、より好ましくは３／４以下である。
　（ｃ）現像前の露光と異なる分光スペクトル分布を有する放射線であって、波長４０５ｎｍ（ｈ線）及び波長４３６ｎｍ（ｇ線）を含み、波長３１３ｎｍ（ｊ線）及び波長３６５ｎｍ（ｉ線）におけるピーク強度が、波長４０５ｎｍ（ｈ線）のピーク強度及び波長４３６ｎｍ（ｇ線）のピーク強度のうち、より小さいピーク強度に対して１／４以下、好ましくは１／１０以下、更に好ましくは１／２０である放射線。なお、かかる波長３１３ｎｍ（ｊ線）及び波長３６５ｎｍ（ｉ線）におけるピーク強度の下限は特に制限されない。
　この場合、現像前の露光は、波長３６５ｎｍ（ｉ線）、波長４０５ｎｍ（ｈ線）及び波長４３６ｎｍ（ｇ線）を含む放射線であって、波長３１３ｎｍ（ｊ線）におけるピーク強度が、波長３６５ｎｍ（ｉ線）におけるピーク強度に対して１／６未満である放射線が好ましい。 Further, the exposure source spectrum in the case of performing additional exposure processing is preferably a continuous spectrum, and more preferably has a different spectral distribution from the exposure before development. For example, the following radiations (a) to (c) can be mentioned.
(a) Radiation having a spectral distribution different from that of exposure before development, and whose peak intensity at a wavelength of 313 nm (J line) is 1/6 or more than 1/3 of the peak intensity at a wavelength of 365 nm (i line). Radiation that is less than.
(b) Radiation having a spectral distribution different from that of exposure before development, and whose peak intensity at a wavelength of 313 nm (J-line) is 1/3 or more of the peak intensity at a wavelength of 365 nm (i-line) . Although the upper limit of the peak intensity at a wavelength of 313 nm is not particularly limited, it is preferably smaller than the peak intensity at a wavelength of 365 nm, and more preferably 3/4 or less.
(c) Radiation having a spectral distribution different from that of exposure before development, including a wavelength of 405 nm (H line) and a wavelength of 436 nm (G line), with peaks at wavelengths of 313 nm (J line) and 365 nm (i line). The intensity is 1/4 or less, preferably 1/10 or less, more preferably 1/20 of the smaller peak intensity of the peak intensity at a wavelength of 405 nm (h line) and the peak intensity at a wavelength of 436 nm (g line). radiation. Note that the lower limit of the peak intensity at a wavelength of 313 nm (J-line) and a wavelength of 365 nm (i-line) is not particularly limited.
In this case, the exposure before development is radiation including a wavelength of 365 nm (i-line), a wavelength of 405 nm (h-line), and a wavelength of 436 nm (g-line), and the peak intensity at a wavelength of 313 nm (j-line) is 365 nm ( Radiation having a peak intensity of less than 1/6 with respect to the peak intensity in i-line) is preferred.
　このような分光特性を示す放射線は、例えば、上記のような分光特性を示す光源を用いるか、又は高圧水銀灯から放射された放射線に紫外線カットフィルタやバンドバスフィルタを介して得ることができる。 Radiation exhibiting such spectral characteristics can be obtained, for example, by using a light source exhibiting spectral characteristics as described above, or by passing radiation emitted from a high-pressure mercury lamp through an ultraviolet cut filter or a bandpass filter.
　現像後の露光での照射量（露光量）は、３０～４０００ｍＪ／ｃｍ２が好ましく、５０～３５００ｍＪ／ｃｍ２がより好ましい。現像前の露光で用いられる光の波長と、現像後の露光で用いられる光の波長の差は、２００ｎｍ以下であることが好ましく、１００～１５０ｎｍであることがより好ましい。 The irradiation amount (exposure amount) in the exposure after development is preferably 30 to 4000 mJ/cm 2 , more preferably 50 to 3500 mJ/cm 2 . The difference between the wavelength of light used for exposure before development and the wavelength of light used for exposure after development is preferably 200 nm or less, more preferably 100 to 150 nm.
＜表示装置＞
　本発明の表示装置は、上述した本発明の膜を有する。表示装置としては、液晶表示装置や有機エレクトロルミネッセンス表示装置などが挙げられる。表示装置の定義や各表示装置の詳細については、例えば「電子ディスプレイデバイス（佐々木昭夫著、（株）工業調査会、１９９０年発行）」、「ディスプレイデバイス（伊吹順章著、産業図書（株）平成元年発行）」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術（内田龍男編集、（株）工業調査会、１９９４年発行）」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。 <Display device>
The display device of the present invention has the film of the present invention described above. Examples of the display device include a liquid crystal display device and an organic electroluminescence display device. For the definition of a display device and details of each display device, see, for example, "Electronic Display Devices (written by Akio Sasaki, Kogyo Chosenkai Co., Ltd., published in 1990)" and "Display Devices (written by Junaki Ibuki, published by Sangyo Tosho Co., Ltd.)". (published in 1989). Further, liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994)". There is no particular restriction on the liquid crystal display device to which the present invention can be applied, and for example, the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology."
