WO2023149272A1 - 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
WO2023149272A1
WO2023149272A1 PCT/JP2023/001989 JP2023001989W WO2023149272A1 WO 2023149272 A1 WO2023149272 A1 WO 2023149272A1 JP 2023001989 W JP2023001989 W JP 2023001989W WO 2023149272 A1 WO2023149272 A1 WO 2023149272A1
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group
resin composition
mass
compounds
resin
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PCT/JP2023/001989
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English (en)
Japanese (ja)
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俊佑 柳
憲晃 佐藤
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富士フイルム株式会社
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Publication of WO2023149272A1 publication Critical patent/WO2023149272A1/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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C08K5/1539—Cyclic anhydrides
    • 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
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/23—Azo-compounds
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters

Definitions

  • the present invention relates to a resin composition containing a coloring material.
  • the present invention also relates to a film, an optical filter, a solid-state imaging device, and an image display device using the resin composition.
  • optical filters such as color filters are manufactured using a resin composition containing a coloring material and a resin.
  • an object of the present invention is to provide a resin composition with excellent storage stability. Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, and an image display device.
  • the present invention provides the following.
  • the resin B includes a resin b having a repeating unit b1 containing at least one group selected from a urea group and a urethane group.
  • the repeating unit b1 is a repeating unit containing a urea group.
  • R 11 represents a hydrogen atom or an alkyl group
  • X 11 represents a divalent linking group
  • R 12 is a polycyclic aromatic ring group, an aliphatic hydrocarbon group having 3 or more carbon atoms, a monocyclic aromatic hydrocarbon group having an electron-withdrawing group or an electron-donating group as a substituent
  • an electron-withdrawing represents a monocyclic aromatic heterocyclic group optionally having a group or an electron-donating group as a substituent, or a group represented by formula (R-101); -L 101 -(R 101 -O) n1 -R 102 (R-101)
  • L 101 represents a single bond or a divalent linking group
  • R 101 represents an alkylene group
  • R 102 represents a hydrogen atom or an alkyl group
  • n1 is an integer of 2 to
  • ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the resin b further contains a repeating unit b2 having a graft chain.
  • the graft chain is a polymer chain containing a repeating unit having a structure selected from a polyether structure and a polyester structure.
  • the graft chain is a polymer chain containing a polyalkyleneoxy structure.
  • ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the pigment contains at least one selected from diketopyrrolopyrrole pigments, isoindoline pigments, quinophthalone pigments and azo pigments.
  • ⁇ 9> A film obtained using the resin composition according to any one of ⁇ 1> to ⁇ 8>.
  • An optical filter including the film according to ⁇ 9>.
  • ⁇ 11> A solid-state imaging device including the film according to ⁇ 9>.
  • ⁇ 12> An image display device comprising the film according to ⁇ 9>.
  • ⁇ is used to include the numerical values before and after it as lower and upper limits.
  • a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent.
  • an "alkyl group” includes not only an alkyl group having no 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.
  • Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • EUV light extreme ultraviolet rays
  • (meth)acrylate” represents both or either acrylate and methacrylate
  • (meth)acryl represents both or either acrylic and methacrylic
  • (meth) ) acryloyl refers to acryloyl and/or methacryloyl.
  • Me in the structural formulas 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).
  • total solid content refers to the total mass of all components of the composition excluding the solvent.
  • pigment means a coloring material that is difficult to dissolve in a solvent.
  • the term "process” includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .
  • the resin composition of the present invention is a resin composition containing a coloring material A containing a pigment and a resin B,
  • the content of the coloring material A in the total solid content of the resin composition is 50% by mass or more
  • the resin B is characterized by containing a resin b having a repeating unit b1 containing at least one group selected from a urea group and a urethane group.
  • the resin composition of the present invention by including the resin b described above, the viscosity of the resin composition is increase over time can be suppressed. Therefore, the resin composition of the present invention has excellent storage stability.
  • the reason why such an effect is obtained is presumed to be as follows. Since the resin b contains a repeating unit b1 containing at least one group selected from a urea group and a urethane group, the urethane group or urea group contained in the repeating unit b1 interacts with the pigment through hydrogen bonding to form a surface of the pigment. It is presumed that the resin b strongly adsorbs to the pigment, and as a result, the resin b exists in the vicinity of the pigment in the resin composition. Therefore, it is presumed that the aggregation of the pigment could be suppressed by the resin b, and as a result, the storage stability of the resin composition could be improved.
  • the resin b of the resin composition of the present invention can suppress the aggregation of the pigment, the pigment has excellent dispersibility, and the generation of coarse particles can be suppressed.
  • the resin composition of the present invention when the resin composition of the present invention is patterned by photolithography, it is possible to suppress the generation of development residues.
  • the reason why such an effect is obtained is that the resin b1 is strongly adsorbed on the surface of the pigment by hydrogen bonding, so that the emulsifying action of the pigment during development is enhanced, and the resin composition in the unexposed area is efficiently removed by development. It is presumed that this is because For these reasons, the resin composition of the present invention can also suppress the generation of development residues.
  • the resin composition of the present invention is preferably used as a resin composition for optical filters.
  • the optical filter include a color filter, a near-infrared transmission filter, a near-infrared cut filter, and the like, and a color filter is preferable.
  • the resin composition of the present invention is preferably used for a solid-state imaging device. More specifically, it is preferably used as a resin composition for optical filters used in solid-state imaging devices, and more preferably used as a resin composition for forming colored pixels of color filters used in solid-state imaging devices.
  • color filters include filters having colored pixels that transmit light of specific wavelengths.
  • colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels, and red pixels are more preferable.
  • the colored pixels of the color filter can be formed using a resin composition containing a chromatic coloring material.
  • the maximum absorption wavelength of the near-infrared cut filter preferably exists in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm.
  • the transmittance of the near-infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Also, the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.
  • the ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at a wavelength of 550 nm is preferably 20 to 500, more preferably 50 to 500. , more preferably 70-450, and particularly preferably 100-400.
  • a near-infrared cut filter can be formed using a resin composition containing a near-infrared absorbing colorant.
  • a near-infrared transmission filter is a filter that transmits at least part of near-infrared rays.
  • the near-infrared transmission filter is preferably a filter that blocks at least part of visible light and transmits at least part of near-infrared light.
  • 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 has a transmittance in the wavelength range of 1100 to 1300 nm. Filters satisfying spectral characteristics with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) are preferred.
  • the near-infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (5).
  • the maximum 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 transmittance in the wavelength range of 800 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum 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 transmittance in the wavelength range of 900 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum 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 transmittance in the wavelength range of 1000 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum 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 transmittance in the wavelength range of 1100 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum 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 transmittance in the wavelength range of 1200 to 1500 nm is A filter that 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 light shielding film.
  • the solid content concentration of the resin composition of the present invention 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, and even more preferably 15% by mass or less.
  • the resin composition of the present invention contains coloring material A (hereinafter referred to as coloring material).
  • coloring material A examples include white colorants, black colorants, chromatic colorants, and near-infrared absorption colorants.
  • a pigment derivative can also be used as the coloring material.
  • the white colorant includes not only a pure white colorant but also a light gray colorant close to white (for example, grayish white, light gray, etc.).
  • the coloring material contained in the resin composition of the present invention contains a pigment.
  • the pigment may be either an inorganic pigment or an organic pigment, but an organic pigment is preferred from the viewpoints of color variation, ease of dispersibility, safety, and the like.
  • the pigment preferably contains at least one selected from chromatic pigments and near-infrared absorbing pigments, and more preferably contains a chromatic pigment.
  • the coloring material is at least selected from the group consisting of phthalocyanine pigments, dioxazine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, azo pigments, azomethine pigments, diketopyrrolopyrrole pigments, pyrrolopyrrole pigments, isoindoline pigments and quinophthalone pigments. It preferably contains one type, and more preferably contains at least one selected from the group consisting of pyrrolopyrrole pigments, diketopyrrolopyrrole pigments, isoindoline pigments, quinophthalone pigments and azo pigments. It is more preferable to contain at least one selected from the group consisting of pyrrolopyrrole pigments and diketopyrrolopyrrole pigments, because it remarkably exhibits the above.
  • the average primary particle size of the pigment is preferably 1 to 200 nm.
  • the lower limit is preferably 5 nm or more, more preferably 10 nm or more.
  • the upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less.
  • the primary particle size of the pigment can be determined from the photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment.
  • the average primary particle size in the present invention is the arithmetic mean value of the primary particle sizes of 400 primary particles of the pigment. Further, the primary particles of the pigment refer to independent particles without agglomeration.
  • the crystallite size of the organic pigment and pigment derivative is preferably 0.1 to 50 nm, more preferably 0.5 to 30 nm, and even more preferably 1 to 15 nm.
  • the crystallite size can be obtained from the half width of the diffraction angle peak using an X-ray diffractometer, and is calculated using Scherrer's formula.
  • the crystallite size of organic pigments and pigment derivatives can be adjusted by known methods such as adjustment of production conditions and pulverization after production.
  • the coloring material contained in the resin composition of the present invention preferably contains a pigment and a pigment derivative.
  • Pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton. Details of the pigment derivative will be described later.
  • the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
  • the coloring material contained in the resin composition of the present invention may further contain a dye.
  • a dye When a dye is included, the content of the dye is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the pigment.
  • the upper limit is preferably 80 parts by mass or less, more preferably 70 parts by mass or less.
  • the lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more. Only one dye may be used, or two or more dyes may be used in combination.
  • the coloring material contained in the resin composition of the present invention substantially does not contain a dye. According to this aspect, a film having excellent light resistance and heat resistance can be formed. “Substantially free of dye” means that the content of dye in the coloring material is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably no dye. .
  • chromatic coloring materials include coloring materials having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. Examples thereof include yellow colorants, orange colorants, red colorants, green colorants, purple colorants, and blue colorants.
  • the chromatic colorant is preferably a pigment (chromatic pigment), more preferably a red pigment, a yellow pigment, and a blue pigment, and still more preferably a red pigment and a blue pigment. Specific examples of chromatic pigments include those shown below.
  • red colorants 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 It is preferably a compound, more preferably a diketopyrrolopyrrole compound. Also, the red colorant is preferably a pigment.
  • red colorant examples include C.I. I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, 297 and other red pigments.
  • a red colorant a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, a diketopyrrolopyrrole described in paragraph numbers 0016 to 0022 of Japanese Patent No.
  • 10-2019-0140741 anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140744, JP 2020 A perylene compound described in JP-A-079396, a diketopyrrolopyrrole compound described in paragraphs 0025 to 0041 of JP-A-2020-066702, and the like can also be used.
  • a red colorant a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton is used.
  • C.I. I. Pigment Red 122, 177, 254, 255, 264, 269 and 272 are preferred, C.I. I. Pigment Red 254, 264, 272 are more preferred, and C.I. I. Pigment Red 254, 272 are more preferred.
  • green colorants examples include phthalocyanine compounds, squarylium compounds, etc., preferably phthalocyanine compounds, and more preferably phthalocyanine pigments. Also, the green colorant is preferably a pigment.
  • green colorants include C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65 and 66 are included. Further, as a green colorant, a halogenated zinc phthalocyanine having 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 number of chlorine atoms of 2 to 5 Pigments can also be used. Specific examples include compounds described in International Publication No. 2015/118720. In addition, as a green colorant, the compound described in Chinese Patent Application No.
  • 106909027 the phthalocyanine compound having a phosphoric acid ester as a ligand described in WO 2012/102395, described in JP 2019-008014.
