WO2023120036A1 - 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
WO2023120036A1
WO2023120036A1 PCT/JP2022/043599 JP2022043599W WO2023120036A1 WO 2023120036 A1 WO2023120036 A1 WO 2023120036A1 JP 2022043599 W JP2022043599 W JP 2022043599W WO 2023120036 A1 WO2023120036 A1 WO 2023120036A1
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Prior art keywords
group
compounds
compound
resin composition
resin
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PCT/JP2022/043599
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English (en)
Japanese (ja)
Inventor
翔一 中村
和也 尾田
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富士フイルム株式会社
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Priority to JP2023569204A priority Critical patent/JPWO2023120036A1/ja
Publication of WO2023120036A1 publication Critical patent/WO2023120036A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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.
  • CCD charge-coupled device
  • a color filter is manufactured using a resin composition containing a coloring material.
  • Patent Document 1 describes manufacturing a color filter using a colored photosensitive resin composition containing a dye, a pigment, a resin, a polymerizable compound, a polymerization initiator, and an ultraviolet absorber.
  • the resin composition after storage may be used to manufacture the film.
  • the resin composition has insufficient stability over time, the coloring material and the like aggregate during storage of the resin composition, and the viscosity of the resin composition tends to increase over time. Furthermore, even when a film is formed under the same film forming conditions, as the storage period of the resin composition becomes longer, the difference in film thickness from the case of using the resin composition immediately after production (film thickness difference) tends to increase.
  • an object of the present invention is to provide a resin composition with excellent stability over time. Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, and an image display device.
  • a resin composition containing a coloring material, an ultraviolet absorber, and a resin The ultraviolet absorber includes an ultraviolet absorber having a basic group, and the ultraviolet absorber having a basic group is at least one selected from benzophenone compounds, benzoate compounds, benzotriazole compounds, triazine compounds and cyanoacrylate compounds. is a compound of The above resin is a resin composition containing a resin having an acid group.
  • ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the ultraviolet absorber having a basic group has a molecular weight of 500 or less.
  • ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, further comprising a polymerizable compound and a photopolymerization initiator.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the coloring material contains a dye.
  • ⁇ 7> A film obtained using the resin composition according to any one of ⁇ 1> to ⁇ 6>.
  • ⁇ 8> An optical filter including the film according to ⁇ 7>.
  • ⁇ 9> A solid-state imaging device including the film according to ⁇ 7>.
  • ⁇ 10> An image display device comprising the film according to ⁇ 7>.
  • the present invention can provide a resin composition with excellent stability over time.
  • the present invention can provide films, optical filters, solid-state imaging devices, and image display devices.
  • ⁇ 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.
  • the symbols before or after the name are terms used to distinguish the constituent elements, the types of constituent elements, the It does not limit the number and the superiority or inferiority of the constituent elements.
  • 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.
  • 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, an ultraviolet absorber, and a resin,
  • the ultraviolet absorber includes an ultraviolet absorber having a basic group, and the ultraviolet absorber having a basic group is at least one selected from benzophenone compounds, benzoate compounds, benzotriazole compounds, triazine compounds and cyanoacrylate compounds.
  • is a compound of The resin is characterized by including a resin having an acid group.
  • the resin composition of the present invention has excellent stability over time. That is, the resin composition of the present invention has a small change in viscosity over time, and can suppress an increase in the viscosity of the resin composition even after long-term storage. In addition, even when the resin composition immediately after production and the resin composition after storage are formed under the same film-forming conditions, the difference in the thickness of the resulting film (film thickness difference) is small. It is possible to suppress variations in the thickness of the film to be formed. Although the detailed reason why such an effect is obtained is unknown, the resin composition of the present invention contains the above-mentioned ultraviolet absorber having a basic group and a resin having an acid group. It is presumed that this is because a network of a coloring material, an ultraviolet absorber having a basic group, and a resin having an acid group is easily formed, thereby suppressing aggregation of the coloring material.
  • the resin composition of the present invention a film having excellent light resistance can be formed.
  • the UV absorber having the above-mentioned basic group as the UV absorber, the UV absorber is more likely to exist in the vicinity of the coloring material in the film, and the decomposition and modification of the coloring material due to light irradiation are effectively prevented. It is presumed that this is because it was possible to effectively suppress
  • 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.
  • 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 may be a filter (transparent film) that transmits both visible light and near-infrared light, and is a filter that blocks at least part of visible light and transmits at least part of near-infrared light. good too.
  • 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.
  • 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 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 a coloring material.
  • colorants include white colorants, black colorants, chromatic colorants, and near-infrared absorption colorants.
  • 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 colorant preferably contains at least one selected from the group consisting of a chromatic colorant, a black colorant, and a near-infrared absorbing colorant, and more preferably contains a chromatic colorant.
  • the colorant preferably contains two or more chromatic colorants and a near-infrared absorbing colorant.
  • black may be formed by a combination of two or more chromatic colorants.
  • the colorant preferably contains a black colorant and a near-infrared absorbing colorant.
  • the resin composition of the present invention can be preferably used as a resin composition for forming a near-infrared transmission filter. For a combination of two or more chromatic colorants to form a black color, see JP-A-2013-077009, JP-A-2014-130338, International Publication No. 2015/166779, and the like.
  • the colorant is substantially only a chromatic colorant.
  • a color filter having a high color value and excellent color separation ability can be formed.
  • the colorant when the colorant is substantially only a chromatic colorant, it means that the content of the chromatic colorant in the colorant is 99% by mass or more. % by mass or more, and it is more preferable that the colorant is only a chromatic colorant.
  • the coloring material may be a pigment or a dye.
  • 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 diameter of the pigment can be determined from the image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment.
  • the average primary particle size in this specification is the arithmetic mean value of the primary particle sizes of 400 primary particles of the pigment.
  • the primary particles of the pigment refer to independent particles without agglomeration.
  • the term "pigment” refers to a coloring material that is difficult to dissolve in a solvent.
  • the pigment has a solubility of less than 1 g in both 100 g of water at 23°C and 100 g of cyclohexanone at 23°C.
  • the term “dye” refers to a coloring material that dissolves in water or an organic solvent. The solubility of the dye in 100 g of cyclohexanone at 23° C.
  • the crystallite size obtained from the half width of the peak derived from any crystal face in the X-ray diffraction spectrum when CuK ⁇ rays of the pigment are used as the X-ray source is preferably 0.1 nm to 100 nm, and preferably 0.1 nm to 100 nm. It is more preferably 5 nm to 50 nm, still more preferably 1 nm to 30 nm, and particularly preferably 5 nm to 25 nm.
  • a preferred embodiment of the coloring material used in the resin composition is a coloring material containing a dye.
  • Color unevenness of the film can be further suppressed by using a material containing a dye as the coloring material.
  • the content of the dye in the coloring material is preferably 20% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more.
  • the upper limit can be 100% by mass or less.
  • the colorant may be substantially only a dye. According to this aspect, color unevenness of the film can be further suppressed.
  • the case where the coloring material is substantially only a dye means that the content of the dye in the coloring material is 99% by mass or more, and is 99.9% by mass or more.
  • the coloring material is only a dye.
  • Colorants may include pigments and dyes.
  • the content of the dye is preferably 10 to 80 parts by mass with respect to 100 parts by mass of the pigment.
  • the upper limit is preferably 70 parts by mass or less, more preferably 60 parts by mass or less.
  • the lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more.
  • the coloring material may be substantially only a pigment. According to this aspect, the reliability of the resulting film can be further improved.
  • the colorant when the colorant is substantially only a pigment, it means that the content of the pigment in the colorant is 99% by mass or more, and is 99.9% by mass or more. is preferable, and it is more preferable that the coloring material is only a pigment.