　また、有機エレクトロルミネッセンス表示装置は、マイクロディスプレイであってもよい。マイクロディスプレイの表示面の対角の長さは、例えば、４インチ以下とすることができ、２インチ以下とすることもでき、１インチ以下とすることもでき、０．２インチ以下とすることもできる。マイクロディスプレイの用途としては、特に限定はないが、電子ビューファインダー、スマートグラス、ヘッドマウントディスプレイなどが挙げられる。 Additionally, the organic electroluminescent display device may be a microdisplay. The diagonal length of the display surface of the microdisplay can be, for example, 4 inches or less, 2 inches or less, 1 inch or less, and 0.2 inches or less. You can also do it. Applications of microdisplays include, but are not limited to, electronic viewfinders, smart glasses, head-mounted displays, and the like.
　有機エレクトロルミネッセンス表示装置は、白色有機エレクトロルミネッセンス素子からなる光源を有するものであってもよい。白色有機エレクトロルミネッセンス素子としては、タンデム構造であることが好ましい。有機エレクトロルミネッセンス素子のタンデム構造については、特開２００３－０４５６７６号公報、三上明義監修、「有機ＥＬ技術開発の最前線－高輝度・高精度・長寿命化・ノウハウ集－」、技術情報協会、３２６－３２８ページ、２００８年などに記載されている。有機ＥＬ素子が発光する白色光のスペクトルは、青色領域（４３０ｎｍ－４８５ｎｍ）、緑色領域（５３０ｎｍ－５８０ｎｍ）及び黄色領域（５８０ｎｍ－６２０ｎｍ）に強い極大発光ピークを有するものが好ましい。これらの発光ピークに加え更に赤色領域（６５０ｎｍ－７００ｎｍ）に極大発光ピークを有するものがより好ましい。 The organic electroluminescent display device may have a light source made of a white organic electroluminescent element. The white organic electroluminescent device preferably has a tandem structure. Regarding the tandem structure of organic electroluminescent elements, see Japanese Patent Application Laid-open No. 2003-045676, supervised by Akiyoshi Mikami, "The forefront of organic EL technology development - High brightness, high precision, long life, collection of know-how", Technical Information Association. , pp. 326-328, 2008. The spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430 nm to 485 nm), green region (530 nm to 580 nm), and yellow region (580 nm to 620 nm). In addition to these emission peaks, it is more preferable to have a maximum emission peak in the red region (650 nm to 700 nm).
　有機エレクトロルミネッセンス表示装置は、カラーフィルタを有していてもよい。カラーフィルタは、下地層上に設けられていてもよい。また、カラーフィルタと白色有機エレクトロルミネッセンス素子を組み合わせて、３原色の光を取り出す方式の有機エレクトロルミネッセンス表示装置においては、透明画素を設けて、白色光をそのまま発光に利用してもよい。このようにすることで、表示装置の輝度を高めることもできる。また、有機エレクトロルミネッセンス表示装置は、カラーフィルタ上にレンズを有していてもよい。レンズの形状としては、光学系設計により導出された様々な形状をとることができ、例えば、凸形状、凹形状などが挙げられる。例えば凹形状（凹型レンズ）とすることで光の集光性を向上させやすい。また、レンズは、カラーフィルタと直接接していてもよく、レンズとカラーフィルタとの間に、密着層や平坦化層などの他の層を設けてもよい。また、レンズは、国際公開第２０１８／１３５１８９号に記載の態様にて配置して用いることもできる。 The organic electroluminescent display device may have a color filter. The color filter may be provided on the base layer. Furthermore, in an organic electroluminescent display device that extracts light of three primary colors by combining a color filter and a white organic electroluminescent element, transparent pixels may be provided and the white light may be used as it is for light emission. By doing so, the brightness of the display device can also be increased. Further, the organic electroluminescent display device may have a lens on the color filter. The shape of the lens can take various shapes derived from optical system design, such as a convex shape and a concave shape. For example, by having a concave shape (concave lens), it is easy to improve the light condensing property. Further, the lens may be in direct contact with the color filter, or other layers such as an adhesion layer or a flattening layer may be provided between the lens and the color filter. Further, the lenses can also be used by being arranged in the manner described in International Publication No. 2018/135189.
　有機エレクトロルミネッセンス表示装置は、基板上に少なくとも赤色、緑色、青色を表示する有機エレクトロルミネッセンス素子と、この有機エレクトロルミネッセンス素子と同色の着色層を有機エレクトロルミネッセンス素子の上部に有する有機エレクトロルミネッセンス表示装置であってもよい。このような有機エレクトロルミネッセンス表示装置としては、特開２０２２－０６６８５９号公報に記載されている有機エレクトロルミネッセンス表示装置などが挙げられる。 An organic electroluminescent display device is an organic electroluminescent display device that has an organic electroluminescent element that displays at least red, green, and blue on a substrate, and a colored layer having the same color as the organic electroluminescent element above the organic electroluminescent element. There may be. Examples of such an organic electroluminescent display device include the organic electroluminescent display device described in JP-A No. 2022-066859.
＜固体撮像素子＞
　本発明の着色組成物および硬化膜は、固体撮像素子に用いることもできる。固体撮像素子の構成としては、固体撮像素子として機能する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。 <Solid-state image sensor>
The colored composition and cured film of the present invention can also be used in solid-state imaging devices. The configuration of the solid-state image sensor is not particularly limited as long as it functions as a solid-state image sensor, but examples include the following configurations.
