WO2024034445A1 - Composition de résine, film, filtre optique, élément d'imagerie à semi-conducteurs et dispositif d'affichage d'image - Google Patents

Composition de résine, film, filtre optique, élément d'imagerie à semi-conducteurs et dispositif d'affichage d'image Download PDF

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Publication number
WO2024034445A1
WO2024034445A1 PCT/JP2023/027927 JP2023027927W WO2024034445A1 WO 2024034445 A1 WO2024034445 A1 WO 2024034445A1 JP 2023027927 W JP2023027927 W JP 2023027927W WO 2024034445 A1 WO2024034445 A1 WO 2024034445A1
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group
resin composition
resin
mass
compounds
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PCT/JP2023/027927
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English (en)
Japanese (ja)
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祐士 金子
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富士フイルム株式会社
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Publication of WO2024034445A1 publication Critical patent/WO2024034445A1/fr

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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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

Definitions

  • the present invention relates to a resin composition containing particles.
  • the present invention also relates to a film, an optical filter, a solid-state image sensor, and an image display device using the resin composition.
  • Resin compositions containing particles are used, for example, to form optical filters such as color filters. Further, the use of a resin composition containing particles in which a thiol compound is blended is also being considered.
  • Patent Document 1 discloses an invention relating to a black photosensitive resin composition containing an oxime ester photopolymerization initiator and containing a polyfunctional thiol as a chain transfer agent. .
  • Resin compositions containing particles tend to have viscosity and other properties that increase over time due to particles agglomerating during storage. In recent years, there has been a demand for further improvement in the storage stability of resin compositions containing particles.
  • the present invention provides the following.
  • R 1 to R 4 each independently represent an alkylene group
  • X 1 to X 4 each independently represent a hydrogen atom, a thiol group, or a hydroxy group, and at least two of X 1 to X 4 are thiol groups.
  • ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein at least three of X 1 to X 4 in formula (1) are thiol groups.
  • ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein R 1 to R 4 of the above formula (1) are each independently a methylene group or an ethylene group.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the particles are an organic pigment.
  • ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the particles are inorganic pigments.
  • the resin includes at least one selected from a graft polymer, a star polymer, a block copolymer, and a resin in which at least one end of the polymer chain is capped with an acid group, ⁇ 1> to The resin composition according to any one of ⁇ 7>.
  • ⁇ 10> A film obtained using the resin composition according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 12> A solid-state imaging device having the film according to ⁇ 10>.
  • ⁇ 13> An image display device comprising the film according to ⁇ 10>.
  • the present invention it is possible to provide a resin composition that can form a film that has excellent storage stability and excellent solvent resistance. Further, according to the present invention, it is possible to provide a film, an optical filter, a solid-state image sensor, and an image display device using the resin composition.
  • ⁇ is used to include the numerical values described before and after it as a lower limit and an upper limit.
  • the description that does not indicate substituted or unsubstituted includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the term "alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • EUV light extreme ultraviolet rays
  • (meth)acrylate” represents acrylate and/or methacrylate
  • (meth)acrylic represents both acrylic and/or methacrylic
  • (meth)acrylate” represents acrylic and/or methacrylate.
  • Acryloyl refers to either or both of acryloyl and methacryloyl.
  • Me in the structural formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
  • near-infrared rays refer to light with a wavelength of 700 to 2500 nm.
  • the total solid content refers to the total mass of all components of the composition excluding the solvent.
  • the term "process” is used not only to refer to an independent process, but also to include a process in which the intended effect of the process is achieved even if the process cannot be clearly distinguished from other processes. .
  • the resin composition of the present invention is characterized by containing a compound represented by formula (1), particles, a resin, a polymerizable monomer having an ethylenically unsaturated bond-containing group, and a solvent.
  • the resin composition of the present invention has excellent storage stability and can form a film with excellent solvent resistance.
  • the reason why such an effect is obtained is presumed to be due to the following.
  • the compound represented by formula (1) (hereinafter also referred to as a specific thiol compound) is a compound having a high density of thiol groups, with 2 to 4 thiol groups bonded to a specific alkylene core site. Since the specific thiol compound has a high density of thiol groups, it is presumed that it forms ionic bonds and hydrogen bonds with the particle surface in the resin composition. It is presumed that this develops a particle surface protection function, reduces the cohesive force with other particles, and improves dispersibility.
  • the resin composition of the present invention further contains a photopolymerization initiator
  • excessive mobility of radicals generated from the photopolymerization initiator (Diffusion) can be suppressed to reduce photoresponsiveness, and exposure latitude can be improved. Therefore, when the resin composition of the present invention further contains a photopolymerization initiator, the exposure latitude is wide, and such a resin composition is preferably used as a resin composition for pattern formation in photolithography. It will be done.
  • the resin composition of the present invention is preferably used as a resin composition for optical filters.
  • the optical filter include color filters, near-infrared transmission filters, near-infrared cut filters, etc., and color filters are preferred.
  • the resin composition of the present invention is preferably used for solid-state imaging devices. More specifically, it is preferably used as a resin composition for an optical filter used in a solid-state imaging device, and more preferably used as a resin composition for forming colored pixels in a color filter used in a solid-state imaging device.
  • color filters include filters that have colored pixels that transmit light of a specific wavelength.
  • colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
  • Examples of near-infrared cut filters include filters whose maximum absorption wavelength is in the wavelength range of 700 to 1800 nm.
  • the maximum absorption wavelength of the near-infrared cut filter is preferably in the wavelength range of 700 to 1300 nm, more preferably in the wavelength range of 700 to 1100 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. Further, the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.
  • absorbance Amax/absorbance A550 which is 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. , more preferably from 70 to 450, particularly preferably from 100 to 400.
  • a near-infrared transmission filter is a filter that transmits at least a portion of near-infrared rays.
  • the near-infrared transmitting filter is preferably a filter that blocks at least a portion of visible light and transmits at least a portion of near-infrared rays.
  • the near-infrared transmission filter has 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 transmittance in the wavelength range of 1100 to 1300 nm.
  • Preferred examples include filters that satisfy spectral characteristics with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more).
  • the near-infrared transmission filter is preferably a filter that satisfies any of the following spectral characteristics (1) to (5).
  • the maximum value of transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 800 to 1500 nm is 20% or less (preferably 15% or less, more preferably 10% or less).
  • 70% or more preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 900 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1000 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1100 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1200 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the resin composition of the present invention can also be used as a resin composition for forming transparent films, light-shielding films, light-scattering films, light-refractive films, electrical insulation films, and the like.
  • the resin composition of the present invention is also preferably a resin composition for pattern formation by photolithography.
  • the resin composition of the present invention when used as a resin composition for pattern formation by photolithography, it is preferable that the resin composition of the present invention further contains a photopolymerization initiator.
  • the resin composition of the present invention it is preferable to use a resin containing a resin having an acid group.
  • the solid content concentration of the resin composition is preferably 5 to 30% by mass.
  • the lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more.
  • the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less.
  • the resin composition of the present invention contains a compound represented by formula (1) (hereinafter also referred to as a specific thiol compound).
  • R 1 to R 4 each independently represent an alkylene group
  • X 1 to X 4 each independently represent a hydrogen atom, a thiol group, or a hydroxy group
  • at least two of X 1 to X 4 are thiol groups.
  • the alkylene group represented by R 1 to R 4 in formula (1) preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and more preferably 1 or 2 carbon atoms.
  • R 1 to R 4 are preferably methylene groups or ethylene groups.
  • R 1 is preferably a methylene group or an ethylene group, more preferably an ethylene group.
  • R 1 is preferably a methylene group or an ethylene group, more preferably a methylene group.
  • R 2 is preferably a methylene group or an ethylene group, more preferably an ethylene group.
  • R 2 is preferably a methylene group or an ethylene group, more preferably a methylene group.
  • R 3 is preferably a methylene group or an ethylene group, more preferably an ethylene group.
  • R 3 is preferably a methylene group or an ethylene group, more preferably a methylene group.
  • R 4 is preferably a methylene group or an ethylene group, more preferably an ethylene group.
  • R 4 is preferably a methylene group or an ethylene group, more preferably a methylene group.
  • X 1 to X 4 each independently represent a hydrogen atom, a thiol group, or a hydroxy group, and at least two of X 1 to X 4 are thiol groups. It is preferable that at least three of X 1 to X 4 are thiol groups, and more preferably that all of X 1 to X 4 are thiol groups, because the solvent resistance of the obtained film can be further improved. preferable. It is also preferable that one or two of X 1 to X 4 are hydroxy groups. In this embodiment, the coating properties of the resin composition can be improved.
  • Specific examples of the specific thiol compound include compounds having the following structure.
  • the content of the specific thiol compound in the total solid content of the resin composition is preferably 0.1 to 20% by mass.
  • the lower limit is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and even more preferably 1.0% by mass or more.