  • chromatic coloring materials include coloring materials having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. Examples thereof include green colorants, red colorants, yellow colorants, purple colorants, blue colorants, and orange colorants.
  • green colorants examples include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred.
  • Specific examples of the green colorant include C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65 and 66 are included.
  • 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.
  • 106909027 the phthalocyanine compound having a phosphoric acid ester as a ligand described in WO 2012/102395, described in JP 2019-008014.
  • the phthalocyanine compound, the phthalocyanine compound described in JP-A-2018-180023, the compound described in JP-A-2019-038958, the aluminum phthalocyanine compound described in JP-A-2020-070426, JP-A-2020-076995 Core-shell type dyes described in, diarylmethane compounds described in JP-A-2020-504758, and the like can also be used.
  • the green coloring material is C.I. I. Pigment Green 7, 36, 58, 59, 62 and 63 are preferred, C.I. I. Pigment Green 7, 36, 58 are more preferred.
  • 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. Specific examples of the red colorant include C.I. I.
  • 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 -Perylene compounds described in JP-A-079396, perylene compounds described in JP-A-2020-083982, xanthene compounds described in JP-A-2018-035345, paragraph numbers 0025 to 0041 of JP-A-2020-066702
  • the described diketopyrrolopyrrole compounds and the like can also be used.
  • 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.
  • Lumogen F Orange 240 manufactured by BASF, red pigment, perylene pigment
  • red colorant can also be used as the red colorant.
  • the red coloring material is C.I. I. Pigment Red 81:4,122,177,254,264,269,272 is preferred, C.I. I. Pigment Red 122, 177, 254, 264 and 272 are more preferred.
  • yellow colorants examples include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds and perylene compounds.
  • the yellow colorant is preferably a pigment, more preferably an azo pigment, an azomethine pigment, an isoindoline pigment, a pteridine pigment, a quinophthalone pigment or a perylene pigment, and even more preferably an azo pigment or an isoindoline pigment.
  • Specific examples of the yellow coloring material include C.I. I.
  • a nickel azobarbiturate complex having the following structure can also be used.
  • JP 2020-033525 Compounds described in, compounds described in JP-A-2020-033524, compounds described in JP-A-2020-033523, compounds described in JP-A-2020-033522, described in JP-A-2020-033521 Compounds described in WO 2020/045200, compounds described in WO 2020/045199, compounds described in WO 2020/045197, azo described in JP 2020-093994 compound, the perylene compound described in International Publication No. 2020/105346, the quinophthalone compound described in Japanese Patent Publication No. 2020-517791, the compound represented by the following formula (QP1), the compound represented by the following formula (QP2) can also be used. Moreover, those obtained by polymerizing these compounds are also preferably used from the viewpoint of improving the color value.
  • X 1 to X 16 each independently represent a hydrogen atom or a halogen atom
  • 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 0016 of Japanese Patent No. 6443711.
  • Y 1 to Y 3 each independently represent a halogen atom.
  • n and m are integers of 0 to 6; p is an integer of 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.
  • the yellow coloring material is C.I. I. Pigment Yellow 129, 138, 139, 150, 185, 231 and 233 are preferred, and C.I. I. Pigment Yellow 129, 139, 150 and 185 are more preferred.
  • 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.
  • Examples of the purple colorant include xanthene compounds, quinacridone compounds, dioxazine compounds, and pyrromethene compounds, with xanthene compounds, quinacridone compounds, and dioxazine compounds being preferred.
  • Specific examples of the purple colorant include C.I. I. Purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61 are included.
  • the purple colorant is C.I. I. Pigment Violet 23 is preferred.
  • Phthalocyanine compounds can be mentioned as blue colorants.
  • Specific examples of the blue colorant 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.
  • the blue colorant is C.I. I. Pigment Blue 15:3, 15:4, 15:6, 16 are preferred.
  • 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 an organic solvent. 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.
  • the chromatic colorants include diarylmethane compounds described in JP-A-2020-504758, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, and JP-A-2020-117638.
  • Xanthene compounds described phthalocyanine compounds described in International Publication No. 2020/174991, isoindoline compounds described in JP-A-2020-160279 or salts thereof,
  • Korean Patent Publication No. 10-2020-0069442 described Compound represented by Formula 1, compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069730, represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069070 Compounds, compounds represented by Formula 1 described in Korean Patent Publication No.
  • 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. When two or more chromatic colorants are used in combination, black may be formed by combining two or more chromatic colorants. Examples of such combinations include the following aspects (1) to (7).
  • a mode containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant are examples of such combinations.
  • 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 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 can also use the titanium oxide described in "Titanium Oxide Physical Properties and Applied Technology Manabu Seino, Pages 13-45, June 25, 1991, published by Gihodo Publishing".
  • 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 the 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.
  • the black colorant is preferably a pigment (black pigment).
  • the black colorant means a colorant that exhibits absorption over the entire wavelength range of 400 to 700 nm.
  • inorganic black colorants include carbon black, titanium black, graphite, etc. Carbon black and titanium black are preferred, and titanium black is more preferred.
  • Titanium black is black particles containing titanium atoms, 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.
  • 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.
  • 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.
  • the description in paragraphs 0020 to 0105 of JP-A-2012-169556 can be referred to, and the contents thereof are incorporated herein.
  • Commercially available examples of titanium black 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 examples include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred.
  • bisbenzofuranone compound JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, International Publication No. 2014/208348, JP-A-2015-525260, etc. compounds, for example, available as "Irgaphor Black" manufactured by BASF.
  • a perylene compound examples include compounds described in JP-A-01-170601, JP-A-02-034664, and the like.
  • perylene black Liogen Black FK4280, etc. described in paragraphs 0016 to 0020 of JP-A-2017-226821 may be used.
  • the near-infrared absorbing colorant is preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm and 1400 nm or less.
  • the maximum absorption wavelength of the near-infrared absorbing colorant is preferably 1200 nm or less, more preferably 1000 nm or less, and even more preferably 950 nm or less.
  • the near-infrared absorbing colorant preferably has an A 550 /A max ratio of the absorbance A 550 at a wavelength of 550 nm to the absorbance A max at the maximum absorption wavelength of 0.1 or less, and preferably 0.05 or less.
  • the near-infrared absorbing colorant may be a pigment or a dye, preferably a pigment, more preferably an organic pigment.
  • the near-infrared absorbing colorant is not particularly limited, but pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, tria
  • pyrrolopyrrole compounds cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, tria
  • reelmethane compounds include reelmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, and dithiolene metal complexes.
  • 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.
  • phthalocyanine compound examples 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, and 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.
  • 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.
  • the content of the coloring material in the total solid content of the resin composition is preferably 20 to 80% by mass.
  • the lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more.
  • the upper limit is preferably 75% by mass or less, more preferably 70% by mass or less.
  • the resin composition of the present invention may contain only one colorant, or may contain two or more colorants. When two or more coloring materials are included, the total amount thereof preferably falls within the above range.
  • the resin composition of the present invention contains a resin.
  • the resin is blended, for example, for dispersing a pigment in a resin composition or as a binder.
  • a resin that is mainly used to disperse a pigment 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 weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000.
  • the upper limit is more preferably 1,000,000 or less, and particularly preferably 500,000 or less.
  • the lower limit is more preferably 4000 or more, particularly preferably 5000 or more.
  • Resins include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, and polyamideimide resins. , polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and the like. One of these resins may be used alone, or two or more may be mixed and used.
  • a resin containing a resin having an acid group is used.
  • a resin having an acid group may be contained as a dispersant or as a binder.
