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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
• • 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
  • C08F4/00—Polymerisation catalysts
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing 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
  • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
  • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • 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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
  • H10F39/80—Constructional details of image sensors
  • H10F39/805—Coatings
  • H10F39/8053—Colour filters

Definitions

• the present invention relates to a curable composition containing a photopolymerization initiator and a radically polymerizable compound.
• the present invention also relates to a pixel manufacturing method, a film, an optical filter, a solid-state imaging device, and an image display device using the curable composition.
• Curable compositions containing a photopolymerization initiator and a radically polymerizable compound can be polymerized and cured by exposure to light, and are therefore used in optical filters, photocurable inks, photosensitive printing plates, various photoresists, etc.
• Patent Document 1 describes the formation of blue pixels in a color filter using a curable composition containing a blue pigment, a photopolymerization initiator, and a radically polymerizable compound containing a polyfunctional urethane acrylate compound.
• the present inventors conducted extensive research into the curable composition disclosed in Patent Document 1 and found that when this curable composition is used to form pixels by photolithography, the resulting pixels are prone to cracks and chipping. Furthermore, they found that the line width of the resulting pixels is prone to change due to fluctuations in the exposure wavelength during exposure, and that the sensitivity of the curable composition varies greatly with fluctuations in the exposure wavelength.
• the object of the present invention is therefore to provide a curable composition that can form pixels while suppressing the occurrence of cracks and chipping, and can suppress variations in the line width of the resulting pixels even if the exposure wavelength during exposure varies.
• the present invention also provides a pixel manufacturing method, a film, an optical filter, a solid-state imaging device, and an image display device.
• the present invention provides the following.
• a color material A photopolymerization initiator; A radical polymerizable compound, A resin,
• the photopolymerization initiator contains a compound represented by formula (1) or formula (2), a curable composition comprising a polyfunctional urethane (meth)acrylate compound;
• n, p, and q each independently represent 0 or 1.
• X1 and X2 each independently represent a divalent linking group containing at least one ring selected from the group consisting of an aromatic ring and a heterocycle;
• R 1 represents a hydrogen atom, a halogen atom, a nitro group or an acyl group;
• R 11 to R 13 each independently represent an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group;
• L 1 to L 3 each independently represent a single bond or a divalent linking group;
• R 21 to R 26 each independently represent a hydrogen atom or a monovalent organic group;
• L 11 to L 13 each independently represent -(CR L1 R L2 ) m -,
• R L1 and R L2 each independently represent a hydrogen atom or a monovalent organic group, and
• m represents an integer of 1 to 4.
• ⁇ 2> The curable composition according to ⁇ 1>, in which the content of the coloring material in the total solid content of the curable composition is 55 mass% or more.
• ⁇ 3> The curable composition according to ⁇ 1> or ⁇ 2>, in which the polyfunctional urethane (meth)acrylate compound has an ethylenically unsaturated bond-containing group value of 7 mmol/g or more.
• ⁇ 4> The curable composition according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the polyfunctional urethane (meth)acrylate compound in the total solid content of the curable composition is 0.1 to 7 mass %.
• ⁇ 5> The curable composition according to any one of ⁇ 1> to ⁇ 4>, wherein the content of the polyfunctional urethane (meth)acrylate compound is 10 to 300 parts by mass per 100 parts by mass of the compound represented by Formula (1) or Formula (2).
• ⁇ 6> The curable composition according to any one of ⁇ 1> to ⁇ 5>, wherein the polyfunctional urethane (meth)acrylate compound is a compound having an isocyanuric ring structure.
• the resin includes a resin having a graft chain.
• X 1 in the formula (1) and X 2 in the formula (2) are each independently a group represented by any one of formulas (X-1) to (X-14).
• * represents a bond.
• Ar X1 represents an arylene group or a heteroarylene group;
• R X1 to R X9 each independently represent a hydrogen atom or a monovalent organic group.
• ⁇ 10> A step of forming a curable composition layer on a support using the curable composition according to any one of ⁇ 1> to ⁇ 9>; a step of patternwise exposing the curable composition layer to light having a wavelength of 150 nm to 300 nm; and developing and removing the unexposed area of the curable composition layer.
• ⁇ 11> A film obtained by curing the curable composition according to any one of ⁇ 1> to ⁇ 9>.
• ⁇ 12> An optical filter comprising the film according to ⁇ 11>.
• ⁇ 13> A solid-state imaging device comprising the film according to ⁇ 11>.
• ⁇ 14> An image display device comprising the film according to ⁇ 11>.
• the present invention can provide a curable composition that can form pixels while suppressing the occurrence of cracks and chipping, and can suppress variations in the line width of the resulting pixels even if the exposure wavelength during exposure varies.
• the present invention can also provide a pixel manufacturing method, a film, an optical filter, a solid-state imaging device, and an image display device.
• alkyl group encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
• exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
• Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, active rays or radiation such as electron beams.
• (meth)acrylate refers to both or either of acrylate and methacrylate
• (meth)acrylic refers to both or either of acrylic and methacrylic
• (meth)acryloyl refers to both or either of acryloyl and methacryloyl.
• Me 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 values calculated as polystyrene standards measured by GPC (gel permeation chromatography).
• the total solids content refers to the total mass of all components of the composition excluding the solvent.
• a pigment means a coloring material that is difficult to dissolve in a solvent.
• the term "process” refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved.
• the curable composition of the present invention comprises Color material and A photopolymerization initiator; A radical polymerizable compound, A resin,
• the photopolymerization initiator contains a compound represented by formula (1) or formula (2),
• the radical polymerizable compound is characterized by including a polyfunctional urethane (meth)acrylate compound.
• the curable composition of the present invention when pixels are formed by photolithography, the occurrence of cracks and chipping can be suppressed and pixels can be formed.
• the heating temperature during film formation is increased, the occurrence of cracks can be suppressed.
• the exposure wavelength during exposure varies, the variation in the line width of the resulting pixels can be suppressed.
• the reason for obtaining such effects is presumed to be as follows. It is presumed that the multifunctional urethane (meth)acrylate compound has high cohesive strength and flexible intermolecular interactions due to its structure, and therefore can promote the hardening of the acrylic portion (the hardening reaction of the (meth)acryloyl group).
• the compound represented by formula (1) or formula (2) is highly lipophilic due to the presence of an alicyclic group, and is presumed to be able to be dispersed and mixed almost uniformly even when combined with various materials having different hydrophilicity or lipophilicity to form a composition, and is presumed to be able to easily interact with a polyfunctional urethane (meth)acrylate compound and to further promote the curing of the polyfunctional urethane (meth)acrylate compound. Therefore, it is presumed that the curable composition of the exposed part can be sufficiently cured during exposure, and a film having high film strength and excellent flexibility can be formed.
• the edge of the exposed part can be prevented from being removed by the developer during development, and pixels with reduced chipping can be formed. Furthermore, even if the film is heated at a high temperature (e.g., 250°C or higher) during film formation, the film has high strength and excellent flexibility, so it is presumed that the occurrence of cracks due to the heat treatment can be suppressed. It is presumed that for these reasons, the occurrence of cracks and chips is suppressed and pixels can be formed.
• a high temperature e.g. 250°C or higher
• the radical polymerizable compound such as the polyfunctional urethane (meth)acrylate compound can be cured almost uniformly and sufficiently during exposure, and a crosslinked structure derived from the radical polymerizable compound can be formed almost uniformly in the film. For this reason, it is presumed that excessive penetration of the developer into the film in the exposed area during development can be suppressed.
• this crosslinked structure also has urethane bonds derived from the polyfunctional urethane (meth)acrylate compound, it is presumed that the synergistic effect of hydrogen bonds due to the urethane bonds can further suppress the penetration of the developer into the film in the exposed area during development, and the film in the exposed area can be suppressed from being developed and removed. For these reasons, it is presumed that the variation in the line width of the obtained pixels can be suppressed even if the exposure wavelength during exposure fluctuates.
• the curable composition of the present invention is preferably used as a curable composition for optical filters.
• optical filters include color filters, near-infrared transmission filters, and near-infrared cut filters, and color filters are preferred.
• An example of a color filter is a filter having colored pixels that transmit light of a specific wavelength.
• the colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels, with red pixels being more preferable.
• the colored pixels of the color filter can be formed using a curable composition that contains a chromatic colorant.
• the maximum absorption wavelength of the near-infrared cut filter is preferably in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm.
• the transmittance of the near-infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
• the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.
• the ratio of absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to absorbance A550 at a wavelength of 550 nm is preferably 20 to 500, more preferably 50 to 500, even more preferably 70 to 450, and particularly preferably 100 to 400.
• the near-infrared cut filter can be formed using a curable composition containing a near-infrared absorbing colorant.
• the near-infrared transmission filter is a filter that transmits at least a part of the near-infrared light.
• the near-infrared transmission filter is preferably a filter that blocks at least a part of the visible light and transmits at least a part of the near-infrared light.
• a filter that satisfies the spectral characteristics of a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1300 nm is preferably mentioned.
• the near-infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (5).
• the curable composition of the present invention can also be used as a light-shielding film.
• the solids concentration of the curable composition of the present invention is preferably 5 to 30% by mass.
• the lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more.
• the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
• the curable composition of the present invention contains a coloring material.
• the coloring material include a white coloring material, a black coloring material, a chromatic coloring material, and a near-infrared absorbing coloring material.
• the white coloring material includes not only pure white coloring materials, but also light gray coloring materials close to white (e.g., grayish white, light gray, etc.).
• the coloring material may be a pigment or a dye.
• a pigment and a dye may be used in combination.
• the pigment may be either an inorganic pigment or an organic pigment, but from the standpoint of a wide range of color variations, ease of dispersion, safety, etc., it is preferable that the pigment is an organic pigment.
• the coloring material preferably contains a pigment.
• the average primary particle diameter of the pigment is preferably 1 to 200 nm.
• the lower limit is preferably 5 nm or more, and 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 the pigment can be determined from a photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment.
• the crystallite size of the pigment determined from the half-width of a peak derived from any crystal plane in the X-ray diffraction spectrum when CuK ⁇ radiation is used as the X-ray source, is preferably 0.1 to 100 nm, more preferably 0.5 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 can be measured according to DIN 66131: determination of the specific surface area of solids by gas adsorption according to the BET (Brunauer, Emmett and Teller) method.
• the chromatic coloring materials include coloring materials having a maximum absorption wavelength in the wavelength range of 400 to 700 nm, such as green coloring materials, red coloring materials, yellow coloring materials, purple coloring materials, blue coloring materials, and orange coloring materials.
• the red colorant may be a diketopyrrolopyrrole compound, anthraquinone compound, an azo compound, a naphthol compound, an azomethine compound, a xanthene compound, a quinacridone compound, a perylene compound, or a thioindigo compound, preferably a diketopyrrolopyrrole compound, an anthraquinone compound, or an azo compound, more preferably a diketopyrrolopyrrole compound.
• the red colorant is preferably a pigment (red pigment), more preferably a diketopyrrolopyrrole pigment.
• red colorant a compound described in paragraph 0034 of International Publication No. 2022/085485 and a brominated diketopyrrolopyrrole compound described in JP-A-2020-085947 can also be used.
• Green colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred.
• the green colorant is preferably a pigment (green pigment), and more preferably a phthalocyanine pigment.
• green colorants include green pigments such as C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66.
• halogenated zinc phthalocyanine pigments having an average 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 can also be used as green colorants.
• Specific examples include compounds described in WO 2015/118720.
• compounds described in paragraph 0029 of WO 2022/085485, aluminum phthalocyanine compounds described in JP 2020-070426 A, and diarylmethane compounds described in JP 2020-504758 A can also be used as green colorants.
• Preferred green colorants are C.I. Pigment Green 7, 36, 58, 62, and 63.
• Orange colorants include diketopyrrolopyrrole compounds and azo compounds.
• the orange colorant is preferably a pigment (orange pigment).
• Specific examples of orange colorants include orange pigments such as C.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, and 73.