  • the upper limit is preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less.
  • only one type of specific thiol compound may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
  • the resin composition of the present invention can contain thiol compounds other than the above-mentioned specific thiol compounds.
  • examples of other thiol compounds include compounds having one or more thiol groups, and preferably compounds having two or more thiol groups.
  • the upper limit of the number of thiol groups contained in other thiol compounds is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • thiol compounds include compounds described in paragraph numbers 0100 to 0103 of International Publication No. 2019/188652.
  • commercially available products include PEMP (manufactured by SC Organic Chemical Co., Ltd., thiol compound), Suncella M (manufactured by Sanshin Chemical Industry Co., Ltd., thiol compound), and Karenz MT BD1 (manufactured by Showa Denko K.K., thiol compound). etc. can also be mentioned.
  • the content of other thiol compounds in the total solid content of the resin composition is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.
  • the lower limit can be 0.1% by mass or more.
  • the content of other thiol compounds is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less, based on 100 parts by mass of the specific thiol compound. preferable.
  • the lower limit can be 1 part by mass or more.
  • only one type of other thiol compound may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
  • the resin composition of the present invention does not substantially contain other thiol compounds.
  • the case where the resin composition of the present invention does not substantially contain other thiol compounds means that the content of other thiol compounds in the total solid content of the resin composition is 0.01% by mass or less. However, it is preferably 0.005% by mass or less, and more preferably does not contain other thiol compounds.
  • the resin composition of the present invention contains particles.
  • Particles include organic pigments and inorganic pigments. Specific examples of the particles include white or colorless pigments, black pigments, chromatic pigments, and near-infrared absorbing pigments.
  • the average primary particle diameter of the particles is preferably 1 to 200 nm.
  • the lower limit is preferably 5 nm or more, more preferably 10 nm or more.
  • the upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less.
  • the primary particle size of the particles can be determined from a photograph obtained by observing the primary particles using a transmission electron microscope. Specifically, the projected area of the primary particle is determined, and the corresponding circular equivalent diameter is calculated as the primary particle diameter of the particle.
  • the average primary particle diameter of particles in this specification is the arithmetic mean value of the primary particle diameters of 400 primary particles.
  • primary particles refer to independent particles without agglomeration.
  • the crystallite size determined from the half-value width of the peak derived from any crystal plane in the X-ray diffraction spectrum when CuK ⁇ rays of the particles are used as the X-ray source is preferably 0.1 to 100 nm, and preferably 0.1 to 100 nm. It is more preferably from 5 to 50 nm, even more preferably from 1 to 30 nm, and particularly preferably from 5 to 25 nm.
  • the specific surface area of the particles is preferably 1 to 300 m 2 /g.
  • the lower limit is preferably 10 m 2 /g or more, more preferably 30 m 2 /g or more.
  • the upper limit is preferably 250 m 2 /g or less, more preferably 200 m 2 /g or less.
  • the value of the specific surface area is determined according to DIN 66131: determination of the specific surface area of solids by gas adsorption according to the BET (Brunauer, Emmett and Teller) method. (Measurement of specific surface area of solids).
  • chromatic pigment examples include green pigments, red pigments, yellow pigments, violet pigments, blue pigments, and orange pigments.
  • the chromatic pigment may be an organic pigment or an inorganic pigment.
  • the chromatic pigment is an organic pigment.
  • the green pigment examples include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred.
  • the green pigment is a pigment.
  • Specific examples of green pigments include C.I. I. Examples include green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66.
  • halogenated zinc phthalocyanine pigments have an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12, and an average of 2 to 5 chlorine atoms. You can also use Specific examples include compounds described in International Publication No. 2015/118720.
  • the green pigment a compound described in paragraph number 0029 of International Publication No. 2022/085485, an aluminum phthalocyanine compound described in JP 2020-070426, etc. can also be used.
  • the green pigment is C. I. (Color Index) Pigment Green 7, 36, 58, 59, 62, 63 are preferred; I. Pigment Green 7, 36, 58, and 59 are more preferred.
  • red pigments examples include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, and diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds. is preferable, and a diketopyrrolopyrrole compound is more preferable.
  • the red pigment is a pigment. Specific examples of red pigments include C.I. I.
  • red pigment a compound described in paragraph number 0034 of International Publication No. 2022/085485 and a brominated diketopyrrolopyrrole compound described in JP-A No. 2020-085947 can also be used.
  • the red pigment is C. I. Pigment Red 122, 177, 179, 254, 255, 264, 269, 272, 291 are preferred; I. Pigment Red 254, 264, and 272 are more preferred.
  • yellow pigments examples include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds.
  • the yellow pigment is preferably a pigment, more preferably an azo pigment, an azomethine pigment, an isoindoline pigment, a pteridine pigment, a quinophthalone pigment, or a perylene pigment, and more preferably an azo pigment or an azomethine pigment.
  • Specific examples of yellow pigments include C.I. I.
  • an azobarbituric acid nickel complex having the following structure can also be used as the yellow pigment.
  • the orange pigment is 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, 73, etc. orange pigments.
  • purple pigment examples include purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.
  • 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, 88 etc. It will be done.
  • an aluminum phthalocyanine compound having a phosphorus atom can also be used as the blue pigment. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A No. 2012-247591 and paragraph number 0047 of JP-A No. 2011-157478.
  • Two or more chromatic pigments may be used in combination. Moreover, when using a combination of two or more types of chromatic pigments, black may be formed by a combination of two or more types of chromatic pigments. Examples of such combinations include the following embodiments (1) to (7).
  • An embodiment containing a red pigment, a blue pigment, a yellow pigment, and a green pigment An embodiment containing a red pigment, a blue pigment, a yellow pigment, and a green pigment.
  • white or colorless pigment examples include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, and water.
  • examples include inorganic pigments such as aluminum oxide, calcium silicate, aluminum silicate, and zinc sulfide.
  • white pigments described in paragraph numbers 0040 to 0043 of International Publication No. 2022/085485 can be used as the white pigment.
  • the white pigment is silica particles.
  • silica particles include silica particles in which multiple spherical silica particles are connected in a beaded manner, silica particles in which multiple spherical silica particles are connected in a planar manner, silica particles with a hollow structure, and solid silica particles. It will be done.
  • black pigment The black pigment is not particularly limited, and known ones can be used.
  • the black pigment may be an inorganic pigment (inorganic black pigment) or an organic pigment (organic black pigment). Note that in this specification, black pigment means a pigment that exhibits absorption over the entire wavelength range of 400 to 700 nm.
  • Examples of the inorganic black pigment include carbon black, titanium black, graphite, etc. Carbon black and titanium black are preferred, and titanium black is more preferred. Titanium black is black particles containing titanium atoms, and lower titanium oxide and titanium oxynitride are preferable. As the titanium black, titanium black described in paragraph number 0044 of International Publication No. 2022/085485 can be used.
  • organic black pigment examples include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred.
  • organic black pigment a compound described in paragraph number 0166 of International Publication No. 2022/065215 can be used.
  • perylene black Liogen Black FK4280, etc.
  • JP 2017-226821 A may be used as the organic black pigment.
  • the near-infrared absorbing pigment is preferably a compound having a maximum absorption wavelength on the longer wavelength side than a wavelength of 700 nm.
  • the near-infrared absorbing pigment is preferably a compound having a maximum absorption wavelength in a wavelength range of more than 700 nm and 1800 nm or less, more preferably a compound having a maximum absorption wavelength in a wavelength range of more than 700 nm and 1400 nm or less, and a wavelength of 700 nm or less.
  • the compound has a maximum absorption wavelength in a range exceeding 700 nm and not more than 1200 nm, and particularly preferably a compound having a maximum absorption wavelength in a range exceeding 700 nm and not more than 1000 nm.
  • the ratio A 1 / A 2 between the absorbance A 1 at a wavelength of 500 nm and the absorbance A 2 at the maximum absorption wavelength of the near-infrared absorbing pigment is preferably 0.08 or less, and more preferably 0.04 or less.
  • the near-infrared absorbing pigment is an organic pigment.
  • Near-infrared absorbing pigments include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, Examples include azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, and the like. Specific examples of these include compounds described in paragraph number 0114 of International Publication No. 2022/065215.
  • examples of near-infrared absorbing pigments include the compound described in paragraph number 0121 of International Publication No. 2022/065215, the squarylium compound described in JP-A-2020-075959, and the Korean Patent Publication No. 10-2019-0135217.
  • the copper complex described in JP-A No. 2021-195515, the croconic acid compound described in JP-A No. 2022-022070, and the near-infrared absorbing pigment described in JP-A No. 2022-022070 can also be used.
  • tungsten oxide represented by the following formula described in paragraph number 0025 of European Patent No. 3,628,645 can also be used.
  • M 1 and M 2 represent ammonium cations or metal cations, a is 0.01 to 0.5, b is 0 to 0.5, c is 1, and d is 2.5 to 3.
