WO2023022120A1 - Composition, film, optical filter, optical sensor, image display apparatus, and structural body - Google Patents

Composition, film, optical filter, optical sensor, image display apparatus, and structural body Download PDF

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Publication number
WO2023022120A1
WO2023022120A1 PCT/JP2022/030851 JP2022030851W WO2023022120A1 WO 2023022120 A1 WO2023022120 A1 WO 2023022120A1 JP 2022030851 W JP2022030851 W JP 2022030851W WO 2023022120 A1 WO2023022120 A1 WO 2023022120A1
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composition
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group
compounds
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PCT/JP2022/030851
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French (fr)
Japanese (ja)
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大貴 瀧下
貴規 田口
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富士フイルム株式会社
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Priority to KR1020247003841A priority Critical patent/KR20240028496A/en
Publication of WO2023022120A1 publication Critical patent/WO2023022120A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C08F290/126—Polymers of unsaturated carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/66007—Multistep manufacturing processes
    • H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
    • H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
    • H01L29/66946—Charge transfer devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/762—Charge transfer devices

Definitions

  • the present invention relates to a composition containing a silicone-based surfactant.
  • the present invention also relates to films, optical filters, optical sensors, image display devices and structures.
  • a composition containing a surfactant is used in the composition used to manufacture optical filters such as color filters for optical sensors.
  • Patent Document 1 discloses a colored resin composition containing (A) a colorant, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator, wherein (B ) The dispersant contains a dispersant (b) having a predetermined repeating unit, and the colored resin composition contains (F) a surfactant in the total solid content of 0.01% by mass or more. Inventions relating to compositions are disclosed.
  • Optical filters used in optical sensors and image display devices generally have multiple types of pixels.
  • the second and subsequent types of pixels are sequentially formed using the second and subsequent types of pixel-forming compositions. Manufactured by forming.
  • Such an optical filter is manufactured, for example, by forming partition walls for partitioning each pixel on a support, and then sequentially forming each type of pixel between the partition walls.
  • an object of the present invention is to provide a composition capable of forming a film in which color mixing is suppressed.
  • Another object of the present invention is to provide a film, an optical filter, an optical sensor, an image display device and a structure.
  • the present invention provides the following.
  • a curable compound a silicone-based surfactant A; including a solvent and
  • the silicone surfactant A has a surface tension of 26 mN at 25° C. when a solution having a solid concentration of 1000 ppm by mass is prepared by dissolving the silicone surfactant A in propylene glycol monomethyl ether acetate. / m or more, Composition.
  • the curable compound contains a resin and a polymerizable monomer, The composition according to ⁇ 1>, further comprising a photopolymerization initiator.
  • ⁇ 3> The composition according to ⁇ 1> or ⁇ 2>, further comprising a colorant.
  • the silica particles are selected from silica particles having a shape in which a plurality of spherical silicas are connected in a beaded shape, silica particles having a shape in which a plurality of spherical silicas are connected in a plane, and silica particles having a hollow structure.
  • ⁇ 7> The composition according to any one of ⁇ 4> to ⁇ 6>, wherein the content of the inorganic particles in the total solid content of the composition is 20% by mass or more.
  • ⁇ 8> The composition according to any one of ⁇ 1> to ⁇ 7>, wherein the silicone surfactant A has a hydroxyl value of 80 mgKOH/g or more.
  • silicone surfactant A is a carbinol-modified dialkylpolysiloxane.
  • silicone surfactant A is a dimethylpolysiloxane having an alkyleneoxy group and a hydroxy group.
  • ⁇ 12> The composition according to any one of ⁇ 1> to ⁇ 11>, wherein the content of the silicone surfactant A in the composition is 1 to 1000 mass ppm.
  • ⁇ 13> A film obtained using the composition according to any one of ⁇ 1> to ⁇ 12>.
  • ⁇ 14> An optical filter comprising the film according to ⁇ 13>.
  • An optical sensor comprising the film according to ⁇ 13>.
  • ⁇ 16> An image display device comprising the film according to ⁇ 13>.
  • the present invention it is possible to provide a composition, a film, an optical filter, an optical sensor, an image display device, and a structure capable of forming a film with suppressed color mixing.
  • FIG. 2 is an enlarged view schematically showing silica particles having a shape in which a plurality of spherical silica particles are connected in a beaded shape.
  • 1 is a side sectional view showing one embodiment of a structure of the present invention; FIG. It is the top view seen from just above the support body in the same structure.
  • ⁇ 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.
  • near-infrared light refers to light with a wavelength of 700 to 2500 nm.
  • 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 “pigment” means a coloring material that is difficult to dissolve in a solvent.
  • the term "process” includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .
  • composition of the first aspect of the invention comprises a curable compound; a silicone-based surfactant A; including a solvent and The silicone surfactant A has a surface tension of 26 mN/ m or more.
  • composition of the second aspect of the present invention is inorganic particles; a silicone-based surfactant A; including a solvent and
  • the silicone surfactant A has a surface tension of 26 mN/ m or more.
  • composition of the present invention a film with suppressed color mixing can be formed.
  • the composition of the present invention can enhance the affinity of the surface of the obtained film for water by containing the silicone-based surfactant A.
  • another pixel or the like is formed.
  • deposits of other pixel-forming compositions are easily removed from the film surface by the developer or rinse solution, and as a result, residues of other pixel-forming compositions are less likely to be left on the film surface. For this reason, it is presumed that the composition of the present invention was able to form a film in which color mixing was suppressed.