  • a resin having an acid group can be used, for example, as an alkali-soluble resin.
  • Examples of the acid group of the acid group-containing resin include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group, with the carboxy group being preferred.
  • 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.
  • 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 is a monomer 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 dimer”). It is also preferred to include repeating units derived from components.
  • 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.
  • the acid group-containing resin preferably also contains repeating units derived from the compound represented by formula (X).
  • 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. preferable.
  • 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.).
  • the resin having an acid group preferably contains repeating units having a polymerizable group.
  • the polymerizable group includes an ethylenically unsaturated bond-containing group and a cyclic ether group, preferably an ethylenically unsaturated bond-containing group.
  • ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.
  • Cyclic ether groups include epoxy groups and oxetanyl groups.
  • the resin having an acid group contains at least one repeating unit (hereinafter also referred to as repeating unit Ep) selected from repeating units represented by formula (Ep-1) and repeating units represented by formula (Ep-2). It is also preferred to include Hereinafter, a resin having the repeating unit Ep is also referred to as a resin Ep.
  • the resin Ep may contain only one of repeating units represented by the formula (Ep-1) and repeating units represented by the formula (Ep-2). It may contain the repeating unit represented by 1) and the repeating unit represented by formula (Ep-2). When both repeating units are included, the ratio of the repeating unit represented by the formula (Ep-1) to the repeating unit represented by the formula (Ep-2) is the molar ratio represented by the formula (Ep-1).
  • Repeating unit: repeating unit represented by formula (Ep-2) preferably 5:95 to 95:5, more preferably 10:90 to 90:10, 20:80 to 80 :20 is more preferred.
  • L 1 represents a single bond or a divalent linking group
  • R 1 represents a hydrogen atom or a substituent.
  • the substituent represented by R 1 includes an alkyl group and an aryl group, preferably an alkyl group.
  • the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, and even more preferably 1-3.
  • R 1 is preferably a hydrogen atom or a methyl group.
  • the divalent linking group represented by L 1 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S- and groups formed by combining two or more of these.
  • the alkylene group may be linear, branched or cyclic, preferably linear or branched.
  • the alkylene group may have a substituent or may be unsubstituted. A hydroxy group, an alkoxy group, etc. are mentioned as a substituent.
  • the content of the repeating unit Ep in the resin Ep is preferably 1 to 90 mol% of all repeating units in the resin Ep.
  • the upper limit is preferably 80 mol % or less, more preferably 70 mol % or less.
  • the lower limit is preferably 2 mol % or more, more preferably 3 mol % or more.
  • the resin having an acid group is also preferably a graft resin having an acid group (hereinafter also referred to as an acid graft resin).
  • an acid graft resin By using a graft resin having an acid group as the resin having an acid group, the storage stability of the resin composition can be further improved.
  • An acidic graft resin can be preferably used as a dispersant.
  • the graft resin means a resin containing a repeating unit having a graft chain.
  • the graft chain means a polymer chain branched and extended from the main chain of the repeating unit.
  • the number of atoms excluding hydrogen atoms is preferably 40 to 10,000, the number of atoms excluding hydrogen atoms is more preferably 50 to 2,000, and the number of atoms excluding hydrogen atoms is 60 to 500 is more preferred.
  • the graft chain preferably contains repeating units of at least one structure selected from a polyether structure, a polyester structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure and a polyamide structure. More preferably, it contains repeating units of at least one structure selected from a polyester structure, a poly(meth)acrylic structure and a polystyrene structure.
  • Repeating units of the polyester structure include repeating units of structures represented by formula (G-1), formula (G-4) or formula (G-5).
  • Repeating units of the polyether structure include repeating units of the structure represented by formula (G-2).
  • Repeating units of the poly(meth)acrylic structure include repeating units of the structure represented by formula (G-3).
  • Repeating units of the polystyrene structure include repeating units of the structure represented by formula (G-6).
  • R G1 and R G2 each independently represent an alkylene group.
  • the alkylene group represented by R G1 and R G2 is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 2 to 16 carbon atoms. More preferred is a linear or branched alkylene group having 3 to 12 carbon atoms.
  • R G3 represents a hydrogen atom or a methyl group
  • Q G1 represents -O- or -NH-
  • L G1 represents a single bond or a divalent linking group
  • R G4 represents hydrogen Represents an atom or substituent.
  • the divalent linking group represented by L G1 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably is an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, - COO-, OCO-, -S- and groups formed by combinations of two or more of these may be mentioned.
  • substituents represented by R G4 include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, a heterocyclic thioether group, Examples include ethylenically unsaturated bond-containing groups, epoxy groups, oxetanyl groups, blocked isocyanate groups, and the like.
  • RG5 represents a hydrogen atom or a methyl group
  • RG6 represents an aryl group.
  • the aryl group represented by R G6 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the aryl group represented by RG6 may have a substituent.
  • Substituents include hydroxy group, carboxy group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthioether group, arylthioether group, heterocyclic thioether group, and ethylenically unsaturated Examples include bond-containing groups, epoxy groups, oxetanyl groups, blocked isocyanate groups, and the like.
  • the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
  • substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, and the like. Among them, from the viewpoint of dispersibility of colorants such as pigments, etc., groups having a steric repulsion effect are preferable, and alkyl groups or alkoxy groups having 5 to 24 carbon atoms are preferable.
  • the alkyl group and alkoxy group may be linear, branched or cyclic, preferably linear or branched.
  • the graft chain is represented by formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a), formula (G-5a) or formula (G-6a). structure, more preferably a structure represented by formula (G-1a), formula (G-4a) or formula (G-5a).
  • R G1 and R G2 each represent an alkylene group
  • R G3 represents a hydrogen atom or a methyl group
  • Q G1 represents -O- or -NH-
  • L G1 represents a single bond or represents a divalent linking group
  • RG4 represents a hydrogen atom or a substituent
  • RG5 represents a hydrogen atom or a methyl group
  • RG6 represents an aryl group
  • W100 represents a hydrogen atom or a substituent
  • n1 to n6 each independently represent an integer of 2 or more.
  • R G1 to R G6 , Q G1 and L G1 have the same meanings as R G1 to R G6 , Q G1 and L G1 described in formulas (G-1) to (G-6), and the preferred ranges are also the same. be.
  • W 100 is preferably a substituent.
  • substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, and the like. Among them, a group having a steric repulsion effect is preferable from the viewpoint of dispersibility of a coloring material such as a pigment, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable.
  • the alkyl group and alkoxy group may be linear, branched or cyclic, preferably linear or branched.
  • each of n1 to n6 is preferably an integer of 2 to 100, more preferably an integer of 2 to 80, and even more preferably an integer of 8 to 60.
  • R 1 G1 in each repeating unit when n1 is 2 or more may be the same or different.
  • the arrangement of each repeating unit is not particularly limited, and may be random, alternating, or block. The same applies to formulas (G-2a) to (G-6a).
  • the graft chain has a structure represented by formula (G-1a), formula (G-4a) or formula (G-5a), wherein R G1 is a structure containing two or more different repeating units. is also preferred.
  • Repeating units having a graft chain include repeating units represented by formula (G-100).
  • X G100 represents a trivalent linking group
  • LG100 represents a single bond or a divalent linking group
  • W100 represents a graft chain.
  • the trivalent linking group represented by X G100 includes a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, and a polyether and polystyrene-based linking groups, and poly(meth)acrylic-based linking groups and polyalkyleneimine-based linking groups are preferred.
  • the divalent linking group represented by LG100 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, OCO-, -S- and groups formed by combining two or more of these.
  • the graft chain represented by W 100 includes the graft chain described above.
  • the repeating unit having a graft chain is preferably a repeating unit represented by formula (G-101) or a repeating unit represented by formula (G-102).