  • e is 0.01 to 0.75, n is 1, 2 or 3, m is 1, 2 or 3, and R represents a hydrocarbon group which may have a substituent. represent.
  • the content of particles in the total solid content of the resin composition is preferably 20 to 80% by mass.
  • the lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 45% by mass or more.
  • the upper limit is preferably 75% by mass or less, more preferably 70% by mass or less.
  • the resin composition of the present invention contains a resin.
  • the resin is blended, for example, for use in dispersing particles in a resin composition or for use as a binder.
  • a resin used mainly for dispersing particles is also referred to as a dispersant.
  • this use of the resin is just one example, and the resin can also be used for purposes other than this use.
  • Examples of the resin include (meth)acrylic resin, epoxy resin, (meth)acrylamide resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene.
  • Examples include ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin.
  • examples of the resin include resins described in paragraph numbers 0091 to 0099 of International Publication No.
  • the weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 5000 or more.
  • the resin it is preferable to use a resin having acid groups.
  • the acid group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
  • the acid value of the resin having acid groups is preferably 30 to 500 mgKOH/g.
  • the lower limit is more preferably 40 mgKOH/g or more, particularly preferably 50 mgKOH/g or more.
  • the upper limit is more preferably 400 mgKOH/g or less, even more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less.
  • the weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, more preferably 5,000 to 50,000. Further, the number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.
  • the resin having an acid group preferably contains a repeating unit having an acid group in its side chain, and more preferably contains 5 to 70 mol% of repeating units having an acid group in its side chain based on the total repeating units of the resin.
  • the upper limit of the content of repeating units having acid groups in their side chains is preferably 50 mol% or less, more preferably 30 mol% or less.
  • the lower limit of the content of repeating units having acid groups in their side chains is preferably 10 mol% or more, more preferably 20 mol% or more.
  • a resin having a basic group can also be used.
  • the resin having a basic group is preferably a resin containing a repeating unit having a basic group in its side chain, and a resin having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group.
  • a polymer is more preferable, and a block copolymer having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group is even more preferable.
  • a resin having a basic group can also be used as a dispersant.
  • the amine value of the resin having a basic group is preferably 5 to 300 mgKOH/g.
  • the lower limit is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more.
  • the upper limit is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less.
  • resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (manufactured by BYK Chemie), Solsperse 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 385 00, 39000, 53095, 56000, 7100 (all manufactured by Japan Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like.
  • the resin having a basic group is the block copolymer (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and the block copolymer (B) described in paragraphs 0046 to 0076 of JP2018-156021A. It is also possible to use block copolymer A1, a vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP-A No. 2019-184763, the contents of which are incorporated herein.
  • the content of the resin having a basic group is preferably 20 to 500 parts by mass per 100 parts by mass of the resin having an acid group.
  • the amount is preferably 30 to 300 parts by weight, more preferably 50 to 200 parts by weight.
  • the resin it is also preferable to use a resin having a crosslinkable group.
  • the crosslinkable group include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • the ethylenically unsaturated bond-containing group include a vinyl group, a styrene group, a (meth)allyl group, and a (meth)acryloyl group.
  • the cyclic ether group include an epoxy group and an oxetanyl group, with an epoxy group being preferred.
  • the epoxy group may be a cycloaliphatic epoxy group. Note that 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 resin it is also preferable to use a resin having an aromatic carboxy group (hereinafter also referred to as resin Ac).
  • the aromatic carboxy group may be included in the main chain of the repeating unit, or may be included in the side chain of the repeating unit.
  • the aromatic carboxy group is preferably contained in the main chain of the repeating unit.
  • an aromatic carboxy group refers to a group having a structure in which one or more carboxy groups are bonded to an aromatic ring.
  • the number of carboxy groups bonded to the aromatic ring is preferably 1 to 4, more preferably 1 to 2.
  • the resin Ac is preferably a resin containing at least one type of repeating unit selected from a repeating unit represented by formula (Ac-1) and a repeating unit represented by formula (Ac-2).
  • Ar 1 represents a group containing an aromatic carboxy group
  • L 1 represents -COO- or -CONH-
  • L 2 represents a divalent linking group
  • Ar 10 represents a group containing an aromatic carboxy group
  • L 11 represents -COO- or -CONH-
  • L 12 represents a trivalent linking group
  • P 10 represents a polymer Represents a chain.
  • Examples of the group containing an aromatic carboxy group represented by Ar 1 in formula (Ac-1) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like.
  • Examples of the aromatic tricarboxylic anhydride and aromatic tetracarboxylic anhydride include compounds having the following structures.
  • Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, represented by the following formula (Q-1). or a group represented by the following formula (Q-2).
  • the aromatic carboxy group-containing group represented by Ar 1 may have a crosslinkable group.
  • the crosslinkable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, and more preferably an ethylenically unsaturated bond-containing group.
  • Specific examples of the group containing an aromatic carboxy group represented by Ar 1 include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13). Examples include groups such as
  • n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
  • n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2.
  • n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and preferably 1. More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
  • Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, the above formula (Q- Represents a group represented by 1) or a group represented by the above formula (Q-2).
  • *1 represents the bonding position with L 1 .
  • L 1 represents -COO- or -CONH-, and preferably represents -COO-.
  • the divalent linking group represented by L 2 includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these. Examples include groups combining two or more of the following.
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms.
  • the alkylene group may be linear, branched, or cyclic.
  • the number of carbon atoms in the arylene group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10.
  • the alkylene group and arylene group may have a substituent.
  • the divalent linking group represented by L 2 is preferably a group represented by -L 2a -O-.
  • L 2a is an alkylene group; an arylene group; a group combining an alkylene group and an arylene group; at least one selected from an alkylene group and an arylene group, and -O-, -CO-, -COO-, -OCO-, Examples include a group combining at least one selected from -NH- and -S-, and an alkylene group is preferred.
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms.
  • the alkylene group may be linear, branched, or cyclic.
  • the alkylene group and arylene group may have a substituent. Examples of the substituent include a hydroxy group.
  • the aromatic carboxy group-containing group represented by Ar 10 in formula (Ac-2) has the same meaning as Ar 1 in formula (Ac-1), and the preferred range is also the same.
  • L 11 represents -COO- or -CONH-, preferably -COO-.
  • the trivalent linking group represented by L 12 includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these two groups. Examples include groups that combine more than one species.
  • the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic.
  • the aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • the hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group.
  • the trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2).
  • L 12b represents a trivalent linking group
  • X 1 represents S
  • *1 represents the bonding position with L 11 of formula (Ac-2)
  • *2 represents the bonding position of formula (Ac-2). It represents the bonding position of Ac-2) with P10 .
  • the trivalent linking group represented by L 12b is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-.
  • a hydrocarbon group or a group consisting of a hydrocarbon group and -O- is preferable.
  • L 12c represents a trivalent linking group
  • X 1 represents S
  • *1 represents the bonding position with L 11 of formula (Ac-2)
  • *2 represents formula ( It represents the bonding position of Ac-2) with P10 .
  • the trivalent linking group represented by L 12c is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-.
  • a hydrocarbon group is preferable.
  • P 10 represents a polymer chain.
  • the polymer chain represented by P 10 preferably has at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure.
  • the weight average molecular weight of the polymer chain P 10 is preferably 500 to 20,000.
  • the lower limit is preferably 1000 or more.
  • the upper limit is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less. If the weight average molecular weight of P 10 is within the above range, the dispersibility of the pigment in the resin composition is good.
  • the resin having an aromatic carboxy group is a resin having a repeating unit represented by formula (Ac-2), this resin is preferably used as a dispersant.
  • the polymer chain represented by P 10 may contain a crosslinkable group.
  • the crosslinkable group include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • Such resins are preferably used as dispersants.
  • Examples of the graft polymer include a resin having a repeating unit having a graft chain and a resin having a repeating unit represented by the above-mentioned formula (Ac-2).
  • Examples of the graft chain include a graft chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure.
  • the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkylthioether group, and the like.
  • alkyl groups or alkoxy groups having 5 to 30 carbon atoms are preferred.
  • the alkyl group and the alkoxy group may be linear, branched, or cyclic, and preferably linear or branched.
  • graft polymers include paragraph numbers 0025 to 0094 of JP2012-255128A, paragraphs 0022 to 0097 of JP2009-203462A, and paragraphs 0102 to 0166 of JP2012-255128A. Mention may be made of the resins mentioned.
  • star-shaped polymers include resins with a structure in which a plurality of polymer chains are bonded to a core portion.
  • Specific examples of star-shaped polymers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A No. 2013-043962.
  • the block copolymers include a polymer block having a repeating unit containing an acid group or a basic group (hereinafter also referred to as block A), and a polymer block having a repeating unit not containing an acid group or a basic group. (hereinafter also referred to as block B) is preferably a block copolymer.