  • the composition of the present invention is preferably a composition for optical sensors or image display devices, and more preferably a composition for optical sensors. More specifically, the composition of the present invention can be preferably used as a composition for forming optical filters, partition walls, and the like used in optical sensors, image display devices, and the like.
  • the composition of the first aspect is preferably used as a composition for forming optical filters.
  • the composition of the second aspect is preferably used as a composition for forming partition walls.
  • silica particles are used as the inorganic particles, a film having a small refractive index can be formed, so that it is preferably used as a composition for forming partition walls.
  • optical filters examples include color filters, near-infrared transmission filters, and near-infrared cut filters, with color filters being preferred.
  • color filters include filters having colored pixels that transmit light of a specific wavelength, and at least one colored pixel selected from red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, and magenta pixels.
  • the filter has A color filter can be formed using a composition containing a chromatic colorant.
  • Examples of near-infrared cut filters include filters having a maximum absorption wavelength in the wavelength range of 700 to 1800 nm.
  • the maximum absorption wavelength of the near-infrared cut filter preferably exists in the wavelength range of 700 to 1300 nm, more preferably in the wavelength range of 700 to 1100 nm.
  • the transmittance of the near-infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Also, the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.
  • absorbance Amax/absorbance A550 which is the ratio of absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter and 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 composition containing a near-infrared absorbing colorant.
  • a near-infrared transmission filter is a filter that transmits at least part of near-infrared rays.
  • the near-infrared transmission filter is preferably a filter that blocks at least part of visible light and transmits at least part of near-infrared light.
  • the near-infrared transmission filter has a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm, and has a transmittance in the wavelength range of 1100 to 1300 nm. Filters satisfying spectral characteristics with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) are preferred.
  • the near-infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (5).
  • the maximum transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 800 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 900 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1000 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1100 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1200 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • partition walls include partition walls used for partitioning adjacent pixels when pixels are formed on an imaging area of a solid-state imaging device.
  • pixels include colored pixels, transparent pixels, pixels of a near-infrared transmission filter layer, and pixels of a near-infrared cut filter layer.
  • partition walls for forming a grid structure that partitions pixels. Examples thereof include JP 2012-227478, JP 2010-232537, JP 2009-111225, FIG. 1 of JP 2017-028241, FIG. 4D of JP 2016-201524 and the like.
  • Other examples include partition walls for forming a frame structure around optical filters such as color filters, near-infrared transmission filters, and near-infrared cut filters. An example thereof is the structure described in JP-A-2014-048596, the content of which is incorporated herein.
  • composition of the present invention can also be used as a composition for forming a light shielding film.
  • the composition of the present invention preferably contains a black colorant as a colorant, and more preferably contains a black pigment.
  • the film formed using the composition of the present invention has an optical density (OD: Optical Density) is preferably 2.5 or more, more preferably 3.0 or more. Although the upper limit is not particularly limited, generally 10 or less is preferable. In this specification, the optical density per 1.5 ⁇ m film thickness in the wavelength region of 400 to 1100 nm is 2.5 or more, which means that the optical density per 1.5 ⁇ m film thickness is 2.5 or more in the entire wavelength range of 400 to 1100 nm. is 2.5 or more.
  • the reflectance of the film is preferably less than 8%, more preferably less than 6%, and even more preferably less than 4%.
  • the lower limit is preferably 0% or more.
  • the reflectance is determined from the reflectance spectrum obtained by using a spectroscope V7200 (trade name) VAR unit manufactured by JASCO Corporation to irradiate light with a wavelength of 400 to 1100 nm at an incident angle of 5°. Specifically, the reflectance of the light having the maximum reflectance in the wavelength range of 400 to 1100 nm is taken as the reflectance of the film.
  • the composition of the present invention is also preferably a composition for pattern formation by photolithography. According to this aspect, fine-sized pixels can be easily formed.
  • a composition containing a component having an ethylenically unsaturated bond-containing group e.g., a resin having an ethylenically unsaturated bond-containing group or a monomer having an ethylenically unsaturated bond-containing group
  • a photopolymerization initiator is preferably used as a composition for pattern formation in photolithography.
  • the composition for pattern formation by photolithography further contains an alkali-soluble resin.
  • the solid content concentration of the composition is preferably 5 to 30% by mass.
  • the lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more.
  • the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less.
  • composition of the first aspect contains a curable compound.
  • the curable compound include polymerizable compounds and resins.
  • the resin may be a non-polymerizable resin (a resin having no polymerizable group) or a polymerizable resin (a resin having a polymerizable group).
  • Polymerizable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.
  • cyclic ether group examples include an epoxy group and an oxetanyl group, with the epoxy group being preferred.
  • the epoxy group may be a cycloaliphatic epoxy group.
  • the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
  • the curable compound it is preferable to use one containing at least a resin.
  • a resin preferably a resin having an acid group
  • a polymerizable monomer monomer-type polymerizable compound
  • a resin preferably a resin having an acid group
  • a polymerizable monomer monomer-type polymerizable compound having an ethylenically unsaturated bond-containing group is more preferably used.
  • polymerizable compound examples include compounds having an ethylenically unsaturated bond-containing group and compounds having a cyclic ether group.
  • a compound having an ethylenically unsaturated bond-containing group can be preferably used as a radically polymerizable compound.
  • a compound having a cyclic ether group can also be preferably used as a cationically polymerizable compound.
  • resin-type polymerizable compounds include resins containing repeating units having polymerizable groups.