  • RG100 represents a hydrogen atom or an alkyl group
  • LG101 represents a single bond or a divalent linking group
  • W101 represents a graft chain
  • R G101 and R G102 each independently represent a hydrogen atom or an alkyl group
  • L G102 represents a single bond or a divalent linking group
  • W 102 represents a graft chain.
  • L G101 and W 101 in formula (G-101) are synonymous with L G100 and W 100 in formula (G-100).
  • L G102 and W 102 in formula (G-102) are synonymous with L G100 and W 100 in formula (G-100).
  • the number of carbon atoms in the alkyl group represented by R G100 in formula (G-101) and the alkyl group represented by R G101 and R G102 in formula (G-102) is preferably 1 to 10, and preferably 1 to 5. is more preferred, and 1 to 3 is even more preferred.
  • the alkyl group may be linear, branched or cyclic, but preferably linear.
  • RG100 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
  • R G101 and R G102 are each independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
  • the weight average molecular weight of the repeating unit having a graft chain is preferably 1,000 or more, more preferably 1,000 to 10,000, even more preferably 1,000 to 7,500.
  • the weight-average molecular weight of a repeating unit having a graft chain is a value calculated from the weight-average molecular weight of a raw material monomer used for polymerization of the same repeating unit.
  • a repeating unit having a graft chain can be formed by polymerizing a macromonomer.
  • the macromonomer means a polymer compound in which a polymerizable group is introduced at the terminal of the polymer.
  • the weight average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.
  • the acid group possessed by the acidic graft resin includes a carboxy group, a sulfo group, and a phosphoric acid group, with the carboxy group being preferred from the viewpoint of dispersibility of the pigment.
  • the acid value of the acidic graft resin is preferably 20-150 mgKOH/g.
  • the upper limit is preferably 130 mgKOH/g or less, more preferably 110 mgKOH/g or less.
  • the lower limit is preferably 30 mgKOH/g or more, more preferably 40 mgKOH/g or more.
  • the weight average molecular weight of the acidic graft resin is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, even more preferably 10,000 to 30,000.
  • the number average molecular weight (Mn) of the acidic graft resin is preferably 2,500 to 50,000, more preferably 5,000 to 30,000, even more preferably 5,000 to 15,000.
  • the acidic graft resin is preferably a resin containing a repeating unit having a graft chain and a repeating unit having an acid group.
  • the acidic graft resin preferably contains 1 mol % or more, more preferably 2 mol % or more, and 3 mol % or more of repeating units having a graft chain in all repeating units of the acidic graft resin. is more preferred.
  • the upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, or 50 mol% or less. can.
  • the acidic graft resin preferably contains 1 mol % or more, more preferably 2 mol % or more, and 3 mol % or more of repeating units having an acid group in all repeating units of the acidic graft resin. is more preferred.
  • the upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, or 50 mol% or less. can.
  • the acidic graft resin may further contain repeating units other than the above.
  • Other repeating units include repeating units having a polymerizable group. Examples of the polymerizable group include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • acidic graft resin examples include resins described in paragraphs 0025 to 0094 of JP-A-2012-255128 and resins having structures described in Examples described later.
  • the resin composition of the present invention preferably contains a resin having an aromatic carboxy group (hereinafter also referred to as resin Ac) as a resin having an acid group.
  • resin Ac 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 polymerizable group.
  • the polymerizable group includes an ethylenically unsaturated bond-containing group and a cyclic ether group, 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, and 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 in 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 includes a repeating unit of at least one structure selected from a polyether structure, a polyester structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure and a polyamide structure. mentioned.
  • Examples of repeating units of the polyester structure include repeating units of structures represented by formula (G-1), formula (G-4), or formula (G-5) described above.
  • Repeating units of the polyether structure include repeating units of the structure represented by formula (G-2) described above.
  • Repeating units of the poly(meth)acrylic structure include repeating units of the structure represented by formula (G-3) described above.
  • Repeating units of the polystyrene structure include repeating units of the structure represented by the formula (G-6) described above.
  • 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.
  • 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 has at least one group selected from the group consisting of (meth)acryloyl groups, oxetanyl groups, blocked isocyanate groups and t-butyl groups (hereinafter also referred to as "functional group A").
  • the blocked isocyanate group in the present specification is a group capable of generating an isocyanate group by heat.
  • a group obtained by reacting a blocking agent with an isocyanate group to protect the isocyanate group can be preferably exemplified.
  • blocking agents include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds.
  • Blocking agents include compounds described in paragraphs 0115 to 0117 of JP-A-2017-067930, the contents of which are incorporated herein.
  • the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heating at 90°C to 260°C.
  • the polymer chain represented by P10 has a repeating unit containing an acid group.
  • the acid group includes a carboxy group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group, and the like.
  • the proportion of repeating units containing an acid group in all repeating units constituting P10 is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and 3 to 10% by mass. is more preferred.
  • the resin composition of the present invention can also use a polyimine-based dispersant containing nitrogen atoms in at least one of the main chain and the side chain as the resin having an acid group.
  • the polyimine-based dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom.
  • a resin having The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity.
  • the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
  • the resin composition of the present invention can also use a resin having a structure in which a plurality of polymer chains are bonded to the core portion as the resin having an acid group.
  • resins include, for example, dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.
  • the resin composition of the present invention can also use a commercially available acidic dispersant as a resin having an acid group.
  • a commercially available acidic dispersant include the DISPERBYK series (for example, DISPERBYK-111) manufactured by BYK Chemie, and the Solsperse series manufactured by Lubrizol Japan.
  • the pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can be used, the contents of which are incorporated herein.
  • the resin composition of the present invention may further contain a resin containing no acid group.
  • resins are not particularly limited, and include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, and polyarylene ether phosphine oxide.
  • a resin having a basic group can also be used as a resin that does not contain an acid group.
  • 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.
  • Examples of the resin having a basic group include block copolymers (B) described in paragraphs 0063 to 0112 of JP-A-2014-219665, and paragraphs 0046-0076 of JP-A-2018-156021. and block copolymer A1.
  • the resin content in the total solid content of the resin composition is preferably 5 to 40% by mass.
  • the lower limit is preferably 10% by mass or more.
  • the upper limit is preferably 35% by mass or less, more preferably 30% by mass or less.
  • the content of the acid group-containing resin in the total solid content of the resin composition is preferably 5 to 40% by mass.
  • the lower limit is preferably 10% by mass or more.
  • the upper limit is preferably 35% by mass or less, more preferably 30% by mass or less.
  • 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 contains an ultraviolet absorber.
  • ultraviolet absorber refers to an organic compound having a function of absorbing ultraviolet rays, and means a compound different from a photopolymerization initiator that efficiently generates active species such as radicals upon irradiation with ultraviolet rays. do.
  • the ultraviolet absorber is preferably a compound that absorbs ultraviolet rays, converts them into heat energy, and emits it.
  • the ultraviolet absorber is preferably a compound that is stable against ultraviolet rays. That is, the ultraviolet absorber is preferably a compound that is resistant to molecular breakage due to reactions such as decomposition, oxidation, and reduction when irradiated with ultraviolet rays.
  • the ultraviolet absorber is preferably a compound having a maximum absorption wavelength in the wavelength range of 300 to 420 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 330 to 400 nm, and a wavelength of 350 to 390 nm. It is more preferable that the compound has a maximum absorption wavelength in the range of .
  • the maximum value of the molar absorption coefficient in the wavelength range of 300 to 420 nm of the ultraviolet absorber is preferably 5000 L mol -1 cm -1 or more, and is preferably 10000 L mol -1 cm -1 or more. More preferably, it is 13000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more.