  • the core-shell type dyes described in can also be used.
  • C.I. I. Pigment Green 7, 36, 58, 62 and 63 are preferred, C.I. I. Pigment Greens 36 and 58 are more preferred. Used.
  • orange colorants include C.I. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. of orange pigments.
  • yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds and perylene compounds.
  • Specific examples of the yellow coloring material include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166,
  • a nickel azobarbiturate complex having the following structure can also be used.
  • Quinophthalone compounds quinophthalone compounds described in JP-A-2008-074986, quinophthalone compounds described in JP-A-2008-074985, quinophthalone compounds described in JP-A-2008-050420, JP-A-2008-031281
  • the quinophthalone compound described, the quinophthalone compound described in JP-B-48-032765, the quinophthalone compound described in JP-A-2019-008014, the quinophthalone compound described in JP-A-6607427, and JP-A-2019-073695 The quinophthalone compound described, the quinophthalone compound described in JP-B-48-032765, the quinophthalone compound described in JP-A-2019-008014, the quinophthalone compound described in JP-A-6607427, and JP-A-2019-073695.
  • the methine dye described the methine dye described in JP-A-2019-073696, the methine dye described in JP-A-2019-073697, the methine dye described in JP-A-2019-073698, Korean Patent No. 10- Compounds described in 2014-0034963, compounds described in JP 2017-095706, compounds described in Taiwan Patent Application Publication No. 201920495, compounds described in Patent No.
  • JP 2020-033525 Compounds described in JP-A-2020-033524, compounds described in JP-A-2020-033523, compounds described in JP-A-2020-033522, JP-A-2020-033521 Compounds described in, compounds described in WO 2020/045200, compounds described in WO 2020/045199, compounds described in WO 2020/045197, described in JP 2020-093994
  • X 1 to X 16 each independently represent a hydrogen atom or a halogen atom, and Z 1 represents an alkylene group having 1 to 3 carbon atoms.
  • Specific examples of the compound represented by formula (QP1) include compounds described in paragraph number 0016 of Japanese Patent No. 6443711 .
  • Y 1 to Y 3 each independently represent a halogen atom.
  • n and m are integers from 0 to 6; p is an integer from 0 to 5; (n+m) is 1 or more.
  • Specific examples of the compound represented by formula (QP2) include compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.
  • purple coloring materials include C.I. I. Purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61 are included.
  • blue colorants include C.I. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc. pigments.
  • An aluminum phthalocyanine compound having a phosphorus atom can also be used as the blue colorant.
  • Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A-2012-247591 and paragraph number 0047 of JP-A-2011-157478.
  • a diarylmethane compound described in JP-T-2020-504758 can also be used as a green colorant or a blue colorant.
  • the pyrrolopyrrole pigment has a crystallite size of 140 ⁇ or less in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes ( ⁇ 1 ⁇ 1 ⁇ 1) of the crystal lattice planes. is also preferred. Further, the physical properties of the pyrrolopyrrole pigment are preferably set as described in paragraphs 0028 to 0073 of JP-A-2020-097744.
  • the pigment it is also preferable to use a halogenated zinc phthalocyanine pigment having a Raman spectrum described in Japanese Patent No. 6744002 from the viewpoint of enhancing spectral characteristics.
  • a dioxazine pigment with a controlled contact angle described in WO 2019/107166 from the viewpoint of viscosity adjustment.
  • Dyes can also be used as chromatic colorants.
  • the dye is not particularly limited, and known dyes can be used.
  • a pigment multimer can also be used as a chromatic colorant.
  • the dye multimer is preferably a dye dissolved in a solvent and used. Further, the dye multimer may form particles. When the dye multimer is particles, it is usually used in a state of being dispersed in a solvent.
  • the particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in JP-A-2015-214682.
  • a 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.
  • a plurality of dye structures in one molecule may be the same dye structure or 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 3000 or more, and even more preferably 6000 or more.
  • the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
  • Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016/031442, etc. Compounds can also be used.
  • chromatic colorants triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP-A-2020-117638, and International Publication No. 2020/174991.
  • the halogenated zinc phthalocyanine pigment described in Patent No. 6809649, JP 2020- Isoindoline compounds described in JP-A-180176 can be used.
  • the chromatic colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, may be used in the rod-like structure, or may be used in both structures.
  • Two or more chromatic colorants may be used in combination.
  • the combination of two or more chromatic colorants may form black. Examples of such combinations include the following aspects (1) to (7).
  • the resin composition of the present invention forms a near-infrared transmission filter. It can be preferably used as a resin composition for (1) A mode containing a red colorant and a blue colorant. (2) A mode containing a red colorant, a blue colorant, and a yellow colorant. (3) A mode containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant.
  • a mode containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant (5) A mode containing a red colorant, a blue colorant, a yellow colorant, and a green colorant. (6) A mode containing a red colorant, a blue colorant, and a green colorant. (7) A mode containing a yellow colorant and a purple colorant.
  • White colorants include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, Examples include hollow resin particles and inorganic pigments (white pigments) such as zinc sulfide.
  • the white pigment is preferably particles containing titanium atoms, more preferably titanium oxide.
  • the white pigment is preferably particles having a refractive index of 2.10 or more for light with a wavelength of 589 nm. The aforementioned refractive index is preferably 2.10 to 3.00, more preferably 2.50 to 2.75.
  • the white pigment the titanium oxide described in "Titanium Oxide Physical Properties and Applied Technology Manabu Seino, Pages 13-45, June 25, 1991, published by Gihodo Publishing" can also be used.
  • the white pigment is not only made of a single inorganic substance, but also particles combined with other materials may be used.
  • particles having voids or other materials inside, particles having a core particle to which a large number of inorganic particles are attached, and core-shell composite particles consisting of a core particle made of polymer particles and a shell layer made of inorganic nanoparticles are used. is preferred.
  • the core and shell composite particles composed of the core particles composed of the polymer particles and the shell layer composed of the inorganic nanoparticles for example, the description of paragraphs 0012 to 0042 of JP-A-2015-047520 can be referred to, The contents of which are incorporated herein.
  • Hollow inorganic particles can also be used as the white pigment.
  • a hollow inorganic particle is an inorganic particle having a structure having a cavity inside, and refers to an inorganic particle having a cavity surrounded by an outer shell.
  • Examples of hollow inorganic particles include hollow inorganic particles described in JP 2011-075786, WO 2013/061621, JP 2015-164881, etc., the contents of which are incorporated herein. be
  • the black colorant is not particularly limited, and known ones can be used.
  • inorganic black colorants include inorganic pigments (black pigments) such as carbon black, titanium black, and graphite. Carbon black and titanium black are preferred, and titanium black is more preferred.
  • Titanium black is black particles containing titanium atoms, preferably low order titanium oxide or titanium oxynitride. Titanium black can be surface-modified as necessary for the purpose of improving dispersibility, suppressing cohesion, and the like. For example, it is possible to coat the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, treatment with a water-repellent substance as disclosed in Japanese Patent Laid-Open No.
  • Titanium black preferably has a small primary particle size and an average primary particle size of individual particles. Specifically, the average primary particle size is preferably 10 to 45 nm. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms and Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50, may be mentioned. Regarding the dispersion, the description in paragraphs 0020 to 0105 of JP-A-2012-169556 can be referred to, and the contents thereof are incorporated herein.
  • titanium black Commercially available examples include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilac D ( Trade name: manufactured by Ako Kasei Co., Ltd.) and the like.
  • organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds.
  • bisbenzofuranone compounds include compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, etc.
  • "Irgaphor Black” manufactured by BASF Corporation. Available.
  • perylene compounds include compounds described in paragraphs 0016 to 0020 of JP-A-2017-226821, C.I. I. Pigment Black 31, 32 and the like.
  • the azomethine compound include compounds described in JP-A-01-170601, JP-A-02-034664, and the like.
  • the coloring material used in the resin composition of the present invention may be the above-described black coloring material only, or may further include a chromatic coloring material. According to this aspect, it is easy to obtain a resin composition capable of forming a film having excellent light-shielding properties in the visible region.
  • Preferred combinations of black colorants and chromatic colorants include, for example, the following.
  • A-1 An embodiment containing an organic black colorant and a blue colorant.
  • A-2) A mode containing an organic black colorant, a blue colorant and a yellow colorant.
  • A-3) An embodiment containing an organic black colorant, a blue colorant, a yellow colorant and a red colorant.
  • A-4) An embodiment containing an organic black colorant, a blue colorant, a yellow colorant and a purple colorant.
  • the near-infrared absorbing colorant is preferably a compound having a maximum absorption wavelength on the longer wavelength side than the wavelength of 700 nm.
  • the infrared absorbent is preferably a compound having a maximum absorption wavelength in the range of 700 nm to 1800 nm, more preferably a compound having a maximum absorption wavelength in the range of 700 nm to 1400 nm.
  • a compound having a maximum absorption wavelength in the range of more than 1200 nm or less is more preferable, and a compound having a maximum absorption wavelength in the range of more than 700 nm and 1000 nm or less is particularly preferable.
  • 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 colorant is preferably 0.08 or less, more preferably 0.04 or less.
  • the near-infrared absorbing colorant is preferably a pigment, more preferably an organic pigment.
  • Near-infrared absorbing colorants include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, and pyrromethene compounds. , azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, and the like.
  • pyrrolopyrrole compound compounds described in paragraph numbers 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph numbers 0037-0052 of JP-A-2011-068731, WO 2015/166873 Compounds described in Paragraph Nos. 0010 to 0033 and the like.
  • examples of the squarylium compound include compounds described in paragraph numbers 0044 to 0049 of JP-A-2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese Patent No. 6065169, and paragraph number 0040 of WO 2016/181987.
  • Examples of croconium compounds include compounds described in JP-A-2017-082029.
  • As the iminium compound for example, compounds described in JP-A-2008-528706, compounds described in JP-A-2012-012399, compounds described in JP-A-2007-092060, International Publication No. 2018/043564 and the compounds described in paragraphs 0048 to 0063 of.
  • Examples of the phthalocyanine compound include compounds described in paragraph number 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraph numbers 0013 to 0029 of JP-A-2013-195480. compounds, vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, vanadium phthalocyanine compounds described in International Publication No. 2020/071486, and phthalocyanine compounds described in International Publication No. 2020/071470. Examples of naphthalocyanine compounds include compounds described in paragraph number 0093 of JP-A-2012-077153. Dithiolene metal complexes include compounds described in Japanese Patent No. 5733804.
  • metal oxides include indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide.
  • metal borides include lanthanum boride.
  • Commercially available lanthanum boride products include LaB 6 -F (manufactured by Nippon New Metal Co., Ltd.).
  • a metal boride the compound as described in international publication 2017/119394 can also be used.
  • commercially available products of indium tin oxide include F-ITO (manufactured by DOWA Hitech Co., Ltd.).
  • the near-infrared absorbing colorant the squarylium compound described in JP-A-2017-197437, the squarylium compound described in JP-A-2017-025311, the squarylium compound described in International Publication No. 2016/154782, the patent Squarylium compounds described in Japanese Patent No. 5884953, squarylium compounds described in Japanese Patent No. 6036689, squarylium compounds described in Japanese Patent No. 5810604, squarylium compounds described in paragraph numbers 0090 to 0107 of International Publication No.