  • the molecular weight of the monomer type polymerizable compound is preferably less than 2000, more preferably 1500 or less.
  • the lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 or more.
  • the weight average molecular weight (Mw) of the resin-type polymerizable compound is preferably 2,000 to 2,000,000.
  • the upper limit of the weight average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit of the weight average molecular weight is preferably 3000 or more, more preferably 5000 or more.
  • the compound having an ethylenically unsaturated bond-containing group as a polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.
  • Specific 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-2013-253224.
  • Examples of compounds having an ethylenically unsaturated bond-containing group include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetra(meth)acrylate (commercially available).
  • KAYARAD D-320 manufactured by Nippon Kayaku Co., Ltd.
  • dipentaerythritol penta(meth)acrylate commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.
  • dipentaerythritol hexa(meth)acrylate ) Acrylate commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.
  • the (meth)acryloyl groups of these compounds are ethylene glycol and / Or a compound having a structure linked via a propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer).
  • Examples of compounds having an ethylenically unsaturated bond-containing group include diglycerin EO (ethylene oxide)-modified (meth)acrylate (commercially available as M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (Shin-Nakamura Chemical Industry ( 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 Nippon Kayaku Co., Ltd.) Toagosei Co., Ltd.), NK Oligo UA-7200 (Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (Taisei Fine Chemical Co., Ltd.), Light acrylate POB-A0 (Kyoeish
  • Examples of compounds having an ethylenically unsaturated bond-containing group include trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, and ethylene oxide isocyanurate. It is also preferable to use trifunctional (meth)acrylate compounds such as modified tri(meth)acrylate and pentaerythritol tri(meth)acrylate. Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305.
  • M-303, M-452, M-450 manufactured by Toagosei Co., Ltd.
  • a compound having an ethylenically unsaturated bond-containing group may further have an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group.
  • an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group.
  • Commercially available products of such compounds include Aronix M-305, M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
  • a compound having a caprolactone structure can also be used as the compound having an ethylenically unsaturated bond-containing group.
  • the descriptions in paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, the contents of which are incorporated herein.
  • Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as a series from Nippon Kayaku Co., Ltd.
  • a compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used as the compound having an ethylenically unsaturated bond-containing group.
  • Such a compound is preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and/or a propyleneoxy group, and is a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group. More preferably, it is a tri- to hexa-functional (meth)acrylate compound having 4 to 20 ethyleneoxy groups.
  • a polymerizable compound having a fluorene skeleton can also be used as the compound having an ethylenically unsaturated bond-containing group.
  • Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).
  • the compound having an ethylenically unsaturated bond-containing group it is also preferable to use a compound such as toluene that does not substantially contain environmentally regulated substances.
  • Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
  • Examples of compounds having an ethylenically unsaturated bond-containing group include UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA- 306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 ( Kyoeisha Chemical Co., Ltd.) and the like are also preferably used.
  • Compounds having a cyclic ether group include compounds having an epoxy group, compounds having an oxetanyl group, and the like, and compounds having an epoxy group are preferred.
  • Compounds having an epoxy group include compounds having 1 to 100 epoxy groups in one molecule.
  • the upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less.
  • the lower limit of the number of epoxy groups is preferably two or more.
  • a compound having a cyclic ether group may be a low-molecular compound (for example, a molecular weight of less than 1000) or a macromolecule (for example, a molecular weight of 1000 or more, and 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 composition of the present invention can use a resin as a curable compound. It is preferable to use a curable compound containing at least a resin.
  • the resin is blended, for example, for dispersing a pigment or the like in the composition or for a binder.
  • a resin that is mainly used to disperse a pigment or the like in a composition is also called a dispersant.
  • such uses of the resin are only examples, and the resin can be used for purposes other than such uses.
  • a resin having a polymerizable group also corresponds to a polymerizable compound.
  • the weight average molecular weight of the resin is preferably 3,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 5000 or more.
  • resins include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, Polyamide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, and the like.
  • norbornene resin is preferable from the viewpoint of improving heat resistance.
  • Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (for example, ARTON F4520). Further, as the resin, the resin described in the examples of International Publication No.
  • a resin having a fluorene skeleton can also be preferably used.
  • the description of US Patent Application Publication No. 2017/0102610 can be referred to, the content of which is incorporated herein.
  • the resin the resin described in paragraphs 0199 to 0233 of JP-A-2020-186373, the alkali-soluble resin described in JP-A-2020-186325, and the Korean Patent Publication No. 10-2020-0078339.
  • a resin represented by the formula 1 can also be used.
  • a resin having an acid group As the resin.
  • acid groups include carboxy groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. Only one kind of these acid groups may be used, or two or more kinds thereof may be used.
  • a resin having an acid group can be used, for example, as an alkali-soluble resin.
  • the acid value of the resin having acid groups is preferably 30-500 mgKOH/g.
  • the lower limit is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more.
  • the upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.
  • a resin containing a repeating unit derived from a compound represented by the formula (ED1) and/or a compound represented by the formula (ED2) (hereinafter, these compounds may be referred to as an "ether dimer"). It is also preferred to include
  • 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 description in JP-A-2010-168539 can be referred to.
  • paragraph number 0317 of JP-A-2013-029760 can be referred to, the content of which is incorporated herein.
  • polymerizable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • repeating unit Ep at least one type of repeating unit selected from repeating units represented by formula (Ep-1) and repeating units represented by formula (Ep-2).