　基板上に、固体撮像素子（ＣＣＤ（電荷結合素子）イメージセンサ、ＣＭＯＳ（相補型金属酸化膜半導体）イメージセンサ等）の受光エリアを構成する複数のフォトダイオードおよびポリシリコン等からなる転送電極を有し、フォトダイオードおよび転送電極上にフォトダイオードの受光部のみ開口した遮光膜を有し、遮光膜上に遮光膜全面およびフォトダイオード受光部を覆うように形成された窒化シリコン等からなるデバイス保護膜を有し、デバイス保護膜上に、カラーフィルタを有する構成である。更に、デバイス保護膜上であってカラーフィルタの下（基板に近い側）に集光手段（例えば、マイクロレンズ等。以下同じ）を有する構成や、カラーフィルタ上に集光手段を有する構成等であってもよい。また、カラーフィルタの画素は、隔壁により例えば格子状に仕切られた空間に埋め込まれていてもよい。この場合の隔壁の屈折率は、画素の屈折よりも低いことが好ましい。このような構造を有する撮像装置の例としては、特開２０１２－２２７４７８号公報、特開２０１４－１７９５７７号公報、国際公開第２０１８／０４３６５４号、米国特許出願公開第２０１８／００４０６５６号明細書に記載の装置が挙げられる。固体撮像素子を備えた撮像装置は、デジタルカメラや、撮像機能を有する電子機器（携帯電話等）の他、車載カメラや監視カメラ用としても用いることができる。 The substrate has a plurality of photodiodes that constitute the light receiving area of a solid-state image sensor (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon or the like. A device protective film made of silicon nitride or the like is formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a configuration in which a color filter is provided on the device protective film. Furthermore, a configuration in which a light condensing means (for example, a microlens, etc., the same applies hereinafter) is provided on the device protective film and below the color filter (on the side closer to the substrate), or a configuration in which the condensing means is provided on the color filter, etc. There may be. Furthermore, the pixels of the color filter may be embedded in a space partitioned, for example, in a grid pattern by partition walls. In this case, the refractive index of the partition wall is preferably lower than that of the pixel. Examples of imaging devices having such a structure are described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, International Publication No. 2018/043654, and US Patent Application Publication No. 2018/0040656. The following devices are mentioned. An imaging device including a solid-state imaging device can be used not only as a digital camera or an electronic device having an imaging function (such as a mobile phone), but also as an in-vehicle camera or a surveillance camera.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。 The present invention will be explained in more detail with reference to Examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
＜顔料分散液の製造＞
　下記表に示す顔料１～４と、顔料誘導体１の１．５質量部と、分散剤１の５．２５質量部と、プロピレングリコールモノメチルエーテルアセテートの７９．７５質量部とからなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）により３時間混合および分散した後、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２０００ｋｇ／ｃｍ２の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行なった。この分散処理を１０回繰り返し、顔料分散液を得た。 <Production of pigment dispersion>
A mixed solution consisting of pigments 1 to 4 shown in the table below, 1.5 parts by mass of pigment derivative 1, 5.25 parts by mass of dispersant 1, and 79.75 parts by mass of propylene glycol monomethyl ether acetate, After mixing and dispersing for 3 hours using a bead mill (zirconia beads 0.3 mm diameter), the flow rate was adjusted to 2000 kg/cm 2 using a high-pressure dispersion machine NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reduction mechanism. Dispersion treatment was performed at 500 g/min. This dispersion treatment was repeated 10 times to obtain a pigment dispersion.
　顔料誘導体１：下記構造の化合物
　分散剤１：下記構造の樹脂（主鎖の括弧に付した数値は、各繰り返し単位のモル比を表し、側鎖の括弧に付した数値は、繰り返し単位の繰り返し数を表す。重量平均分子量は２００００である。）
 Pigment derivative 1: Compound with the following structure
Dispersant 1: Resin with the following structure (The number in parentheses of the main chain represents the molar ratio of each repeating unit, and the number in parentheses of the side chain represents the number of repeating units. The weight average molecular weight is 20,000.)
　ＰＲ２５４　：　Ｃ．Ｉ．ピグメントレッド２５４
　ＰＲ１７７　：　Ｃ．Ｉ．ピグメントレッド１７７
　ＰＲ２６４　：　Ｃ．Ｉ．ピグメントレッド２６４
　ＰＲ２６９　：　Ｃ．Ｉ．ピグメントレッド２６９
　ＰＲ２９１　：　Ｃ．Ｉ．ピグメントレッド２９１
　ＰＹ１３９　：　Ｃ．Ｉ．ピグメントイエロー１３９
　ＰＹ１５０　：　Ｃ．Ｉ．ピグメントイエロー１５０
　ＰＹ１８５　：　Ｃ．Ｉ．ピグメントイエロー１８５
　ＰＧ７　：　Ｃ．Ｉ．ピグメントグリーン７
　ＰＧ３６　：　Ｃ．Ｉ．ピグメントグリーン３６
　ＰＧ５８　：　Ｃ．Ｉ．ピグメントグリーン５８
　ＰＢ１５：４　：　Ｃ．Ｉ．ピグメントブルー１５：４
　ＰＢ１５：６　：　Ｃ．Ｉ．ピグメントブルー１５：６
　ＰＶ２３　：　Ｃ．Ｉ．ピグメントバイオレット２３ PR254: C. I. pigment red 254
PR177: C. I. pigment red 177
PR264: C. I. pigment red 264
PR269: C. I. pigment red 269
PR291: C. I. pigment red 291
PY139: C. I. pigment yellow 139
PY150: C. I. pigment yellow 150
PY185: C. I. pigment yellow 185
PG7: C. I. pigment green 7
PG36: C. I. pigment green 36
PG58: C. I. pigment green 58
PB15:4: C. I. pigment blue 15:4
PB15:6: C. I. pigment blue 15:6
PV23: C. I. pigment violet 23
＜着色組成物の製造＞
　下記表に記載の下記素材を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、着色組成物を製造した。含有量の欄に記載の数値の単位は質量部である。 <Manufacture of colored composition>
The following materials listed in the table below were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) with a pore size of 0.45 μm to produce a colored composition. The unit of the numerical value described in the content column is parts by mass.