  • amide-linked squarylium compounds compounds having a pyrrole bis-type squarylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazole bis-type squarylium compounds described in JP-A-2017-082029, JP-A-2017 -Asymmetric compounds described in paragraphs 0027 to 0114 of JP-A-068120, pyrrole ring-containing compounds (carbazole type) described in JP-A-2017-067963, phthalocyanine compounds described in Japanese Patent No. 6251530, A squarylium compound described in JP-A-2020-075959, a copper complex described in Korean Patent Publication No. 10-2019-0135217, and the like can also be used.
  • pigment derivative in the present invention, a pigment derivative can also be used as the coloring material. In the present invention, it is preferable to use a pigment and a pigment derivative together.
  • Pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.
  • Dye skeletons constituting pigment derivatives include a quinoline dye skeleton, a benzimidazolone dye skeleton, a benzoisoindole dye skeleton, a benzothiazole dye skeleton, an iminium dye skeleton, a squarylium dye skeleton, a croconium dye skeleton, an oxonol dye skeleton, and a pyrrolopyrrole dye.
  • diketopyrrolopyrrole dye skeleton azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, quinacridone dye skeleton, dioxazine dye skeleton, perinone dye skeleton, perylene dye skeleton, thioindigo dye skeleton, Isoindoline dye skeletons, isoindolinone dye skeletons, quinophthalone dye skeletons, dithiol dye skeletons, triarylmethane dye skeletons, pyrromethene dye skeletons, and the like can be mentioned.
  • the acid group includes a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imidic 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, phosphonium ion and the like.
  • the carboxylic acid amide group a group represented by —NHCOR X1 is preferable.
  • sulfonic acid amide group a group represented by —NHSO 2 R X2 is preferable.
  • the imidic acid group is preferably a group represented by —SO 2 NHSO 2 R X3 , —CONHSO 2 R X4 , —CONHCOR X5 or —SO 2 NHCOR X6 , more preferably —SO 2 NHSO 2 R X3 .
  • R X1 to R X6 each independently represent an alkyl group or an aryl group.
  • the alkyl groups and aryl groups represented by R X1 to R X6 may have substituents.
  • the substituent is preferably a halogen atom, more preferably a fluorine atom.
  • Basic groups include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups.
  • Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
  • the pigment derivative include the compounds described in Examples below, the compounds described in JP-A-56-118462, the compounds described in JP-A-63-264674, and JP-A-01-217077.
  • Compounds described in, compounds described in JP-A-03-009961, compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, described in JP-A-03-045662 The compound, the compound described in JP-A-04-285669, the compound described in JP-A-06-145546, the compound described in JP-A-06-212088, the compound described in JP-A-06-240158 , the compound described in JP-A-10-030063, the compound described in JP-A-10-195326, the compound described in paragraph numbers 0086 to 0098 of WO 2011/024896, WO 2012/102399
  • the content of the coloring material in the total solid content of the resin composition is 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more, and 65% by mass or more. is more preferred.
  • the upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and even more preferably 75% by mass or less.
  • the pigment content in the total solid content of the resin composition is preferably 30% by mass or more, more preferably 45% by mass or more, and even more preferably 55% by mass or more.
  • the upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and even more preferably 75% by mass or less. Since the resin composition of the present invention exhibits excellent storage stability even when the pigment content is high, the effects of the present invention are exhibited more remarkably when the pigment content is high.
  • the content of the pigment in the colorant is preferably 20-100% by mass, more preferably 50-100% by mass, and even more preferably 70-100% by mass. Further, the total content of the pigment and the pigment derivative in the colorant is preferably 25 to 100% by mass, more preferably 55 to 100% by mass, and further preferably 75 to 100% by mass. preferable.
  • the resin composition of the present invention contains resin B (hereinafter referred to as resin).
  • resin is blended, for example, for dispersing a pigment or the like in a resin composition or for a binder.
  • a resin mainly used for dispersing a pigment or the like in a resin composition is also called a dispersant.
  • such uses of the resin are only examples, and the resin can be used for purposes other than such uses.
  • the resin contained in the resin composition of the present invention includes a resin b (hereinafter also referred to as a specific resin) having a repeating unit b1 containing at least one group selected from urea groups and urethane groups.
  • the specific resin will be described below.
  • the specific resin includes repeating units b1 (hereinafter also referred to as repeating units b1) containing at least one group selected from urea groups and urethane groups.
  • the repeating unit b1 is preferably a repeating unit containing a urea group.
  • the repeating unit b1 is preferably a repeating unit represented by formula (b1-1).
  • R 1 represents a hydrogen atom or an alkyl group
  • X 1 represents a divalent linking group
  • X 2 represents -O- or -NH-
  • R 2 represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aromatic heterocyclic group or a group represented by formula (R-101); -L 101 -(R 101 -O) n1 -R 102 (R-101)
  • L 101 represents a single bond or a divalent linking group
  • R 101 represents an alkylene group
  • R 102 represents a hydrogen atom or an alkyl group
  • n1 is an integer of 2 to 45 represents
  • the number of carbon atoms in the alkyl group represented by R 1 is preferably 1-10, more preferably 1-3, and still more preferably 1.
  • R 1 is preferably a hydrogen atom or a methyl group.
  • the divalent linking group represented by X 1 includes a hydrocarbon group, -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S- and these A group formed by combining two or more of
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • the number of carbon atoms in the hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-12.
  • the hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.
  • the divalent linking group represented by X 1 is -COO-CH 2 -CH 2 -, -COO-CH 2 -CH 2 -O-CH 2 -CH 2 -, -C 6 H 4 -, or -C 6 H 4 —CH 2 — is preferred.
  • X2 represents -O- or -NH-, preferably -NH-.
  • the number of carbon atoms in the aliphatic hydrocarbon group represented by R 2 is 1 or more, and the hydrophobic interaction further improves the pigment adsorption, and the storage stability of the resin composition can be further improved. It is preferably 3 or more, more preferably 5 or more, and even more preferably 8 or more. The upper limit is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear or branched because it can further improve the storage stability of the resin composition. It is more preferable to have Examples of aliphatic hydrocarbon groups include alkyl groups, alkenyl groups and alkynyl groups. The aliphatic hydrocarbon group may have a substituent. Substituents include the substituent T described below. Moreover, it is also preferable that the aliphatic hydrocarbon group does not have a substituent.
  • the aromatic hydrocarbon group and aromatic heterocyclic group represented by R 2 may be monocyclic or polycyclic.
  • the heteroatom constituting the ring of the aromatic heterocyclic group preferably contains at least one selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably contains a nitrogen atom.
  • the number of heteroatoms constituting the ring of the aromatic heterocyclic group is preferably 1-4, more preferably 1-3, even more preferably 1 or 2.
  • the aromatic hydrocarbon group represented by R 2 is polycyclic, the number of ring structures contained in the aromatic hydrocarbon group is preferably 2-10.
  • the upper limit is preferably 8 or less, more preferably 5 or less.
  • the lower limit is preferably 3 or more, more preferably 4 or more, because the storage stability of the resin composition can be further improved.
  • the aromatic heterocyclic group represented by R 2 is polycyclic, the number of ring structures contained in the aromatic heterocyclic group is preferably 2-10.
  • the upper limit is preferably 8 or less, more preferably 5 or less.
  • the lower limit is preferably 3 or more, more preferably 4 or more, because the storage stability of the resin composition can be further improved.
  • the aromatic hydrocarbon group and aromatic heterocyclic group represented by R 2 may have a substituent. Substituents include a substituent T described later, and are preferably electron-withdrawing groups or electron-donating groups.
  • the electron-withdrawing group is a substituent group that more easily attracts electrons to the bonding atom side than a hydrogen atom
  • the electron-donating group is a substituent group that is more likely to bond than a hydrogen atom. It is a substituent that easily donates electrons to the side of the atom
  • the Specific examples of electron-withdrawing groups include halogen atoms, halogenated alkyl groups, alkoxycarbonyl groups, cyano groups, nitro groups, carboxy groups, sulfonyl groups and the like.
  • Specific examples of the electron-donating group include an alkyl group, an alkoxy group, a hydroxy group, an amino group and the like, preferably an alkoxy group, a hydroxy group or an amino group.
  • the ⁇ - ⁇ interaction can further improve the pigment adsorptivity. It is possible to further improve the storage stability of the resin composition.
  • the aromatic hydrocarbon group represented by R 2 has an electron-withdrawing group or an electron-donating group as a substituent, the electronic state of the urea group or urethane group is changed to further improve the pigment adsorptivity. It is possible to further improve the storage stability of the resin composition.
  • the aromatic heterocyclic group represented by R 2 is a monocyclic ring, the electronic state of the urea group or urethane group site can be varied to further improve the pigment adsorptivity and the storage stability of the resin composition. can be further improved.
  • the aromatic hydrocarbon group represented by R 2 When the aromatic hydrocarbon group represented by R 2 is monocyclic, it preferably has an electron-withdrawing group or an electron-donating group as a substituent. When the aromatic hydrocarbon group represented by R 2 is polycyclic, it may or may not have a substituent. The aromatic heterocyclic group represented by R 2 may or may not have a substituent.
  • L 101 in formula (R-101) represented by R 2 represents a single bond or a divalent linking group.
  • the divalent linking group includes a hydrocarbon group, a group in which two or more hydrocarbon groups are linked via a single bond or a divalent linking group, and the like. Examples of divalent linking groups for bonding hydrocarbon groups include -O-, -CO-, -COO-, -OCO-, -NH-, -NHCO-, -CONH-, -SO-, and -SO 2 - and -S- and the like.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-12.
  • the hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.
  • R 101 in formula (R-101) represented by R 2 represents an alkylene group.
  • the alkylene group represented by R 101 preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 2 or 3 carbon atoms.
  • the alkylene group represented by R 101 is preferably linear or branched.
  • R 102 in formula (R-101) represented by R 2 represents a hydrogen atom or an alkyl group.
  • the number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-20.
  • Alkyl groups are preferably straight or branched.
  • the alkyl group may have a substituent.
  • a halogen atom, an aryl group, etc. are mentioned as a substituent.
  • the alkyl group is preferably an unsubstituted alkyl group.
  • n1 in the formula (R-101) represented by R2 represents an integer of 2-45.
  • the lower limit of n1 is preferably 4 or more, more preferably 6 or more, and even more preferably 9 or more.
  • the upper limit is preferably 40 or less, more preferably 30 or less, and even more preferably 23 or less.
  • R 2 is a group represented by formula (R-101)
  • the storage stability of the resin composition can be improved.
  • the repeating unit b1 is preferably a repeating unit represented by formula (b1-2).
  • R 11 represents a hydrogen atom or an alkyl group
  • X 11 represents a divalent linking group
  • R 12 is a polycyclic aromatic ring group, an aliphatic hydrocarbon group having 3 or more carbon atoms, a monocyclic aromatic hydrocarbon group having an electron-withdrawing group or an electron-donating group as a substituent
  • an electron-withdrawing represents a monocyclic aromatic heterocyclic group optionally having a group or an electron-donating group as a substituent, or a group represented by the above formula (R-101).
  • R 11 and X 11 in formula (b1-2) are synonymous with R 1 and X 1 in formula (b1-1).
  • the polycyclic aromatic ring group represented by R 12 in formula (b1-2) may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group.
  • a polycyclic aromatic hydrocarbon group is preferable because it can further improve the storage stability of the resin composition.
  • the number of ring structures contained in the polycyclic aromatic ring group is preferably 2-10.
  • the upper limit is preferably 8 or less, more preferably 5 or less.
  • the lower limit is preferably 3 or more, more preferably 4 or more, because the storage stability of the resin composition can be further improved.