• an azobarbituric acid nickel complex having the following structure can also be used.
• the compounds described in paragraphs 0031 to 0033 of WO 2022/085485, the methine dyes described in JP 2019-073695 A, and the methine dyes described in JP 2019-073696 A can be used.
• purple colorants examples include oxazine compounds, quinacridone compounds, perylene compounds, and indigo compounds, with oxazine compounds being preferred.
• the purple colorant is preferably a pigment (purple pigment).
• Specific examples of purple colorants include purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.
• blue coloring materials examples include phthalocyanine compounds and squarylium compounds, and phthalocyanine compounds are preferred.
• the blue coloring material is preferably a pigment (blue pigment).
• blue coloring materials include blue pigments such as C.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, and 88.
• Aluminum phthalocyanine compounds having phosphorus atoms can also be used as blue coloring materials. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A No. 2012-247591 and paragraph 0047 of JP-A No. 2011-157478.
• Dyes can also be used as chromatic colorants.
• the dyes There are no particular limitations on the dyes, and any known dyes can be used. Examples include pyrazole azo, anilino azo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyrromethene dyes.
• a dye polymer can also be used as a chromatic colorant.
• the dye polymer is preferably a dye dissolved in a solvent.
• the dye polymer may form particles. When the dye polymer is a particle, it is usually used in a state of being dispersed in a solvent.
• a particulate dye polymer can be obtained, for example, by emulsion polymerization, and examples of the compound and manufacturing method described in JP-A-2015-214682 include the compound and manufacturing method described in JP-A-2015-214682.
• the dye polymer has two or more dye structures in one molecule, and preferably has three or more dye structures. There is no particular limit to the upper limit, but it can be 100 or less.
• the multiple dye structures in one molecule may be the same dye structure or different dye structures.
• the weight average molecular weight (Mw) of the dye polymer is preferably 2000 to 50000.
• the lower limit is more preferably 3000 or more, and even more preferably 6000 or more.
• the upper limit is more preferably 30000 or less, and even more preferably 20000 or less.
• the dye multimer may be a compound described in JP2011-213925A, JP2013-041097A, JP2015-028144A, JP2015-030742A, WO2016/031442, etc.
• chromatic colorants there may be mentioned a triarylmethane dye polymer described in Korean Patent Publication No. 10-2020-0028160, a xanthene compound described in JP 2020-117638 A, a phthalocyanine compound described in WO 2020/174991 A, an isoindoline compound or a salt thereof described in JP 2020-160279 A, a compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069442 A, a compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069730 A, a compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069070 A, Compounds represented by formula 1 described in Korean Patent Publication No.
• 10-2020-0069067 compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069062, halogenated zinc phthalocyanine pigments described in Japanese Patent No. 6809649, isoindoline compounds described in JP-A-2020-180176, phenothiazine compounds described in JP-A-2021-187913, halogenated zinc phthalocyanines described in WO 2022/004261, and halogenated zinc phthalocyanines described in WO 2021/250883 can be used.
• the chromatic colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, may be used in the rod-shaped structure, or may be used in both structures.
• chromatic colorants quinophthalone compounds represented by formula 1 in Korean Patent Publication No. 10-2020-0030759, polymer dyes described in Korean Patent Publication No. 10-2020-0061793, chromatic colorants described in JP-A-2022-029701, isoindoline compounds described in WO 2022/014635, aluminum phthalocyanine compounds described in WO 2022/024926, compounds described in JP-A-2022-045895, and compounds described in WO 2022/050051.
• Two or more chromatic coloring materials may be used in combination.
• the combination of two or more chromatic coloring materials may form a black color. Examples of such combinations include the following embodiments (1) to (7).
• the curable composition of the present invention can be preferably used as a curable composition for forming a near-infrared transmission filter.
• An embodiment containing a red color material, a blue color material, a yellow color material, and a purple color material (3) An embodiment containing a red color material, a blue color material, a yellow color material, and a purple color material. (4) An embodiment containing a red color material, a blue color material, a yellow color material, a purple color material, and a green color material. (5) An embodiment containing a red color material, a blue color material, a yellow color material, and a green color material. (6) An embodiment containing a red color material, a blue color material, and a green color material. (7) An embodiment containing a yellow coloring material and a purple coloring material.
• the white coloring material examples include inorganic pigments such as 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, and zinc sulfide.
• the white coloring material can be the white pigment described in paragraphs 0040 to 0043 of WO 2022/085485.
• the black coloring material is not particularly limited, and any known material can be used.
• the black coloring material may be an inorganic black coloring material or an organic black coloring material.
• the black coloring material is preferably a pigment.
• the black coloring material means a coloring material that exhibits absorption over the entire wavelength range of 400 to 700 nm.
• inorganic black colorants include carbon black, titanium black, graphite, etc., with carbon black and titanium black being preferred, and titanium black being more preferred.
• Titanium black is black particles containing titanium atoms, and low-order titanium oxide and titanium oxynitride are preferred.
• As titanium black the titanium black described in paragraph 0044 of WO 2022/085485 can be used.
• organic black colorants examples include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred.
• organic black colorant the compounds described in paragraph number 0166 of International Publication No. 2022/065215 can be used.
• perylene black Liogen Black FK4280, etc.
• perylene black described in paragraphs 0016 to 0020 of JP-A-2017-226821
• black azo pigments described in JP-A-2022-121935 may also be used.
• the near-infrared absorbing colorant is preferably a compound having a maximum absorption wavelength longer than 700 nm.
• the near-infrared absorbing colorant is preferably a compound having a maximum absorption wavelength in the range of more than 700 nm to 1800 nm, more preferably a compound having a maximum absorption wavelength in the range of more than 700 nm to 1400 nm, even more preferably a compound having a maximum absorption wavelength in the range of more than 700 nm to 1200 nm, and particularly preferably a compound having a maximum absorption wavelength in the range of more than 700 nm to 1000 nm.
• the ratio A 1 /A 2 between the absorbance A 1 at a wavelength of 500 nm of the near-infrared absorbing colorant and the absorbance A 2 at the maximum absorption wavelength is preferably 0.08 or less, more preferably 0.04 or less.
• the near-infrared absorbing colorant is preferably a pigment, more preferably an organic pigment.
• Near-infrared absorbing colorants include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, etc. Specific examples of these include the compounds described in paragraph 0114 of WO 2022/065215.
• Examples of infrared absorbing colorants include the compound described in paragraph 0121 of WO 2022/065215, the squarylium compound described in JP 2020-075959 A, the copper complex described in Korean Patent Publication No. 10-2019-0135217 A, the croconic acid compound described in JP 2021-195515 A, the near infrared absorbing dye described in JP 2022-022070 A, and the near infrared absorbing dye described in WO 2019 It is also possible to use the croconium compounds described in JP 2019-127549 A, the compounds described in WO 2022/059619 A, the compounds described in JP 2022-151682 A, the squarylium compounds described in JP 2022-188858 A, the compounds described in JP 2022-184710 A, and the compounds described in JP 2022-189736 A.
• the content of the colorant in the total solid content of the curable composition is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more.
• the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.
• the pigment content in the total solid content of the curable composition is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more.
• the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.
• the pigment content in the coloring material is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass.
• the curable composition of the present invention contains a photopolymerization initiator.
• the photopolymerization initiator is preferably a photoradical polymerization initiator.
• a compound represented by formula (1) or (2) is used as a photopolymerization initiator.
• the compound represented by formula (1) or (2) is also referred to as a specific oxime ester compound.
• n, p, and q each independently represent 0 or 1.
• X1 and X2 each independently represent a divalent linking group containing at least one ring selected from the group consisting of an aromatic ring and a heterocycle;
• R 1 represents a hydrogen atom, a halogen atom, a nitro group or an acyl group;
• R 11 to R 13 each independently represent an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group;
• L 1 to L 3 each independently represent a single bond or a divalent linking group;
• R 21 to R 26 each independently represent a hydrogen atom or a monovalent organic group;
• L 11 to L 13 each independently represent -(CR L1 R L2 ) m -,
• R L1 and R L2 each independently represent a hydrogen atom or a monovalent organic group, and
• m represents an integer of 1 to 4.
• n 0 or 1
• p and q each independently represent 0 or 1, and are preferably 0.
• X1 in formula (1) and X2 in formula (2) each independently represent a divalent linking group containing at least one ring selected from the group consisting of an aromatic ring and a heterocyclic ring.
• Examples of the divalent linking group represented by X 1 in formula (1) and X 2 in formula (2) include a divalent aromatic ring group, a divalent heterocyclic group, a divalent group in which two or more aromatic rings are bonded via a single bond or a linking group, a divalent group in which two or more heterocycles are bonded via a single bond or a linking group, and a divalent group in which an aromatic ring and a heterocycle are bonded via a single bond or a linking group.
• Examples of the linking group that bonds the above-mentioned aromatic rings, heterocyclic groups, or aromatic rings and heterocycles include -CH 2 -, -O-, -CO-, -S-, -NR x -, and groups combining these.
• R x represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
• X 1 in formula (1) and X 2 in formula (2) are each preferably independently a group represented by any one of formulas (X-1) to (X-14), and more preferably a group represented by formula (X-2), formula (X-4), formula (X-8) or formula (X-14).
• * represents a bond.
• Ar X1 represents an arylene group or a heteroarylene group; R X1 to R X9 each independently represent a hydrogen atom or a monovalent organic group.
• the monovalent organic group represented by R X1 to R X9 includes an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group.
• the number of carbon atoms in the alkyl group is preferably 1 to 15, and more preferably 1 to 10.
• the alkyl group may be linear, branched, or cyclic.
• the alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heterocyclic group.
• the number of carbon atoms in the alkenyl group is preferably 2 to 15, and more preferably 2 to 10.
• the alkenyl group may be linear, branched, or cyclic.
• the alkenyl group may have a substituent.
• the substituent include a halogen atom, an aryl group, and a heterocyclic group.
• the number of carbon atoms in the alkynyl group is preferably 2 to 15, and more preferably 2 to 10.
• the alkynyl group may be linear, branched, or cyclic.
• the alkynyl group may have a substituent.
• the substituent include a halogen atom, an aryl group, and a heterocyclic group.
• the number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6.
• the aryl group may have a substituent.
• Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group.
• the heterocyclic group is preferably a 5- or 6-membered ring.
• the heteroatoms contained in the heterocyclic group are preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
• the number of heteroatoms contained in the heterocyclic group is preferably 1 to 3.
• the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
• Ar X1 represents an arylene group or a heteroarylene group, and is preferably an arylene group.
• the arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, further preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms.
• the heteroarylene group is preferably a 5- or 6-membered ring.
• the heteroatoms contained in the heteroarylene group are preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
• the number of heteroatoms contained in the heteroarylene group is preferably 1 to 3.
• R 1 in formula (1) represents a hydrogen atom, a halogen atom, a nitro group or an acyl group, preferably a nitro group or an acyl group, and more preferably an acyl group.
• the halogen atom represented by R 1 includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• the acyl group represented by R 1 is preferably a group represented by -C(O)-R 101.
• R 101 represents an aryl group or a heterocyclic group, and is preferably an aryl group.
• the number of carbon atoms in the aryl group represented by R 101 is preferably 6 to 20, and more preferably 6 to 12.
• the aryl group may have a substituent.
• substituents include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an arylamino group, a heteroaryloxy group, a heteroarylthio group, a heteroarylamino group, a cyano group, a nitro group, a hydroxy group, a carboxy group, a halogen atom, and an acyl group.
• the heterocyclic group represented by R 101 is preferably a 5-membered or 6-membered ring.
• the heteroatoms contained in the heterocyclic group are preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
• the number of heteroatoms contained in the heterocyclic group is preferably 1 to 3.
• the heterocyclic group may have a substituent.
• substituents examples include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an arylamino group, a heteroaryloxy group, a heteroarylthio group, a heteroarylamino group, a cyano group, a nitro group, a hydroxy group, a carboxy group, a halogen atom, and an acyl group.