  • a resin hereinafter also referred to as resin Ep
  • the resin Ep may contain only one of the repeating units represented by the formula (Ep-1) and the repeating unit represented by the formula (Ep-2). -1) and the repeating unit represented by formula (Ep-2) may be 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 100 mol% of all repeating units in the resin Ep.
  • the upper limit is preferably 90 mol % or less, more preferably 80 mol % or less.
  • the lower limit is preferably 2 mol % or more, more preferably 3 mol % or more.
  • the resin Ep may have other repeating units in addition to the repeating unit Ep.
  • Other repeating units include a repeating unit having an acid group, a repeating unit having an ethylenically unsaturated bond-containing group, and the like.
  • the acid group includes a phenolic hydroxy group, a carboxy group, a sulfo group, and a phosphoric acid group, preferably a phenolic hydroxy group or a carboxy group, more preferably a carboxy group.
  • ethylenically unsaturated bond-containing groups examples include vinyl groups, styrene groups, (meth)allyl groups, and (meth)acryloyl groups.
  • the content of the repeating unit having an acid group in the resin Ep is preferably 5 to 85 mol% of all repeating units in the resin Ep.
  • the upper limit is preferably 60 mol % or less, more preferably 40 mol % or less.
  • the lower limit is preferably 8 mol% or more, more preferably 10 mol% or more.
  • the content of the repeating unit having an ethylenically unsaturated bond-containing group in the resin Ep is 1 to 65 mol% of the total repeating units of the resin Ep. is preferably The upper limit is preferably 45 mol % or less, more preferably 30 mol % or less. The lower limit is preferably 2 mol % or more, more preferably 3 mol % or more.
  • the resin Ep preferably further contains a repeating unit having an aromatic hydrocarbon ring.
  • the aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.
  • the aromatic hydrocarbon ring may have a substituent. An alkyl group etc. are mentioned as a substituent.
  • the content of the repeating unit having an aromatic hydrocarbon ring is 1 to 65 mol in all repeating units of the resin having a cyclic ether group. %.
  • the upper limit is preferably 45 mol % or less, more preferably 30 mol % or less.
  • the lower limit is preferably 2 mol % or more, more preferably 3 mol % or more.
  • Repeating units having an aromatic hydrocarbon ring include repeating units derived from monofunctional polymerizable compounds having an aromatic hydrocarbon ring, such as vinyl toluene and benzyl (meth)acrylate.
  • R 1 represents a hydrogen atom or a methyl group
  • R 21 and R 22 each independently represent an alkylene group
  • n represents an integer of 0-15.
  • the number of carbon atoms in the alkylene group represented by R 21 and R 22 is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly 2 or 3.
  • n is preferably an integer of 0-5, more preferably an integer of 0-4, even more preferably an integer of 0-3.
  • 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.).
  • resin Ac a resin having an aromatic carboxy group
  • the aromatic carboxy group may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit.
  • the aromatic carboxy group is preferably contained in the main chain of the repeating unit.
  • an aromatic carboxy group is a group having a structure in which one or more carboxy groups are bonded to an aromatic ring.
  • the number of carboxy groups bonded to the aromatic ring is preferably 1-4, more preferably 1-2.
  • the composition of the present invention preferably contains a resin as a dispersant.
  • Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins).
  • the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups.
  • the acidic dispersant (acidic resin) a resin having an acid group content of 70 mol % or more is preferable when the total amount of the acid group and the basic group is 100 mol %.
  • the acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g.
  • a basic dispersant represents a resin in which the amount of basic groups is greater than the amount of acid groups.
  • a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and basic groups is 100 mol %.
  • the basic group possessed by the basic dispersant is preferably an amino group.
  • the resin used as the dispersant is also preferably a graft resin.
  • graft resin for details of the graft resin, reference can be made to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
  • the resin used as the dispersant is also preferably a polyimine-based dispersant containing nitrogen atoms in at least one of its main chain and side chains.
  • 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 used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core.
  • 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 used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain.
  • the content of repeating units having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70, of the total repeating units of the resin. More preferably, it is mol %.
  • resins described in JP-A-2018-087939, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, Polyethyleneimine having a polyester side chain described in International Publication No. 2016/104803, a block copolymer described in International Publication No. 2019/125940, a block polymer having an acrylamide structural unit described in JP-A-2020-066687 , a block polymer having an acrylamide structural unit described in JP-A-2020-066688, a dispersant described in WO 2016/104803, and the like can also be used.
  • Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like.
  • Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like.
  • the content of the curable compound in the total solid content of the composition is preferably 1 to 70% by mass.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.
  • the upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
  • the composition of the present invention may contain only one kind of curable compound, or may contain two or more kinds. When two or more curable compounds are included, the total amount thereof is preferably within the above range.
  • the content of the polymerizable compound is preferably 1 to 70% by mass based on the total solid content of the composition.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.
  • the upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
  • the composition of the present invention may contain only one polymerizable compound, or may contain two or more polymerizable compounds. When two or more polymerizable compounds are included, the total amount thereof is preferably within the above range.
  • the content of the polymerizable monomer is preferably 1 to 50% by mass based on the total solid content of the composition.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.
  • the upper limit is preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.
  • the composition of the present invention may contain only one polymerizable monomer, or may contain two or more polymerizable monomers. When two or more polymerizable monomers are included, the total amount thereof is preferably within the above range.
  • the content of the resin is preferably 1 to 70% by mass based on the total solid content of the composition.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.
  • the upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
  • the content of the resin having an acid group is preferably 1 to 70% by mass based on the total solid content of the composition.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.