　上記表に記載の原料のうち、略語で示した原料の詳細は以下の通りである。 Among the raw materials listed in the table above, details of the raw materials indicated by abbreviations are as follows.
（顔料分散液）
　Ｐ－Ｒ１～Ｐ－Ｒ５、Ｐ－Ｇ１～Ｐ－Ｇ８、Ｐ－Ｂ１～Ｐ－Ｂ３：上述した顔料分散液Ｐ－Ｒ１～Ｐ－Ｒ５、Ｐ－Ｇ１～Ｐ－Ｇ８、Ｐ－Ｂ１～Ｐ－Ｂ３ (Pigment dispersion)
P-R1 to P-R5, P-G1 to PG8, P-B1 to P-B3: Pigment dispersions P-R1 to P-R5, PG1 to PG8, P-B1 to P-P -B3
（重合開始剤）
　Ａ１：Ｉｒｇａｃｕｒｅ　ＯＸＥ０２（ＢＡＳＦ社製、光ラジカル重合開始剤、オキシム化合物）
　Ａ２：ＫＡＹＡＣＵＲＥ　ＤＥＴＸ－Ｓ（日本化薬（株）製、光ラジカル重合開始剤、下記構造の化合物）
　Ａ３：Ｉｒｇａｃｕｒｅ　ＯＸＥ０１（ＢＡＳＦ社製、光ラジカル重合開始剤、オキシム化合物）
　Ａ４：Ｏｍｎｉｒａｄ　２９５９（ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製、光ラジカル重合開始剤、α－ヒドロキシケトン化合物） (Polymerization initiator)
A1: Irgacure OXE02 (manufactured by BASF, photoradical polymerization initiator, oxime compound)
A2: KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd., photoradical polymerization initiator, compound with the following structure)
A3: Irgacure OXE01 (manufactured by BASF, photoradical polymerization initiator, oxime compound)
A4: Omnirad 2959 (manufactured by IGM Resins B.V., photoradical polymerization initiator, α-hydroxyketone compound)
（酸発生剤）
　ＰＡＧ１：ＩＲＧＡＣＵＲＥ　ＰＡＧ－１０３（ＢＡＳＦ社製、下記構造の化合物、オキシムスルホネート化合物、光酸発生剤）
　ＰＡＧ２：ＭＯＰ－トリアジン（三和ケミカル（株）製、下記構造の化合物、トリアジン化合物、光酸発生剤）
　ＴＡＧ１：サンエイド　ＳＩ－６０（三新化学工業（株）製、スルホニウム塩、熱酸発生剤） (acid generator)
PAG1: IRGACURE PAG-103 (manufactured by BASF, compound with the following structure, oxime sulfonate compound, photoacid generator)
PAG2: MOP-triazine (manufactured by Sanwa Chemical Co., Ltd., compound with the following structure, triazine compound, photoacid generator)
TAG1: Sunaid SI-60 (manufactured by Sanshin Chemical Industry Co., Ltd., sulfonium salt, thermal acid generator)
（塩基発生剤）
　ＰＢＧ１：ＷＰＢＧ－０１８（富士フイルム和光純薬（株）製、下記構造の化合物、カルバメート化合物、光塩基発生剤）
　ＰＢＧ２：ＷＰＢＧ－２２６（富士フイルム和光純薬（株）製、下記構造の化合物、オニウム塩、光塩基発生剤）
　ＰＢＧ３：下記構造の化合物（オニウム塩、光塩基発生剤）
　ＰＢＧ４：アセトフェノン－Ｏ－プロパノイルオキシム（光塩基発生剤、アシルオキシム化合物）
　ＴＢＧ１：Ｕ－ＣＡＴ　ＳＡ１（サンアプロ（株）製、熱塩基発生剤） (base generator)
PBG1: WPBG-018 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., compound with the following structure, carbamate compound, photobase generator)
PBG2: WPBG-226 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., compound with the following structure, onium salt, photobase generator)
PBG3: Compound with the following structure (onium salt, photobase generator)
PBG4: Acetophenone-O-propanoyloxime (photobase generator, acyloxime compound)
TBG1: U-CAT SA1 (manufactured by San-Apro Co., Ltd., thermal base generator)
（樹脂）
　Ｂ１：下記構造の樹脂（主鎖に付記した数値はモル比である。重量平均分子量１１０００、酸価６９ｍｇＫＯＨ／ｇ）の４０質量％プロピレングリコールモノメチルエーテルアセテート溶液
　Ｂ２：以下の方法で合成した樹脂
　セパラブル４口フラスコに温度計、冷却管、窒素ガス導入管、滴下管および撹拌装置を取り付けた反応容器にシクロヘキサノン１９６質量部を仕込み、８０℃に昇温し、反応容器内を窒素置換した後、滴下管より、ｎ－ブチルメタクリレート３７．２質量部、２－ヒドロキシエチルメタクリレート１２．９質量部、メタクリル酸１２．０質量部、パラクミルフェノールエチレンオキサイド変性アクリレート（東亞合成社製「アロニックスＭ１１０」）２０．７質量部、２，２’－アゾビスイソブチロニトリル１．１質量部の混合物を２時間かけて滴下した。滴下終了後、更に３時間反応を継続した後、室温まで冷却して下記構造の樹脂を得た。重量平均分子量（Ｍｗ）は２６０００であった。
 (resin)
B1: 40% by mass propylene glycol monomethyl ether acetate solution of resin with the following structure (the numbers appended to the main chain are molar ratios; weight average molecular weight 11000, acid value 69 mgKOH/g)
B2: Resin synthesized by the following method 196 parts by mass of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80 ° C. After purging the inside of the reaction vessel with nitrogen, 37.2 parts by mass of n-butyl methacrylate, 12.9 parts by mass of 2-hydroxyethyl methacrylate, 12.0 parts by mass of methacrylic acid, paracumylphenol ethylene oxide modified acrylate ( A mixture of 20.7 parts by mass of "Aronix M110" manufactured by Toagosei Co., Ltd. and 1.1 parts by mass of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours, and then cooled to room temperature to obtain a resin having the following structure. The weight average molecular weight (Mw) was 26,000.