  • polycyclic aromatic ring groups include naphthalene ring groups, anthracene ring groups, acenaphthene ring groups, acenaphthylene ring groups, phenalene ring groups, phenanthrene ring groups, fluorene ring groups, pyrene ring groups, quinoline ring groups, and isoquinoline ring groups. group, a quinoxaline ring group, a pentacene ring group, a benzopyrene ring group, a chrysene group, a triphenylene group, a corannulene ring group, a coronene group, an ovalen ring group, and the like.
  • the polycyclic aromatic ring group may or may not have a substituent.
  • Substituents include the substituent T described later. Substituents may be electron withdrawing or electron donating groups.
  • the number of carbon atoms in the aliphatic hydrocarbon group represented by R 12 in formula (b1-2) is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear or branched because it can further improve the storage stability of the resin composition. is more preferable.
  • Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group, preferably an alkyl group, more preferably a straight-chain alkyl group.
  • the aliphatic hydrocarbon group may or may not have a substituent.
  • Substituents include the substituent T described below. Substituents may be electron withdrawing or electron donating groups.
  • Examples of the monocyclic aromatic hydrocarbon group represented by R 12 in formula (b1-2) include a benzene ring group.
  • the heteroatom constituting the ring of the monocyclic aromatic heterocyclic group represented by R 12 preferably contains at least one selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably contains a nitrogen atom. .
  • the number of heteroatoms constituting the ring of the aromatic heterocyclic group is preferably 1-4, more preferably 1-3, even more preferably 1 or 2.
  • the monocyclic aromatic heterocyclic group is preferably a 5- or 6-membered ring, more preferably a 6-membered ring.
  • the electron-withdrawing group possessed by the above monocyclic aromatic hydrocarbon group represented by R 12 in formula (b1-2) and the above monocyclic aromatic heterocyclic group represented by R 12 may have Electron-withdrawing groups include the electron-withdrawing groups described above.
  • the monocyclic aromatic hydrocarbon group preferably has an electron-withdrawing group at the para-position of the aromatic hydrocarbon group. According to this aspect, the storage stability of the resin composition can be further improved.
  • the monocyclic aromatic hydrocarbon group and the monocyclic aromatic heterocyclic group may have two or more electron-withdrawing groups.
  • Examples of the donating group include the electron donating groups described above.
  • the monocyclic aromatic hydrocarbon group and the monocyclic aromatic heterocyclic group may have two or more electron donating groups.
  • repeating unit b1 examples include repeating units A-1 to A-48 described in Examples described later.
  • the content of the repeating unit b1 in the specific resin is preferably 1 to 60% by mass.
  • the lower limit is preferably 10% by mass or more, more preferably 15% by mass or more.
  • the upper limit is preferably 55% by mass or less, more preferably 50% by mass or less.
  • the specific resin preferably contains a repeating unit b2 having a graft chain (hereinafter also referred to as a repeating unit b2) in addition to the repeating unit b1.
  • a repeating unit b2 By including the repeating unit b2 in the specific resin, the storage stability of the resin composition can be further improved. Furthermore, the dispersibility of the pigment can be further improved, and the generation of coarse particles can be suppressed.
  • Examples of the graft chain that the repeating unit b2 has include a polymer chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure and a poly(meth)acrylic structure, and a polymer chain selected from a polyether structure and a polyester structure. It is preferably a polymer chain containing a repeating unit having a structure with a polyether structure, and more preferably a polymer chain having a polyether structure. Moreover, the polymer chain having the polyether structure is preferably a polymer chain containing a polyalkyleneoxy structure. That is, the graft chain is preferably a polymer chain containing a polyalkyleneoxy structure.
  • the polyalkyleneoxy structure is a structure composed of two or more alkyleneoxy groups, with the alkyleneoxy group as a repeating unit.
  • the polyalkyleneoxy structure may be composed of one type of alkyleneoxy group, or may be composed of two types of alkyleneoxy groups.
  • the number of carbon atoms in the alkyleneoxy group constituting the polyalkyleneoxy structure is preferably 1 to 5, more preferably 1 to 3, still more preferably 2 or 3, and particularly preferably 2.
  • the number of alkyleneoxy groups constituting the polyalkyleneoxy structure is preferably 4-40.
  • the lower limit is preferably 5 or more, more preferably 8 or more.
  • the upper limit is preferably 35 or less, more preferably 30 or less.
  • the above polyalkyleneoxy structure is preferably a polytetramethyleneoxy structure, a polypropyleneoxy structure, a polyethyleneoxy structure, a polytetramethyleneoxy-polyethyleneoxy copolymer structure and a polypropyleneoxy-polyethyleneoxy copolymer structure, and a polyethyleneoxy structure and a polytetramethyleneoxy-polyethylene
  • An oxy copolymer structure and a polypropyleneoxy-polyethyleneoxy copolymer structure are more preferred, and a polyethyleneoxy structure is even more preferred.
  • the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
  • substituents include alkyl groups, alkoxy groups, aryl groups, and aryloxy groups.
  • the number of carbon atoms in the alkyl group and alkoxy group is preferably 1-30, more preferably 1-20.
  • Alkyl groups and alkoxy groups are preferably straight-chain or branched. Alkyl groups and alkoxy groups may have a substituent.
  • a halogen atom, an aryl group, etc. are mentioned as a substituent.
  • Alkyl groups and alkoxy groups are preferably unsubstituted alkyl groups.
  • the aryl group and the aryloxy group preferably have 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
  • An aryl group and an aryloxy group may have a substituent.
  • a halogen atom, an alkyl group, etc. are mentioned as a substituent.
  • the terminal structure is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group.
  • a graft chain means a molecular chain branched from the main chain. Moreover, the main chain means a molecular chain having the largest number of branch points.
  • the weight average molecular weight of the grafted chain is preferably 500-30,000, more preferably 1,000-10,000, even more preferably 1,000-10,000.
  • repeating unit b2 examples include repeating units represented by the following formula (b2-1).
  • R b21 to R b23 in formula (b2-1) each independently represent a hydrogen atom or an alkyl group.
  • the number of carbon atoms in the alkyl group represented by R b21 to R b23 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.
  • L b21 in formula (b2-1) represents a single bond or a divalent linking group.
  • the divalent linking group represented by L b21 includes a hydrocarbon group, -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S- and these A group formed by combining two or more of
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • the number of carbon atoms in the hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-12.
  • the hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.
  • a b21 in formula (b2-1) represents a graft chain.
  • the preferred range of the graft chain represented by Ab21 is the same as described above.
  • repeating unit b2 examples include repeating units D-1 to D-7 described in Examples described later.
  • the content of the repeating unit b2 in the specific resin is preferably 1 to 80% by mass.
  • the lower limit is preferably 15% by mass or more, more preferably 30% by mass or more.
  • the upper limit is preferably 75% by mass or less, more preferably 70% by mass or less.
  • the specific resin can further contain a repeating unit b3 having an acid group (hereinafter also referred to as a repeating unit b3) as a repeating unit other than the repeating unit b1 and the repeating unit b2.
  • a repeating unit b3 having an acid group
  • the storage stability of the resin composition can be further improved.
  • the dispersibility of the pigment can be further improved, and the generation of coarse particles can be suppressed.
  • generation of development residue can be further suppressed.
  • the acid group possessed by the repeating unit b3 includes a carboxy group, a phosphoric acid group, a sulfo group and a phenolic hydroxy group, preferably a carboxy group.
  • the number of acid groups contained in the repeating unit b3 may be 1, or may be 2 or more.
  • the number of acid groups contained in the repeating unit b3 is preferably 1 to 4, more preferably 1 or 2.
  • repeating unit b3 examples include repeating units represented by the following formula (b3-1).
  • R b31 to R b33 in formula (b3-1) each independently represent a hydrogen atom or an alkyl group.
  • the number of carbon atoms in the alkyl group represented by R b31 to R b33 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.
  • Lb31 in formula (b3-1) represents a single bond or an n1+1-valent linking group. However, when n3 is 2 or more, L b31 is an n3+1-valent linking group.
  • the n3+1-valent linking group represented by L b31 includes a hydrocarbon group, -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S- and these A group formed by combining two or more of
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • the number of carbon atoms in the hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-12.
  • the hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.
  • a b31 in formula (b3-1) represents an acid group.
  • the acid group represented by Ab31 includes a carboxy group, a phosphoric acid group, a sulfo group and a phenolic hydroxy group, preferably a carboxy group.
  • n3 in formula (b3-1) represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2.
  • repeating unit b3 include repeating units having the structures shown below.
  • the content of the repeating unit b3 in the specific resin is preferably 0.1 to 60% by mass.
  • the lower limit is preferably 1.0% by mass or more, more preferably 2.5% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the specific resin can further contain a repeating unit b4 having a crosslinkable group (hereinafter also referred to as repeating unit b4).
  • Examples of the crosslinkable group possessed by the repeating unit b4 include an ethylenically unsaturated bond-containing group and a cyclic ether group.
  • Examples of ethylenically unsaturated bond-containing groups include vinyl groups, styrene groups, (meth)allyl groups, and (meth)acryloyl groups.
  • Examples of the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred.
  • the epoxy group may be a cycloaliphatic epoxy group.
  • the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
  • repeating unit b4 examples include repeating units represented by the following formula (b4-1).
  • R b41 to R b43 in formula (b4-1) each independently represent a hydrogen atom or an alkyl group.
  • the number of carbon atoms in the alkyl group represented by R b41 to R b43 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.
  • L b41 in formula (b4-1) represents a single bond or a divalent linking group.
  • the divalent linking group represented by L b41 includes a hydrocarbon group, -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S- and these A group formed by combining two or more of
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • the number of carbon atoms in the hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-12.
  • the hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.
  • a b41 in formula (b4-1) represents a crosslinkable group.
  • repeating unit b4 include repeating units having the structures shown below.
  • the content of the repeating unit b4 in the specific resin is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
  • the lower limit may be 2.5% by mass or more, or 5% by mass or more.
  • the specific resin may further contain a repeating unit b5 (hereinafter also referred to as a repeating unit b5) other than the repeating units b1 to b4 described above.
  • repeating unit b5 examples include repeating units having functional groups such as alkyl groups, phenyl groups, hydroxy groups, amino groups, and cyano groups.
  • the content of the repeating unit b5 in the specific resin is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
  • the lower limit can be 2.5% by mass or more, or 5.0% by mass or more.
  • Specific examples of specific resins include resins P1 to P109 shown in Examples described later.
  • the acid value of the specific resin is preferably 10-250 mgKOH/g.
  • the upper limit is preferably 200 mgKOH/g or less, more preferably 180 mgKOH/g or less, and even more preferably 150 mgKOH/g or less.
  • the lower limit is preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more.
  • the weight average molecular weight of the specific resin is preferably 3,000 to 100,000.
  • the lower limit is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, and particularly preferably 12,000 or more.
  • the upper limit is preferably 80,000 or less, more preferably 60,000 or less.
  • the specific absorbance represented by the following formula (A ⁇ ) of the specific resin is preferably 3 or less, more preferably 2 or less, and even more preferably 1 or less.
  • E A/(c ⁇ l) ( A ⁇ )
  • A represents the absorbance of the specific resin at the maximum absorption wavelength at a wavelength of 400 to 800 nm
  • l represents the cell length in cm
  • c represents the concentration of the particular resin in solution, expressed in units of mg/ml.
  • the amount of crosslinkable groups in the specific resin is preferably 0.01 to 2.5 mmol/g.
  • the lower limit is preferably 0.2 mmol/g or more, more preferably 0.5 mmol/g or more.
  • the upper limit is preferably 2 mmol/g or less, more preferably 1.5 mmol/g or less.