  • the upper limit is preferably, for example, 100000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less.
  • the ultraviolet absorber preferably has a ratio of absorbance A2 at a wavelength of 410 nm to absorbance A1 at a wavelength of 365 nm of 0.06 or less, more preferably 0.04 or less, and 0.02 or less. is more preferred.
  • the molecular weight of the ultraviolet absorber is preferably 500 or less, more preferably 400 or less, because it can be dispersed almost uniformly in the film without layer separation.
  • the lower limit of the molecular weight of the ultraviolet absorber can be 200 or more, and can also be 300 or more.
  • the UV absorber is a UV absorber having a basic group and is at least one compound selected from benzophenone compounds, benzoate compounds, benzotriazole compounds, triazine compounds and cyanoacrylate compounds. (hereinafter also referred to as a specific ultraviolet absorber) is used.
  • the basic group of the specific ultraviolet absorber is preferably an amino group. That is, the specific ultraviolet absorber is preferably an amino group-containing ultraviolet absorber.
  • the amino group includes a group represented by -NR a1 R a2 and a cyclic amino group, preferably a group represented by -NR a1 R a2 .
  • R a1 and R a2 each independently represent a hydrogen atom, an alkyl group and an aryl group, preferably an alkyl group.
  • the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, still more preferably 1-3, particularly preferably 2 or 3, and most preferably 2.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the number of carbon atoms in the aryl group is preferably 6-30, more preferably 6-20, even more preferably 6-12.
  • the cyclic amino group includes a pyrrolidine group, a piperidine group, a piperazine group, a morpholine group and the like. These groups may further have a substituent. Substituents include alkyl groups and aryl groups.
  • the basic group possessed by the specific ultraviolet absorber is preferably a dialkylamino group, more preferably a diethylamino group.
  • the specific ultraviolet absorber is at least one selected from benzophenone compounds, benzoate compounds, benzotriazole compounds, triazine compounds and cyanoacrylate compounds, and is a benzotriazole compound for the reason that it has good adsorption to the coloring material. is preferred.
  • the benzotriazole compound is preferably a compound represented by formula (UV-1).
  • R u1 to R u8 each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, or a group represented by formula (R-1). show. At least one of R u1 to R u8 is a group represented by formula (R-1).
  • L a100 represents a single bond or an n+1 valent linking group
  • R a100 represents a basic group
  • n represents an integer of 1-3.
  • n is 1 when La100 is a single bond.
  • the alkyl groups represented by R u1 to R u8 preferably have 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the alkyl group may have a substituent.
  • the alkyl group may have a substituent. Examples of substituents include halogen atoms, aryl groups, and alkoxy groups.
  • the alkoxy groups represented by R u1 to R u8 preferably have 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
  • the alkoxy group is preferably linear or branched, more preferably linear.
  • An alkoxy group may have a substituent.
  • a halogen atom, an aryl group, etc. are mentioned as a substituent.
  • the aryl group represented by R u1 to R u8 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the aryl group may have a substituent.
  • a halogen atom, an alkyl group, an alkoxy group, etc. are mentioned as a substituent.
  • the n+1 valent linking group represented by L a100 in formula (R-1) includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, -O-, -S-, -CO-, -COO-, -OCO-, -SO 2 -, -NR L1 -, -NR L1 CO-, -CONR L1 -, -NR L1 SO 2 -, -SO 2 NR L1 - and groups consisting of combinations thereof.
  • RL1 represents a hydrogen atom, an alkyl group or an aryl group.
  • the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-10, more preferably 1-5, still more preferably 1-3, and even more preferably 2 or 3.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • the number of carbon atoms in the aromatic hydrocarbon group is preferably 6-18, more preferably 6-14, even more preferably 6-10.
  • the heterocyclic group is preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1-3.
  • a heteroatom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 3-30, more preferably 3-18, and more preferably 3-12.
  • the number of carbon atoms in the alkyl group represented by R L1 is preferably 1-20, more preferably 1-15, even more preferably 1-8.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the alkyl group represented by R L1 may further have a substituent.
  • the aryl group represented by R L1 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the n+1-valent linking group represented by L a100 is preferably an aliphatic hydrocarbon group.
  • R a100 in formula (R-1) represents a basic group, preferably an amino group.
  • the amino group includes the group represented by -NR a1 R a2 described above and the cyclic amino group, and the group represented by -NR a1 R a2 is preferable.
  • the preferred range of the amino group is as described above.
  • n in formula (R-1) represents an integer of 1 to 3, preferably 1 or 2, more preferably 1.
  • R u1 to R u4 , R u6 and R u8 in formula (UV-1) are preferably hydrogen atoms.
  • R u5 in formula (UV-1) is preferably a group represented by formula (R-1).
  • R u7 in formula (UV-1) is preferably a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, or a group represented by formula (R-1), and a hydrogen atom or an alkyl group, more preferably an alkyl group.
  • the resin composition of the present invention can further contain other UV absorbers other than the specific UV absorbers described above.
  • Other UV absorbers include conjugated diene compounds, benzotriazole compounds, dibenzoyl compounds, triazine compounds, benzophenone compounds, salicylate compounds, coumarin compounds, acrylonitrile compounds, benzodithiazole compounds, cinnamic acid compounds, ⁇ - ⁇ unsaturated ketones. , carbostyril compounds, merocyanine compounds and the like.
  • the content of other ultraviolet absorbents in the ultraviolet absorbent used in the resin composition of the present invention is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass or less. It is even more preferable to have It is also preferred that the UV absorber is substantially free of other UV absorbers.
  • the term "the ultraviolet absorbent substantially does not contain other ultraviolet absorbents" means that the content of the other ultraviolet absorbents in the ultraviolet absorbent is 1% by mass or less, It is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and particularly preferably does not contain other ultraviolet absorbers.
  • the content of the ultraviolet absorber in the total solid form of the resin composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass.
  • the content of the specific ultraviolet absorber in the total solid form of the resin composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass.
  • the content of the specific ultraviolet absorber is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the coloring material.
  • the lower limit is preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more.
  • the upper limit is preferably 9 parts by mass or less, more preferably 8 parts by mass or less.
  • the content of the specific ultraviolet absorber is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin having an acid group.
  • the lower limit is preferably 1 part by mass or more, more preferably 2 parts by mass or more.
  • the upper limit is preferably 18 parts by mass or less, more preferably 15 parts by mass or less. Only one type of specific ultraviolet absorber 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 can contain a pigment derivative.
  • the coloring agent used in the resin composition of the present invention contains a pigment
  • the resin composition of the present invention preferably contains a pigment derivative.
  • Pigment derivatives are used, for example, as dispersing aids.
  • Pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.
  • a dispersing aid is a material for enhancing the dispersibility of a coloring material such as a pigment in a resin composition.
  • the molecular weight of the pigment derivative is preferably 600 or more, more preferably 650 or more.
  • the upper limit of the molecular weight is preferably 2000 or less, more preferably 1500 or less, even more preferably 1000 or less.
  • Dye skeletons constituting pigment derivatives include quinoline dye skeletons, benzimidazolone dye skeletons, benzoisoindole dye skeletons, benzothiazole dye skeletons, iminium dye skeletons, squarylium dye skeletons, croconium dye skeletons, oxonol dye skeletons, and pyrrolopyrrole dye skeletons.
  • 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,
  • An isoindoline dye skeleton, an isoindolinone dye skeleton, a quinophthalone dye skeleton, an iminium dye skeleton, a dithiol dye skeleton, a triarylmethane dye skeleton, a pyrromethene dye skeleton, and the like are included.
  • 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.