  • the block copolymers include block copolymers (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and blocks described in paragraph numbers 0046 to 0076 of JP2018-156021A. Copolymers A1 can also be used, the contents of which are incorporated herein.
  • the resin in which at least one end of the polymer chain is capped with an acid group is a resin in which at least one end of the polymer chain contains at least one type of structure selected from a polyester structure, a polyether structure, and a poly(meth)acrylic structure.
  • Examples include resins with a structure sealed with acid groups.
  • Examples of the acid group that caps the terminal of the polymer chain include a carboxy group, a sulfo group, and a phosphoric acid group, and a phosphoric acid group is preferable.
  • resins described in paragraph numbers 0052 to 0060 of JP-A No. 2011-213832 can also be used.
  • the dispersant include acidic dispersants (acidic resins) and basic dispersants (basic resins).
  • the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups.
  • the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %.
  • the acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g.
  • the basic dispersant refers to a resin in which the amount of basic groups is greater than the amount of acid groups.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%.
  • the basic group that the basic dispersant has is preferably an amino group.
  • Dispersants are also available as commercial products, and specific examples include the Disperbyk series manufactured by Byk Chemie (for example, Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajisper series manufactured by Ajinomoto Fine Techno Co., Ltd., A208F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), H-3606 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Sandet Examples include ET (manufactured by Sanyo Chemical Industries, Ltd.). Further, the product described in paragraph number 0129 of JP 2012-137564A and the product described in paragraph number 0235 of JP 2017-194662A can also be used as a dispersant.
  • Disperbyk series manufactured by Byk Chemie for example, Disperbyk-111, 161, 2001, etc.
  • the resin contained in the resin composition of the present invention preferably contains a resin as a dispersant, and more preferably contains a resin as a dispersant and a resin as a binder.
  • the content of the resin in the total solid content of the resin composition is preferably 1 to 50% by mass.
  • the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the upper limit is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.
  • the content of the resin having acid groups in the total solid content of the resin composition is preferably 1 to 50% by mass.
  • the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the upper limit is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.
  • the content of the resin having acid groups in the resin contained in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 30% by mass or more. More preferably, it is 50% by mass or more, even more preferably.
  • the content of the resin as a dispersant in the total solid content of the resin composition is preferably 1 to 50% by mass.
  • the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the upper limit is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.
  • the content of the resin as a dispersant is preferably 1 to 100 parts by mass based on 100 parts by mass of particles.
  • the upper limit is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less.
  • the lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more.
  • the content of the resin as a binder in the total solid content of the resin composition is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, It is particularly preferably 10% by mass or less.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
  • the content of the resin as a binder is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and 70 parts by mass or less with respect to 100 parts by mass of the resin as a dispersant. It is even more preferable that there be.
  • the lower limit is preferably 1 part by mass or more, more preferably 5 parts by mass or more.
  • the resin composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more types of resin are included, the total amount thereof is preferably within the above range.
  • the resin composition of the present invention contains a polymerizable monomer having an ethylenically unsaturated bond-containing group (hereinafter also referred to as a polymerizable monomer).
  • a polymerizable monomer having an ethylenically unsaturated bond-containing group hereinafter also referred to as a polymerizable monomer.
  • the ethylenically unsaturated bond-containing group contained in the polymerizable monomer include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group, with a (meth)acryloyl group being preferred.
  • the polymerizable monomer used in the present invention is preferably a radically polymerizable monomer.
  • the molecular weight of the polymerizable monomer is preferably 100 to 2,500.
  • the upper limit is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less.
  • the lower limit is preferably 150 or more, more preferably 250 or more.
  • the polymerizable monomer is preferably a compound containing two or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 2 to 15 ethylenically unsaturated bond-containing groups; More preferably, it is a compound containing 2 to 6 containing groups.
  • the polymerizable monomer is preferably a compound having two or more (meth)acryloyl groups, more preferably a compound having 2 to 15 (meth)acryloyl groups, and more preferably a compound having 2 to 6 (meth)acryloyl groups. It is more preferable that the compound is a compound that has its own properties.
  • the polymerizable monomer is preferably a (meth)acrylate compound having two or more functionalities, more preferably a (meth)acrylate compound having 2 to 15 functions, and preferably a (meth)acrylate compound having 2 to 6 functions. is even more preferable.
  • Specific examples of the polymerizable monomer include compounds described in paragraph numbers 0075 to 0083 of International Publication No. 2022/065215.
  • polymerizable monomers examples include dipentaerythritol triacrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available product: KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) ), dipentaerythritol penta(meth)acrylate (commercial product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercial product: KAYARAD DPHA; Nippon Kayaku Co., Ltd.) Co., Ltd., NK Ester A-DPH-12E; Shin Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues.
  • the content of the polymerizable monomer in the total solid content of the resin composition is preferably 1 to 30% by mass.
  • the lower limit is preferably 2% by mass or more, more preferably 3% 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 17% by mass or less.
  • the content of the polymerizable monomer is preferably 20 to 5000 parts by mass based on 100 parts by mass of the specific thiol compound.
  • the lower limit is preferably 100 parts by mass or more, more preferably 250 parts by mass or more.
  • the upper limit is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less.
  • only one type of polymerizable monomer may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
  • the resin composition of the present invention contains a solvent.
  • Solvents include water and organic solvents.
  • the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
  • paragraph number 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein.
  • Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used.
  • organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, butyl acetate, and 3-methoxypropion.
  • aromatic hydrocarbons benzene, toluene, xylene, ethylbenzene, etc.
  • organic solvents for environmental reasons (for example, 50 mass ppm (parts) based on the total amount of organic solvents). per million), 10 mass ppm or less, and 1 mass ppm or less).
  • an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably 10 mass ppb (parts per billion) or less, for example. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by Toyo Gosei Co., Ltd. (Kagaku Kogyo Nippo, November 13, 2015).
  • Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.
  • the organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one type of isomer may be included, or multiple types may be included.
  • the content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.
  • the content of the organic solvent in the resin 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 resin composition of the present invention preferably does not substantially contain environmentally regulated substances from the viewpoint of environmental regulations.
  • "not substantially containing environmentally controlled substances” means that the content of environmentally controlled substances in the resin composition is 50 mass ppm or less, preferably 30 mass ppm or less. , more preferably 10 mass ppm or less, particularly preferably 1 mass ppm or less.
  • environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • REACH Registration Evaluation Authorization and Restriction of CHemicals
  • PRTR Policy Release and It is registered as an environmentally regulated substance under the Transfer Register Act
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • methods for reducing environmentally controlled substances include a method of heating or reducing pressure in the system to raise the temperature above the boiling point of the environmentally controlled substance to distill off the environmentally controlled substances from the system.
  • distillation methods include the stage of raw materials, the stage of products made by reacting raw materials (for example, resin solution or polyfunctional monomer solution after polymerization), or the stage of resin compositions prepared by mixing these compounds. It is possible at any stage.
  • the resin composition of the present invention can contain a polymerization initiator.
  • the polymerization initiator include photopolymerization initiators and thermal polymerization initiators, with photopolymerization initiators being preferred.
  • a resin composition containing a photopolymerization initiator as a polymerization initiator has a wide exposure latitude and is preferably used as a resin composition for pattern formation in photolithography.
  • the polymerization initiator preferably contains at least one selected from oxime compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, and acylphosphine compounds, and more preferably contains an oxime compound.
  • the polymerization initiator is preferably a radical polymerization initiator.
  • thermal polymerization initiator examples include 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismarenonitrile, dimethyl-(2,2')-azobis(2-methyl organic peroxides such as tert-butylperoxybenzoate, benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
  • AIBN 2,2'-azobisisobutyronitrile
  • 3-carboxypropionitrile examples include azobismarenonitrile, dimethyl-(2,2')-azobis(2-methyl organic peroxides such as tert-butylperoxybenzoate, benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
  • photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, and the like.
  • halogenated hydrocarbon derivatives e.g., compounds with a triazine skeleton, compounds with 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, and the like.
  • photopolymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and hexaarylbylene compounds.
  • imidazole compounds onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds, oxime compounds, ⁇ -hydroxyketones
  • the compound is more preferably a compound selected from a compound, an ⁇ -aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound.
  • photopolymerization initiators compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, 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, etc. can be mentioned.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, and Irgacure 117. 3, Irgacure 2959, Irgacure 127 (all BASF (manufactured by a company).
  • Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, and Irgacure 36.
  • Irgacure 369E Irgacure 379EG (all manufactured by BASF) (manufactured by).
  • Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.
  • Examples of oxime compounds include the compound described in paragraph 0142 of International Publication No. 2022/085485, the compound described in Patent No. 5430746, the compound described in Patent No. 5647738, and the general formula (1 ) and the compounds described in paragraphs 0022 to 0024, and the compounds represented by the general formula (1) and the compounds described in paragraphs 0117 to 0120 of JP-A-2021-170089.
  • oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like.
  • photopolymerization initiators include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, oxime compounds having a fluorine atom, oxime compounds having a nitro group, and benzofuran skeleton.
  • An oxime compound having a carbazole skeleton bonded with a substituent having a hydroxy group, and compounds described in paragraphs 0143 to 0149 of International Publication No. 2022/085485 can also be used.
  • oxime compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm.
  • the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably from 1000 to 300,000, even more preferably from 2000 to 300,000, and even more preferably from 5000 to 200,000. It is particularly preferable that there be.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
  • a difunctional, trifunctional or more functional photoradical polymerization initiator may be used as the photopolymerization initiator.
  • a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained.
  • the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time, thereby improving the stability of the resin composition over time.
  • Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include compounds described in paragraph 0148 of International Publication No. 2022/065215.
  • the content of the polymerization initiator in the total solid content of the resin composition is preferably 0.5 to 20% by mass.
  • the lower limit is preferably 1% by mass or more, more preferably 2% by mass or more.
  • the upper limit is preferably 15% by mass or less, more preferably 10% by mass or less.
  • the content of the polymerization initiator is preferably 20 to 1,000 parts by mass based on 100 parts by mass of the specific thiol compound.
  • the lower limit is preferably 30 parts by mass or more, more preferably 50 parts by mass or more.
  • the upper limit is preferably 800 parts by mass or less, more preferably 500 parts by mass or less.
  • only one type of polymerization initiator may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
  • the resin composition of the present invention can contain a pigment derivative.
  • Pigment derivatives are used, for example, as particle dispersion aids.
  • the pigment derivative include compounds having at least one structure selected from the group consisting of a pigment structure and a triazine structure, and an acid group or a basic group.
  • the above dye structures include squarylium dye structure, pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure, anthraquinone dye structure, dianthraquinone dye structure, benzisoindole dye structure, thiazine indigo dye structure, and azo dye structure.
  • quinophthalone dye structure phthalocyanine dye structure, naphthalocyanine dye structure, dioxazine dye structure, perylene dye structure, perinone dye structure, benzimidazolone dye structure, benzothiazole dye structure, benzimidazole dye structure and benzoxazole dye structure
  • Squarylium dye structures pyrrolopyrrole dye structures, diketopyrrolopyrrole dye structures, phthalocyanine dye structures, quinacridone dye structures and benzimidazolone dye structures are preferred, and squarylium dye structures and pyrrolopyrrole dye structures are more preferred.
  • Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imide acid group, and salts thereof.
  • Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + , etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ , etc.), ammonium ions, imidazolium ions, pyridinium ions, Examples include phosphonium ions.
  • As the carboxylic acid amide group a group represented by -NHCOR A1 is preferable.
  • a group represented by -NHSO 2 R A2 is preferable.
  • the imide acid group is preferably a group represented by -SO 2 NHSO 2 R A3 , -CONHSO 2 R A4 , -CONHCOR A5 or -SO 2 NHCOR A6 , and -SO 2 NHSO 2 R A3 is more preferred.
  • R A1 to R A6 each independently represent an alkyl group or an aryl group.
  • the alkyl group and aryl group represented by R A1 to R A6 may have a substituent.
  • the substituent is preferably a halogen atom, more preferably a fluorine atom.
  • Examples of the basic group include an amino group, a pyridinyl group and its salts, an ammonium group salt, and a phthalimidomethyl group.
  • Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
  • pigment derivatives include the compounds described in the Examples described below, the compounds described in paragraph 0124 of International Publication No. 2022/085485, and the benzimidazolone compounds or salts thereof described in JP 2018-168244.
  • a compound having an isoindoline skeleton described in the general formula (1) of Patent No. 6996282 can also be used.
  • the content of the pigment derivative in the total solid content of the resin composition is preferably 0.3 to 20% by mass.
  • the lower limit is preferably 0.6% by mass or more, more preferably 0.9% by mass or more.
  • the upper limit is preferably 15% by mass or less, more preferably 12.5% by mass or less, and even more preferably 10% by mass or less.
  • the content of the pigment derivative is preferably 1 to 30 parts by mass based on 100 parts by mass of the pigment.
  • the lower limit is preferably 2 parts by mass or more, more preferably 3 parts by mass or more.
  • the upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.
  • only one type of pigment derivative may be used, or two or more types may be used in combination. When two or more types are used in combination, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention can also contain polyalkyleneimine.
  • Polyalkyleneimines are used, for example, as particle dispersion aids.
  • Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine, and is a polymer having at least a secondary amino group.
  • the polyalkyleneimine may contain a primary amino group or a tertiary amino group in addition to the secondary amino group.
  • the polyalkyleneimine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group, respectively.
  • the alkylene imine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
  • alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, etc. Ethyleneimine or propyleneimine is preferable, and ethyleneimine is more preferable. preferable.
  • the molecular weight of the polyalkylene imine is preferably 200 or more, more preferably 250 or more.
  • the upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less.
  • the molecular weight of the polyalkylene imine if the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkylene imine is the value calculated from the structural formula.
  • the molecular weight of a specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used.
  • the value of the number average molecular weight measured by the viscosity method is used. If the viscosity method cannot be used or it is difficult to measure, the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) is used.
  • the amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
  • the polyalkyleneimine is polyethyleneimine.
  • the polyethyleneimine preferably contains a primary amino group of 10 mol% or more, more preferably 20 mol% or more, based on the total of the primary amino group, secondary amino group, and tertiary amino group. It is more preferable that the content is mol % or more.
  • Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).
  • the content of polyalkyleneimine in the total solid content of the resin composition is preferably 0.1 to 5% by mass.
  • the lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
  • the upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
  • the content of polyalkyleneimine is preferably 0.5 to 20 parts by weight per 100 parts by weight of the pigment.
  • the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more.
  • the upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. Only one type of polyalkylene imine may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
  • the resin composition of the present invention may contain a dye.
  • a dye There are no particular restrictions on the dye, and known dyes can be used. Examples of the dye include chromatic dyes, black dyes, and near-infrared absorbing dyes. As the dye, known dyes can be used.
  • a dye multimer can also be used as the dye. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less.
  • the plurality of dye structures contained in one molecule may be the same dye structure or may be different dye structures.
  • the weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000.
  • the lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more.
  • the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
  • the dye multimers are disclosed in JP 2011-213925, JP 2013-041097, JP 2015-028144, JP 2015-030742, JP 2016-102191, International Publication No. 2016/ Compounds described in No. 031442 and the like can also be used.
  • the content of the dye in the total solid content of the resin composition is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and 5% by mass or less. It is even more preferable that it is, and it is particularly preferable that it is 1% by mass or less. It is also preferable that the resin composition of the present invention does not substantially contain dye.
  • the case where the dye is not substantially contained means that the content of the dye in the total solid content of the resin composition is 0.1% by mass or less, and 0.01% by mass It is preferable that it is below, and it is more preferable that it contains no dye.
  • the resin composition of the present invention can contain a compound having a cyclic ether group.
  • the cyclic ether group include an epoxy group and an oxetanyl group.
  • the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound).
  • epoxy compounds include those described in paragraph numbers 0034 to 0036 of JP2013-011869, paragraphs 0147 to 0156 of JP2014-043556, and paragraphs 0085 to 0092 of JP2014-089408.
  • Compounds, compounds described in JP 2017-179172, xanthene type epoxy resins described in JP 2021-195421, and xanthene epoxy resins described in JP 2021-195422 can also be used.
  • the compound having a cyclic ether group may be a low-molecular compound (e.g., molecular weight less than 2,000, further, molecular weight less than 1,000), or a macromolecule (e.g., molecular weight 1,000 or more, in the case of a polymer, a weight average molecular weight may be 1000 or more).
  • the weight average molecular weight of the compound having a cyclic ether group is preferably 200 to 100,000, more preferably 500 to 50,000.
  • the upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly 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, and G-0130SP.
  • -0250SP G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all of which are epoxy group-containing polymers manufactured by NOF Corporation).
  • the content of the compound having a cyclic ether group in the total solid content of the resin composition is preferably 0.1 to 20% by mass.
  • the lower limit is, for example, preferably 0.5% by mass or more, more preferably 1% by mass or more.
  • the upper limit is, for example, preferably 15% by mass or less, more preferably 10% by mass or less.
  • the number of compounds having a cyclic ether group may be one, or two or more. In the case of two or more types, it is preferable that the total amount thereof falls within the above range.
  • the resin composition of the present invention can contain an ultraviolet absorber.
  • the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. Specific examples of such compounds include the compound described in paragraph number 0179 of International Publication No. 2022/085485, the reactive triazine ultraviolet absorber described in JP 2021-178918, and JP 2022-007884. It is also possible to use the ultraviolet absorbers described in .