  • the upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
  • the content of the alkali-soluble resin is preferably 1 to 70% by mass based on the total solid content of the composition.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.
  • the upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
  • the content of the resin as a dispersant is preferably 0.1 to 30% by mass based on the total solid content of the composition.
  • the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
  • the content of the resin as a dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the pigment.
  • the upper limit is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less.
  • the lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more.
  • the composition of the present invention may contain only one resin, or may contain two or more resins. When two or more resins are included, the total amount thereof is preferably within the above range.
  • the composition of the first aspect contains a silicone-based surfactant A (hereinafter referred to as a specific silicone-based surfactant) exhibiting a specific surface tension shown below.
  • a silicone-based surfactant A hereinafter referred to as a specific silicone-based surfactant
  • the surface tension of the solution is preferably 26.5 mN/m or more, more preferably 27 mN/m or more, and even more preferably 27.2 mN/m or more.
  • the upper limit is preferably 28 mN/m or less.
  • a silicone-based surfactant is a compound having a repeating unit containing a siloxane bond in its main chain and containing a hydrophobic part and a hydrophilic part in one molecule.
  • the specific silicone-based surfactant is preferably a compound containing no fluorine atoms. According to this aspect, the uniformity of the surface tension is likely to be improved, and the effects of the present invention are likely to be obtained more remarkably.
  • the hydroxyl value of the specific silicone surfactant is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more, still more preferably 100 mgKOH/g or more, and preferably 110 mgKOH/g or more. Especially preferred. If the hydroxyl value of the specific silicone-based surfactant is 80 mgKOH/g or more, the affinity of the film surface for water can be further enhanced.
  • the upper limit of the hydroxyl value of the specific silicone surfactant is preferably 200 mgKOH/g or less, more preferably 190 mgKOH/g or less, and 180 mgKOH/g or less from the viewpoint of the function as a surfactant. is more preferred.
  • the kinematic viscosity at 25° C. of the specific silicone surfactant is preferably 40 mm 2 /s or less, more preferably 38 mm 2 /s or less, even more preferably 36 mm 2 /s or less. If the kinematic viscosity of the specific silicone-based surfactant is 40 mm 2 /s or less, the fluidity is high, so the fluidity of the film surface obtained by using the composition of the present invention can be enhanced. Therefore, when another pixel is formed using another pixel-forming composition at a position adjacent to the film formed using the composition of the present invention, the fluidity of the film surface is high.
  • the lower limit of the kinematic viscosity of the specific silicone-based surfactant is preferably 10 mm 2 /s or more, more preferably 15 mm 2 /s or more, and 20 mm 2 /s or more from the viewpoint of the function of the surfactant. is more preferable, and 25 mm 2 /s or more is particularly preferable.
  • the weight-average molecular weight of the specific silicone-based surfactant is preferably 500-30,000.
  • the specific silicone-based surfactant is preferably modified polysiloxane.
  • modified polysiloxane include compounds having a structure in which substituents are introduced into the side chains and/or terminals of polysiloxane.
  • substituents include groups containing functional groups selected from amino groups, epoxy groups, alicyclic epoxy groups, hydroxyl groups, mercapto groups, carboxy groups, fatty acid ester groups and fatty acid amide groups, and groups containing polyether chains. and is preferably a group containing a hydroxy group, more preferably a group having an alkyleneoxy group and a hydroxy group.
  • the group containing a hydroxy group is preferably a group represented by formula (G-1) or a group represented by formula (G-2).
  • G-1 a group represented by formula (G-2)
  • G-2 a group represented by formula (G-2)
  • LG1 represents a single bond or a divalent linking group.
  • the divalent linking group represented by L G1 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms). , more preferably 6 to 12 arylene groups), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S- and two or more of these A group formed by combination is mentioned.
  • m1 represents an integer of 0 or 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5.
  • R G1 represents an alkylene group.
  • the number of carbon atoms in the alkylene group is preferably 1-10, more preferably 1-5, still more preferably 1-3, and particularly preferably 2 or 3.
  • the alkylene group represented by R G1 may be linear or branched.
  • the alkylene groups represented by m1 R G1 may be the same or different.
  • Groups containing polyether chains include groups represented by the following formula (G-11) and groups represented by formula (G-12).
  • LG11 represents a single bond or a divalent linking group.
  • the divalent linking group represented by L G11 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms). , more preferably 6 to 12 arylene groups), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S- and two or more of these A group formed by combination is mentioned.
  • m2 represents a number of 2 or more, preferably 2-200.
  • R G11 represents an alkylene group.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms.
  • the alkylene group represented by R G11 may be linear or branched.
  • the alkylene groups represented by m2 R G11 may be the same or different.
  • R G12 represents an alkyl group or an aryl group.
  • the number of carbon atoms in the alkyl group represented by R 1 G12 is preferably 1-10, more preferably 1-5, even more preferably 1-3.
  • Alkyl groups may be straight or branched.
  • the aryl group represented by R G12 preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the specific silicone-based surfactant is preferably carbinol-modified polysiloxane, more preferably carbinol-modified dialkylpolysiloxane. Moreover, the specific silicone-based surfactant is preferably dimethylpolysiloxane having an alkyleneoxy group and a hydroxy group.
  • the specific silicone surfactant is preferably a compound represented by formula (Si-1) or formula (Si-2).