• R 11 in formula (1), and R 12 and R 13 in formula (2) each independently represent an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group, preferably an alkyl group or an aryl group, more preferably an alkyl group.
• the number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3.
• the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
• the alkyl group may have a substituent, but is preferably an unsubstituted alkyl group.
• the alkyl group is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group.
• the number of carbon atoms in the alkoxy group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3.
• the alkoxy group is preferably linear or branched, and more preferably linear.
• the alkoxy group may have a substituent, but is preferably unsubstituted.
• the number of carbon atoms in the aryl group and aryloxy group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6.
• the aryl group and aryloxy group may have a substituent, but are preferably unsubstituted.
• the number of carbon atoms constituting the ring of the heteroaryl group and heteroaryloxy group is preferably 1 to 15, and more preferably 1 to 10.
• the types of heteroatoms constituting the ring of the heteroaryl group and heteroaryloxy group include nitrogen atoms, oxygen atoms, and sulfur atoms.
• the number of heteroatoms constituting the ring of the heteroaryl group and heteroaryloxy group is preferably 1 to 3, and more preferably 1 to 2.
• the heteroaryl group and heteroaryloxy group may be a single ring or a condensed ring.
• the heteroaryl group and heteroaryloxy group may have a substituent.
• L 1 in formula (1), and L 2 and L 3 in formula (2) each independently represent a single bond or a divalent linking group, and are preferably divalent linking groups.
• the divalent linking groups represented by L 1 to L 3 are preferably alkylene groups.
• the number of carbon atoms in the alkylene group is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 2.
• L 1 to L 3 are preferably methylene groups or ethylene groups, and more preferably ethylene groups.
• R 21 and R 22 in formula (1) and R 23 to R 26 in formula (2) each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.
• Examples of the monovalent organic group represented by R 21 to R 26 include an alkyl group and an aryl group, and preferably an alkyl group.
• L 11 and R 22 in formula (1), and L 12 and L 13 in formula (2) each independently represent -(CR L1 R L2 ) m -
• R L1 and R L2 each independently represent a hydrogen atom or a monovalent organic group
• m represents an integer of 1 to 4.
• the monovalent organic group represented by R L1 and R L2 includes an alkyl group and an aryl group, and is preferably an alkyl group.
• R L1 and R L2 are preferably hydrogen atoms.
• m represents an integer of 1 to 4, preferably 3 or 4, and more preferably 3.
• specific examples of specific oxime ester compounds include the compounds shown below, the compounds described in paragraphs 0092 to 0096 of JP2012-113104A, and the compounds described in paragraph 0041 of JP2012-189997A.
• the specific oxime ester compound may be a commercially available product.
• Commercially available specific oxime ester compounds include TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, TR-PBG-345, TR-PBG-346, TR-PBG-358, TR-PBG-365, TR-PBG-380, TR-PBG-610, TR-PBG-A, and TR-PBG-B (manufactured by TRONLY).
• the curable composition of the present invention may further contain a photopolymerization initiator other than the specific oxime ester compound described above (hereinafter, also referred to as other photopolymerization initiator).
• a photopolymerization initiator other than the specific oxime ester compound described above hereinafter, also referred to as other photopolymerization initiator.
• the content of the other photopolymerization initiator is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the specific oxime ester compound.
• the upper limit is preferably 300 parts by mass or less, more preferably 200 parts by mass or less.
• the lower limit is preferably 20 parts by mass or more, more preferably 50 parts by mass or more.
• photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, etc.
• halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
• acylphosphine compounds e.g., acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, etc.
• the other photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a hexaarylbiimidazole compound, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, or a 3-aryl substituted coumarin compound, more preferably an oxime compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, or an acylphosphine compound, further preferably an oxime compound, an acylphosphine compound, or an ⁇ -aminoketone compound, and still more
• photopolymerization initiators include compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A, compounds described in Japanese Patent No. 6301489 A, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol. 19, No.
• hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.
• ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (all manufactured by BASF), etc.
• Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF), etc.
• Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (all manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (all manufactured by BASF), etc.
• Examples of oxime compounds include the compound described in paragraph 0142 of WO 2022/085485, the compound described in Japanese Patent No. 5,430,746, the compound described in Japanese Patent No. 5,647,738, the compound represented by general formula (1) and the compounds described in paragraphs 0022 to 0024 of JP 2021-173858 A, the compound represented by general formula (1) and the compounds described in paragraphs 0117 to 0120 of JP 2021-170089 A, and the like.
• oxime compound examples 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 that can be used include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, oxime compounds having a fluorine atom, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, oxime compounds in which a substituent having a hydroxyl group is bonded to a carbazole skeleton, and compounds described in paragraphs 0143 to 0149 of WO 2022/085485.
• X 1a represents a divalent linking group containing at least one ring selected from the group consisting of an aromatic ring and a heterocycle;
• R 1a represents a hydrogen atom or an acyl group;
• R2a represents an alkyl group or an aryl group;
• R 3a and R 4a each independently represent a hydrogen atom or an alkyl group;
• Alk 1 and Alk 2 each independently represent an alkyl group;
• n represents 0 or 1.
• Examples of the divalent linking group represented by X 1a in formula (OX-1) include a divalent aromatic ring group, a divalent heterocyclic group, a divalent group in which two or more aromatic rings are bonded via a single bond or a linking group, a divalent group in which two or more heterocycles are bonded via a single bond or a linking group, and a divalent group in which an aromatic ring and a heterocycle are bonded via a single bond or a linking group.
• Examples of the linking group that bonds the above-mentioned aromatic rings, heterocyclic groups, or aromatic rings and heterocycles include -CH 2 -, -O-, -CO-, -S-, -NR x1 -, and groups combining these.
• R x1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
• Specific examples of the divalent linking group represented by X 1a include groups represented by any of formulas (X-1) to (X-14) shown as specific examples of the divalent linking group represented by X 1 in formula (1) and X 2 in formula (2) above.
• a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6) or formula (X-8) is preferred, and a group represented by formula (X-2) or formula (X-6) is more preferred.
• R 1a in formula (OX-1) represents a hydrogen atom or an acyl group, and is preferably an acyl group.
• the preferred range of the acyl group is the same as that of the acyl group represented by R 1 in formula (1).
• R 2a in formula (OX-1) represents an alkyl group or an aryl group, and is preferably an alkyl group because the reactivity of the generated radical is high.
• the number of carbon atoms of the alkyl group represented by R 2a is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3.
• the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
• the alkyl group may have a substituent, but is preferably an unsubstituted alkyl group.
• the alkyl group represented by R 2a is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group.
• the number of carbon atoms in the aryl group represented by R 2a is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6.
• the aryl group may have a substituent, but is preferably an unsubstituted aryl group.
• R 3a and R 4a each independently represent a hydrogen atom or an alkyl group, and preferably a hydrogen atom.
• the number of carbon atoms in the alkyl group represented by R 3a and R 4a is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3.
• the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
• the alkyl group may have a substituent, but is preferably an unsubstituted alkyl group.
• Alk 1 and Alk 2 each independently represent an alkyl group.
• the number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3.
• the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
• the alkyl group may have a substituent, but is preferably an unsubstituted alkyl group.
• n 0 or 1, and is preferably 0.
• Another photopolymerization initiator that can be used is a compound represented by formula (OX-2).
• R 1b and R 2b each independently represent a substituent
• R 3b to R 7b each independently represent a hydrogen atom or a substituent
• Ar 1b represents an aromatic ring group or a heterocyclic group which may have a substituent
• n represents 0 or 1.
• Examples of the substituent represented by R 1b and R 2b include an alkyl group and an aryl group, and an alkyl group is preferable.
• the number of carbon atoms of the alkyl group is preferably 1 to 15, and more preferably 1 to 10.
• the alkyl group may be linear, branched, or cyclic.
• the alkyl group may have a substituent.
• Examples of the substituent include a halogen atom, an aryl group, an alkenyl group, an alkynyl group, and a heterocyclic group.
• the number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6.
• the aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group.
• R 3b to R 7b include a halogen atom, an alkyl group and an aryl group, the alkyl group and the aryl group being as described above.
• R 3b to R 7b are preferably hydrogen atoms.
• Ar 1b represents an aromatic ring group or a heterocyclic group which may have a substituent, and Ar 1b is preferably an aromatic ring group which may have a substituent.
• the aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.
• the substituent includes a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a nitro group, and an acyl group, and is preferably an acyl group.
• the preferred range of the acyl group is the same as that of the acyl group represented by R 1 in formula (1).
• Another photopolymerization initiator that can be used is a compound represented by formula (OX-3).
• Ar 1c represents a (k+m+1)-valent aromatic ring group or a (k+m+1)-valent heterocyclic group
• Ar 2c represents a (k+2)-valent aromatic ring group or a (k+2)-valent heterocyclic group
• R 1c to R 3c each independently represent a substituent
• L 1c represents a single bond or CR 11c R 12c
• R 11c and R 12c each independently represent a hydrogen atom, an alkyl group, or an aryl group
• X 1c represents -O- or -S-
• k represents 0 or 1
• m represents an integer of 0 to 4
• n represents 0 or 1.
• Examples of the substituent represented by R 1c and R 2c include an alkyl group and an aryl group, and an alkyl group is preferable.
• the number of carbon atoms of the alkyl group is preferably 1 to 15, and more preferably 1 to 10.
• the alkyl group may be linear, branched, or cyclic.
• the alkyl group may have a substituent.
• Examples of the substituent include a halogen atom, an aryl group, an alkenyl group, an alkynyl group, and a heterocyclic group.
• the number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6.
• the aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group.
• the substituent represented by R3c includes a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group, and is preferably an acyl group.
• the preferred range of the acyl group is the same as that of the acyl group represented by R1 in formula (1).
• Ar 1c represents a (k+m+1)-valent aromatic ring group or a (k+m+1)-valent heterocyclic group, and is preferably a (k+m+1)-valent aromatic ring group.
• the aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.
• Ar2c represents a (k+2)-valent aromatic ring group or a (k+2)-valent heterocyclic group, and is preferably a (k+2)-valent aromatic ring group.
• the aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.
• k represents 0 or 1, and is preferably 0.
• n represents an integer from 0 to 4, preferably 0 or 1, and more preferably 1.
• a bifunctional or trifunctional or higher functional photopolymerization initiator may be used as another photopolymerization initiator.
• Specific examples of bifunctional or trifunctional or higher functional photopolymerization initiators include the compounds described in paragraph 0148 of WO 2022/065215.
• the content of the photopolymerization initiator in the total solid content of the curable composition is preferably 1 to 10 mass%.
• the lower limit is preferably 1.5 mass% or more, and more preferably 2 mass% or more.
• the upper limit is preferably 9 mass% or less, and more preferably 8 mass% or less.
• the content of the specific oxime ester compound in the total solid content of the curable composition is preferably 1 to 10 mass%.
• the lower limit is preferably 1.5 mass% or more, and more preferably 2 mass% or more.
• the upper limit is preferably 9 mass% or less, and more preferably 8 mass% or less.
• the content of the specific oxime ester compound in the photopolymerization initiator used in the curable composition of the present invention is preferably from 10 to 100 mass%, more preferably from 30 to 100 mass%, and even more preferably from 50 to 100 mass%. It is also preferred that the photopolymerization initiator used in the curable composition of the present invention is substantially the specific oxime ester compound alone. According to this embodiment, the effect of the present invention is more significantly exhibited.
• the case where the photopolymerization initiator is substantially the specific oxime ester compound alone means that the content of the specific oxime ester compound in the photopolymerization initiator is 99% by mass or more, preferably 99.9% by mass or more, and more preferably the specific oxime ester compound alone.
• the curable composition of the present invention contains a radical polymerizable compound.
• the radical polymerizable compound may be a compound having an ethylenically unsaturated bond-containing group.
• the ethylenically unsaturated bond-containing group may be a vinyl group, a (meth)allyl group, a (meth)acryloyl group, or the like.