  • the content of the ultraviolet absorber in the total solid content of the resin 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 their total amount falls within the above range.
  • the resin composition of the present invention can contain an antioxidant.
  • antioxidants include phenol compounds, phosphite compounds, thioether compounds, and the like.
  • the phenol compound any phenol compound known as a phenolic antioxidant can be used.
  • Preferred phenol compounds include hindered phenol compounds.
  • a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred.
  • the above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms.
  • the antioxidant a compound having a phenol group and a phosphorous acid ester group in the same molecule is also preferable.
  • phosphorus-based antioxidants can also be suitably used.
  • a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl )oxy]ethyl]amine, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
  • antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Co., Ltd.).
  • antioxidants include compounds described in paragraph numbers 0023 to 0048 of Patent No. 6268967, compounds described in International Publication No. 2017/006600, compounds described in International Publication No. 2017/164024, Compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used.
  • the content of the antioxidant in the total solid content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention can contain a polymerization inhibitor.
  • Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred.
  • the content of the polymerization inhibitor in the total solid content of the resin composition is preferably 0.0001 to 5% by mass.
  • the number of polymerization inhibitors may be one, or two or more. In the case of two or more types, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention can contain a silane coupling agent.
  • a silane coupling agent means a silane compound having a hydrolyzable group.
  • the silane coupling agent is preferably a silane compound having a hydrolyzable group and other functional groups.
  • the term "hydrolyzable group" refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkoxy group is preferred.
  • the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, and isocyanate groups. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferable.
  • Specific examples of the silane coupling agent include compounds described in paragraph 0177 of International Publication No. 2022/085485.
  • the content of the silane coupling agent in the total solid content of the resin composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass. preferable. Only one type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention can contain a surfactant.
  • a surfactant various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.
  • the surfactant is preferably a silicone surfactant or a fluorine surfactant.
  • fluorosurfactant compounds described in paragraph numbers 0167 to 0173 of International Publication No. 2022/085485 can be used.
  • nonionic surfactants examples include compounds described in paragraph 0174 of International Publication No. 2022/085485.
  • silicone surfactants examples include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), and TSF- 4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) , BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by BYK Chemie), and the like.
  • 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 resin composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% to 3.0% by mass.
  • the resin composition of the present invention only one type of surfactant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
  • the resin composition of the present invention may contain sensitizers, curing accelerators, thermosetting accelerators, plasticizers, and other auxiliary agents (e.g., conductive particles, fillers, antifoaming agents, flame retardants), as necessary. , a leveling agent, a peeling accelerator, a fragrance, a surface tension regulator, a chain transfer agent, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. As these components, the compounds described in paragraph 0182 of International Publication No. 2022/085485 can be used.
  • the resin composition of the present invention may also contain a light resistance improver.
  • the light resistance improver include compounds described in paragraph number 0183 of International Publication No. 2022/085485.
  • the resin composition of the present invention is substantially free of terephthalic acid ester.
  • substantially not containing means that the content of terephthalic acid ester is 1000 mass ppb or less in the total amount of the resin composition, more preferably 100 mass ppb or less, Particularly preferred is zero.
  • perfluoroalkyl sulfonic acids and their salts may be regulated.
  • perfluoroalkylsulfonic acids particularly perfluoroalkylsulfonic acids whose perfluoroalkyl group has 6 to 8 carbon atoms
  • salts thereof and perfluoroalkylsulfonic acids
  • the content of fluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid whose perfluoroalkyl group has 6 to 8 carbon atoms) and its salt is 0.01 ppb to 1,000 ppb based on the total solid content of the resin composition.
  • the resin composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt.
  • a compound that can be substituted for perfluoroalkylsulfonic acid and its salt and a compound that can be substituted for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid
  • Compounds that can be substituted for regulated compounds include, for example, compounds that are excluded from regulated targets due to differences in the number of carbon atoms in perfluoroalkyl groups.
  • the resin composition of the present invention may contain perfluoroalkyl sulfonic acids and salts thereof, and perfluoroalkyl carboxylic acids and salts thereof, within the maximum allowable range.
  • the container for storing the resin composition is not particularly limited, and any known container can be used. Further, as the storage container, the container described in paragraph 0187 of International Publication No. 2022/085485 can be used.
  • the resin composition of the present invention can be prepared by mixing the above-mentioned components.
  • the resin composition may be prepared by simultaneously dissolving and/or dispersing all components in a solvent, or, if necessary, each component may be prepared as two or more solutions or dispersions as appropriate.
  • the resin composition may be prepared by mixing these at the time of use (at the time of application).
  • a process of dispersing particles such as pigments.
  • mechanical forces used for dispersing particles include compression, squeezing, impact, shearing, cavitation, and the like.
  • Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like.
  • JP 2015-157893 A "Practical Application Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be suitably used.
  • the particles may be refined in a salt milling step.
  • the descriptions in JP-A No. 2015-194521 and JP-A No. 2012-046629 can be referred to, for example.
  • the resin composition In preparing the resin composition, it is preferable to filter the resin composition with a filter for the purpose of removing foreign substances and reducing defects.
  • a filter for the purpose of removing foreign substances and reducing defects.
  • Examples of the type of filter and filtration method used for filtration include the filters and filtration methods described in paragraph numbers 0196 to 0199 of International Publication No. 2022/085485.
  • the film of the present invention is a film obtained from the resin composition of the present invention described above.
  • the film thickness of the film of the present invention can be adjusted as appropriate depending on the purpose.
  • the film 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 can be used for color filters, near-infrared transmission filters, near-infrared cut filters, black matrices, light-shielding films, light-scattering films, light-refractive films, electrical insulation films, and the like.
  • the film of the present invention can 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.
  • the film of the present invention can be manufactured through a step of applying the resin composition of the present invention.
  • the film manufacturing method preferably further includes a step of forming a pattern (pixel). Examples of methods for forming patterns (pixels) include photolithography and dry etching, with photolithography being preferred.
  • Pattern formation by the photolithography method includes a step of forming a resin composition layer on a support using the resin composition of the present invention, a step of exposing the resin composition layer to light in a pattern, and a step of exposing the resin composition layer to light. It is preferable to include a step of developing and removing the exposed portion to form a pattern (pixel). If necessary, a step of baking the resin composition layer (pre-bake step) and a step of baking the developed pattern (pixel) (post-bake step) may be provided.
  • a resin composition layer is formed on a support using the resin 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. may 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.
  • the silicon substrate may be provided with a base layer for improving adhesion with the upper layer, preventing substance diffusion, or flattening the substrate surface.
  • the surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferable that the angle is 30 to 80° when measured with water.
  • a known method can be used as a method for applying the resin composition.
  • dropping method drop casting
  • slit coating method spray method; roll coating method; spin coating method; casting coating method; slit and spin method;
  • inkjet for example, on-demand method, piezo method, thermal method
  • ejection printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc.
  • Examples include various printing methods; transfer method using a mold, etc.; nanoimprint method, etc.
  • the application method for inkjet is not particularly limited, and for example, the method shown in "Expanding and Usable Inkjet - Infinite Possibilities Seen in Patents," Published February 2005, Sumibe Techno Research (especially from page 115). 133 pages), and methods described in JP-A No. 2003-262716, JP-A No. 2003-185831, JP-A No. 2003-261827, JP-A No. 2012-126830, JP-A No. 2006-169325, etc. Can be mentioned. Furthermore, regarding the method of applying the resin composition, the descriptions in International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and the contents of these are incorporated herein.
  • the resin composition layer formed on the support may be dried (prebaked). If the film is manufactured by a low-temperature process, prebaking may not be performed.
  • the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower.
  • the lower limit can be, for example, 50°C or higher, or 80°C or higher.
  • the prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, oven, or the like.
  • the resin composition layer is exposed in a pattern (exposure step).
  • the resin composition layer can be exposed in a pattern by exposing the resin composition layer to light through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. This allows the exposed portion to be cured.
  • Radiation (light) that can be used during exposure includes g-line, i-line, etc. Furthermore, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm). Furthermore, a long-wave light source of 300 nm or more can also be used. As a light source, an electrodeless ultraviolet lamp system, a hybrid ultraviolet and infrared curing can be used.
  • pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the millisecond level or less).
  • the 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 carried out in the atmosphere, for example, exposure may be carried out in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially
  • the exposure may be carried out in an oxygen-free environment (without oxygen), or in a high oxygen atmosphere with an oxygen concentration of more than 21 vol% (for example, 22 vol%, 30 vol%, or 50 vol%).
  • the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000W/m 2 to 100000W/m 2 (for example, 5000W/m 2 , 15000W/m 2 , or 35000W/m 2 ). Can be done.
  • the oxygen concentration and the exposure illuminance may be appropriately combined.
  • the illumination intensity may be 10,000 W/m 2 at an oxygen concentration of 10% by volume, or 20,000 W/m 2 at an oxygen concentration of 35% by volume.