  • R S1 to R S7 each independently represent an alkyl group or an aryl group
  • X S1 represents a group represented by the above formula (G-1) or a group represented by formula (G-2)
  • n1 represents a number from 2 to 200;
  • R S11 to R S16 each independently represent an alkyl group or an aryl group
  • X S11 and X S12 each independently represent a group represented by formula (G-1) or a group represented by formula (G-2)
  • n11 represents a number from 2 to 200
  • the number of carbon atoms in the alkyl group represented by R S1 to R S7 in formula (Si-1) and the alkyl group represented by R S11 to R S16 in formula (Si-2) is preferably 1 to 10, more preferably 1 to 5. 1 to 3 are more preferred, and 1 is particularly preferred.
  • the above alkyl group may be linear or branched, but preferably linear.
  • the number of carbon atoms in the aryl group represented by R S1 to R S7 in formula (Si-1) and the aryl group represented by R S11 to R S16 in formula (Si-2) is preferably 6 to 20, more preferably 6 to 12. 6 is particularly preferred.
  • R S1 to R S7 and R S11 to R S16 are preferably methyl groups or phenyl groups, more preferably methyl groups.
  • n1 and n11 are preferably numbers from 1 to 100.
  • Specific examples of specific silicone-based surfactants include the compounds described in the examples below.
  • the content of the specific silicone-based surfactant in the composition is preferably 1 to 1000 mass ppm.
  • the lower limit is preferably 0.5 mass ppm or more, and preferably 1 mass ppm or more.
  • the upper limit is preferably 750 mass ppm or less, more preferably 500 mass ppm or less.
  • the composition of the first aspect may contain a surfactant (hereinafter also referred to as another surfactant) other than the specific silicone surfactant described above.
  • a surfactant hereinafter also referred to as another surfactant
  • Other surfactants include fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and the like.
  • silicone-based surfactants other than the above-mentioned specific silicone-based surfactants can also be used as other surfactants.
  • JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-132503 and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein.
  • Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 and F-144.
  • the fluorosurfactant has a molecular structure with a functional group containing a fluorine atom, and an acrylic compound in which the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied is also suitable.
  • fluorine-based surfactants include MegaFac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Mega Fac DS-21.
  • fluorosurfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant.
  • fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.
  • a block polymer can also be used as the fluorosurfactant.
  • the fluorosurfactant has 2 or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) (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 a surfactant.
  • m represents 1 or 2
  • n represents an integer of 1 to 4
  • a represents 1 or 2
  • X a + is a valent metal ion, primary ammonium ion, Represents secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH4 + .
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fuji
  • Cationic surfactants include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridium salts, imidazolium salts, and the like. Specific examples include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, stearamidomethylpyridinium chloride and the like.
  • Anionic surfactants include dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyletherdisulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl Sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, t-octylphenoxyethoxypolyethoxyethyl sodium sulfate and the like.
  • the content of other surfactants in the composition is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and even more preferably 250 mass ppm or less.
  • the lower limit can be, for example, 1 ppm by mass or more.
  • the content of the other surfactant is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and 25 parts by mass or less with respect to 100 parts by mass of the specific silicone surfactant. is more preferable.
  • the lower limit can be, for example, 1 part by mass or more. It is also preferred that the compositions of the present invention do not contain other surfactants.
  • the composition of the first aspect contains a solvent.
  • Solvents include water and organic solvents.
  • the type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition.
  • organic solvents include aliphatic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, amide solvents, sulfoxide solvents, and aromatic solvents. Examples include solvents. For these details, reference can be made to paragraph 0223 of WO2015/166779, the content of which is incorporated herein.
  • Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used.
  • organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol Acetate, butyl carbitol acetate, propylene
  • 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 mass ppm or less, or 1 mass ppm or less).
  • an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content.
  • 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 ppt (parts per trillion) level by mass 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 solvent content in the composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, even more preferably 30 to 90% by mass.
  • the composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are included, the total amount thereof is preferably within the above range.
  • the composition of the first aspect preferably contains a coloring material.
  • a composition for forming optical filters more specifically, for forming pixels of optical filters.
  • colorants examples include white colorants, black colorants, chromatic colorants, and near-infrared absorbing 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 at least one selected from the group consisting of a chromatic colorant and a black colorant. It is more preferable to contain a seed, and it is still more preferable to contain a chromatic coloring material.
  • 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 composition of the present invention can be preferably used as a composition for forming a near-infrared transmission filter.
  • the coloring material may be a pigment or a dye, but is preferably a pigment.
  • 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.
  • 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.
  • the green colorant is preferably a pigment.
  • 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.
  • the compound described in Chinese Patent Application No. 106909027 the phthalocyanine compound having a phosphoric acid ester as a ligand described in WO 2012/102395, described in JP 2019-008014.
  • the 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 and 59 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 compound 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 122, 177, 179, 254, 255, 264, 269, 272 and 291 are preferred, and C.I. I. Pigment Red 254, 264, 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 more preferably an azo pigment or an azomethine pigment.
  • Specific examples of the yellow coloring material include C.I. I.
  • a nickel azobarbiturate complex having the following structure can also be used.
  • 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 117, 129, 138, 139, 150 and 185 are 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.
  • C.I. I. Purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61 are included.
  • 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. be done.
  • 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.
  • 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 Application Techniques 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 in which a large number of inorganic particles are attached to a core particle, and core-shell composite particles consisting of a core particle made of polymer particles and a shell layer made of inorganic nanoparticles are used. is preferred.