• the molecular weight of the radically polymerizable compound (weight average molecular weight when it is difficult to calculate the molecular weight from the structural formula) is preferably less than 5,000, more preferably less than 3,000, and even more preferably less than 2,500.
• the lower limit is preferably 300 or more.
• Polyfunctional urethane (meth)acrylate compound In the curable composition of the present invention, a polyfunctional urethane (meth)acrylate compound is used as the radically polymerizable compound.
• Multifunctional urethane (meth)acrylate compounds can be obtained, for example, by reacting a (meth)acrylate having a hydroxyl group with a multifunctional isocyanate, or by reacting a (meth)acrylate having an isocyanate group with a multifunctional alcohol.
• Examples of the (meth)acrylate having a hydroxy group include compounds having one (meth)acryloyl group and one hydroxy group in one molecule, such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; Compounds having two (meth)acryloyl groups and one hydroxy group in one molecule, such as trimethylolpropane di(meth)acrylate and glycerol di(meth)acrylate; Compounds having three or more (meth)acryloyl groups and one hydroxy group in one molecule, such as pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, and dipentaerythri
• Aromatic diisocyanates include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether
• These include tert-butyl diisocyanate, 4,4',4"-triphenylmethane triisocyanate, ⁇ , ⁇ '-diisocyanate-1,3-dimethylbenzene (also known as m-xylylene diisocyanate), ⁇ , ⁇ '-diisocyanate-1,4-dimethylbenzene (also known as p-
• Aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.
• biuret compounds examples include biuret compounds of hexamethylene diisocyanate (Sumidur N-75, manufactured by Sumika Bayer Urethane Co., Ltd.; Duranate 24A-90CX, manufactured by Asahi Kasei Corporation).
• Examples of the nurate form include a nurate form of hexamethylene diisocyanate (Sumidur N-3300, manufactured by Sumika Bayer Urethane Co., Ltd.), a nurate form of isophorone diisocyanate (Desmodur Z-4370, manufactured by Sumika Bayer Urethane Co., Ltd.), and a nurate form of tolylene diisocyanate.
• the nurate form is preferably a nurate form having an isocyanuric ring represented by formula (Is-1).
• a multifunctional urethane (meth)acrylate compound having a structure in which the (meth)acryloyl group spreads three-dimensionally can be obtained.
• the crosslinking efficiency can be improved and the strength of the film can be further increased.
• the occurrence of cracks and the occurrence of missing pixels can be more effectively suppressed.
• R is1 to R is3 each independently represent a group having an isocyanate group.
• the adduct may be a bifunctional or higher isocyanate compound obtained by reacting the aromatic isocyanate, aliphatic isocyanate, or alicyclic isocyanate with a polyfunctional alcohol.
• examples include a hexamethylene diisocyanate adduct of trimethylolpropane (Takenate D-160N, manufactured by Mitsui Chemicals, Inc.), a tolylene diisocyanate adduct of trimethylolpropane (Takenate D-102, manufactured by Mitsui Chemicals, Inc.), a xylylene diisocyanate adduct of trimethylolpropane (Takenate D-110N, manufactured by Mitsui Chemicals, Inc.), and an isophorone diisocyanate adduct of trimethylolpropane (Takenate D-140N, manufactured by Mitsui Chemicals, Inc.).
• the biuret form, nurate form, and adduct form are obtained as a mixture, but the nurate form, which contains a high content of isocyanuric rings, can be obtained by heating a polyfunctional isocyanate with a carboxylate such as potassium octylate or potassium acetate, a diazabicycloundecene carboxylate, a diazabicycloundecene phenolate, an amine, or a quaternary ammonium salt.
• a carboxylate such as potassium octylate or potassium acetate
• a diazabicycloundecene carboxylate such as potassium octylate or potassium acetate
• diazabicycloundecene carboxylate such as potassium octylate or potassium acetate
• diazabicycloundecene carboxylate such as potassium octylate or potassium acetate
• diazabicycloundecene carboxylate such as potassium
• polyfunctional alcohol examples include aliphatic or alicyclic diols such as ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohe
• Examples of the (meth)acrylates having an isocyanate group include compounds having one (meth)acryloyl group and one isocyanate group in one molecule, such as 2-methacryloyloxyethyl isocyanate (Karenz MOI, manufactured by Resonac Co., Ltd.) and 2-acryloyloxyethyl isocyanate (Karenz AOI, manufactured by Resonac Co., Ltd.); and compounds having two or more (meth)acryloyl groups and one isocyanate group in one molecule, such as 1,1-(bisacryloyloxymethyl)ethyl isocyanate (Karenz BEI, manufactured by Resonac Co., Ltd.).
• Karenz MOI 2-methacryloyloxyethyl isocyanate
• Karenz AOI 2-acryloyloxyethyl isocyanate
• Karenz BEI 1,1-(bisacryloyloxymethyl)ethyl isocyanate
• the polyfunctional urethane (meth)acrylate compound preferably has 3 or more (meth)acryloyl groups in one molecule, more preferably 6 or more, even more preferably 10 or more, and particularly preferably 12 or more.
• the upper limit of the number of (meth)acryloyl groups is preferably 20 or less.
• a polyfunctional urethane (meth)acrylate compound having three or more (meth)acryloyl groups in one molecule can be obtained, for example, by reacting a compound having two or more (meth)acryloyl groups and one hydroxyl group in one molecule with a compound having two or more isocyanate groups, or by reacting a compound having one (meth)acryloyl group and one hydroxyl group in one molecule with a compound having three or more isocyanate groups.
• the polyfunctional urethane (meth)acrylate compound may have an acid group.
• This embodiment provides the effect of excellent developability and less residue generation.
• the acid group include a carboxy group, a phosphate group, and a sulfo group, with a carboxy group being preferred.
• a polyfunctional urethane (meth)acrylate compound having an acid group can be obtained, for example, by reacting a polyfunctional urethane (meth)acrylate compound with a compound having a mercapto group and a carboxy group, or by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxy group and a hydroxy acid.
• Examples of compounds having a mercapto group and a carboxyl group include thioglycolic acid, 3-mercaptopropionic acid, and thiomalic acid.
• polyfunctional isocyanates and (meth)acrylates having hydroxyl groups include those mentioned above.
• hydroxy acids examples include hydroxy acids having one hydroxy group, such as glycolic acid, lactic acid, tartronic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, malic acid, citric acid, isocitric acid, citramalic acid, leucinic acid, ricinoleic acid, ricineraidic acid, cerebroic acid, salicylic acid, creosote acid, vanillic acid, syringic acid, mandelic acid, benzilic acid, atrolactic acid, mellitic acid, coumaric acid, ferulic acid, and sinapic acid;
• the hydroxy acids include hydroxy acids having two or more hydroxy groups, such as tartaric acid, mevalonic acid, pantoic acid, shikimic acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, orselliic acid, caffeic acid, and umbelic acid.
• Hydroxy acids obtained by reacting some of the hydroxy groups of a polyfunctional alcohol with a polybasic acid anhydride can also be used.
• polyfunctional alcohols include those mentioned above.
• the polybasic acid anhydride is not particularly limited as long as it is a compound containing one or more acid anhydride groups in the molecule.
• aliphatic dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, butylsuccinic anhydride, hexylsuccinic anhydride, octylsuccinic anhydride, dodecylsuccinic anhydride, butylmaleic anhydride, pentylmaleic anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecylmaleic anhydride, butylglutamic anhydride, hexylglutamic anhydride, heptylglutamic anhydride, octylglutamic anhydride, decylglutamic anhydride, and dodecylglutamic anhydride;
• examples of such anhydrides include alicyclic dibasic acids such as ethyl tetrahydrophthalic anhydride,
• the polyfunctional urethane (meth)acrylate compound is preferably a compound having an isocyanuric ring structure. According to this aspect, when forming pixels by photolithography, the variation in the line width of the resulting pixels can be further suppressed even if the exposure wavelength during exposure varies.
• the polyfunctional urethane (meth)acrylate compound having an isocyanuric ring structure is preferably a compound represented by formula (Is-10). According to this embodiment, in addition to the above-mentioned effects, the occurrence of cracks and pixel defects can be more effectively suppressed.
• R is11 to R is13 each independently represent a group having one or more (meth)acryloyl groups.
• the groups represented by R is11 to R is13 are preferably groups having 1 to 10 (meth)acryloyl groups, more preferably groups having 2 to 8 (meth)acryloyl groups, and even more preferably groups having 2 to 6 (meth)acryloyl groups.
• the molecular weight of the polyfunctional urethane (meth)acrylate compound is preferably less than 5,000, more preferably less than 3,000 because this can more effectively suppress the occurrence of cracks, and even more preferably less than 2,500.
• the lower limit is preferably 800 or more.
• the urethane value of the polyfunctional urethane (meth)acrylate compound is preferably 0.2 to 4 mmol/g.
• the lower limit is preferably 0.3 mmol/g or more, and more preferably 0.5 mmol/g or more, because this can further suppress the occurrence of chipping during pixel formation.
• the upper limit is preferably 3 mmol/g or less, and more preferably 2 mmol/g or less.
• the urethane value of the polyfunctional urethane (meth)acrylate compound is a value calculated by dividing the number of urethane groups contained in one molecule of the polyfunctional urethane (meth)acrylate compound by the molecular weight of the polyfunctional urethane (meth)acrylate compound.
• the upper limit is preferably 10 mmol/g or less.
• the isocyanuric ring value of the polyfunctional urethane (meth)acrylate compound is preferably 0.2 to 2 mmol/g.
• the lower limit is preferably 0.3 mmol/g or more, more preferably 0.4 mmol/g or more, and even more preferably 0.5 mmol/g or more, for the reason that when forming pixels by photolithography, the variation in the line width of the resulting pixels can be further suppressed even if the exposure wavelength during exposure fluctuates.
• the upper limit is preferably 1.5 mmol/g or less.
• the isocyanuric ring value of the polyfunctional urethane (meth)acrylate compound is a value calculated by dividing the number of isocyanuric rings contained in one molecule of the polyfunctional urethane (meth)acrylate compound by the molecular weight of the polyfunctional urethane (meth)acrylate compound.
• the acid value of the polyfunctional urethane (meth)acrylate compound is preferably 150 mg KOH/g or less, more preferably 100 mg KOH/g or less, and even more preferably 80 mg KOH/g or less.
• polyfunctional urethane (meth)acrylate compounds include the polyfunctional urethane (meth)acrylate compounds (U-1) to (U-30) synthesized in Synthesis Examples 1 to 30 in the Examples described below.
• the curable composition of the present invention may contain a radical polymerizable compound (hereinafter, also referred to as other radical polymerizable compound) other than the above-mentioned polyfunctional urethane (meth)acrylate compound.
• a radical polymerizable compound hereinafter, also referred to as other radical polymerizable compound
• the polyfunctional urethane (meth)acrylate compound in combination with the other radical polymerizable compound, the effect of obtaining a balance between the curing sensitivity and the pattern formability such as pattern defects and residues can be obtained.
• the content of the other radical polymerizable compound is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the polyfunctional urethane (meth)acrylate compound.
• the upper limit is preferably 300 parts by mass or less, more preferably 200 parts by mass or less.
• the lower limit is preferably 30 parts by mass or more, more preferably 50 parts by mass or more.
• the other radical polymerizable compound may be in any chemical form, such as a monomer, prepolymer, or oligomer, but is preferably a monomer.
• the molecular weight of the other radical polymerizable compound is preferably 100 to 2500.
• 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 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 other radical polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and even more preferably a compound containing 3 to 6 ethylenically unsaturated bond-containing groups.
• the other radical polymerizable compound is preferably a 3-15 functional (meth)acrylate compound, and more preferably a 3-6 functional (meth)acrylate compound.
• Specific examples of radical polymerizable compounds include the compounds described in paragraphs 0075 to 0083 of WO 2022/065215 and the compounds described in Taiwan Patent Application Publication No. 201832008.