（モノマー）
　Ｍ１：下記構造の化合物（ラジカル重合性モノマー）
　Ｍ２：下記構造の化合物（ラジカル重合性モノマー）
 (monomer)
M1: Compound with the following structure (radical polymerizable monomer)
M2: Compound with the following structure (radical polymerizable monomer)
（環状エーテル基を有する化合物）
　Ｅ１：下記構造の化合物（分子量４０６）
　Ｅ２：下記構造の化合物（分子量４５２）
　Ｅ３：下記構造の化合物の混合物（左側の構造の化合物の分子量２０４、右側の構造の化合物の分子量２６０）
　Ｅ４：下記構造の化合物の混合物（左側の構造の化合物の分子量３０４、右側の構造の化合物の分子量２４６）
　Ｅ５：下記構造の化合物（分子量３３４）
　Ｅ６：下記構造の化合物（分子量１８６）
　Ｅ７：ＥＨＰＥ３１５０（（株）ダイセル製、下記構造のエポキシ樹脂、環状エーテル基の含有量５．７０ｍｍｏｌ／ｇ、重量平均分子量２２８２、ｎ＝１５、Ｒ＝Ｃ６Ｈ１３Ｏ２）
　ｃＥ１：下記構造のエポキシポリマー（主鎖に付記した数値は繰り返し単位の質量比である、重量平均分子量１００００）
 (Compound having a cyclic ether group)
E1: Compound with the following structure (molecular weight 406)
E2: Compound with the following structure (molecular weight 452)
E3: Mixture of compounds with the following structure (molecular weight of the compound with the structure on the left: 204, molecular weight of the compound with the structure on the right: 260)
E4: Mixture of compounds with the following structure (molecular weight of the compound with the structure on the left: 304, molecular weight of the compound with the structure on the right: 246)
E5: Compound with the following structure (molecular weight 334)
E6: Compound with the following structure (molecular weight 186)
E7: EHPE3150 (manufactured by Daicel Corporation, epoxy resin with the following structure, cyclic ether group content 5.70 mmol/g, weight average molecular weight 2282, n=15, R=C 6 H 13 O2)
cE1: Epoxy polymer with the following structure (the number appended to the main chain is the mass ratio of repeating units, weight average molecular weight 10,000)
（界面活性剤）
　Ｇ１：ＫＦ－６００１（信越化学工業（株）製、シリコーン系界面活性剤）
　Ｇ２：ＤＯＷＳＩＬ　ＳＨ８４００　ＦＬＵＩＤ（ダウ・東レ（株）製、シリコーン系界面活性剤） (surfactant)
G1: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone surfactant)
G2: DOWSIL SH8400 FLUID (manufactured by Dow Toray Industries, Inc., silicone surfactant)
（溶剤）
　Ｓ１：プロピレングリコールモノメチルエーテルアセテート
　Ｓ２：シクロペンタノン
　Ｓ３：シクロヘキサノン (solvent)
S1: Propylene glycol monomethyl ether acetate S2: Cyclopentanone S3: Cyclohexanone
＜保存安定性の評価＞
　上記で得られた製造直後の着色組成物の粘度（Ｖ１）を、粘度計（東機産業（株）製、ＲＥ－８５Ｌ）を用いて測定した。この着色組成物を４０℃の温度条件のもとで３日間静置した後、粘度（Ｖ２）を測定した。下記式から増粘率を算出し、下記評価基準に従って保存安定性を評価した。なお、着色組成物の粘度は２３℃に温度調整を施した状態で測定した。評価基準は下記の通りとし、評価結果は下記表に記載した。
　増粘率（％）＝［（粘度（Ｖ２）－粘度（Ｖ１））／粘度（Ｖ１）］×１００
　５：増粘率が０．２５％未満である
　４：増粘率が０．２５％以上１％未満である
　３：増粘率が１％以上２．５％未満である
　２：増粘率が２．５％以上５％未満である
　１：増粘率が５％以上である <Evaluation of storage stability>
The viscosity (V1) of the colored composition obtained above immediately after production was measured using a viscometer (manufactured by Toki Sangyo Co., Ltd., RE-85L). After this colored composition was allowed to stand for 3 days under a temperature condition of 40° C., the viscosity (V2) was measured. The viscosity increase rate was calculated from the following formula, and the storage stability was evaluated according to the following evaluation criteria. In addition, the viscosity of the colored composition was measured in a state where the temperature was adjusted to 23°C. The evaluation criteria were as follows, and the evaluation results are listed in the table below.