  • a pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative) can also be used as the pigment derivative.
  • the maximum value ( ⁇ max) of the molar extinction coefficient of the transparent pigment derivative in the wavelength region of 400 to 700 nm is preferably 3000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less, and 1000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less. is more preferable, and 100 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less is even more preferable.
  • the lower limit of ⁇ max is, for example, 1 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more, and may be 10 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more.
  • pigment derivatives include compounds described in JP-A-56-118462, compounds described in JP-A-63-264674, compounds described in JP-A-01-217077, JP-A-03- 009961, the compound described in JP-A-03-026767, the compound described in JP-A-03-153780, the compound described in JP-A-03-045662, JP-A-04-285669 Compounds described in publications, compounds described in JP-A-06-145546, compounds described in JP-A-06-212088, compounds described in JP-A-06-240158, JP-A-10-030063 Compounds described, compounds described in JP-A-10-195326, compounds described in paragraphs 0086 to 0098 of WO 2011/024896, WO 2012/102399 described in paragraphs 0063 to 0094 Compounds, compounds described in paragraph number 0082 of WO 2017/038252, compounds described in paragraph number 0171 of JP 2015-151530, J
  • 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.
  • the total content of the pigment derivative and the colorant is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and 50% by mass of the total solid content of the resin composition. More than % by mass is particularly preferred.
  • the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.
  • the resin composition of the present invention may contain only one type of pigment derivative, or may contain two or more types. When two or more pigment derivatives are included, the total amount thereof is preferably within the above range.
  • the dispersion stability of the resin composition can be further improved.
  • a pigment derivative with excellent visible transparency it is possible to suppress the color change of the film after the heat resistance test and the light resistance test, and the heat resistance and light resistance are further improved.
  • a chromatic pigment derivative and a transparent pigment derivative in combination it is possible to achieve higher levels of dispersion stability, heat resistance, and light resistance.
  • the resin composition of the present invention preferably contains a polymerizable compound.
  • a polymerizable compound known compounds that can be crosslinked by radicals, acids or heat can be used.
  • the polymerizable compound is preferably a compound having an ethylenically unsaturated bond-containing group. Examples of 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 100-3000.
  • the upper limit is more preferably 2000 or less, and even more preferably 1500 or less.
  • the lower limit is more preferably 150 or more, even more preferably 250 or more.
  • the polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, an ethylenically unsaturated bond Compounds containing 3 to 6 containing groups are more preferred.
  • the polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.
  • polymerizable compound examples 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.
  • dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available as KAYARAD D-320 manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and their (meth)acryloyl groups via ethylene glycol and/or propylene glycol residues
  • Compounds of conjugated structures (eg SR454,
  • diglycerin EO ethylene oxide modified (meth) acrylate
  • pentaerythritol tetraacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A -TMMT
  • 1,6-hexanediol diacrylate manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA
  • RP-1040 manufactured by Nippon Kayaku Co., Ltd.
  • Aronix TO-2349 manufactured by Toagosei Co., Ltd.
  • NK Oligo UA-7200 manufactured by Shin-Nakamura Chemical Co., Ltd.
  • DPHA-40H manufactured by Nippon Kayaku Co., Ltd.
  • the polymerizable compound includes 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 can also be used.
  • 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 can also be used as the polymerizable compound.
  • the acid group includes a carboxy group, a sulfo group, a phosphoric acid group and the like, and a carboxy group is preferred.
  • Commercially available polymerizable compounds having an acid group include Aronix M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
  • the acid value of the polymerizable compound having an acid group is preferably 0.1-40 mgKOH/g, more preferably 5-30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the solubility in the developer is good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and handling.
  • a compound having a caprolactone structure can also be used as the polymerizable compound.
  • Commercially available polymerizable compounds having a caprolactone structure include KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.).
  • a polymerizable compound having an alkyleneoxy group can also be used as the polymerizable compound.
  • the polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 3 to 4 having 4 to 20 ethyleneoxy groups.
  • a hexafunctional (meth)acrylate compound is more preferred.
  • Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer Co., Ltd., and an isobutyleneoxy group manufactured by Nippon Kayaku Co., Ltd. KAYARAD TPA-330, which is a trifunctional (meth)acrylate having three.
  • a polymerizable compound having a fluorene skeleton can also be used as the polymerizable compound.
  • the polymerizable compound having a fluorene skeleton is preferably a bifunctional polymerizable compound.
  • Polymerizable compounds having a fluorene skeleton include compounds having a partial structure represented by the following formula (Fr).
  • a wavy line represents a bond
  • R f1 and R f2 each independently represent a substituent
  • m and n each independently represent an integer of 0 to 5.
  • m R f1 may be the same or different, and two R f1 out of m R f1 are bonded to form a ring; good too.
  • n R f2 may be the same or different, and two R f2 out of n R f2 are bonded to form a ring; good too.
  • Substituents represented by R f1 and R f2 include a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, —OR f11 , —COR f12 , —COOR f13 , —OCOR f14 and —NR f15.
  • R f16 —NHCOR f17 , —CONR f18 R f19 , —NHCONR f20 R f21 , —NHCOOR f22 , —SR f23 , —SO 2 R f24 , —SO 2 OR f25 , —NHSO 2 R f26 or —SO 2 NR f27 and R f28 .
  • R f11 to R f28 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
  • polymerizable compounds having a fluorene skeleton include compounds having the following structures.
  • Commercially available polymerizable compounds having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).
  • the polymerizable compound it is also preferable to use a compound that does not substantially contain environmentally regulated substances such as toluene.
  • environmentally regulated substances such as toluene.
  • Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
  • the content of the polymerizable compound in the total solid content of the resin composition is preferably 0.1 to 50% by mass.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more.
  • the upper limit is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. Only one polymerizable compound may be used, or two or more thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof falls within the above range.
  • the resin composition of the present invention preferably 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 range to the visible range 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. are 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-2017-019766, compounds described in Patent 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-(O-acetyloxime) and the like.
  • 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 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.
  • 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).
  • Irgacure OXE01 manufactured by BASF
  • Irgacure OXE02 manufactured by BASF
  • 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 stability over time 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 30% by mass.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
  • the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
  • a photoinitiator may use only 1 type and may use 2 or more types. 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, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol acetate, butylcarbylate tall acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-di
  • 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, and 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 vacuum distillation and crosslinking between molecules.
  • 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 compound having a cyclic ether group.
  • Cyclic ether groups include epoxy groups and oxetanyl groups.
  • the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound).
  • the compound having a cyclic ether group may be a low-molecular-weight compound (for example, a molecular weight of less than 1000) or a high-molecular-weight compound (macromolecule) (for example, a molecular weight of 1000 or more; in the case of a polymer, a weight-average molecular weight of 1000 or more).
  • the weight average molecular weight of the cyclic ether group is preferably from 200 to 100,000, more preferably from 500 to 50,000.
  • the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.
  • the content of the compound having a cyclic ether group in the total solid content of the resin composition is preferably 0.1 to 20% by mass.
  • the lower limit is 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 kind of compound having a cyclic ether group 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 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 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.).
  • 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 kind of silane coupling agent 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 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. Examples of surfactants include surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015/166779, and surfactants described in JP 2020-008634. incorporated into the book.
  • 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 As the fluorine-based surfactant, JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- 132503, paragraphs 0117-0132, 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.
  • fluorine-based surfactants have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes. It can be used preferably.
  • 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 + represents 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), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin D-6112 , D-
  • silicone surfactants include DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (the above, Dow ⁇ Toray Co., Ltd.), 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), etc. are mentioned.
  • 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.
  • 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.
  • an antioxidant is contained, only one kind of antioxidant may be used, or two or more kinds thereof may be 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, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein.