• Other preferred radical polymerizable compounds include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product: KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product: KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds in which the (meth)acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues (e.g.,
• radical polymerizable compounds examples include diglycerol EO (ethylene oxide) modified (meth)acrylate (commercially available product is M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (KAYARAD HDDA, manufactured by Nippon Kayaku Co., Ltd.), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
• diglycerol EO ethylene oxide
• methacrylate commercially available product is M-460; manufactured by Toagosei Co., Ltd.
• NK Ester A-TMMT pentaerythritol tetraacrylate
• KAYARAD HDDA 1,6-hexanediol
• NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical 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 (all manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. can also be used.
• the radical polymerizable compound may be a radical polymerizable compound having a fluorene skeleton.
• the radical polymerizable compound having a fluorene skeleton is preferably a bifunctional radical polymerizable compound.
• the radical polymerizable compound having a fluorene skeleton may be a compound having a partial structure represented by the following formula (Fr).
• * represents a bond
• R f1 and R f2 each independently represent a substituent
• m and n each independently represent an integer of 0 to 5.
• m R f1s may be the same or different from each other, and two of the m R f1s may be bonded to each other to form a ring.
• n R f2s may be the same or different from each other, and two of the n R f2s may be bonded to each other to form a ring.
• R f1 and R f2 examples include a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, -OR f11 , -COR f12 , -COOR f13 , -OCOR f14 , -NR f15 R f16 , -NHCOR f17 , -CONR f18 R f19 , -NHCONR f20 R f21 , -NHCOOR f22 , -SR f23 , -SO 2 R f24 , -SO 2 OR f25 , -NHSO 2 R f26 , and -SO 2 NR f27 R f28 .
• Each of R f11 to R f28 independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
• radical polymerizable compound having a fluorene skeleton examples include compounds having the following structure: Furthermore, commercially available products of the radical polymerizable compound having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).
• the radically polymerizable compound contained in the curable composition may contain, as another radically polymerizable compound, a compound having an ethylenically unsaturated bond-containing group that was not obtained as a polyfunctional urethane (meth)acrylate compound during the synthesis of the above-mentioned polyfunctional urethane (meth)acrylate compound.
• the content of the radical polymerizable compound in the total solid content of the curable composition is preferably 0.1 to 15 mass%, more preferably 0.1 to 10 mass%, and even more preferably 0.1 to 7 mass%.
• the lower limit is preferably 0.5 mass% or more, more preferably 1 mass% or more, and even more preferably 2 mass% or more.
• the content of the polyfunctional urethane (meth)acrylate compound in the total solid content of the curable composition is preferably 0.1 to 15 mass%, more preferably 0.1 to 10 mass%, and even more preferably 0.1 to 7 mass%.
• the lower limit is preferably 1 mass% or more, and more preferably 2 mass% or more.
• the content of the polyfunctional urethane (meth)acrylate compound in the radically polymerizable compound contained in the curable composition is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and even more preferably 30 to 100% by mass.
• the radical polymerizable compound used in the curable composition of the present invention is substantially only a polyfunctional urethane (meth)acrylate compound. According to this embodiment, the effects of the present invention are more significantly exhibited.
• the radical polymerizable compound when substantially only a polyfunctional urethane (meth)acrylate compound, it means that the content of the polyfunctional urethane (meth)acrylate compound in the radical polymerizable compound is 99% by mass or more, preferably 99.9% by mass or more, and more preferably only a specific oxime ester compound.
• the content of the polyfunctional urethane (meth)acrylate compound is preferably 10 to 500 parts by mass, and more preferably 10 to 300 parts by mass, per 100 parts by mass of the specific oxime ester compound described above. If the ratio of the polyfunctional urethane (meth)acrylate compound to the specific oxime ester compound is within the above range, the effects of the present invention are more pronounced.
• the lower limit is preferably 20 parts by mass or more, and more preferably 50 parts by mass or more.
• the curable composition of the present invention may contain only one type of radical polymerizable compound, or may contain two or more types. When two or more types of radical polymerizable compounds are contained, it is preferable that the total amount thereof is within the above range.
• the curable composition of the present invention contains a resin.
• the resin is blended, for example, for dispersing pigments and the like in the curable composition or for use as a binder.
• a resin that is mainly used for dispersing pigments and the like in the curable composition is also called a dispersant.
• such uses of the resin are merely examples, and the resin can also be used for purposes other than such uses.
• the weight average molecular weight (Mw) of the resin is preferably 5,000 to 2,000,000.
• the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
• the lower limit is preferably 6,000 or more, and more preferably 7,000 or more.
• resins examples include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins.
• examples of the resin include the resins described in paragraphs 0091 to 0099 of WO 2022/065215, the blocked polyisocyanate resins described in JP 2016-222891 A, the resins described in JP 2020-122052 A, the resins described in JP 2020-111656 A, the resins described in JP 2020-139021 A, and the resins described in JP 2017-138503 A having a structural unit having a ring structure in the main chain and a biphenyl group in the side chain.
• the resin it is preferable to use a resin having an acid group.
• the acid group include a carboxy group, a phosphate 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 preferably 40 mgKOH/g or more, and more preferably 50 mgKOH/g or more.
• the upper limit is preferably 400 mgKOH/g or less, more preferably 300 mgKOH/g or less, and even more 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, and more preferably 5,000 to 50,000.
• 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 on the side chain, and more preferably contains 5 to 70 mol% of the repeating units having an acid group on the side chain out of all the repeating units of the resin.
• the upper limit of the content of repeating units having an acid group on the side chain is preferably 50 mol% or less, and more preferably 30 mol% or less.
• the lower limit of the content of repeating units having an acid group on the side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.
• the curable composition of the present invention also preferably 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 the side chain, more preferably a copolymer having a repeating unit having a basic group in the side chain and a repeating unit not having a basic group, and even more preferably a block copolymer having a repeating unit having a basic group in the side chain and a repeating unit not having a basic group.
• the 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 with basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (all manufactured by BYK-Chemie), Solsperse 11200, 13240, 13650, 13940, 24 000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Lubrizol Japan), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like.
• the resin having a basic group may be a block copolymer (B) described in paragraphs 0063 to 0112 of JP 2014-219665 A, a block copolymer A1 described in paragraphs 0046 to 0076 of JP 2018-156021 A, or a vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP 2019-184763 A, the contents of which are incorporated herein by reference.
• the curable composition of the present invention also preferably contains both a resin having an acid group and a resin having a basic group. According to this embodiment, the storage stability of the curable composition can be further improved.
• the content of the resin having a basic group is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 50 to 200 parts by mass per 100 parts by mass of the resin having an acid group.
• a resin having an aromatic carboxy group As the resin, it is also preferable to use a resin having an aromatic carboxy group.
• the aromatic carboxy group may be included in the main chain of a repeating unit, or may be included in a side chain of the repeating unit. It is preferable that the aromatic carboxy group is included in the main chain of a 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 an aromatic ring is preferably 1 to 4, and more preferably 1 to 2.
• resins having an aromatic carboxy group include the resins described in paragraphs 0082 to 0107 of WO 2021/166858.
• the resin it is also preferable to use a resin having a crosslinkable group.
• the crosslinkable group include ethylenically unsaturated bond-containing groups such as vinyl groups, (meth)allyl groups, and (meth)acryloyl groups, as well as cyclic ether groups such as epoxy groups and oxetanyl groups.
• the curable composition of the present invention preferably contains a resin having a graft chain (hereinafter, also referred to as a graft resin).
• the graft resin can be used as a dispersant, but may also be used as a binder.
• the graft chain means a polymer chain that branches out from the main chain of a repeating unit.
• the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and even more preferably 60 to 500 atoms excluding hydrogen atoms.
• the graft chain preferably contains repeating units of at least one structure selected from a polyether structure, a polyester structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure, more preferably contains repeating units of at least one structure selected from a polyether structure, a polyester structure, a poly(meth)acrylic structure, and a polystyrene structure, and further preferably contains repeating units of a polyether structure or a polyester structure because of excellent pigment dispersibility, and particularly preferably contains repeating units of a polyester structure.
• Examples of the repeating unit of the polyester structure include a repeating unit of the structure represented by formula (G-1), formula (G-4) or formula (G-5).
• Examples of the repeating unit of the polyether structure include a repeating unit of the structure represented by formula (G-2).
• Examples of the repeating unit of the poly(meth)acrylic structure include a repeating unit of the structure represented by formula (G-3).
• Examples of the repeating unit of the polystyrene structure include a repeating unit of the structure represented by formula (G-6).
• R G1 and R G2 each independently represent an alkylene group.
• the alkylene group represented by R G1 and R G2 is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms, and even more preferably a linear or branched alkylene group having 3 to 12 carbon atoms.
• R G3 represents a hydrogen atom or a methyl group
• Q G1 represents --O-- or --NH--
• L G1 represents a single bond or a divalent linking group
• R G4 represents a hydrogen atom or a substituent.
• Examples of the divalent linking group represented by L G1 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these.
• an alkylene group preferably an alkylene group having 1 to 12 carbon atoms
• an alkyleneoxy group preferably an alkyleneoxy group having 1 to 12 carbon atoms
• an oxyalkylenecarbonyl group preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms
• an arylene group preferably an arylene
• Examples of the substituent represented by R G4 include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a blocked isocyanate group.
• R G5 represents a hydrogen atom or a methyl group
• R G6 represents an aryl group.
• the number of carbon atoms in the aryl group represented by R G6 is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
• the aryl group represented by R G6 may have a substituent.
• substituents examples include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a blocked isocyanate group.
• the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
• the substituent may be a group represented by formula (W-1). -L w1 -R w1 ...(W-1)
• L w1 represents a single bond or a divalent linking group.
• R w1 represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, or a heteroarylthioether group.
• Examples of the divalent linking group represented by L w1 include an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, OCO-, -CONR L1 -, -S-, and a group combining two or more of these groups.
• R L1 represents a hydrogen atom, an alkyl group, or an aryl group.
• R w1 is preferably an alkyl group or an alkoxy group.
• the graft chain is preferably a structure represented by the following formula (G-1a), (G-2a), (G-3a), (G-4a), (G-5a) or (G-6a), and more preferably a structure represented by formula (G-1a), (G-4a) or (G-5a).
• R G1 and R G2 each represent an alkylene group
• R G3 represents a hydrogen atom or a methyl group
• Q G1 represents -O- or -NH-
• L G1 represents a single bond or a divalent linking group
• R G4 represents a hydrogen atom or a substituent
• R G5 represents a hydrogen atom or a methyl group
• R G6 represents an aryl group
• W 100 represents a hydrogen atom or a substituent
• n1 to n6 each independently represent an integer of 2 or more.
• R G1 to R G6 , Q G1 , and L G1 are synonymous with R G1 to R G6 , Q G1 , and L G1 described in formulas (G-1) to (G-6), and the preferred ranges are also the same.
• W 100 is preferably a substituent.
• substituents include the group represented by formula (W-1) above.
• n1 to n6 are each preferably an integer from 2 to 100, more preferably an integer from 2 to 80, and even more preferably an integer from 8 to 60.
• R G1 in each repeating unit may be the same or different.
• the arrangement of each repeating unit is not particularly limited and may be random, alternating, or block. The same applies to formulas (G-2a) to (G-6a).
• the graft chain has a structure represented by formula (G-1a), formula (G-4a), or formula (G-5a), and R G1 contains two or more different repeating units.
• the graft resin is preferably a resin having a repeating unit having a graft chain.
• An example of the repeating unit having a graft chain is a repeating unit represented by formula (e3).
• a e30 represents a trivalent linking group
• L e30 represents a single bond or a divalent linking group
• W e30 represents a graft chain.
• Examples of the trivalent linking group represented by A e30 include a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, a polyether linking group, and a polystyrene linking group.
• a poly(meth)acrylic linking group or a polyalkyleneimine linking group is preferable, and a poly(meth)acrylic linking group is more preferable.