Viscosity increase rate (%) = [(viscosity (V2) - viscosity (V1)) / viscosity (V1)] x 100
5: The viscosity increase rate is less than 0.25% 4: The viscosity increase rate is 0.25% or more and less than 1% 3: The viscosity increase rate is 1% or more and less than 2.5% 2: The viscosity increase rate is 2.5% or more and less than 5% 1: Thickening rate is 5% or more
＜耐湿性の評価＞
　上記で得られた着色組成物を、スピンコーターを用いて、乾燥後の仕上がり膜厚が１．５μｍとなるようにガラス基板上に塗布し、８０℃のホットプレート上で２分間乾燥させた。その後、超高圧水銀ランプを用いて、露光照度２０ｍＷ／ｃｍ２、露光量１０００ｍＪ／ｃｍ２の条件で露光した。次いで、１００℃のホットプレート上で２０分間加熱し、放冷して、硬化膜を形成した。
　得られた硬化膜に対し白色発光ダイオード光を照射しながら、温度８５℃、湿度８５％の条件下にて１０００時間曝す耐湿性試験を実施した。耐湿性試験前後の硬化膜の分光透過率を測定した。波長４００～１１００ｎｍの範囲において、測定波長ごとに透過率の変化率を算出し、それらの変化率の中の最大値を指標に下記のとおり耐湿性を評価した。
　なお、白色発光ダイオード光の光源には、面発光光源（ＬＥＤＶＨ３９０－Ｗ、ミスミ製）を用いた。
　５：指標となる変化率が１％以下である。
　４：指標となる変化率が１％より大きく２％以下である
　３：指標となる変化率が２％より大きく３％以下である
　２：指標となる変化率が３％より大きく４％以下である
　１：指標となる変化率が４％より大きい <Evaluation of moisture resistance>
The colored composition obtained above was applied onto a glass substrate using a spin coater so that the finished film thickness after drying was 1.5 μm, and dried on a hot plate at 80° C. for 2 minutes. Thereafter, exposure was performed using an ultra-high pressure mercury lamp under conditions of an exposure illuminance of 20 mW/cm 2 and an exposure amount of 1000 mJ/cm 2 . Next, it was heated on a hot plate at 100° C. for 20 minutes and allowed to cool to form a cured film.
A humidity resistance test was carried out in which the obtained cured film was exposed to white light emitting diode light for 1000 hours at a temperature of 85° C. and a humidity of 85%. The spectral transmittance of the cured film before and after the moisture resistance test was measured. In the wavelength range of 400 to 1100 nm, the rate of change in transmittance was calculated for each measured wavelength, and the moisture resistance was evaluated as follows using the maximum value of these rates of change as an index.
Note that a surface emitting light source (LEDVH390-W, manufactured by Misumi) was used as a light source for white light emitting diode light.
5: The rate of change serving as an index is 1% or less.
4: The indicator change rate is greater than 1% and 2% or less. 3: The indicator change rate is greater than 2% and 3% or less. 2: The indicator change rate is greater than 3% and 4% or less. Yes 1: The indicator change rate is greater than 4%
　上記評価結果を下記表に記す。また、着色組成物中の全固形分中における着色剤の含有量を着色剤の含有量の欄に記し、着色組成物中の全固形分中における発生剤（酸発生剤または塩基発生剤）の含有量を発生剤の含有量の欄に記す。 The above evaluation results are shown in the table below. In addition, the content of the coloring agent in the total solid content of the coloring composition is recorded in the column of colorant content, and the content of the coloring agent (acid generator or base generator) in the total solid content of the coloring composition is recorded. Record the content in the generator content column.
　上記表に示すように、実施例は、保存安定性が良好で、耐湿性に優れた硬化膜を製造することができた。 As shown in the table above, in the examples, cured films with good storage stability and excellent moisture resistance could be produced.

Claims (15)

  1. 　着色剤と、
    　樹脂と、
    　ラジカル重合性モノマーと、
    　ラジカル重合開始剤と、
    　酸発生剤および塩基発生剤からなる群より選択される少なくとも１種の発生剤と、
    　分子量が５０００以下の環状エーテル基を有する化合物Ａと、を含む着色組成物であって、
    　前記着色組成物の全固形分中における前記着色剤の含有量が３５質量％以上であり、
    　前記着色組成物の全固形分中における前記発生剤の含有量が２～１５質量％である、着色組成物。     colorant and
    resin and
    a radically polymerizable monomer,
    a radical polymerization initiator,
    at least one generator selected from the group consisting of acid generators and base generators;
    A colored composition comprising a compound A having a cyclic ether group with a molecular weight of 5000 or less,
    The content of the coloring agent in the total solid content of the coloring composition is 35% by mass or more,
    A colored composition in which the content of the generator in the total solid content of the colored composition is 2 to 15% by mass.
  2. 　前記化合物Ａの分子量が１５００以下である、請求項１に記載の着色組成物。 The colored composition according to claim 1, wherein the compound A has a molecular weight of 1500 or less.