  • the core and shell composite particles composed of the core particles composed of the polymer particles and the shell layer composed of the inorganic nanoparticles for example, the description of paragraphs 0012 to 0042 of JP-A-2015-047520 can be referred to, The contents of which are incorporated herein.
  • Hollow inorganic particles can also be used as the white pigment.
  • a hollow inorganic particle is an inorganic particle having a structure having a cavity inside, and refers to an inorganic particle having a cavity surrounded by an outer shell.
  • Examples of hollow inorganic particles include hollow inorganic particles described in JP 2011-075786, WO 2013/061621, JP 2015-164881, etc., the contents of which are incorporated herein. be
  • the black colorant is not particularly limited, and known ones can be used.
  • 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 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 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 composition of the first aspect can contain a photoinitiator.
  • a polymerizable monomer When used as the curable compound, it 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. is mentioned.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above company) and the like.
  • ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by Irgacure 369E, Irgacure 379EG). made), etc.
  • acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).
  • Examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No.
  • oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropane-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(
  • An oxime compound having a fluorene ring can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466, compounds described in Japanese Patent No. 6636081, and compounds described in Korean Patent Publication No. 10-2016-0109444. mentioned.
  • an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
  • Specific examples of such oxime compounds include compounds described in WO2013/083505.
  • An oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of.
  • An oxime compound having a nitro group can be used as the photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.
  • An oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator.
  • Specific examples include OE-01 to OE-75 described in WO 2015/036910.
  • an oxime compound in which a substituent having a hydroxyl group is bonded to the carbazole skeleton can also be used.
  • Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
  • an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used.
  • the electron-withdrawing group possessed by the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
  • a benzoyl group may have a substituent.
  • substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group.
  • a sulfanyl group or an amino group is more preferred.
  • the oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
  • R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group
  • R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group,
  • electron-withdrawing groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups, with acyl groups and nitro groups being preferred.
  • An acyl group is more preferred, and a benzoyl group is even more preferred, because a film having excellent properties can be easily formed.
  • R X12 is an electron-withdrawing group
  • R X10 , R X11 , R X13 and R X14 are preferably hydrogen atoms.
  • oxime compound OX examples include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.
  • oxime compounds preferably used in the present invention are shown below, but the present invention is not limited to these.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
  • the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1000 to 300000, further preferably 2000 to 300000, even more preferably 5000 to 200000. It is particularly preferred to have
  • the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • 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, the precipitation becomes difficult over time, and the stability over time of the 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 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.
  • the composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more photopolymerization initiators are included, the total amount thereof preferably falls within the above range.
  • the composition of the first aspect can contain 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.
  • 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, Isoindoline dye skeletons, isoindolinone dye skeletons, quinophthalone dye skeletons, iminium dye skeletons, dithiol dye skeletons, triarylmethane dye skeletons, pyrromethene dye skeletons, and the like can be mentioned.
  • the acid group includes a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imidic acid group and salts thereof.
  • Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ion and the like.
  • the carboxylic acid amide group a group represented by —NHCOR X1 is preferable.
  • sulfonic acid amide group a group represented by —NHSO 2 R X2 is preferable.
  • the imidic acid group is preferably a group represented by —SO 2 NHSO 2 R X3 , —CONHSO 2 R X4 , —CONHCOR X5 or —SO 2 NHCOR X6 , more preferably —SO 2 NHSO 2 R X3 .
  • R X1 to R X6 each independently represent an alkyl group or an aryl group.
  • the alkyl groups and aryl groups represented by R X1 to R X6 may have substituents.
  • the substituent is preferably a halogen atom, more preferably a fluorine atom.
  • Basic groups include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups.
  • Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
  • 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, compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, compounds 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, JP 2011-25
  • 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 above pigment. Further, 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 composition. % or more is particularly preferred.
  • the upper limit is preferably 70% by mass or less, more preferably 65% by mass or less.
  • the 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. By containing two or more pigment derivatives, the dispersion stability of the 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. Further, by using a pigment derivative having a pigment skeleton and a pigment derivative excellent in visible transparency, dispersion stability, heat resistance, and light resistance can all be achieved at a higher level.
  • the composition of the first aspect can also contain a polyalkyleneimine.
  • Polyalkyleneimines are used, for example, as dispersing aids for pigments.
  • a dispersing aid is a material that enhances the dispersibility of the pigment in the composition.
  • a polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine and has at least a secondary amino group.
  • the polyalkyleneimine may contain a primary amino group or a tertiary amino group in addition to the secondary amino group.
  • the polyalkyleneimine is preferably a polymer having a branched structure each containing a primary amino group, a secondary amino group and a tertiary amino group.
  • the number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2.
  • the molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more.
  • the upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less.
  • the molecular weight of the polyalkyleneimine when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula.
  • the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used.
  • the value of the number average molecular weight measured by the viscosity method is used.
  • the value of the number average molecular weight in terms of polystyrene measured by the GPC (gel permeation chromatography) method is used.
  • the amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
  • alkyleneimine examples include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine and the like, preferably ethyleneimine or propyleneimine, more preferably ethyleneimine. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. In addition, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more, of the primary amino group with respect to the total of the primary amino group, the secondary amino group and the tertiary amino group. , more preferably 30 mol % or more.
  • Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, P-1000 (manufactured by Nippon Shokubai Co., Ltd.).
  • the content of polyalkyleneimine in the total solid content of the composition is preferably 0.1 to 5% by mass.
  • the lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
  • the upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
  • the content of the polyalkyleneimine is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the pigment.
  • the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more.