  • 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 with a protecting 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 protecting 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 an aromatic group-containing phosphonium salt described in JP-A-2020-079833.
  • 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 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 the publication, compounds described in paragraph numbers 0101 to 0125 of JP-A-2012-145604, compounds
  • 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 the fluoroalkylcarboxylic acid (especially perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is 0.01 ppb to 1,000 ppb 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 contents do 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 of the present invention 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 resin and a bottle with a 7-layer structure of 6 types of resin are used for the purpose of suppressing the contamination of raw materials and compositions with impurities. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351.
  • the resin composition of the present invention can be prepared by mixing the aforementioned components. In preparing the resin composition, all components may be dissolved and/or dispersed in a solvent at the same time to prepare the resin composition, or if necessary, each component may be appropriately prepared as two or more solutions or dispersions. , these may be mixed at the time of use (at the time of coating) 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 step. 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.
  • any filter that has been conventionally used for filtration or the like can be used without particular limitation.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyethylene
  • polyolefin resins such as polypropylene (PP) (including high-density, ultra-high-molecular-weight polyolefin resin).
  • PP polypropylene
  • polypropylene including high density polypropylene
  • nylon are preferred.
  • 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. .
  • fiber-like filter media include polypropylene fiber, nylon fiber, and glass fiber.
  • 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 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.
  • the film of the present invention is a film obtained using 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 using the film of the present invention as a color filter, the film of the present invention preferably has a hue of green, red, blue, cyan, magenta or yellow. Moreover, the film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
  • the maximum absorption wavelength of the film of the present invention preferably exists in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm. More preferably, it exists in the wavelength range of 700 to 1000 nm.
  • the transmittance of the film over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Further, it is preferable that the transmittance of the film at least at one point in the wavelength range of 700 to 1800 nm is 20% or less.
  • the absorbance Amax/absorbance A550 which is the ratio of the absorbance Amax at the maximum absorption wavelength and the absorbance A550 at a wavelength of 550 nm, is preferably 20 to 500, more preferably 50 to 500, and 70 to 450. more preferably 100 to 400.
  • the film of the present invention preferably has, for example, any one of the following spectral characteristics (i1) to (i5).
  • a film having such spectral characteristics can block light in the wavelength range of 400 to 640 nm and transmit light in the wavelength range of 750 nm 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).
  • a film having such spectral characteristics can block light in the wavelength range of 400 to 750 nm and transmit light in the wavelength range of 850 nm 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).
  • a film having such spectral characteristics can block light in the wavelength range of 400 to 830 nm and transmit light in the wavelength range of 950 nm 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).
  • a film having such spectral properties can block light in the wavelength range of 400 to 950 nm and transmit light in the wavelength range of 1050 nm 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).
  • a film having such spectral characteristics can block light in the wavelength range of 400 to 1050 nm and transmit light in the wavelength range of 1150 nm or more.
  • the optical filter of the present invention has the film of the present invention as described above.
  • the optical filter includes a color filter, a near-infrared transmission filter, a near-infrared cut filter, and the like, and is preferably a color filter.
  • a color filter it is preferable to have the film of the present invention as a colored pixel of the color filter.
  • 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 optical filter of the present invention can be used for optical sensors such as solid-state imaging devices, image display devices, and the like.
  • the film thickness of the film of the present invention can be appropriately adjusted according to the purpose.
  • the film thickness of the pixels included in the optical filter is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 0.6 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more.
  • the width of pixels included in the optical filter is preferably 0.4 to 10.0 ⁇ m.
  • the lower limit is preferably 0.4 ⁇ m or more, more preferably 0.5 ⁇ m or more, and even more preferably 0.6 ⁇ m or more.
  • the upper limit is preferably 5.0 ⁇ m or less, more preferably 2.0 ⁇ m or less, even more preferably 1.0 ⁇ m or less, and even more preferably 0.8 ⁇ m or less.
  • the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
  • the membrane of the present invention can be produced through a step of applying the resin composition of the present invention to a support.
  • the film manufacturing method further includes the step of forming a pattern.
  • the pattern forming method include 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. and a step of developing and removing the exposed portion to form a pattern. If necessary, a step of baking the resin composition layer (pre-baking step) and a step of baking the developed pattern (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.
  • CCD charge-coupled device
  • CMOS complementary metal oxide semiconductor
  • 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.
  • 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 preferred.
  • 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 portion of the resin composition layer is removed by development to form a pattern.
  • 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 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 low refractive index for 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.
  • ⁇ Production of dispersion liquid> A liquid mixture obtained by mixing the materials shown in the table below in the amounts shown in the table below was mixed and dispersed for 3 hours using a bead mill (zirconia beads with a diameter of 0.1 mm) to prepare a dispersion liquid. Thereafter, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) equipped with a decompression mechanism, dispersion treatment was carried out under conditions of a pressure of 2000 kg/cm 2 and a flow rate of 500 g/min. This dispersing treatment was repeated up to 10 times to obtain a dispersion.
  • the unit of the numerical value described in the column of compounding amount in the table below is parts by mass.
  • the blending amounts of the colorant, pigment derivative and dispersant are values in terms of solid content.
  • P-1 Compound having the following structure (near-infrared absorbing pigment)
  • P-2 Compound having the following structure (near-infrared absorbing pigment)
  • (pigment derivative) Syn-1 a compound having the following structure (molecular weight 769)
  • Syn-2 a compound having the following structure (molecular weight 688)
  • Syn-3 a compound having the following structure (molecular weight 863)
  • Syn-4 a compound having the following structure (molecular weight 768)
  • Syn-5 a compound having the following structure (molecular weight 784)
  • Syn-6 Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.)
  • Resin B-1 synthesized by the following method.
  • Resin B-1 is a resin having acid groups. 50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, 20 parts by mass of (3-ethyloxetan-3-yl) methyl methacrylate, and 45.4 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were charged into a reaction vessel, and the atmosphere was The gas was replaced with nitrogen gas. Heat the inside of the reaction vessel to 70° C., add 6 parts by mass of 3-mercapto-1,2-propanediol, add 0.12 parts by mass of AIBN (azobisisobutyronitrile), and react for 12 hours.
  • PMEA propylene glycol monomethyl ether acetate
  • B-2 Resin having the following structure (resin having an acid group.
  • the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 24,000, acid value: 52. 5 mg KOH/g)
  • B-3 Resin having the following structure (resin having an acid group.
  • the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 21,000, acid value: 74. 9 mg KOH/g)
  • B-4 Resin having the following structure (resin having an acid group.
  • the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units.
  • B-5 Resin having the following structure (resin having an acid group.
  • the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 21,000, acid value: 36. 0 mg KOH/g)
  • B-6 Resin having the following structure (resin having an acid group. Numerical values attached to the main chain are molar ratios. Weight average molecular weight: 11000, acid value: 69.2 mgKOH/g)
  • B-7 Resin having the following structure (resin having an acid group.
  • the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units.