  • the unexposed areas of the resin composition layer are developed and removed to form a pattern (pixel).
  • the unexposed areas of the resin composition layer can be removed by development using a developer.
  • the unexposed portions of the resin composition layer in the exposure step are eluted into the developer, leaving only the photocured portions.
  • the temperature of the developer is preferably, for example, 20 to 30°C.
  • the development time is preferably 20 to 180 seconds. Furthermore, in order to improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
  • Examples of the developer include organic solvents, alkaline developers, and alkaline developers are preferably used.
  • the developer and cleaning method after development the developer and cleaning method described in paragraph number 0214 of International Publication No. 2022/085485 can be used.
  • Additional exposure processing and post-bake are post-development curing processing to complete curing.
  • the heating temperature in post-baking is, for example, preferably 100 to 240°C, more preferably 200 to 240°C.
  • Post-baking can be carried out in a continuous or batch manner using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to maintain the developed film under the above conditions.
  • the light used for exposure is preferably light with a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
  • Pattern formation by the dry etching method includes the steps of forming a resin composition layer on a support using the resin composition of the present invention, and curing the entire resin composition layer to form a cured product layer; A step of forming a photoresist layer on this cured material layer, a step of exposing the photoresist layer in a pattern and then developing it to form a resist pattern, and etching the cured material layer using this resist pattern as a mask. It is preferable to include a step of dry etching using gas. In forming the photoresist layer, it is preferable to further perform a prebaking process.
  • the optical filter of the present invention has the film of the present invention described above.
  • Types of optical filters include color filters, near-infrared cut filters, near-infrared transmission filters, etc., and color filters are preferred.
  • the color filter preferably has the film of the present invention as its pixels, and more preferably has the film of the present invention as its colored pixels.
  • Optical filters can be used in solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors), image display devices, and the like.
  • CCDs charge-coupled devices
  • CMOSs complementary metal oxide semiconductors
  • the film thickness of the film of the present invention can be adjusted as appropriate depending on the purpose.
  • the film 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 width of the pixels included in the optical filter is preferably 0.4 to 10.0 ⁇ m.
  • the lower limit is preferably 0.4 ⁇ m or more, more preferably 0.5 ⁇ m or more, and even more preferably 0.6 ⁇ m or more.
  • the upper limit is preferably 5.0 ⁇ m or less, more preferably 2.0 ⁇ m or less, even more preferably 1.0 ⁇ m or less, and even more preferably 0.8 ⁇ m or less.
  • the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
  • each pixel included in the optical filter has high flatness.
  • the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example.
  • the surface roughness of a pixel can be measured using, for example, an AFM (atomic force microscope) Dimension 3100 manufactured by Veeco.
  • the contact angle of water on the pixel can be set to a suitable value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT-A type (manufactured by Kyowa Interface Science Co., Ltd.).
  • the volume resistance value of the pixel is high.
  • the volume resistance value of the pixel is preferably 10 9 ⁇ cm or more, more preferably 10 11 ⁇ cm or more.
  • the upper limit is not specified, it is preferably 10 14 ⁇ cm or less, for example.
  • the volume resistance value of a pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest).
  • a protective layer may be provided on the surface of the film of the present invention.
  • various functions such as oxygen blocking, low reflection, hydrophilic and hydrophobic properties, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted.
  • the thickness of the protective layer is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
  • Examples of the method for forming the protective layer include a method of applying a resin composition for forming the protective layer, a chemical vapor deposition method, and a method of pasting a molded resin with an adhesive.
  • Components constituting the protective layer include (meth)acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide.
  • Resin polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Examples include resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al 2 O 3 , Mo, SiO 2 , Si 2 N 4 and the like, and two or more of these components may be contained.
  • the protective layer preferably contains a polyol resin, SiO 2 and Si 2 N 4 .
  • the protective layer preferably contains a (meth)acrylic resin and a fluororesin.
  • the protective layer may contain organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants, and other additives, as necessary. It may contain.
  • organic/inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like.
  • the absorber for light of a specific wavelength a known absorber can be used.
  • the content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, based on the total weight of the protective layer.
  • the protective layers described in paragraph numbers 0073 to 0092 of JP 2017-151176 A can also be used.
  • the optical filter may have a base layer.
  • the surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferable that the angle is 30 to 80° when measured with water.
  • the optical filter may have a structure in which each pixel is embedded in a space partitioned into a lattice shape by partition walls, for example.
  • the solid-state imaging device of the present invention has the film of the present invention described above.
  • the structure of the solid-state image sensor of the present invention is not particularly limited as long as it includes the film of the present invention and functions as a solid-state image sensor, but examples include the following structures.
  • the substrate has a plurality of photodiodes that constitute the light receiving area of a solid-state image sensor (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon or the like.
  • a device protective film made of silicon nitride or the like is formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a configuration in which a color filter is provided on the device protective film.
  • the color filter may have a structure in which each pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls.
  • the partition wall preferably has a low refractive index for each pixel. Examples of imaging devices having such a structure include devices described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, and International Publication No. 2018/043654.
  • an ultraviolet absorbing layer may be provided within the structure of the solid-state image sensor to improve light resistance.
  • An imaging device equipped with the solid-state imaging device of the present invention can be used not only as a digital camera or an electronic device having an imaging function (such as a mobile phone), but also as a vehicle-mounted camera or a surveillance camera.
  • the image display device of the present invention has the film of the present invention described above.
  • Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device.
  • Examples of an image display device and details of each image display device see, for example, “Electronic Display Devices (written by Akio Sasaki, Kogyo Chosenkai Co., Ltd., published in 1990)” and “Display Devices (written by Junaki Ibuki, published by Sangyo Tosho)”. Co., Ltd., issued in 1989).
  • liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994)".
  • Next Generation Liquid Crystal Display Technology edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994.
  • the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology.”
  • ⁇ Production of dispersion> A mixture of the raw materials listed in the table below was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.3 mm in diameter). Next, dispersion treatment was performed using a high-pressure dispersion machine NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reduction mechanism under conditions of a pressure of 2000 kg/cm 2 and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a dispersion liquid. Note that the numerical value of the amount of dispersant added is a numerical value in terms of solid content.
  • the raw materials used for the dispersion are as follows.
  • PG36 C. I. Pigment Green 36 (phthalocyanine pigment, green pigment)
  • PG58 C. I. Pigment Green 58 (phthalocyanine pigment, green pigment)
  • PR254 C. I. Pigment Red 254 (diketopyrrolopyrrole pigment, red pigment)
  • PR264 C. I. Pigment Red 264 (diketopyrrolopyrrole pigment, red pigment)
  • PR272 C. I. Pigment Red 272 (diketopyrrolopyrrole pigment, red pigment) PR291:C.
  • I. Pigment Red 291 (diketopyrrolopyrrole pigment, red pigment) PR177:C.
  • I. Pigment Red 177 anthraquinone pigment, red pigment) PO71:C. I.
  • Pigment Orange 71 (diketopyrrolopyrrole pigment, orange pigment) PY138:C.
  • Pigment Yellow 138 quinophthalone pigment, yellow pigment
  • Pigment Yellow 139 isoindoline pigment, yellow pigment
  • Pigment Yellow 150 (azo pigment, yellow pigment)
  • Pigment Yellow 185 (isoindoline pigment, yellow pigment)
  • Pigment Yellow 215 (pteridine pigment, yellow pigment) TiO 2 : Titanium oxide
  • TiNO Titanium oxynitride
  • ZrO 2 Zirconium oxide
  • (dispersant) B-1 Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 24000, acid value 47 mgKOH/g)
  • B-2 Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 16000, acid value 67 mgKOH/g)
  • Resin B-4 synthesized by the following method 50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, 20 parts by mass of t-butyl methacrylate, and 45.4 parts by mass of PGMEA (propylene glycol monomethyl ether acetate) were charged into a reaction vessel, and the atmosphere was changed to nitrogen gas. Replaced with. The inside of the reaction vessel was heated to 70°C, 6 parts by mass of 3-mercapto-1,2-propanediol was added, and further 0.12 parts by mass of AIBN (azobisisobutyronitrile) was added. Allowed time to react. It was confirmed by solid content measurement that 95% had reacted.
  • PGMEA propylene glycol monomethyl ether acetate
  • B-6 Resin with the following structure (block copolymer. The numbers appended to the main chain are mass ratios. Amine value 71 mgKOH/g, weight average molecular weight 9900)
  • B-8 Resin with the following structure (weight average molecular weight 2500, number average molecular weight 1200.
  • pigment derivative Syn-1: Compound with the following structure (basic pigment derivative)
  • a resin composition was manufactured by mixing the materials listed in the table below.