• Examples of the divalent linking group represented by L e30 include an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, OCO-, -CONR x3 -, -S-, and a group combining two or more of these groups.
• R x3 represents a hydrogen atom, an alkyl group, or an aryl group.
• the alkylene group and the arylene group may have a substituent.
• the graft chain represented by W e30 includes the above-mentioned graft chain.
• the content of repeating units having graft chains is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 3 mol% or more, of all repeating units of the graft resin.
• the upper limit can be 90 mol% or less, 80 mol% or less, or 70 mol% or less.
• the graft resin may further have a repeating unit having an acid group.
• the acid group include a carboxy group, a sulfo group, and a phosphate group, and from the viewpoint of pigment dispersibility, a carboxy group is preferred.
• the content of repeating units having an acid group is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 3 mol% or more, of all repeating units of the graft resin.
• the upper limit can be 90 mol% or less, 80 mol% or less, or 70 mol% or less.
• the graft resin may further have a repeating unit having a crosslinkable group.
• the crosslinkable group include ethylenically unsaturated bond-containing groups such as vinyl groups, (meth)allyl groups, and (meth)acryloyl groups, as well as cyclic ether groups such as epoxy groups and oxetanyl groups.
• the content of repeating units having crosslinkable groups is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 3 mol% or more, of all repeating units of the graft resin.
• the upper limit can be 90 mol% or less, 80 mol% or less, or 70 mol% or less.
• the weight average molecular weight of the graft resin is preferably 5,000 to 100,000.
• the upper limit is preferably 80,000 or less, and more preferably 60,000 or less.
• the lower limit is preferably 6,000 or more, and more preferably 8,000 or more.
• the acid value of the graft resin is preferably 30 to 500 mgKOH/g.
• the upper limit is preferably 400 mgKOH/g or less, more preferably 300 mgKOH/g or less.
• the lower limit is preferably 40 mgKOH/g or more, more preferably 50 mgKOH/g or more.
• the curable composition of the present invention preferably contains a resin as a dispersant.
• dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins).
• the term "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 the acid groups and the basic groups is 100 mol%.
• the acid group possessed by the acidic dispersant (acidic resin) 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 is greater than the amount of acid groups when the total amount of the acid groups and the basic groups is 100 mol%.
• the basic group possessed by the basic dispersant is preferably an amino group.
• the resin used as the dispersant is a graft resin.
• the graft resin include those mentioned above.
• the resin used as the dispersant is a resin having an aromatic carboxy group.
• resins having an aromatic carboxy group include those mentioned above.
• the resin used as the dispersant is preferably a polyimine-based dispersant containing nitrogen atoms in at least one of the main chain and side chain.
• the polyimine-based dispersant is preferably a resin having a main chain with a partial structure having a functional group with a pKa of 14 or less, a side chain with 40 to 10,000 atoms, and having a basic nitrogen atom in at least one of the main chain and side chain.
• the basic nitrogen atom so long as it is a nitrogen atom that exhibits basicity.
• polyimine-based dispersants please refer to the description in paragraphs 0102 to 0166 of JP 2012-255128 A, the contents of which are incorporated herein by reference.
• the resin used as the dispersant is preferably one having a structure in which multiple polymer chains are bonded to a core portion.
• resins include dendrimers (including star-shaped polymers).
• dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP 2013-043962 A.
• the resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain.
• the content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol % or more of the total repeating units of the resin, more preferably 10 to 80 mol %, and even more preferably 20 to 70 mol %.
• resins described in JP 2018-087939 A, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6,432,077 A, polyethyleneimine having a polyester side chain described in WO 2016/104803 A, block copolymers described in WO 2019/125940 A, block polymers having an acrylamide structural unit described in JP 2020-066687 A, block polymers having an acrylamide structural unit described in JP 2020-066688 A, dispersants described in WO 2016/104803 A, and the like can also be used.
• Dispersants are also available as commercially available products, and specific examples include the DISPERBYK series manufactured by BYK Chemie, the SOLSPERSE series manufactured by Lubrizol Nippon, the Efka series manufactured by BASF, and the AJISPER series manufactured by Ajinomoto Fine-Techno Co., Ltd.
• the products described in paragraph 0129 of JP2012-137564A and the products described in paragraph 0235 of JP2017-194662A can also be used as dispersants.
• the resin content in the total solid content of the curable composition is preferably 1 to 60% by mass.
• the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more.
• the upper limit is preferably 50% by mass or less, more preferably 40% by mass or less.
• the content of the graft resin in the resin contained in the curable composition is preferably 50 to 100% by mass.
• the lower limit is preferably 60% by mass or more, more preferably 70% by mass or more.
• the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less.
• the content of the resin is preferably 10 to 500 parts by mass relative to 100 parts by mass of the radical polymerizable compound.
• the lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more.
• the upper limit is preferably 400 parts by mass or less, more preferably 300 parts by mass or less.
• the curable composition of the present invention may contain only one type of resin, or may contain two or more types of resins. When two or more types of resins are contained, the total amount thereof is preferably within the above range.
• the curable composition of the present invention preferably contains a chain transfer agent. According to this embodiment, it is possible to further increase the sensitivity when exposed to light having a wavelength of 150 nm to 300 nm, such as KrF radiation.
• the chain transfer agent include thiol compounds, thiocarbonylthio compounds, and aromatic ⁇ -methylalkenyl dimers, and a thiol compound is preferable.
• the chain transfer agent include the compounds described in paragraphs 0093 to 0113 of WO 2019/188652.
• the thiol compound used as the chain transfer agent is a compound having one or more thiol groups, and preferably a compound having two or more thiol groups.
• the upper limit of the number of thiol groups contained in the thiol compound is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. It is particularly preferable that the thiol compound is a compound having two thiol groups.
• Examples of the n-valent group represented by L S1 in formula (SH-1) include a hydrocarbon group, a heterocyclic group, -O-, -S-, -NR S1 -, -CO-, -COO-, -OCO-, -SO 2 -, or a group consisting of a combination thereof.
• R S1 represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably a hydrogen atom.
• the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
• the aliphatic hydrocarbon group may be cyclic or noncyclic.
• the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.
• the hydrocarbon group may have a substituent or may not have a substituent.
• the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a monocyclic ring or a condensed ring.
• the heterocyclic group may be a monocyclic ring or a condensed ring.
• the heterocyclic group is preferably a 5-membered or 6-membered ring.
• the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Examples of heteroatoms constituting the heterocyclic group include nitrogen atoms, oxygen atoms, and sulfur atoms.
• the number of carbon atoms constituting L1 is preferably 3 to 100, and more preferably 6 to 50.
• n represents an integer of 1 or more.
• the upper limit of n is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.
• the lower limit of n is preferably 2 or more.
• thiol compounds include the compounds described in the Examples below and the compounds described in paragraphs 0100 to 0103 of WO 2019/188652.
• Commercially available thiol compounds include PEMP (manufactured by SC Organic Chemical Co., Ltd.), Suncerar M (manufactured by Sanshin Chemical Industry Co., Ltd.), Karenz MTBD1, Karenz MTPE1, Karenz MTNR1, and Karenz MTTPMB (all manufactured by Resonac Co., Ltd.).
• the molecular weight of the chain transfer agent is preferably 200 or more.
• the upper limit is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less, because this increases the SH valence per weight.
• the content of the chain transfer agent in the total solid content of the curable composition is preferably 0.001 to 5% by mass.
• the upper limit is preferably 3% by mass or less, more preferably 1% by mass or less.
• the lower limit is preferably 0.05% by mass or more, more preferably 0.01% by mass or more.
• the content of the chain transfer agent is preferably 0.1 to 100 parts by mass relative to 100 parts by mass of the specific oxime ester compound.
• the upper limit is preferably 80 parts by mass or less, and more preferably 50 parts by mass or less.
• the lower limit is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more. Only one type of chain transfer agent 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 curable composition of the present invention may contain a pigment derivative.
• the pigment derivative is used, for example, as a dispersing aid.
• a dispersing aid is a material for increasing the dispersibility of a coloring material such as a pigment in the curable composition.
• Pigment derivatives include compounds having at least one structure selected from the group consisting of a dye structure and a triazine structure, and an acid group or a basic group.
• the above dye structures include a quinoline dye structure, a benzimidazolone dye structure, a benzisoindole dye structure, a benzothiazole dye structure, an iminium dye structure, a squarylium dye structure, a croconium dye structure, an oxonol dye structure, a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, an azo dye structure, an azomethine dye structure, a phthalocyanine dye structure, a naphthalocyanine dye structure, an anthraquinone dye structure, a quinacridone dye structure, a dioxazine dye structure, a perinone dye structure, a perylene dye structure, a thiazineindigo dye structure, a thioindigo dye structure, an isoindoline dye structure, an isoindolinone dye structure, a quinophthalone dye structure, a dithiol dye structure
• Examples of the acid group contained in the pigment derivative include a carboxy group, a sulfo group, a phosphate group, a boronic acid group, an imidic acid group, and salts thereof.
• Examples of the atom or atomic group constituting the salt include an alkali metal ion (Li + , Na + , K +, etc.), an alkaline earth metal ion (Ca2 + , Mg2 +, etc.), an ammonium ion, an imidazolium ion, a pyridinium ion, and a phosphonium ion.
• a group represented by -SO 2 NHSO 2 R X1 , -CONHSO 2 R X2 , -CONHCOR X3 or -SO 2 NHCOR X4 is preferred, a group represented by -SO 2 NHSO 2 R X1 , -CONHSO 2 R X2 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 each independently represent an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, 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 still 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 still more preferably 6.
• Basic groups contained in pigment derivatives include amino groups, pyridinyl groups and their salts, salts of ammonium groups, and phthalimidomethyl groups.
• Atoms or atomic groups that constitute the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
• amino group examples include a group represented by --NR.sub.x11R.sub.x12 and a cyclic amino group.
• R x11 and R x12 each independently represent a hydrogen atom, an alkyl group or an aryl group, and are preferably an alkyl group. That is, the amino group is preferably a dialkylamino group.
• the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
• the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
• the alkyl group may have a substituent.
• the number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
• the aryl group may have a substituent.
• Cyclic amino groups include pyrrolidine groups, piperidine groups, piperazine groups, and morpholine groups. These groups may further have a substituent.
• the pigment derivative may be a pigment derivative having excellent visible transparency (hereinafter, also referred to as a transparent pigment derivative).
• the maximum molar absorption coefficient ( ⁇ max) of the transparent pigment derivative in the wavelength region of 400 to 700 nm is preferably 3000 L mol -1 cm -1 or less, more preferably 1000 L mol -1 cm -1 or less, 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 the Examples below, the compounds described in paragraph 0124 of WO 2022/085485, the benzimidazolone compounds or salts thereof described in JP 2018-168244 A, and the compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282.
• the content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the pigment.
• the total content of the pigment derivative and colorant is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more, based on the total solid content of the curable composition.
• the upper limit is preferably 80% by mass or less, and more preferably 75% by mass or less. Only one type of pigment derivative may be used, or two or more types may be used in combination.
• the curable composition of the present invention may also contain a polyalkyleneimine.
• the polyalkyleneimine is used, for example, as a dispersing aid for pigments.
• the dispersing aid is a material for enhancing the dispersibility of coloring materials such as pigments in the curable composition.
• the polyalkyleneimine is a polymer obtained by ring-opening polymerization of an 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.
• the number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.
• the molecular weight of the polyalkyleneimine 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 polyalkyleneimine is the value calculated from the structural formula.
• the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the number average molecular weight value measured by the boiling point elevation method is used.
• the number average molecular weight value measured by the viscosity method is used.
• the number average molecular weight value measured in polystyrene equivalent value by GPC (gel permeation chromatography) method 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.
• alkyleneimines include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred.
• the polyalkyleneimine is particularly preferably polyethyleneimine.
• the polyethyleneimine preferably contains primary amino groups in an amount of 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total of the primary amino groups, secondary amino groups, and tertiary amino groups.