  • the crosslinkable group amount of the specific resin is a numerical value representing the molar amount of the crosslinkable group per 1 g of the solid content of the specific resin.
  • the resin composition of the present invention can contain a resin different from the specific resin described above (hereinafter also referred to as other resin).
  • resins include, for example, (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, Examples include polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins. Further, as the resin, the resin described in the examples of International Publication No.
  • the weight average molecular weight (Mw) of other resins 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 other resin it is preferable to use a resin having an acid group.
  • acid groups include carboxy groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups.
  • the acid value of the resin having acid groups is preferably 30-500 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, still more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less.
  • the weight average molecular weight (Mw) of the acid group-containing resin is preferably 5,000 to 100,000, more preferably 5,000 to 50,000.
  • the number average molecular weight (Mn) of the resin having an acid group is preferably 1,000 to 20,000.
  • the resin having an acid group preferably contains a repeating unit having an acid group on its side chain, and more preferably contains 5 to 70 mol % of repeating units having an acid group on its side chain in all repeating units of the resin.
  • the upper limit of the content of repeating units having an acid group in a side chain is preferably 50 mol % or less, more preferably 30 mol % or less.
  • the lower limit of the content of repeating units having an acid group in the side chain is preferably 10 mol % or more, more preferably 20 mol % or more.
  • resin having an acid group JP 2012-208494, paragraph numbers 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, paragraph numbers 0685 to 0700), JP 2012-198408
  • the descriptions in paragraphs 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated herein.
  • resin which has an acid group can also use a commercial item.
  • the method for introducing the acid group into the resin is not particularly limited, but includes, for example, the method described in Japanese Patent No. 6349629 .
  • a method for introducing an acid group into a resin a method of reacting an acid anhydride with a hydroxy group generated by a ring-opening reaction of an epoxy group to introduce an acid group can also be mentioned.
  • resins having basic groups 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. It is more preferably a polymer, and more preferably a block copolymer having a repeating unit having a basic group on its side chain and a repeating unit containing no basic group. Resins having basic groups can also be used as dispersants.
  • the amine value of the resin having basic groups is preferably 5-300 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, 38 500, 39000, 53095, 56000, 7100 (manufactured by Nippon Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (manufactured by BASF) and the like.
  • the resin having a basic group is a block copolymer (B) described in paragraph numbers 0063 to 0112 of JP-A-2014-219665, and described in paragraph numbers 0046-0076 of JP-A-2018-156021. It is also possible to use the block copolymer A1 described above and vinyl resins having basic groups described in paragraphs 0150 to 0153 of JP-A-2019-184763, the contents of which are incorporated herein.
  • the storage stability of the resin composition can be further improved.
  • the content of the resin having a basic group is 20 to 500 parts by mass with respect to 100 parts by mass of the resin having an acid group. It is preferably from 30 to 300 parts by mass, and even more preferably from 50 to 200 parts by mass.
  • resins include a monomer component containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimers"). It is also preferable to use a resin containing a repeating unit derived from.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • R 1 represents a hydrogen atom or a methyl group
  • R 21 and R 22 each independently represent an alkylene group
  • n represents an integer of 0-15.
  • the number of carbon atoms in the alkylene group represented by R 21 and R 22 is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly 2 or 3.
  • n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.
  • Examples of the compound represented by formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of paracumylphenol.
  • Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
  • Crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • ethylenically unsaturated bond-containing groups include vinyl groups, styrene groups, (meth)allyl groups, and (meth)acryloyl groups.
  • the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred.
  • the epoxy group may be a cycloaliphatic epoxy group.
  • the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
  • resin Ac a resin having an aromatic carboxy group
  • the aromatic carboxy group may be contained in the main chain of the repeating unit or may be contained 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 is 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 1-4, more preferably 1-2.
  • Resin Ac is preferably a resin containing at least one repeating unit selected from repeating units represented by formula (Ac-1) and repeating units represented by formula (Ac-2).
  • Ar 1 represents a group containing an aromatic carboxyl group
  • L 1 represents -COO- or -CONH-
  • L 2 represents a divalent linking group
  • Ar 10 represents a group containing an aromatic carboxyl 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 aromatic carboxy group-containing group represented by Ar 1 in formula (Ac-1) include structures derived from aromatic tricarboxylic acid anhydrides, structures derived from aromatic tetracarboxylic acid anhydrides, and the like.
  • Examples of aromatic tricarboxylic anhydrides and aromatic tetracarboxylic anhydrides 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 group containing an aromatic carboxyl 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, 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). and the like.
  • n1 represents an integer of 1 to 4, preferably 1 or 2, more preferably 2.
  • n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and still 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, 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- 1) or a group represented by the above formula (Q-2).
  • *1 represents the bonding position with L1 .
  • L 1 represents -COO- or -CONH-, preferably -COO-.
  • the divalent linking group represented by L 2 in formula (Ac-1) includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and these A group obtained by combining two or more of The number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, even more preferably 1-15.
  • the alkylene group may be linear, branched or cyclic.
  • the arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • An alkylene group and an arylene group may have a substituent. A hydroxy group etc.
  • 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 combination of an alkylene group and an arylene group; at least one selected from an alkylene group and an arylene group; Examples include groups in which at least one selected from —NH— and —S— are combined, and alkylene groups are preferred.
  • the number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, even more preferably 1-15.
  • the alkylene group may be linear, branched or cyclic. An alkylene group and an arylene group may have a substituent. A hydroxy group etc. are mentioned as a substituent.
  • the group containing an aromatic carboxyl 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 in formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and 2 of these Groups in which more than one species are combined are included.
  • Hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-15.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, even more preferably 6-10.
  • the hydrocarbon group may have a substituent. A hydroxy group etc. are mentioned as a substituent.
  • the trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), 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 formula ( The binding position of Ac-2) with P10 is shown.
  • the trivalent linking group represented by L 12b includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- is preferably a hydrocarbon group or a group of a combination of a hydrocarbon group and —O—.
  • 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 ( The binding position of Ac-2) with P10 is shown.
  • the trivalent linking group represented by L 12c includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- and the like, preferably a hydrocarbon group.
  • P 10 in formula (Ac-2) represents a polymer chain.
  • the polymer chain represented by P10 preferably has at least one structure selected from polyester structure, polyether structure, polystyrene structure and poly(meth)acrylic structure.
  • the weight average molecular weight of the polymer chain P10 is preferably 500-20,000.
  • the lower limit is preferably 1000 or more.
  • the upper limit is preferably 10,000 or less, more preferably 5,000 or less, even more preferably 3,000 or less. If the weight average molecular weight of P10 is within the above range, the dispersibility of the pigment in the composition is good.
  • the resin having an aromatic carboxyl group is a resin having repeating units represented by formula (Ac-2), this resin is preferably used as a dispersant.
  • the polymer chain represented by P10 may contain crosslinkable groups.
  • Crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • the other resin it is preferable to use at least one selected from graft polymers, star polymers, block copolymers, and resins in which at least one end of the polymer chain is blocked with an acid group.
  • 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 formula (Ac-2).
  • Examples of graft chains include graft chains 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 substituents include alkyl groups, alkoxy groups, alkylthioether groups, and the like.
  • a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 30 carbon atoms is preferable.
  • the alkyl group and alkoxy group may be linear, branched or cyclic, preferably linear or branched.
  • graft polymer examples include paragraph numbers 0025 to 0094 of JP-A-2012-255128, paragraph numbers 0022-0097 of JP-A-2009-203462, and paragraph numbers 0102-0166 of JP-A-2012-255128. Mention may be made of the resins mentioned.
  • Star-shaped polymers include resins with a structure in which multiple polymer chains are bonded to the core.
  • Specific examples of the star polymer include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.
  • 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 containing no acid group or basic group. (hereinafter also referred to as block B).
  • Block copolymers include block copolymers (B) described in paragraph numbers 0063 to 0112 of JP-A-2014-219665, and blocks described in paragraph numbers 0046-0076 of JP-A-2018-156021. Copolymer A1 can also be used, the contents of which are incorporated herein.
  • At least one end of the polymer chain containing at least one structure selected from a polyester structure, a polyether structure and a poly(meth)acrylic structure is A resin having a structure sealed with an acid group can be mentioned.
  • a carboxy group, a sulfo group, and a phosphoric acid group are examples of the acid group that seals the end of the polymer chain.
  • Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins).
  • the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups.
  • the acidic dispersant (acidic resin) a resin having an acid group content of 70 mol % or more is preferable when the total amount of the acid group and the basic group is 100 mol %.
  • the acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g.
  • a basic dispersant represents a resin in which the amount of basic groups is greater than the amount of acid groups.
  • a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and basic groups is 100 mol %.
  • the basic group possessed by the basic dispersant is preferably an amino group.
  • Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine Techno Co., Ltd. Ajisper series, A208F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), H-3606 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Sandet ET (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
  • the product described in paragraph number 0129 of JP-A-2012-137564 and the product described in paragraph number 0235 of JP-A-2017-194662 can also be used as a dispersant.
  • the resin content in the total solid content of the resin composition is preferably 1 to 50% by mass.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the content of the specific resin in the total solid content of the resin composition is preferably 1 to 50% by mass.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the content of the specific resin in the resin contained in the resin composition is preferably 10 to 100% by mass, more preferably 25 to 100% by mass, and even more preferably 45 to 100% by mass.
  • the resin composition of the present invention may contain only one type of resin, or may contain two or more types. When two or more resins are included, the total amount thereof is preferably within the above range.
  • the resin composition of the present invention preferably contains a polymerizable compound.
  • the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group.
  • ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.
  • the polymerizable compound used in the present invention is preferably a radically polymerizable compound.
  • the polymerizable compound may be in any chemical form such as monomer, prepolymer, oligomer, etc., but monomer is preferred.
  • the molecular weight of the polymerizable compound is preferably 100-2500.
  • the upper limit is preferably 2000 or less, more preferably 1500 or less.
  • the lower limit is preferably 150 or more, more preferably 250 or more.
  • the lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and even more preferably 5 mmol/g or more.
  • the upper limit is preferably 12 mmol/g or less, more preferably 10 mmol/g or less, and even more preferably 8 mmol/g or less.
  • the polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 4 or more ethylenically unsaturated bond-containing groups.
  • the upper limit of the ethylenically unsaturated bond-containing groups is preferably 15 or less, more preferably 10 or less, even more preferably 6 or less, from the viewpoint of storage stability of the resin composition.
  • the polymerizable compound is preferably a tri- or more functional (meth) acrylate compound, more preferably a 3- to 15-functional (meth) acrylate compound, and a 3- to 10-functional (meth) acrylate compound.
  • the polymerizable compound include paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph numbers 0254-0257 of JP-A-2008-292970, and JP-A-2008-292970. 2013-253224, paragraphs 0034 to 0038, JP 2012-208494, paragraph 0477, JP 2017-048367, JP 6057891, the compound described in JP 6031807 , the contents of which are incorporated herein.
  • polymerizable compounds examples include dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and modified products of these compounds. mentioned.
  • Modified compounds include compounds having a structure in which the (meth)acryloyl groups of the above compounds are bonded through an alkyleneoxy group, such as ethoxylated dipentaerythritol hexa(meth)acrylate. Specific examples include compounds represented by formula (Z-4) and compounds represented by formula (Z-5).
  • E is each independently -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)- , y each independently represents an integer of 0 to 10, and each X independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxy group.
  • the total number of (meth)acryloyl groups is 3 or 4
  • the sum of m is an integer of 0 to 40.