  • M-1 KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
  • M-2 NK ester A-DPH-12E (ethoxylated dipentaerythritol polyacrylate (5-6 functional acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • M-4 Succinic acid modified dipentaerythritol pentaacrylate
  • M-5 Dipentaerythritol hexaacrylate
  • binder Resin with the following structure (the numerical value appended to the main chain is the molar ratio.
  • b2 Resin with the following structure (the numerical value appended to the main chain is the molar ratio.
  • b3 Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units.
  • b4 Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units.
  • (surfactant) W-1 Solution of KF-6001 (polydimethylsiloxane modified with carbinol at both ends, hydroxyl value 62 mgKOH/g, manufactured by Shin-Etsu Chemical Co., Ltd.) whose solid concentration was adjusted to 1% by mass with propylene glycol monomethyl ether acetate
  • W -2 Solution of BYK-330 (manufactured by BYK Chemie) whose solid concentration was adjusted to 1% by mass with propylene glycol monomethyl ether acetate
  • W-3 The following compound (% indicating the proportion of repeating units is mol%. Weight 1% by mass propylene glycol monomethyl ether acetate solution of average molecular weight: 14000)
  • Viscosity change (%) ((
  • Viscosity change is 0.0% or more and less than 3.0%
  • a transparent base material (CT-4000L, manufactured by Fujifilm Electronics Materials Co., Ltd.) was applied to a glass wafer with a diameter of 8 inches (20.32 cm) to a dry film thickness of 0.1 ⁇ m, and dried. After forming the base layer, heat treatment was performed at 220° C. for 5 minutes to obtain a glass wafer with the base layer. Next, each resin composition was applied onto the base layer of the base layer-equipped glass wafer using a spin coater so that the film thickness after prebaking would be 1.5 ⁇ m, and was applied using a hot plate at 110°C for 120 seconds. Heat treatment (prebake) was performed.
  • the glass wafer on which the puddle-developed film has been formed is fixed to the horizontal rotary table using a vacuum chuck method, and while the glass wafer is rotated at a rotation speed of 50 rpm by a rotating device, pure water is poured from above the center of rotation. was supplied in a shower form from a jet nozzle for rinsing treatment, and then spray-dried. Thereafter, heat treatment (post-bake) was performed for 5 minutes using a 220° C. hot plate to form 2 cm square pixels.
  • the glass wafer on which the above pixels were formed was immersed in cyclohexanone heated to 50°C for 15 minutes, and the OD value (optical density) in the wavelength range of 400 to 700 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Tech Corporation). Measured using The change in OD value of the pixel before and after immersion in cyclohexanone was examined, and the solvent resistance was evaluated based on the fluctuation rate at the wavelength that showed the maximum fluctuation rate. The fluctuation rate of the OD value for each wavelength of light was determined based on the following formula.
  • Variation rate of OD value (%) ((
  • a to C it is at a level that poses no problem in practical use.
  • C The rate of change in the OD value is 5% or more and less than 10%.
  • D The rate of change in the OD value is 5% or more and less than 10%. 10% or more
  • a transparent base material (CT-4000L, manufactured by Fujifilm Electronics Materials Co., Ltd.) was applied on a silicon wafer with a diameter of 8 inches (20.32 cm) to a dry film thickness of 0.1 ⁇ m, and dried. After forming the base layer, heat treatment was performed at 220° C. for 5 minutes to obtain a silicon wafer with the base layer. Next, each resin composition was applied onto the base layer of a silicon wafer with a base layer to form a coating film. Then, heat treatment (prebaking) was performed for 120 seconds using a 100° C. hot plate so that the dry film thickness of this coating film was 0.5 ⁇ m.
  • the silicon wafer on which the paddle-developed film has been formed is fixed to a horizontal rotary table using a vacuum chuck method, and while the silicon wafer is rotated at a rotation speed of 50 rpm by a rotation device, pure water is poured from above the center of rotation.
  • a rinsing treatment was performed by supplying it in a shower form from a jet nozzle, and then spray drying.
  • heat treatment was performed at 200° C. for 300 seconds using a hot plate to form pixels.
  • the line width of the pixel was measured using a scanning electron microscope (S-9260A, manufactured by Hitachi High-Tech Corporation). The exposure amount at which the pixel line width was 0.9 ⁇ m was defined as the optimum exposure amount.
  • the exposure amount was changed to various exposure amounts from 10 to 500 mJ/ cm2 , and the exposure amount width was determined to allow the line width of the pixel after post-baking to be 0.9 ⁇ m ⁇ 10%. I asked for it. This value was divided by the optimum exposure amount and expressed as a percentage (%), and the value was evaluated as the exposure latitude.
  • a to C is at a level that poses no practical problem.
  • B The exposure latitude value is 12% or more and less than 15%.
  • C The exposure latitude value is 9% or more and less than 12%.
  • D The exposure latitude value is less than 9%.
  • the examples had excellent storage stability and solvent resistance. Furthermore, the evaluation of exposure latitude was also good. Furthermore, the resin compositions of Examples had good coating properties. Examples 34 and 35 had particularly excellent coating properties.
  • a transparent base material (CT-4000L, manufactured by Fujifilm Electronics Materials Co., Ltd.) was applied on a silicon wafer with a diameter of 8 inches (20.32 cm) to a dry film thickness of 0.1 ⁇ m, and dried. After forming the base layer, heat treatment was performed at 220° C. for 5 minutes to obtain a silicon wafer with the base layer. Next, the resin composition of Example 34, Example 35, or Comparative Example 1 was applied onto the base layer of the base layer-equipped silicon wafer to form a coating film. When the obtained coating films were observed with an optical microscope, no coating unevenness was observed in the coating films formed using the resin compositions of Examples 34 and 35, and the coating properties were good. On the other hand, foreign matter was observed in the coating film formed using the resin composition of Comparative Example 1.
  • Example 1001, 1002, Comparative Example 1001 The resin compositions of Example 1, Example 14, and Comparative Example 1 were subjected to the same operations except that the photopolymerization initiator was changed to tert-butyl peroxybenzoate, which is a thermal polymerization initiator. , a resin composition of Comparative Example 1001 was produced.
  • a transparent base material (CT-4000L, manufactured by Fujifilm Electronics Materials Co., Ltd.) was applied to a glass wafer with a diameter of 8 inches (20.32 cm) to a dry film thickness of 0.1 ⁇ m, and dried. After forming the base layer, heat treatment was performed at 220° C. for 5 minutes to obtain a glass wafer with the base layer.
  • each resin composition was applied onto the base layer of the base layer-equipped glass wafer using a spin coater so that the film thickness after pre-baking was 0.5 ⁇ m, and was applied for 30 seconds using a hot plate at 150°C.
  • Heat treatment was performed to form a film.
  • the glass wafer on which the above film was formed was immersed in cyclohexanone heated to 50°C for 15 minutes, and the OD value (optical density) in the wavelength range of 400 to 700 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Tech Corporation).
  • the solvent resistance was evaluated using the same method as above. When the resin compositions of Examples 1001 and 1002 were used, the solvent resistance evaluation results were both A. On the other hand, when the resin composition of Comparative Example 1001 was used, the solvent resistance evaluation result was D.

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Abstract

L'invention concerne : une composition de résine contenant un composé représenté par la formule (1), des particules, une résine, un monomère polymérisable ayant un groupe contenant une liaison éthyléniquement insaturée, et un solvant ; un film utilisant ladite composition de résine ; un filtre optique ; un élément d'imagerie à semi-conducteurs ; et un dispositif d'affichage d'image. Dans la formule (1), chacun de R1 à R4 représente indépendamment un groupe alkylène ; chacun de X1 à X4 représente indépendamment un atome d'hydrogène, un groupe thiol ou un groupe hydroxy ; et au moins deux parmi X1 à X4 sont des groupes thiol.
PCT/JP2023/027927 2022-08-10 2023-07-31 Composition de résine, film, filtre optique, élément d'imagerie à semi-conducteurs et dispositif d'affichage d'image WO2024034445A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012036379A (ja) * 2010-07-14 2012-02-23 Toyo Ink Sc Holdings Co Ltd 顔料用分散剤、及びそれを用いた顔料組成物
JP2013223859A (ja) * 2012-03-19 2013-10-31 Toyo Ink Sc Holdings Co Ltd 硬化性分散剤とその製造方法、及びそれを用いた顔料組成物
JP2022043679A (ja) * 2020-09-04 2022-03-16 株式会社トクヤマ フォトクロミック組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012036379A (ja) * 2010-07-14 2012-02-23 Toyo Ink Sc Holdings Co Ltd 顔料用分散剤、及びそれを用いた顔料組成物
JP2013223859A (ja) * 2012-03-19 2013-10-31 Toyo Ink Sc Holdings Co Ltd 硬化性分散剤とその製造方法、及びそれを用いた顔料組成物
JP2022043679A (ja) * 2020-09-04 2022-03-16 株式会社トクヤマ フォトクロミック組成物

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