  • B-8 Resin having the following structure (resin having an acid group. Numerical values attached to the main chain are molar ratios. Weight average molecular weight: 12000, acid value: 216.6 mgKOH/g)
  • Green Dispersions 1-12 Green Dispersions 1-12 as described above Yellow dispersions 1-18: Yellow dispersions 1-18 described above Red dispersions 1-12: Red dispersions 1-12 described above Blue Dispersions 1-11: Blue Dispersions 1-11 described above Violet dispersions 1-3: Violet dispersions 1-3 described above IR dispersions 1 and 2: IR dispersions 1 and 2 described above
  • M-1 a compound having the following structure
  • M-3 a compound having the following structure
  • M-4 a compound having the following structure
  • M-5 a compound having the following structure
  • M-6 a compound having the following structure
  • M-8 a compound having the following structure
  • C-1 Resin having the following structure (resin having an acid group. Numerical values attached to the main chain are molar ratios. Weight average molecular weight: 11000, acid value: 69.2 mgKOH/g)
  • C-2 Resin having the following structure (resin having an acid group. Numerical values attached to the main chain are molar ratios. Weight average molecular weight: 14,000, acid value: 70 mgKOH/g)
  • C-3 Resin having the following structure (resin having an acid group. Numerical values attached to the main chain are molar ratios. Weight average molecular weight: 21,000, acid value: 80 mgKOH/g)
  • C-4 Resin having the following structure (resin having an acid group. Numerical values attached to the main chain are molar ratios. Weight average molecular weight: 13,000, acid value: 100 mgKOH/g)
  • C-5 Resin having the following structure (resin having an acid group. Numerical values attached to the main chain are molar ratios. Weight average molecular weight: 30,000, acid value: 75 mgKOH/g)
  • C-6 Resin having the following structure (resin having an acid group. Numerical values attached to the main chain are molar ratios. Weight average molecular weight: 9100, acid value: 120 mgKOH/g)
  • C-7 Resin having the following structure (resin having an acid group.
  • the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 19,000, acid value: 89. 5 mg KOH/g)
  • C-8 Resin having the following structure (resin having an acid group. Numerical values attached to the main chain are molar ratios. Weight average molecular weight: 11,500, acid value: 33.1 mgKOH/g)
  • I-1 Irgacure OXE02 (manufactured by BASF, oxime compound)
  • I-2 to I-5 I-7: compounds having the following structures
  • U-1 compound having the following structure (ultraviolet absorber having a basic group, benzotriazole compound, molecular weight 310)
  • U-2 Compound having the following structure (ultraviolet absorber having a basic group, benzotriazole compound, molecular weight 296)
  • U-3 Compound having the following structure (ultraviolet absorber having a basic group, benzotriazole compound, molecular weight 352)
  • U-4 compound having the following structure (ultraviolet absorber having a basic group, benzotriazole compound, molecular weight 338)
  • U-5 compound having the following structure (ultraviolet absorber having a basic group, benzotriazole compound, molecular weight 338)
  • U-6 compound having the following structure (ultraviolet absorber having a basic group, benzotriazole compound, molecular weight 339)
  • U-7 compound having the following structure (ultraviolet absorber having a basic group, benzotriazole compound, molecular weight 339)
  • UV absorber having no basic group UB: Sumisorb 400 (manufactured by Sumika Chemtech Co., Ltd., a compound having the following structure.
  • Ultraviolet absorber having no basic group UC: compound having the following structure (conjugated diene compound)
  • the resin composition produced above was stored at 45°C for 3 days.
  • the viscosity of the resin composition was measured before and after storage, and the viscosity stability over time was evaluated using the viscosity change rate calculated from the following formula.
  • the viscosity of the resin composition was measured with a viscometer (product name “RE-85 type viscometer” manufactured by Toki Sangyo Co., Ltd.).
  • the measurement conditions for the viscosity were set at a rotation speed of 20 rpm and a temperature of 25°C.
  • Viscosity change rate
  • a film having a thickness of 500 nm was formed using the resin composition immediately after production as described above. Furthermore, after storing the resin composition produced above at 45° C. for 3 days, a film was formed under the same film forming conditions as those using the resin composition immediately after production. The difference in film thickness before and after storage was compared, and film thickness stability was evaluated according to the following criteria.
  • the substrate used for film formation is an 8-inch (20.32 cm) silicon wafer, and the film is formed by applying a resin composition onto the substrate by spin coating, and then using a hot plate at 100 ° C. for 2 minutes. heated.
  • Film thickness difference
  • the resin compositions of Examples were superior to the resin compositions of Comparative Examples in terms of viscosity stability over time and film thickness stability over time, and were superior in stability over time.
  • Example 1 even when surfactant W-1 was changed to surfactants W-2 to W-46 shown below, similar effects were obtained. Similar effects were obtained even when the polymerization inhibitor was omitted.
  • W-2 FZ-2122 (manufactured by Dow Toray Co., Ltd., silicone surfactant)
  • W-3 BYK-322 (manufactured by BYK-Chemie, silicone surfactant)
  • W-4 BYK-323 (manufactured by BYK-Chemie, silicone surfactant)
  • W-6 BYK-3760 (manufactured by BYK-Chemie, silicone surfactant)
  • W-7 BYK-UV3510 (manufactured by BYK-Chemie, silicone surfactant)
  • W-8 KF-6001 (Shin-Etsu Chemical, silicone surfactant)
  • W-10 Megafac F-554 (DIC Corporation, fluor

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Abstract

L'invention concerne une composition de résine ayant une excellente stabilité dans le temps, un film, un filtre optique, un élément d'imagerie à semi-conducteurs et un dispositif d'affichage d'image. La composition de résine comprend un matériau colorant, un absorbeur d'ultraviolets et une résine, l'absorbeur d'ultraviolets comprenant un absorbeur d'ultraviolets qui a un groupe basique, l'absorbeur d'ultraviolets ayant un groupe basique étant au moins un composé choisi parmi un composé benzophénone, un composé benzoate, un composé benzotriazole, un composé triazine et un composé cyanoacrylate, et la résine comprenant une résine qui a un groupe acide.
PCT/JP2022/043599 2021-12-22 2022-11-25 Composition de résine, film, filtre optique, élément d'imagerie à semi-conducteurs et dispositif d'affichage d'image WO2023120036A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11158163A (ja) * 1997-11-27 1999-06-15 Chemiprokasei Kaisha Ltd ３−アミノベンゾトリアゾール系化合物、その用途およびその製造方法
WO2018043218A1 (fr) * 2016-08-30 2018-03-08 富士フイルム株式会社 Composition photosensible, film durci, filtre optique, corps stratifié, procédé de formation de motif, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et capteur infrarouge
JP2018116258A (ja) * 2017-01-16 2018-07-26 東洋インキＳｃホールディングス株式会社 感光性着色組成物、カラーフィルタ用感光性着色組成物、およびカラーフィルタ
JP2019210289A (ja) * 2018-06-05 2019-12-12 エバーライト ケミカル インダストリアル コーポレイション レッドシフトを有する新規なベンゾトリアゾール紫外線吸収剤及びその用途
WO2022202204A1 (fr) * 2021-03-22 2022-09-29 富士フイルム株式会社 Composition colorante, film, filtre optique, élément d'imagerie à semi-conducteurs et dispositif d'affichage d'image

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11158163A (ja) * 1997-11-27 1999-06-15 Chemiprokasei Kaisha Ltd ３−アミノベンゾトリアゾール系化合物、その用途およびその製造方法
WO2018043218A1 (fr) * 2016-08-30 2018-03-08 富士フイルム株式会社 Composition photosensible, film durci, filtre optique, corps stratifié, procédé de formation de motif, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et capteur infrarouge
JP2018116258A (ja) * 2017-01-16 2018-07-26 東洋インキＳｃホールディングス株式会社 感光性着色組成物、カラーフィルタ用感光性着色組成物、およびカラーフィルタ
JP2019210289A (ja) * 2018-06-05 2019-12-12 エバーライト ケミカル インダストリアル コーポレイション レッドシフトを有する新規なベンゾトリアゾール紫外線吸収剤及びその用途
WO2022202204A1 (fr) * 2021-03-22 2022-09-29 富士フイルム株式会社 Composition colorante, film, filtre optique, élément d'imagerie à semi-conducteurs et dispositif d'affichage d'image

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