  • the total number of (meth)acryloyl groups is 5 or 6
  • each n independently represents an integer of 0-10, and the sum of each n is an integer of 0-60.
  • m is preferably an integer of 0-6, more preferably an integer of 0-4.
  • the sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
  • n is preferably an integer of 0-6, more preferably an integer of 0-4.
  • the sum of n is preferably an integer of 3-60, more preferably an integer of 3-24, and particularly preferably an integer of 6-12.
  • E in formula (Z-4) or formula (Z-5), that is, -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)- is A form in which the end on the oxygen atom side is bonded to X is preferred.
  • Polypentaerythritol poly(meth)acrylates represented by the following formula (Z-6) can also be used as the polymerizable compound.
  • X 1 to X 6 each independently represent a hydrogen atom or a (meth)acryloyl group, and n represents an integer of 1-10. However, at least one of X 1 to X 6 is a (meth)acryloyl group.
  • the polymerizable compound used in the present invention is at least one selected from the group consisting of dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol poly(meth)acrylate and modified products thereof. Seeds are preferred.
  • Commercially available products include KAYARAD D-310, DPHA, DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.), NK Ester A-DPH-12E, TPOA-50 (manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. mentioned.
  • diglycerin EO ethylene oxide modified (meth) acrylate
  • pentaerythritol tetra (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-TMMT
  • 1,6-hexanediol diacrylate manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA
  • RP-1040 manufactured by Nippon Kayaku Co., Ltd.
  • Aronix TO-2349 Toagosei Co., Ltd.
  • NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), Light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL80 (manufactured by Daicel Allnex, amine-containing tetrafunctional acrylate) and the like can also be used.
  • trimethylolpropane tri(meth)acrylate trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, isocyanuric acid ethylene oxide-modified tri(meth)acrylate
  • trifunctional (meth)acrylate compounds such as pentaerythritol tri(meth)acrylate.
  • Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305.
  • M-303, M-452, M-450 manufactured by Toagosei Co., Ltd.
  • a compound having an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group can be used as the polymerizable compound.
  • Commercially available products of such compounds include Aronix M-305, M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
  • a compound having a caprolactone structure can also be used as the polymerizable compound.
  • the descriptions in paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, the contents of which are incorporated herein.
  • Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd.
  • a polymerizable compound having a fluorene skeleton can also be used.
  • Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).
  • the polymerizable compound it is also preferable to use a compound such as toluene that does not substantially contain environmentally regulated substances.
  • a compound such as toluene that does not substantially contain environmentally regulated substances.
  • Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
  • urethane acrylates such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765
  • urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418.
  • the polymerizable compound includes UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, Commercially available products such as T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.
  • the content of the polymerizable compound in the total solid content of the resin composition is preferably 1 to 35% by mass.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the lower limit is preferably 2% by mass or more, more preferably 5% by mass or more.
  • the resin composition of the present invention may contain only one polymerizable compound, or may contain two or more polymerizable compounds. When two or more polymerizable compounds are included, the total amount thereof is preferably within the above range.
  • the resin composition of the present invention can contain a photopolymerization initiator.
  • the resin composition of the present invention preferably further contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet region to the visible region are preferred.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
  • acylphosphine compounds e.g., acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
  • photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbi 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 compounds, ⁇ -aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds.
  • hexaarylbiimidazole compounds include 2,2′,4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1′-biimidazole, etc. is mentioned.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above, BASF company) and the like.
  • Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 3.
  • acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).
  • Examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No.
  • oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropane-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(
  • An oxime compound having a fluorene ring can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466, compounds described in Japanese Patent No. 6636081, and compounds described in Korean Patent Publication No. 10-2016-0109444. mentioned.
  • an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
  • Specific examples of such oxime compounds include compounds described in WO2013/083505.
  • An oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of.
  • An oxime compound having a nitro group can be used as the photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.
  • An oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator.
  • Specific examples include OE-01 to OE-75 described in WO 2015/036910.
  • an oxime compound in which a substituent having a hydroxyl group is bonded to the carbazole skeleton can also be used.
  • Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
  • an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used.
  • the electron-withdrawing group possessed by the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
  • An acyl group and a nitro group are preferred, an acyl group is more preferred, and a benzoyl group is even more preferred.
  • a benzoyl group may have a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclicoxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group. A sulfanyl group or an amino group is more preferred.
  • the oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
  • R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group
  • R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group,
  • the electron-withdrawing group includes an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group, preferably an acyl group and a nitro group. is more preferably a group, more preferably a benzoyl group.
  • R X12 is an electron-withdrawing group
  • R X10 , R X11 , R X13 and R X14 are preferably hydrogen atoms.
  • oxime compound OX examples include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.
  • oxime compounds preferably used in the present invention are shown below, but the present invention is not limited to these.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
  • the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1000 to 300000, further preferably 2000 to 300000, even more preferably 5000 to 200000. It is particularly preferred to have
  • the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • the photopolymerization initiator it is also preferable to use a combination of Irgacure OXE01 (manufactured by BASF) and/or Irgacure OXE02 (manufactured by BASF) and Omnirad 2959 (manufactured by IGM Resins B.V.).
  • a bifunctional or trifunctional or higher 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 good sensitivity can be obtained.
  • the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the storage stability of the resin composition can be improved.
  • Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
  • the content of the photopolymerization initiator 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 1% by mass or more.
  • the upper limit is preferably 15% by mass or less, more preferably 10% by mass or less.
  • only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention preferably contains a solvent.
  • An organic solvent is mentioned as a solvent.
  • the type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition.
  • Organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For these details, reference can be made to paragraph number 0223 of WO2015/166779, the content of which is incorporated herein. Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used.
  • organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N
  • aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be better reduced for environmental reasons (e.g., 50 mass ppm (parts per million), 10 ppm by mass or less, or 1 ppm by mass or less).
  • an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content.
  • the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, 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 size 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 isomer may be contained, or a plurality of isomers may be contained.
  • 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 solvent in the resin composition is preferably 10-95% by mass, more preferably 20-90% by mass, and even more preferably 30-90% by mass.
  • the resin composition of the present invention does not substantially contain environmentally regulated substances from the viewpoint of environmental regulations.
  • substantially free of environmental regulation substances means that the content of environmental regulation substances in the resin composition is 50 mass ppm or less, preferably 30 mass ppm or less. , is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less.
  • Environmental control substances include, for example, benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • a method for reducing the amount of environmentally regulated substances there is a method in which the system is heated or decompressed to raise the temperature to the boiling point of the environmentally regulated substances or higher, and the environmentally regulated substances are distilled off from the system.
  • distilling off a small amount of environmentally regulated substances it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase the efficiency.
  • a polymerization inhibitor or the like is added and distilled off under reduced pressure in order to suppress the radical polymerization reaction from progressing during the vacuum distillation and the intermolecular cross-linking.
  • These distillation methods are at the stage of raw materials, the stage of reaction products of raw materials (for example, resin solutions and polyfunctional monomer solutions after polymerization), or the stages of resin compositions prepared by mixing these compounds. It is possible at any stage such as
  • the resin composition of the present invention can contain a thermal cross-linking agent as a component other than the resin and polymerizable compound described above.
  • Thermal cross-linking agents include compounds having a cyclic ether group.
  • Cyclic ether groups include epoxy groups and oxetanyl groups.
  • the epoxy group may be a cycloaliphatic epoxy group.
  • the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
  • the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound).
  • Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred.
  • the epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule.
  • the upper limit of the number of epoxy groups contained in the epoxy compound may be, for example, 10 or less, or 5 or less.
  • As for the minimum of the epoxy group contained in an epoxy compound two or more are preferable.
  • As the epoxy compound paragraph numbers 0034 to 0036 of JP-A-2013-011869, paragraph numbers 0147-0156 of JP-A-2014-043556, paragraph numbers 0085-0092 of JP-A-2014-089408.
  • Compounds, compounds described in JP-A-2017-179172 can also be used. The contents of these are incorporated herein.
  • the compound having a cyclic ether group may be a low-molecular compound (e.g., molecular weight less than 2000, further molecular weight less than 1000), or a macromolecular compound (e.g., molecular weight 1000 or more, weight-average molecular weight in the case of polymer is 1000 or more).
  • the weight average molecular weight of the compound having a cyclic ether group is preferably 200-100,000, more preferably 500-50,000.
  • the upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5,000 or less, and still more preferably 3,000 or less.
  • Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (these are epoxy group-containing polymers manufactured by NOF Corporation) and the like. Further, as the compound having a cyclic ether group, the compounds described in the examples described later can also be used.
  • the content of the thermal cross-linking agent in the total solid content of the resin composition is preferably 0.1 to 20% by mass.
  • the lower limit is, for example, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
  • the upper limit is, for example, more preferably 15% by mass or less, and even more preferably 10% by mass or less. Only one kind of thermal cross-linking agent may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention can also contain a polyalkyleneimine.
  • Polyalkyleneimines are used, for example, as dispersing aids for pigments.
  • a dispersing aid is a material for enhancing the dispersibility of a coloring material such as a pigment in a resin composition.
  • Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine.
  • the polyalkyleneimine is preferably a polymer having a branched structure each containing a primary amino group, a secondary amino group and a tertiary amino group.
  • the number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2.
  • the molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more.
  • the upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less.
  • the molecular weight of the polyalkyleneimine when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula.
  • the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the 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.
  • the value of the number average molecular weight in terms of polystyrene measured by the GPC (gel permeation chromatography) method is used.
  • the amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
  • alkyleneimine examples include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine and the like, preferably ethyleneimine or propyleneimine, more preferably ethyleneimine. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. In addition, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more, of the primary amino group with respect to the total of the primary amino group, the secondary amino group and the tertiary amino group. , more preferably 30 mol % or more.
  • Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, P-1000 (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 the polyalkyleneimine is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass 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 kind of polyalkyleneimine may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
  • the resin composition of the present invention may contain a curing accelerator.
  • Curing accelerators include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds and the like.
  • the curing accelerator include compounds described in paragraph numbers 0094 to 0097 of WO 2018/056189, compounds described in paragraph numbers 0246 to 0253 of JP 2015-034963, JP 2013-041165 Compounds described in paragraphs 0186 to 0251 of the publication, ionic compounds described in JP 2014-055114, compounds described in paragraphs 0071 to 0080 of JP 2012-150180, JP 2011-253054 Alkoxysilane compounds having an epoxy group described in JP-A-2005-200157, compounds described in paragraphs 0085 to 0092 of Japanese Patent No. 5765059, and carboxy group-containing epoxy curing agents described in JP-A-2017-036379.
  • the content of the curing accelerator in the total solid content of the resin composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
  • the resin composition of the present invention can contain an ultraviolet absorber.
  • ultraviolet absorbers 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 paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, and paragraph numbers 0317-0317 of JP-A-2013-068814.
  • UV absorber examples include compounds having the following structures.
  • examples of commercially available UV absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.), Tinuvin series and Uvinul series manufactured by BASF, and Sumisorb series manufactured by Sumika Chemtex Co., Ltd. .
  • Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016).
  • the ultraviolet absorber is a compound described in paragraph numbers 0049 to 0059 of Japanese Patent No.
  • 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 ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used.
  • the total amount is preferably 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), 2,2′-methylenebis(4-methyl-6-t-butylphenol), 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. Only one kind of polymerization inhibitor may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount is preferably 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 and other functional groups.
  • the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction.
  • Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group and isocyanate group. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferred.