  3. 　前記化合物Ａは環状エーテル基を４個以上有する、請求項１または２に記載の着色組成物。 The colored composition according to claim 1 or 2, wherein the compound A has four or more cyclic ether groups.
  4. 　前記環状エーテル基はエポキシ基である、請求項１または２に記載の着色組成物。 The colored composition according to claim 1 or 2, wherein the cyclic ether group is an epoxy group.
  5. 　前記酸発生剤は光酸発生剤であり、前記塩基発生剤は光塩基発生剤である、請求項１または２に記載の着色組成物。 The colored composition according to claim 1 or 2, wherein the acid generator is a photoacid generator and the base generator is a photobase generator.
  6. 　前記発生剤は塩基発生剤である、請求項１または２に記載の着色組成物。 The colored composition according to claim 1 or 2, wherein the generator is a base generator.
  7. 　前記塩基発生剤は、カルバメート化合物、アシルオキシム化合物およびオニウム塩からなる群より選択される少なくとも１種を含む、請求項１または２に記載の着色組成物。 The colored composition according to claim 1 or 2, wherein the base generator contains at least one selected from the group consisting of carbamate compounds, acyloxime compounds, and onium salts.
  8. 　前記発生剤と前記化合物Ａとの割合は、前記発生剤１００質量部に対して前記化合物Ａが３０～７００質量部である、請求項１または２に記載の着色組成物。 The coloring composition according to claim 1, wherein the ratio of the generator to the compound A is 30 to 700 parts by mass based on 100 parts by mass of the generator.
  9. 　更に、界面活性剤を含み、
    　前記界面活性剤はシリコーン系界面活性剤を含む、請求項１または２に記載の着色組成物。     Furthermore, it contains a surfactant,
    The colored composition according to claim 1 or 2, wherein the surfactant includes a silicone surfactant.
  10. 　請求項１または２に記載の着色組成物から得られる硬化膜。 A cured film obtained from the coloring composition according to claim 1 or 2.
  11. 　請求項１０に記載の硬化膜を有するカラーフィルタ。 A color filter having the cured film according to claim 10.
  12. 　請求項１０に記載の硬化膜を有する表示装置。 A display device comprising the cured film according to claim 10.
  13. 　請求項１または２に記載の着色組成物を支持体上に塗布して着色組成物層を形成する工程と、
    　前記着色組成物層をパターン状に露光する工程と、
    　露光後の着色組成物層を現像して未露光部の着色組成物層を除去する工程とを含み、
    　全工程を通じて１５０℃以下の温度下で、前記着色組成物層が硬化した膜である硬化膜を得る、硬化膜の製造方法。     A step of applying the colored composition according to claim 1 or 2 onto a support to form a colored composition layer;
    exposing the colored composition layer to light in a pattern;
    developing the colored composition layer after exposure and removing the colored composition layer in the unexposed area,
    A method for producing a cured film, the method comprising obtaining a cured film in which the colored composition layer is cured at a temperature of 150° C. or lower throughout the entire process.
  14. 　全工程を通じて１００℃以下の温度下で前記硬化膜を得る、請求項１３に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 13, wherein the cured film is obtained at a temperature of 100° C. or lower throughout the entire process.
  15. 　露光後の前記着色組成物層を１５０℃以下の温度で加熱した後、前記現像を行う、請求項１３に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 13, wherein the development is performed after the colored composition layer after exposure is heated at a temperature of 150°C or less.
PCT/JP2023/032324 2022-09-16 2023-09-05 Coloring composition, cured film, color filter, display device and method for producing cured film WO2024057999A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022147750 2022-09-16
JP2022-147750 2022-09-16

Publications (1)

Publication Number Publication Date
WO2024057999A1 true WO2024057999A1 (en) 2024-03-21

Family

ID=90274830

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/032324 WO2024057999A1 (en) 2022-09-16 2023-09-05 Coloring composition, cured film, color filter, display device and method for producing cured film

Country Status (1)

Country Link
WO (1) WO2024057999A1 (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009237441A (en) * 2008-03-28 2009-10-15 Fujifilm Corp Colored photosensitive composition, color filter, and display device
JP2010085768A (en) * 2008-09-30 2010-04-15 Dainippon Printing Co Ltd Green curable resin composition, color filter, and display device
JP2012088575A (en) * 2010-10-20 2012-05-10 Jsr Corp Radiation-sensitive composition, cured film and method for forming the same
WO2012090965A1 (en) * 2010-12-27 2012-07-05 旭化成イーマテリアルズ株式会社 Photosensitive phenol resin composition for alkaline development, cured relief pattern, method for producing semiconductor, and biphenyl-diyl-trihydroxybenzene resin
JP2013080207A (en) * 2011-09-22 2013-05-02 Tokyo Ohka Kogyo Co Ltd Photosensitive resin composition, and coating film and color filter using the same
JP2016045248A (en) * 2014-08-20 2016-04-04 富士フイルム株式会社 Photosensitive resin composition, production method of cured film, cured film, liquid crystal display device, organic electroluminescence display device and touch panel
JP2016156856A (en) * 2015-02-23 2016-09-01 三洋化成工業株式会社 Photosensitive composition for forming color filter
WO2018037812A1 (en) * 2016-08-25 2018-03-01 富士フイルム株式会社 Curable composition and production process therefor, cured film and production process therefor, color filter, solid-state imaging element, solid-state imaging device, and infrared sensor
WO2020066871A1 (en) * 2018-09-26 2020-04-02 富士フイルム株式会社 Curable composition, cured film, method for forming pattern, optical filter and photosensor
WO2021125132A1 (en) * 2019-12-20 2021-06-24 株式会社Adeka Carbamoyl oxime compound, and polymerization initiator and polymerizable composition containing said compound
JP2022051490A (en) * 2021-02-22 2022-03-31 サンアプロ株式会社 Photocurable composition and cured body thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009237441A (en) * 2008-03-28 2009-10-15 Fujifilm Corp Colored photosensitive composition, color filter, and display device