• Commercially available polyethyleneimines 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 curable composition is preferably 0.1 to 5 mass%.
• the lower limit is preferably 0.2 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1 mass% or more.
• the upper limit is preferably 4.5 mass% or less, more preferably 4 mass% or less, and even more preferably 3 mass% or less.
• the content of polyalkyleneimine is preferably 0.5 to 20 mass parts per 100 mass parts of pigment.
• the lower limit is preferably 0.6 mass% or more, more preferably 1 mass% or more, and even more preferably 2 mass% or more.
• the upper limit is preferably 10 mass% or less, and even more preferably 8 mass% or less. Only one type of polyalkyleneimine may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.
• the curable composition of the present invention preferably contains a solvent.
• the solvent include organic solvents.
• the type of solvent is not particularly limited as long as the solubility of each component and the coatability of the composition are satisfied.
• the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For details of these, reference can be made to paragraph number 0223 of International Publication No. 2015/166779, the contents of which are incorporated herein by reference.
• ester-based solvents substituted with a cyclic alkyl group and ketone-based 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
• Examples of the ethylene glycol monomethyl ether acetate include 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, 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 diacetone alcohol and 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.
• diacetone alcohol also known as diacetone alcohol and 4-hydroxy-4-methyl-2-pentanone
• 2-methoxypropyl acetate 2-methoxy-1-propanol,
• the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons, etc. (for example, the amount can be 50 ppm (parts per million) by mass or less, 10 ppm by mass or less, or 1 ppm by mass or less, relative to the total amount of organic solvents).
• the metal content of the organic solvent is preferably low.
• the metal content of the organic solvent is preferably, for example, 10 parts per billion (ppb) by mass or less. If necessary, organic solvents with metal contents at the ppt (parts per trillion) by mass level may be used, and such organic solvents are provided, for example, by Toyo Gosei (The Chemical Daily, November 13, 2015).
• Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter.
• the filter used for filtration preferably has a pore size of 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
• the filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.
• the organic solvent may contain isomers (compounds with the same number of atoms but different structures).
• the organic solvent may contain only one type of isomer, or multiple types of isomers.
• the peroxide content in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.
• the content of the solvent in the curable 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 curable composition of the present invention is substantially free of environmentally regulated substances.
• substantially free of environmentally regulated substances means that the content of environmentally regulated substances in the curable composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less.
• environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
• distillation methods can be used at any stage, such as the stage of the raw materials, the stage of the product obtained by reacting the raw materials (for example, a resin solution or a polyfunctional monomer solution after polymerization), or the stage of the curable composition prepared by mixing these compounds.
• the curable composition of the present invention may contain a compound having a cyclic ether group.
• the cyclic ether group include an epoxy group and an oxetanyl group.
• the epoxy group may be an alicyclic epoxy group.
• the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
• the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound).
• the epoxy compound may be a compound having one or more epoxy groups in one molecule, and preferably a compound having two or more epoxy groups.
• the epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule.
• the upper limit of the epoxy groups contained in the epoxy compound may be, for example, 10 or less, or 5 or less.
• the lower limit of the epoxy groups contained in the epoxy compound is preferably 2 or more.
• the compound having a cyclic ether group may be a low molecular weight compound (e.g., a molecular weight of less than 2000, or even less than 1000) or a high molecular weight compound (macromolecule) (e.g., a molecular weight of 1000 or more, or in the case of a polymer, a weight average molecular weight of 1000 or more).
• the weight average molecular weight of the compound having a cyclic ether group is preferably 200 to 100,000, and more preferably 500 to 50,000.
• the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.
• EHPE3150 manufactured by Daicel Corporation
• EPICLON N-695 manufactured by DIC Corporation
• Marproof G-0150M G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOF Corporation, epoxy group-containing polymers).
• the content of the compound having a cyclic ether group in the total solid content of the curable composition is preferably 0.1 to 20 mass%.
• the lower limit is preferably 0.5 mass% or more, and more preferably 1 mass% or more.
• the upper limit is preferably 15 mass% or less, and more preferably 10 mass% or less. Only one type of compound having a cyclic ether group 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 thereof is within the above range.
• the curable composition of the present invention may contain an ultraviolet absorber.
• ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and dibenzoyl compounds. Specific examples of such compounds include the compounds described in paragraph 0179 of International Publication No. 2022/085485, the reactive triazine ultraviolet absorbers described in JP-A-2021-178918, the ultraviolet absorbers described in JP-A-2022-007884, and the compounds described in Korean Patent Publication No. 10-2022-0014454.
• the content of the ultraviolet absorber in the total solid content of the curable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one type of ultraviolet absorber 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 of the ultraviolet absorbers is within the above range.
• the curable composition of the present invention may contain a polymerization inhibitor.
• the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salt (ammonium salt, cerous salt, etc.).
• p-methoxyphenol is preferred.
• the content of the polymerization inhibitor in the total solid content of the curable composition is preferably 0.0001 to 5% by mass.
• the polymerization inhibitor may be one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.
• the curable composition of the present invention may contain a silane coupling agent.
• the silane coupling agent include silane compounds having a hydrolyzable group, and it is preferable that the silane coupling agent is 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 generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
• Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, and an alkoxy group is preferable.
• the silane coupling agent is preferably a compound having an alkoxysilyl group.
• functional groups other than the hydrolyzable group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, and a phenyl group, and an amino group, a (meth)acryloyl group, and an epoxy group are preferable.
• Specific examples of the silane coupling agent include the compounds described in paragraph 0177 of International Publication No.
• the content of the silane coupling agent in the total solid content of the curable composition is preferably 0.1 to 15% by mass.
• the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less.
• the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
• the silane coupling agent may be one type or two or more types. In the case of two or more types, it is preferable that the total amount is within the above range.
• the curable composition of the present invention may contain a surfactant.
• a surfactant various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants may be used.
• the surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant.
• Nonionic surfactants include the compounds described in paragraph 0174 of WO 2022/085485.
• Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419.
• OIL all manufactured by Dow Toray Co., Ltd.
• TSF-4300, TSF-4445, TSF-4460, TSF-4452 all manufactured by Momentive Performance Materials, Inc.
• KP-341, KF-6000, KF-6001, KF-6002, KF-6003 all manufactured by Shin-Etsu Chemical Co., Ltd.
• BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 all 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 curable composition is preferably 0.001% by mass to 5.0% by mass, and more preferably 0.005% by mass to 3.0% by mass.
• the surfactant may be one type or two or more types. When two or more types are used, it is preferable that the total amount is within the above range.
• the curable composition of the present invention may contain an antioxidant.
• the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
• the phenol-based antioxidant include hindered phenol compounds.
• the phenol-based antioxidant is preferably a compound having a substituent at the site (ortho position) adjacent to the phenolic hydroxy group.
• the aforementioned substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms.
• the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
• phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-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, ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite, and tris(2,4-di-tert-butylphenyl)phosphite.
• antioxidants include, for example, Adeka STAB AO-20, Adeka STAB AO-30, Adeka STAB AO-40, Adeka STAB AO-50, Adeka STAB AO-50F, Adeka STAB AO-60, Adeka STAB AO-60G, Adeka STAB AO-80, Adeka STAB AO-330 (manufactured by ADEKA Corporation), and JP-650 (manufactured by Johoku Chemical Industry Co., Ltd.).
• the antioxidant is a compound described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, a compound described in International Publication No. WO 2017/006600, a compound described in International Publication No.
• the content of the antioxidant in the total solid content of the curable composition is preferably 0.01 to 20 mass%, more preferably 0.3 to 15 mass%. Only one type of antioxidant 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 curable composition of the present invention may contain, as necessary, a sensitizer, a plasticizer, and other auxiliaries (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promoters, fragrances, surface tension regulators, chain transfer agents, etc.).
• auxiliaries e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promoters, fragrances, surface tension regulators, chain transfer agents, etc.
• the curable composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film.
• the metal oxide include TiO 2 , ZrO 2 , Al 2 O 3 , and SiO 2.
• the primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm.
• the metal oxide may have a core-shell structure. In this case, the core may be hollow.
• the curable composition of the present invention may contain a light resistance improver.
• the light resistance improver include the compounds described in paragraph 0183 of WO 2022/085485.
• the curable composition of the present invention is substantially free of terephthalic acid esters.
• substantially free means that the content of terephthalic acid esters in the total amount of the curable composition is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.
• the curable composition of the present invention has a melamine content of 10,000 ppm by mass or less.
• the curable composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less.
• the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less.
• Methods for reducing free metals and halogens in the curable composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with ion-exchange resins.
• perfluoroalkylsulfonic acid and its salts may be restricted.
• the content of perfluoroalkylsulfonic acid (particularly perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts, and perfluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts is preferably in the range of 0.01 ppb to 1,000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, based on the total solid content of the curable composition.
• the curable composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts.
• a curable composition that is substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt may be selected.
• Examples of compounds that can be a substitute for regulated compounds include compounds that are excluded from regulation due to the difference in the number of carbon atoms in the perfluoroalkyl group. However, the above content does not prevent the use of perfluoroalkylsulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt.
• the curable composition of the present invention may contain perfluoroalkylsulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt within the maximum allowable range.
• the water content of the curable composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably in the range of 0.1 to 1.0% by mass.
• the water content can be measured by the Karl Fischer method.
• the curable composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (flatness, etc.) and film thickness.
• the viscosity value can be selected appropriately as needed, but for example, a value of 0.3 mPa ⁇ s to 50 mPa ⁇ s at 25°C is preferable, and 0.5 mPa ⁇ s to 20 mPa ⁇ s is more preferable.
• the viscosity can be measured, for example, using a cone-plate type viscometer with the temperature adjusted to 25°C.
• the container for storing the curable composition is not particularly limited, and a known container can be used.
• the container described in paragraph 0187 of WO 2022/085485 can be used as the container.
• the curable composition of the present invention can be prepared by mixing the above-mentioned components.
• all the components may be simultaneously dissolved and/or dispersed in a solvent to prepare the curable composition, or, if necessary, each component may be appropriately prepared as two or more solutions or dispersions, which are mixed at the time of use (at the time of application) to prepare the curable composition.
• the preparation of the curable composition includes a process for dispersing the pigment.
• mechanical forces used to disperse the pigment include compression, squeezing, impact, shear, and cavitation.
• 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, and ultrasonic dispersion.
• a sand mill bead mill
• the process and dispersing machine for dispersing the pigment may be suitably used as described in "Dispersion Technology Encyclopedia, published by Information Technology Co., Ltd., July 15, 2005” or "Dispersion Technology and Industrial Application Practice Focused on Suspension (Solid/Liquid Dispersion System) - Comprehensive Data Collection, published by Management Development Center Publishing Department, October 10, 1978", and in paragraph number 0022 of JP 2015-157893 A.
• a salt milling process may be performed to refine the particles. For the materials, equipment, processing conditions, etc.
• the descriptions in, for example, JP 2015-194521 A and JP 2012-046629 A may be referred to.
• materials for the beads used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass.
• the beads may also be made of an inorganic compound with a Mohs hardness of 2 or more.
• the curable composition may contain 1 to 10,000 ppm of the beads.
• the curable composition When preparing the curable composition, it is preferable to filter the curable composition with a filter for the purpose of removing foreign matter and reducing defects.
• filters and filtration methods used for filtration include the filters and filtration methods described in paragraphs 0196 to 0199 of WO 2022/085485.
• the film of the present invention is obtained from the above-mentioned curable composition of the present invention.
• the film of the present invention can be used for optical filters such as color filters, near-infrared transmission filters, and near-infrared cut filters.
• the thickness of the film of the present invention can be adjusted appropriately depending on the purpose.
• the thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
• the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more.
• the film of the present invention when used as a color filter, the film of the present invention preferably has a green, red, blue, cyan, magenta or yellow hue, and more preferably has a red hue.
• the film of the present invention can also be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels, and more preferably, red pixels.