  • silane coupling agent examples include N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N- ⁇ -aminoethyl- ⁇ -amino propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), ⁇ -aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM
  • silane coupling agent examples include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. , the contents of which are incorporated herein.
  • 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. Only one type of silane coupling agent may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.
  • the resin composition of the present invention can contain a surfactant.
  • a surfactant various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants can be used.
  • the surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant.
  • surfactants reference can be made to surfactants described in paragraphs 0238-0245 of WO2015/166779, the contents of which are incorporated herein.
  • the fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass.
  • a fluorosurfactant having a fluorine content within this range is effective in uniformity of the thickness of the coating film and liquid saving, and has good solubility in the resin composition.
  • JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-132503 and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein.
  • Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, and F-144.
  • the fluorosurfactant has a molecular structure with a functional group containing a fluorine atom, and an acrylic compound in which the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied is also suitable.
  • fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Mega Fac DS-21.
  • fluorosurfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant.
  • fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.
  • a block polymer can also be used as the fluorosurfactant.
  • the fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta)
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol%.
  • a fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used as the fluorosurfactant.
  • Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, MEGAFACE RS-101, RS-102 and RS-718K manufactured by DIC Corporation, and RS-72-K.
  • compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
  • a fluorine-containing imide salt compound represented by formula (fi-1) is also preferable to use as a surfactant.
  • m represents 1 or 2
  • n represents an integer of 1 to 4
  • a represents 1 or 2
  • X a+ is an a-valent metal ion, primary ammonium ion, Represents secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH 4 + .
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fuji
  • Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), 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-based 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% by mass to 3.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.
  • the resin composition of the present invention can contain an antioxidant.
  • Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
  • Phosphorus-based antioxidants can also be suitably used as antioxidants.
  • a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
  • antioxidants examples include 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 Corporation) and the like.
  • antioxidants are compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, compounds described in WO 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 kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, the total amount is preferably within the above range.
  • the resin composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are described, for example, from paragraph number 0183 of JP-A-2012-003225 (paragraph number 0237 of corresponding US Patent Application Publication No. 2013/0034812), paragraph of JP-A-2008-250074 The descriptions of numbers 0101 to 0104, 0107 to 0109, etc.
  • auxiliaries e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.
  • the resin composition of the present invention may contain a latent antioxidant, if necessary.
  • the latent antioxidant is a compound in which the site functioning as an antioxidant is protected by a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst.
  • a compound that functions as an antioxidant by removing the protective group by the reaction is exemplified.
  • Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
  • Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
  • the resin composition of the present invention may contain a compound having a hydroxyl group or an amino group, which is a raw material for synthesis of the specific resin, or a decomposition product of the specific resin.
  • the resin composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film.
  • metal oxides include TiO 2 , ZrO 2 , Al 2 O 3 and SiO 2 .
  • the primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, even more preferably 5 to 50 nm.
  • Metal oxides may have a core-shell structure. Moreover, in this case, the core portion may be hollow.
  • the resin composition of the present invention may contain a light resistance improver.
  • a light resistance improver compounds described in paragraph numbers 0036 to 0037 of JP-A-2017-198787, compounds described in paragraph numbers 0029-0034 of JP-A-2017-146350, JP-A-2017-129774 Compounds described in paragraph numbers 0036 to 0037, 0049 to 0052 of JP 2017-129674 JP 2017-129674 paragraph numbers 0031 to 0034, 0058 to 0059 compounds described in JP 2017-122803 paragraph numbers 0036 to 0037 , compounds described in 0051 to 0054, compounds described in paragraph numbers 0025 to 0039 of WO 2017/164127, compounds described in paragraph numbers 0034 to 0047 of JP 2017-186546, JP 2015-025116 Compounds described in paragraph numbers 0019 to 0041 of JP-A-2012-145604, compounds described in paragraph numbers 0101-0125 of JP-A-2012-103475, compounds
  • the resin composition of the present invention preferably does not substantially contain terephthalic acid ester.
  • substantially free means that the content of the terephthalic acid ester is 1000 mass ppb or less, more preferably 100 mass ppb or less, in the total amount of the resin composition. Zero is particularly preferred.
  • perfluoroalkylsulfonic acid and its salts may be regulated.
  • perfluoroalkylsulfonic acid especially perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
  • perfluoroalkylsulfonic acid especially perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
  • the content of fluoroalkylcarboxylic acid (especially perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is 0.01ppb to 1,000ppb with respect to the total solid content of the resin composition.
  • the resin composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts.
  • a compound that can substitute for perfluoroalkylsulfonic acid and its salt and a compound that can substitute for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and salts thereof may be selected.
  • Compounds that can substitute for the regulated compounds include, for example, compounds excluded from the regulation due to the difference in the number of carbon atoms in the perfluoroalkyl group.
  • the above content does not prevent the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts.
  • the resin composition of the present invention may contain perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts within the maximum permissible range.
  • the water content of the resin composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, more preferably 0.1 to 1.0% by mass.
  • the water content can be measured by the Karl Fischer method.
  • the resin composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (flatness, etc.) and adjusting the film thickness.
  • the viscosity value can be appropriately selected as necessary, and is preferably, for example, 0.3 mPa ⁇ s to 50 mPa ⁇ s, more preferably 0.5 mPa ⁇ s to 20 mPa ⁇ s at 25°C.
  • a method for measuring the viscosity for example, a cone-plate type viscometer can be used, and the viscosity can be measured in a state where the temperature is adjusted to 25°C.
  • the storage container for the resin composition is not particularly limited, and known storage containers can be used.
  • a storage container a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resins and a bottle with a 7-layer structure of 6 types of resins are used for the purpose of suppressing contamination of raw materials and resin compositions. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351.
  • the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the resin composition, and suppressing deterioration of components.
  • the resin composition of the present invention can be prepared by mixing the aforementioned components.
  • all components may be simultaneously dissolved and/or dispersed in a solvent to prepare the resin composition, or if necessary, each component may be appropriately mixed into two or more solutions or dispersions. , these may be mixed at the time of use (at the time of application) to prepare a resin composition.
  • a process of dispersing the pigment when preparing the resin composition.
  • mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like.
  • Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like.
  • beads with a small diameter or to increase the filling rate of the beads so as to increase the pulverization efficiency.
  • the process and dispersing machine for dispersing pigments are described in "Dispersion Technology Complete Works, Information Organization Co., Ltd., July 15, 2005” and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial Practical Application General Documents, Published by Management Development Center Publishing Department, October 10, 1978", the process and dispersing machine described in paragraph number 0022 of JP-A-2015-157893 can be suitably used.
  • the particles may be made finer in the salt milling process. Materials, equipment, processing conditions, etc. used in the salt milling step can be referred to, for example, Japanese Patent Application Laid-Open Nos. 2015-194521 and 2012-046629.
  • Bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel and glass.
  • An inorganic compound having a Mohs hardness of 2 or more can also be used for the beads. 1 to 10000 ppm of the beads may be contained in the resin composition.
  • any filter that has been conventionally used for filtration or the like can be used without particular limitation.
  • fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF)
  • polyamide resins such as nylon (eg nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high-molecular-weight polyolefin resin) and other materials.
  • PP polypropylene
  • nylon including high density polypropylene
  • nylon including high density polypropylene
  • the pore size of the filter is preferably 0.01-7.0 ⁇ m, more preferably 0.01-3.0 ⁇ m, and even more preferably 0.05-0.5 ⁇ m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably.
  • the pore size value of the filter reference can be made to the filter manufacturer's nominal value.
  • Various filters provided by Nippon Pall Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used as filters. .
  • fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers.
  • Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.
  • filters When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed. In addition, the filter can be appropriately selected according to the hydrophilicity/hydrophobicity of the composition.
  • the film of the present invention is a film obtained from the resin composition of the present invention described above.
  • the film of the present invention can be used for optical filters such as color filters, near-infrared transmission filters and near-infrared cut filters.
  • the film thickness of the film of the present invention can be appropriately adjusted according to the purpose.
  • the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more.
  • the film of the present invention when used as a color filter, preferably has a hue of green, red, blue, cyan, magenta or yellow, and may have a hue of green, blue or cyan. More preferably, it has a green hue.
  • 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, and red pixels are more preferable.
  • the film of the present invention can be produced through the step of applying the resin composition of the present invention.
  • the film manufacturing method further includes a step of forming a pattern (pixels).
  • a method for forming the pattern (pixels) includes a photolithography method and a dry etching method, and the photolithography method is preferable.
  • Pattern formation by photolithography includes the steps of forming a resin composition layer on a support using the resin composition of the present invention, exposing the resin composition layer in a pattern, and exposing the resin composition layer to light. forming a pattern (pixels) by developing and removing the exposed portion. If necessary, a step of baking the resin composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.
  • the resin composition of the present invention is used to form a resin composition layer on a support.
  • the support is not particularly limited and can be appropriately selected depending on the application. Examples thereof include glass substrates and silicon substrates, and silicon substrates are preferred. Also, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate.
  • the silicon substrate is formed with a black matrix that isolates each pixel.
  • the silicon substrate may be provided with an underlying layer for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.
  • the surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferably 30 to 80° when measured with water.
  • a known method can be used as a method for applying the resin composition.
  • dropping method drop cast
  • slit coating method spray method
  • roll coating method spin coating
  • methods described in publications inkjet
  • ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc.
  • Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like.
  • the application method for inkjet is not particularly limited.
  • the resin composition layer formed on the support may be dried (pre-baked). Pre-baking may not be performed when the film is manufactured by a low-temperature process.
  • the pre-baking 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, and can also be 80° C. or higher.
  • the pre-bake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, an 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 through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.
  • Radiation (light) that can be used for exposure includes g-line, i-line, and the like.
  • Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used.
  • Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferable.
  • a long-wave light source of 300 nm or more can also be used.
  • the light when exposing, the light may be continuously irradiated and exposed, or may be irradiated and exposed in pulses (pulse exposure).
  • pulse exposure is an exposure method in which light irradiation and pause are repeated in a cycle of short time (for example, less than millisecond level).
  • the dose 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 at the time of exposure can be appropriately selected.
  • the exposure may be in an oxygen-free atmosphere, or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume).
  • the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W/m 2 to 100000 W/m 2 (eg, 5000 W/m 2 , 15000 W/m 2 or 35000 W/m 2 ). can be done.
  • Oxygen concentration and exposure illuminance may be appropriately combined. For example, illuminance of 10000 W/m 2 at oxygen concentration of 10% by volume and illuminance of 20000 W/m 2 at oxygen concentration of 35% by volume.
  • the unexposed portions of the resin composition layer are removed by development to form a pattern (pixels).
  • the development and removal of the unexposed portion of the resin composition layer can be performed using a developer.
  • the unexposed portion of the resin composition layer in the exposure step is eluted into the developer, leaving only the photocured portion.
  • the temperature of the developer is preferably 20 to 30° C., for example.
  • the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the step of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.
  • the developer includes an organic solvent, an alkaline developer, etc., and an alkaline developer is preferably used.
  • an alkaline developer an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable.
  • alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
  • ethyltrimethylammonium hydroxide ethyltrimethylammonium hydroxide
  • benzyltrimethylammonium hydroxide dimethylbis(2-hydroxyethyl)ammonium hydroxide
  • choline pyrrole
  • piperidine 1,8-diazabicyclo-[5.4.0]-7-undecene
  • examples include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate and sodium metasilicate.
  • a compound having a large molecular weight is preferable for the alkaline agent from the standpoint of environment and safety.