JP2010085768A (en) * 2008-09-30 2010-04-15 Dainippon Printing Co Ltd Green curable resin composition, color filter, and display device
JP2012088575A (en) * 2010-10-20 2012-05-10 Jsr Corp Radiation-sensitive composition, cured film and method for forming the same
WO2012090965A1 (en) * 2010-12-27 2012-07-05 旭化成イーマテリアルズ株式会社 Photosensitive phenol resin composition for alkaline development, cured relief pattern, method for producing semiconductor, and biphenyl-diyl-trihydroxybenzene resin
JP2013080207A (en) * 2011-09-22 2013-05-02 Tokyo Ohka Kogyo Co Ltd Photosensitive resin composition, and coating film and color filter using the same
JP2016045248A (en) * 2014-08-20 2016-04-04 富士フイルム株式会社 Photosensitive resin composition, production method of cured film, cured film, liquid crystal display device, organic electroluminescence display device and touch panel
JP2016156856A (en) * 2015-02-23 2016-09-01 三洋化成工業株式会社 Photosensitive composition for forming color filter
WO2018037812A1 (en) * 2016-08-25 2018-03-01 富士フイルム株式会社 Curable composition and production process therefor, cured film and production process therefor, color filter, solid-state imaging element, solid-state imaging device, and infrared sensor
WO2020066871A1 (en) * 2018-09-26 2020-04-02 富士フイルム株式会社 Curable composition, cured film, method for forming pattern, optical filter and photosensor
WO2021125132A1 (en) * 2019-12-20 2021-06-24 株式会社Adeka Carbamoyl oxime compound, and polymerization initiator and polymerizable composition containing said compound
JP2022051490A (en) * 2021-02-22 2022-03-31 サンアプロ株式会社 Photocurable composition and cured body thereof

Similar Documents

Publication Publication Date Title
JP2024009929A (en) Colored photosensitive composition, film, color filter, solid-state imaging device and image display device
WO2022202204A1 (en) Coloring composition, film, optical filter, solid-state imaging element, and image display device
WO2023243414A1 (en) Resin composition, film, optical filter, solid-state imaging element, and image display device
JP7383146B2 (en) Photosensitive compositions, films, color filters, solid-state imaging devices, and image display devices
WO2022168741A1 (en) Colored composition, film, optical filter, solid imaging element, image display device, and compound
WO2022168742A1 (en) Coloring composition, film, optical filter, solid-state imaging element, image display device, and compound
WO2024057999A1 (en) Coloring composition, cured film, color filter, display device and method for producing cured film
TW202413541A (en) Coloring composition, hardened film, color filter, display device and method for manufacturing hardened film
JP7389900B2 (en) Magenta photosensitive resin composition, film, color filter, solid-state imaging device, and image display device
WO2024057998A1 (en) Composition, film, optical filter, solid-state imaging element, image display device, infrared sensor, camera module, compound, and infrared absorbing agent
WO2024018910A1 (en) Coloring composition, film, optical filter, solid-state imaging element, image display device and coloring agent
WO2024058001A1 (en) Coloring composition, film, optical filter, solid-state imaging element, image display device, and compound
WO2024043147A1 (en) Coloring composition, film, optical filter, solid-state imaging element and image display device
WO2024048337A1 (en) Coloring composition, film, optical filter, solid-state imaging element, and image display device
WO2024058000A1 (en) Photosensitive composition, cured film, optical filter, solid-state imaging element, infrared sensor, camera module, optical filter production method, and compound
WO2023228791A1 (en) Coloring composition, film, optical filter, solid-state imaging element and image display device
WO2024004390A1 (en) Curable composition, method for producing cured product, film, optical element, image sensor, solid-state imaging element, image display device, and radical polymerization initiator
WO2024034445A1 (en) Resin composition, film, optical filter, solid-state imaging element, and image display device
WO2024004426A1 (en) Curable composition, method for producing cured product, film, optical element, image sensor, solid-state imaging element, image display device, and radical polymerization initiator
WO2023162790A1 (en) Colored composition, film, color filter, solid imaging element, image display device, and compound
WO2024014300A1 (en) Resin composition, method for producing resin composition, pigment derivative, film, optical filter, solid-state imaging element, and image display device
WO2024004425A1 (en) Curable composition, method for producing cured product, film, optical element, image sensor, solid-state imaging element, image display device, and radical polymerization initiator
WO2024010025A1 (en) Coloring composition, film, color filter, solid-state imaging element, image display device, and compound
WO2024004619A1 (en) Curable composition, method for producing cured product, film, optical element, image sensor, solid-state imaging element, image display device, and radical polymerization initiator
WO2024018941A1 (en) Resin composition, membrane, optical filter, solid-state imaging device, image display device, optical sensor, and camera module

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23865354

Country of ref document: EP

Kind code of ref document: A1