• the method for manufacturing a pixel includes a step of forming a curable composition layer on a support using the curable composition of the present invention, a step of exposing the curable composition layer in a pattern, and a step of developing and removing the unexposed part of the curable composition layer. If necessary, a step of baking the curable composition layer (pre-baking step) and a step of baking the developed pattern (pixel) (post-baking step) may be provided.
• the curable composition layer is formed on a support using the curable composition of the present invention.
• the support is not particularly limited and can be appropriately selected depending on the application.
• a glass substrate, a silicon substrate, etc. can be mentioned, and a silicon substrate is preferable.
• a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the silicon substrate.
• CMOS complementary metal oxide semiconductor
• a black matrix that isolates each pixel may be formed on the silicon substrate.
• a base layer may be provided on the silicon substrate to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface.
• the surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. It is also preferable that the surface contact angle is 30 to 80° when measured with water.
• a known method can be used as a method for applying the curable composition.
• a dropping method drop casting
• a slit coating method for example, a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wetting method (for example, a method described in JP 2009-145395 A); various printing methods such as inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; a transfer method using a mold or the like; and a nanoimprint method.
• the application method described in paragraph 0207 of WO 2022/085485 can also be used.
• the curable composition layer formed on the support may be dried (prebaked).
• prebaking may not be performed.
• the prebaking temperature is preferably 150°C or less, more preferably 120°C or less, and even more preferably 110°C or less.
• the lower limit can be, for example, 50°C or more, and can also be 80°C or more.
• the prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, an oven, etc.
• the curable composition layer is exposed to light in a pattern (exposure step).
• the curable composition layer can be exposed to light in a pattern by using a stepper exposure machine or a scanner exposure machine through a mask having a predetermined mask pattern. This allows the exposed parts to be cured.
• Radiation (light) that can be used for exposure includes g-line and i-line.
• Light with a wavelength of 150 to 300 nm can also be used.
• Examples of light with a wavelength of 150 to 300 nm include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), with KrF line (wavelength 248 nm) being preferred.
• Light with a wavelength of 150 to 300 nm is preferably excimer laser light with a wavelength of 150 to 300 nm.
• a long-wavelength light source of 300 nm or more can be used for exposure.
• the exposure step it is preferable to irradiate the curable composition layer with light having a wavelength of 150 to 300 nm (preferably excimer laser light having a wavelength of 150 to 300 nm) to expose it in a pattern.
• light having a wavelength of 150 to 300 nm preferably excimer laser light having a wavelength of 150 to 300 nm
• the light When exposing, the light may be applied continuously or in pulses (pulse exposure). Pulse exposure is an exposure method in which light is applied and paused repeatedly in short cycles (e.g., milliseconds or less).
• the irradiation amount is, for example, preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2.
• the oxygen concentration during exposure can be appropriately selected, and in addition to being performed under air, for example, exposure may be performed under a low-oxygen atmosphere with an oxygen concentration of 19 volume% or less (e.g., 15 volume%, 5 volume%, or substantially oxygen-free), or exposure may be performed under a high-oxygen atmosphere with an oxygen concentration of more than 21 volume% (e.g., 22 volume%, 30 volume%, or 50 volume%).
• the exposure illuminance can be appropriately set, and can usually be selected from the range of 1000 W/m 2 to 100,000 W/m 2 (e.g., 5,000 W/m 2 , 15,000 W/m 2 , or 35,000 W/m 2 ).
• the oxygen concentration and exposure illuminance may be appropriately combined.
• the oxygen concentration can be 10% by volume and the illuminance can be 10,000 W/m 2
• the oxygen concentration can be 35% by volume and the illuminance can be 20,000 W/m 2 .
• the unexposed parts of the curable composition layer are developed and removed to form a pattern (pixels).
• the unexposed parts of the curable composition layer can be developed and removed using a developer.
• the unexposed parts of the curable composition layer in the exposure step are dissolved into the developer, and only the photocured parts remain.
• the temperature of the developer is preferably, for example, 20 to 30°C.
• the development time is preferably 20 to 180 seconds. In order to improve residue removal, the process of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.
• the developer may be an organic solvent or an alkaline developer, with an alkaline developer being preferred.
• the developer and the washing (rinsing) method after development may be as described in paragraph 0214 of WO 2022/085485.
• Additional exposure processing and post-baking are curing processing after development to complete curing.
• the heating temperature in post-baking is, for example, preferably 100 to 300°C, more preferably 200 to 270°C.
• Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater to achieve the above conditions for the developed film.
• a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater to achieve the above conditions for the developed film.
• the light used for exposure has a wavelength of 400 nm or less.
• additional exposure processing may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
• the optical filter of the present invention has the above-mentioned film of the present invention.
• the types of optical filters include color filters, near-infrared cut filters, and near-infrared transmission filters, and are preferably color filters.
• the color filter preferably has the film of the present invention as its pixel, more preferably has the film of the present invention as its color pixel, and even more preferably has the film of the present invention as its red pixel.
• the optical filter may have a protective layer on the surface of the film of the present invention.
• a protective layer By providing a protective layer, various functions such as oxygen blocking, low reflection, hydrophilicity/hydrophobicity, 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.
• Methods for forming the protective layer include a method of forming the protective layer by applying a resin composition for forming the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive.
• the 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 resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al 2 O 3 , Mo, SiO 2 , and Si 2 N 4 , and may contain two or more of these components.
• the protective layer in the case of a protective layer intended for oxygen blocking, preferably contains a polyol resin, SiO 2 , and Si 2 N 4.
• the protective layer in the case of a protective layer intended for low reflection, preferably contains a (meth)acrylic resin and a fluorine resin.
• a protective layer by applying a resin composition When forming a protective layer by applying a resin composition, known methods such as spin coating, casting, screen printing, and inkjet can be used as a method for applying the resin composition.
• Known organic solvents e.g., propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.
• known chemical vapor deposition methods thermal chemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition
• the protective layer may contain additives such as organic or inorganic fine particles, absorbents for light of specific wavelengths (e.g., ultraviolet light, near infrared light, etc.), refractive index adjusters, antioxidants, adhesion agents, and surfactants, as necessary.
• organic or 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, and barium sulfate.
• Known absorbents can be used as absorbents for light of specific wavelengths.
• the content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, and more preferably 1 to 60% by mass, based on the total mass of the protective layer.
• the protective layer may be the one described in paragraphs 0073 to 0092 of JP2017-151176A.
• the optical filter may have a structure in which each pixel is embedded in a space partitioned by partitions, for example in a grid pattern.
• the solid-state imaging device of the present invention has the above-mentioned film of the present invention.
• the configuration of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.
• the substrate has a plurality of photodiodes constituting the light receiving area of a solid-state imaging element (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor) and a transfer electrode made of polysilicon or the like, a light-shielding film on the photodiodes and the transfer electrode with only the light receiving portion of the photodiode open, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving portion of the photodiode, and a color filter on the device protection film.
• a solid-state imaging element such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor
• a transfer electrode made of polysilicon or the like
• the device protection film may have a light-collecting means (e.g., a microlens, etc.; the same applies below) on the device protection film and below the color filter (the side closer to the substrate), or a light-collecting means on the color filter.
• the color filter may have a structure in which each colored pixel is embedded in a space partitioned by partitions, for example in a lattice shape. In this case, it is preferable that the partitions have a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include those described in JP 2012-227478 A, JP 2014-179577 A, and WO 2018/043654 A.
• an ultraviolet absorbing layer may be provided in the structure of the solid-state imaging element to improve light resistance.
• the imaging device equipped with the solid-state imaging element of the present invention can be used for digital cameras, electronic devices with imaging functions (such as mobile phones), as well as in-vehicle cameras and surveillance cameras.
• the image display device of the present invention has the above-mentioned film of the present invention.
• Examples of the image display device include liquid crystal display devices and organic electroluminescence display devices.
• the definition of the image display device and details of each image display device are described, for example, in "Electronic Display Devices” (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990) and “Display Devices” (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1989).
• the liquid crystal display device is described, for example, in “Next Generation Liquid Crystal Display Technology” (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994).
• There is no particular limitation on the liquid crystal display device to which the present invention can be applied and the present invention can be applied to various types of liquid crystal display devices described in the above "Next Generation Liquid Crystal Display Technology".
• AL-1 4-hydroxybutyl acrylate
• AL-2 glycerol diacrylate
• AL-3 pentaerythritol triacrylate
• AL-4 dipentaerythritol pentaacrylate
• AL-5 malic acid
• CAT-1 N,N-dimethyldodecylamine
• CAT-2 Potassium octylate
• CAT-3 Diazabicycloundecene acetate
• CAT-4 Tetrabutylammonium bromide
• the polyfunctional urethane (meth)acrylate compound (U-21) is a compound having the following structure.
• B-1 Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 20,000, acid value: 66.6 mgKOH/g)
• B-2 Resin having the following structure (the numbers attached to the main chain are molar ratios, and the numbers attached to the side chains are the numbers of repeating units. Weight average molecular weight: 23,000, acid value: 59.6 mgKOH/g)
• B-3 Resin having the following structure (the numbers attached to the main chain are molar ratios, and the numbers attached to the side chains are the numbers of repeating units. Weight average molecular weight: 16,000, acid value: 67 mg KOH/g)
• B-4 Resin having the following structure (weight average molecular weight 18,000, acid value 82.1 mgKOH/g)
• C-1 Resin having the following structure (the numbers attached to the main chain are molar ratios; weight average molecular weight 11,000, acid value 69.2 mgKOH/g)
• C-2 Resin having the following structure (the numbers attached to the main chain are molar ratios; weight average molecular weight 21,000, acid value 80 mgKOH/g)
• A-1 to A-28 Compounds A-1 to A-28 shown as specific examples of the specific oxime ester compound described above
• A-C1 to A-C5 Compounds having the following structures
• An undercoat material (CT-4000L, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied to an 8-inch (20.32 cm) silicon wafer using a spin coater so that the thickness after post-baking would be 0.1 ⁇ m, and the wafer was heated at 220° C. for 300 seconds using a hot plate to form an undercoat layer, thereby obtaining a silicon wafer with an undercoat layer.
• each curable composition was applied by spin coating so that the film thickness after post-baking was 0.5 ⁇ m.
• a hot plate was used to post-bake at 100° C. for 2 minutes to form a curable composition layer.
• the curable composition layer was exposed to KrF rays (light with a wavelength of 248 nm) through a mask (0.5 ⁇ m ⁇ 0.5 ⁇ m) having a pattern, using a KrF scanner exposure machine, under conditions of an illuminance of 35000 W/m 2 and an exposure dose of 100 mJ/cm 2.
• paddle development was performed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH).
• TMAH tetramethylammonium hydroxide
• rinsing was performed with a spin shower, and further washing with pure water was performed.
• a pixel (pattern) was formed by heating at 200° C. for 5 minutes using a hot plate.
• the obtained pixels were observed at 100 points in the image portion (pattern) using a high-resolution FEB (Field Emission Beam) length measuring device (HITACHI CD-SEM) S9380II (manufactured by Hitachi High-Technologies Corporation), and the number of missing pixels was calculated. Note that a pixel with a missing portion in the rectangular portion at the top of the pattern was defined as a missing pixel.
• C 2 missing pixels
• D 3 or 4 missing pixels
• E 5 or more missing pixels
• Condition 1 Using a KrF scanner exposure device, exposure is performed by irradiating KrF rays (light having a wavelength of 248 nm) under conditions of an illuminance of 35,000 W/m 2 and an exposure dose of 100 mJ/cm 2 .
• Condition 2 Using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), exposure is performed by irradiating with i-line (light having a wavelength of 365 nm) at an exposure dose of 100 mJ/cm 2 .
• the curable composition layer after exposure under Condition 1 or Condition 2 was paddle-developed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, the layer was rinsed with a spin shower and further washed with pure water. Then, the layer was heated at 200° C. for 5 minutes using a hot plate to form pixels (patterns).
• TMAH tetramethylammonium hydroxide
• Line width change rate (%) (

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