  • the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
  • the developer may further contain a surfactant. From the viewpoint of transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse liquid to the resin composition layer after development while rotating the support on which the resin composition layer after development is formed.
  • the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support.
  • the moving speed of the nozzle may be gradually decreased.
  • Additional exposure processing and post-baking are post-development curing treatments for complete curing.
  • the heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree.
  • Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. .
  • the light used for exposure preferably has 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 a 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 the cured layer; a step of patternwise exposing the photoresist layer and then developing it to form a resist pattern; and etching the cured layer using the resist pattern as a mask. and dry etching using a gas.
  • a mode in which heat treatment after exposure and heat treatment (post-baking treatment) after development are performed is desirable.
  • pattern formation by a dry etching method descriptions in paragraphs 0010 to 0067 of JP-A-2013-064993 can be referred to, and the contents thereof are incorporated herein.
  • the optical filter of the present invention has the film of the present invention as described above.
  • Types of optical filters include color filters, near-infrared cut filters, and near-infrared transmission filters, and color filters are preferred.
  • the color filter preferably has the film of the invention as its pixels, more preferably has the film of the invention as its color pixels, and even more preferably has the film of the invention as its red pixels.
  • the optical filter may have a protective layer on the surface of the film of the present invention.
  • a protective layer By providing the protective layer, it is possible to impart various functions such as blocking oxygen, reducing reflection, making the film hydrophilic and hydrophobic, and blocking light of a specific wavelength (ultraviolet rays, near-infrared rays, etc.).
  • the thickness of the protective layer is preferably 0.01-10 ⁇ m, more preferably 0.1-5 ⁇ m.
  • Examples of the method of forming the protective layer include a method of applying a protective layer-forming resin composition, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive.
  • Components constituting the protective layer include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, and polyimides.
  • Resins polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, polyol resins, polyvinylidene chloride resins, melamine resins, urethane resins, aramid resins, polyamide resins, alkyd resins, epoxy resins, modified silicone resins, fluorine Resins, polyacrylonitrile resins, cellulose resins, 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 in the case of a protective layer intended to block oxygen, preferably contains a polyol resin, SiO 2 and Si 2 N 4 .
  • the protective layer in the case of a protective layer intended to reduce reflection, preferably contains a (meth)acrylic resin and a fluororesin.
  • a resin composition When a resin composition is applied to form a protective layer, known methods such as spin coating, casting, screen printing, and ink-jetting can be used as methods for applying the resin composition.
  • Known organic solvents eg, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.
  • the protective layer is formed by a chemical vapor deposition method
  • the chemical vapor deposition method includes known chemical vapor deposition methods (thermal chemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method). can be used.
  • the protective layer contains organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index modifiers, antioxidants, adhesion agents, additives such as surfactants. may contain.
  • organic/inorganic fine particles include polymeric fine particles (eg, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like.
  • a known absorber can be used as the absorber for light of a specific wavelength.
  • the content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the protective layer.
  • the protective layer the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.
  • the optical filter may have a structure in which each pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.
  • the solid-state imaging device of the present invention has the film of the present invention described above.
  • the configuration of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device.
  • a plurality of photodiodes and transfer electrodes made of polysilicon or the like are provided on the substrate, forming the light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal-oxide semiconductor) image sensor, etc.). and a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. and a color filter on the device protective film.
  • CCD charge-coupled device
  • CMOS complementary metal-oxide semiconductor
  • the color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.
  • the partition wall preferably has a lower refractive index than each color pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478, JP-A-2014-179577, and International Publication No. 2018/043654.
  • an ultraviolet absorption layer may be provided in the structure of the solid-state imaging device to improve light resistance.
  • An imaging device equipped with the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having an imaging function (mobile phones, etc.), but also for vehicle-mounted cameras and monitoring cameras.
  • the image display device of the present invention has the film of the present invention described above.
  • image display devices include liquid crystal display devices and organic electroluminescence display devices.
  • electroluminescence display devices For a definition of an image display device and details of each image display device, see, for example, “Electronic Display Device (by Akio Sasaki, Industrial Research Institute, 1990)", “Display Device (by Junsho Ibuki, Sangyo Tosho ( Co., Ltd.), issued in 1989), etc.
  • Liquid crystal display devices are described, for example, in “Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied.
  • a precursor polymer was obtained by stirring the mixture for 3 hours. 305.5 g of precursor polymer, 7.00 g (0.035 mol) of 4-hydroxybutyl acrylate glycidyl ether, and 2.42 g (0.011 mol) of N,N-dimethyldodecylamine were placed in a three-necked flask that was sufficiently air-exchanged.
  • Resins P2 to P86 and P104 to P109 were synthesized in the same manner as resin P-1.
  • Resins P1 to P109 and CP1 are resins containing repeating units shown in the table below. The acid value and weight average molecular weight (Mw) of the resin are also shown.
  • Repeating unit 1 A-1 to A-48: Repeating units having the following structure (repeating units having a urea group or a urethane group)
  • the average particle size of the pigment was measured by a dynamic light scattering method using a particle size measuring device (nano SAQLA, manufactured by Otsuka Electronics Co., Ltd.).
  • the viscosity of the pigment dispersion was measured by adjusting the temperature of the pigment dispersion to 25° C. using a viscometer (RE-85L, manufactured by Toki Sangyo Co., Ltd.).
  • PR224 C.I. I. Pigment Red 224 (perylene compound, red pigment)
  • PR254 C.I. I. Pigment Red 254 (diketopyrrolopyrrole compound, red pigment)
  • PR272 C.I. I. Pigment Red 272 (diketopyrrolopyrrole compound, red pigment)
  • PY139 C.I. I. Pigment Yellow 139 (isoindoline compound, yellow pigment)
  • PY150 C.I. I. Pigment Yellow 150 (azo compound, yellow pigment)
  • PY185 C.I. I. Pigment Yellow 185 (isoindoline compound, yellow pigment)
  • PG36 C.I. I.
  • Pigment Green 36 (phthalocyanine compound, green pigment)
  • PB15:6 C.I. I. Pigment Blue 15:6 (phthalocyanine compound, blue pigment)
  • PV23 C.I. I. Pigment Violet 23 (dioxazine compound, purple pigment)
  • PBk32 C.I. I. Pigment Black 32 (perylene compound, organic black pigment)
  • IR colorant 1 compound having the following structure (pyrrolopyrrole compound, near-infrared absorbing pigment)
  • Derivative 1 a compound having the following structure
  • Derivative 2 a compound having the following structure
  • Derivative 3 a compound having the following structure
  • Derivative 4 a compound having the following structure
  • Polymerizable compound 1 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
  • Polymerizable compound 2 KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.)
  • Photoinitiator 1 Irgacure OXE02 (manufactured by BASF, oxime compound)
  • Surfactant 1 KF6000 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant)
  • Polymerization inhibitor 1 p-methoxyphenol
  • Thermal cross-linking agent 1 Compound T-1 having the following structure
  • Solvent 1 Propylene glycol monomethyl ether acetate
  • Solvent 2 Cyclopentanone
  • Solvent 3 Propylene glycol monomethyl ether
  • a composition for forming an underlayer (CT-4000, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied to a thickness of 0.1 ⁇ m after post-baking using a spin coater, and a hot plate was applied. was used to form an underlayer by heating at 220° C. for 300 seconds to obtain an underlayer-attached glass substrate (support).
  • Each resin composition was applied onto the glass substrate with the underlayer by spin coating, and then heated at 100° C. for 2 minutes using a hot plate to form a film having a thickness of 0.5 ⁇ m.
  • Foreign matter contained in this film is detected by a foreign matter evaluation device (Complas III, manufactured by Applied Materials), and foreign matter (coarse particles) with a maximum width of 1.0 ⁇ m or more is visually observed from all the detected foreign matter.
  • the particles were classified, and the number of classified coarse particles having a maximum width of 1.0 ⁇ m or more (the number of coarse particles per 1 cm 2 ) was counted.
  • B The number of coarse particles per 1 cm 2 of the film is 10 or more and less than 30
  • C The number of coarse particles per 1 cm 2 of the film is 30
  • the number of coarse particles per 1 cm 2 of the film is 100 or more
  • the silicon wafer was fixed on a horizontal rotary table by a vacuum chuck method, and the silicon wafer was rotated at 50 rpm by a rotating device. While rotating at , pure water was supplied from above the center of rotation from a jet nozzle in the form of a shower for rinsing, followed by spray drying. Further, heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200° C. to form a pattern (pixels). The silicon wafer on which the pixels were formed was observed with a scanning electron microscope (magnification: 10,000), and the developability was evaluated according to the following evaluation criteria. A: No residue was observed outside the pixel formation area (unexposed area).
  • the resin compositions of Examples were excellent in storage stability and developability, and were able to form films containing less foreign matter.
  • the films obtained from the resin compositions described in Examples can be suitably used for optical filters, solid-state imaging devices, and image display devices.
  • Example 6 similar effects were obtained even when the polymerizable compound 1 was changed to compound M-2 or M-3 having the structure shown below.
  • Example 133 Similar effects were obtained even when the thermal cross-linking agent T-1 was changed to compound T-2 or T-3 having the structure shown below.
  • Surfactant 1 was a compound having the following structure (weight average molecular weight: 14000, percent of repeating units is mol%, fluorosurfactant) or PolyFox PF6320 (OMNOVA) The same effect was obtained even when it was changed to a fluorosurfactant).
  • Example 6 similar effects were obtained even when polymerization inhibitor 1 was changed to compound H-2 or H-3 having the structure shown below.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention concerne une composition de résine contenant une résine B et un colorant A qui contient un pigment, la quantité du colorant A dans la teneur totale en solides de la composition de résine étant d'au moins 50 % en masse, et la résine B contenant une résine b ayant une unité de répétition b1 qui contient au moins un groupe choisi parmi un groupe urée et un groupe uréthane. L'invention concerne également un film, un filtre optique, un élément d'imagerie à semi-conducteurs et un dispositif d'affichage d'image.
PCT/JP2023/001989 2022-02-01 2023-01-24 Composition de résine, film, filtre optique, élément d'imagerie à semi-conducteurs et dispositif d'affichage d'image WO2023149272A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003238836A (ja) * 2002-02-14 2003-08-27 Fuji Photo Film Co Ltd 顔料分散剤、それを含む顔料分散組成物及び着色感光性組成物
WO2009116442A1 (fr) * 2008-03-17 2009-09-24 富士フイルム株式会社 Composition dans laquelle est dispersé un pigment, composition photosensible colorée, composition photodurcissable, filtre coloré, élément d'affichage à cristaux liquides et élément de capture d'image solide
JP2010217839A (ja) * 2009-03-19 2010-09-30 Fujifilm Corp 分散組成物及びその製造方法、遮光性カラーフィルタ用感光性樹脂組成物及びその製造方法、遮光性カラーフィルタ及びその製造方法、並びに固体撮像素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003238836A (ja) * 2002-02-14 2003-08-27 Fuji Photo Film Co Ltd 顔料分散剤、それを含む顔料分散組成物及び着色感光性組成物
WO2009116442A1 (fr) * 2008-03-17 2009-09-24 富士フイルム株式会社 Composition dans laquelle est dispersé un pigment, composition photosensible colorée, composition photodurcissable, filtre coloré, élément d'affichage à cristaux liquides et élément de capture d'image solide
JP2010217839A (ja) * 2009-03-19 2010-09-30 Fujifilm Corp 分散組成物及びその製造方法、遮光性カラーフィルタ用感光性樹脂組成物及びその製造方法、遮光性カラーフィルタ及びその製造方法、並びに固体撮像素子

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