  • the upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. Only one kind of polyalkyleneimine may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
  • the composition of the first aspect can 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 paragraph numbers 0186 to 0251 of the publication, ionic compounds described in JP 2014-055114, compounds described in paragraph numbers 0071 to 0080 of JP 2012-150180, JP 2011-253054 Alkoxysilane compounds having an epoxy group described in JP-A-2005-200557, 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 composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass. Only one curing accelerator may be used, or two or more curing accelerators may be used. When two or more types are used, the total amount thereof is preferably within the above range.
  • the composition of the first aspect can contain an ultraviolet absorber.
  • ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, paragraph numbers 0317-0317 of JP-A-2013-068814.
  • UV absorbers examples include UV-503 (manufactured by Daito Chemical Co., Ltd.), Tinuvin series and Uvinul series manufactured by BASF, and Sumisorb series manufactured by Sumika Chemtex Co., Ltd. .
  • UV-503 manufactured by Daito Chemical Co., Ltd.
  • Tinuvin series and Uvinul series manufactured by BASF Tinuvin series and Uvinul series manufactured by BASF
  • benzotriazole compound the MYUA series made from Miyoshi oil and fats (Chemical Daily, February 1, 2016) is mentioned.
  • the ultraviolet absorber is a compound described in paragraph numbers 0049 to 0059 of Japanese Patent No.
  • a thioaryl group-substituted benzotriazole-type ultraviolet absorber described in can also be used.
  • the content of the ultraviolet absorber in the total solid content of the composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more are used, the total amount thereof is preferably within the above range.
  • the composition of the first aspect can contain a polymerization inhibitor.
  • Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred.
  • the content of the polymerization inhibitor in the total solid content of the composition is preferably 0.0001 to 5% by mass. Only 1 type may be used for a polymerization inhibitor and 2 or more types may be used for it. When two or more types are used, the total amount thereof is preferably within the above range.
  • the composition of the first aspect 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 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 thereof is preferably within the above range.
  • the composition of the first aspect can contain an antioxidant.
  • Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
  • Phosphorus-based antioxidants can also be suitably used as antioxidants.
  • a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
  • antioxidants examples include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like.
  • antioxidants are compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, compounds described in WO 2017/164024, Compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used.
  • the content of the antioxidant in the total solid content of the composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
  • composition of the first aspect may optionally contain sensitizers, 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 composition of the first aspect may also contain latent antioxidants, if desired.
  • the latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst.
  • a compound that functions as an antioxidant by removing the protective group by the reaction is exemplified.
  • Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
  • Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
  • the composition of the first aspect may contain a light resistance improver.
  • a light resistance improver compounds described in paragraph numbers 0036 to 0037 of JP-A-2017-198787, compounds described in paragraph numbers 0029-0034 of JP-A-2017-146350, JP-A-2017-129774 Compounds described in paragraph numbers 0036 to 0037, 0049 to 0052 of JP 2017-129674 JP 2017-129674 paragraph numbers 0031 to 0034, 0058 to 0059 compounds described in JP 2017-122803 paragraph numbers 0036 to 0037 , compounds described in 0051 to 0054, compounds described in paragraph numbers 0025 to 0039 of WO 2017/164127, compounds described in paragraph numbers 0034 to 0047 of JP 2017-186546, JP 2015-025116 Compounds described in paragraph numbers 0019 to 0041 of JP-A-2012-145604, compounds described in paragraph numbers 0101-0125 of JP-A-2012-103475, compounds described
  • perfluoroalkylsulfonic acid and its salts may be regulated.
  • perfluoroalkylsulfonic acid especially perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
  • alkylcarboxylic acid especially perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
  • its salt is in the range of 0.01ppb to 1,000ppb relative to the total solid content of the composition.
  • 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.
  • compositions of the present invention may contain perfluoroalkylsulfonic acids and their salts and perfluoroalkylcarboxylic acids and their salts within the maximum permissible range.
  • composition of the second aspect comprises inorganic particles.
  • inorganic particles include silica particles, titanium oxide particles, strontium titanate particles, barium titanate particles, zinc oxide particles, magnesium oxide particles, zirconium oxide particles, aluminum oxide particles, barium sulfate particles, aluminum hydroxide particles, and calcium silicate. particles, aluminum silicate particles, zinc sulfide particles, etc., and silica particles are preferred.
  • a composition using silica particles as inorganic particles is preferably used as a composition for forming partition walls.
  • silica particles examples include silica particles in which a plurality of spherical silica particles are connected in a beaded shape, silica particles in which a plurality of spherical silica particles are connected in a plane, silica particles with a hollow structure, solid silica particles, and the like. be done.
  • Commercially available solid silica particles include, for example, PL-2L-IPA (manufactured by Fuso Chemical Industry Co., Ltd.).
  • silica particles tend to form a film with a smaller refractive index
  • silica particles having a shape in which a plurality of spherical silicas are linked in a beaded shape silica particles having a shape in which a plurality of spherical silicas are planarly linked
  • Silica particles having a hollow structure are preferred, and silica particles having a shape in which a plurality of spherical silica particles are linked in a beaded shape and silica particles in a shape in which a plurality of spherical silica particles are planarly linked are preferable.
  • a silica particle having a shape in which a plurality of spherical silica particles are linked in a beaded shape and a silica particle having a shape in which a plurality of spherical silica particles are planarly linked are collectively referred to as beaded silica.
  • the silica particles having a shape in which a plurality of spherical silica particles are linked in a beaded shape may have a shape in which a plurality of spherical silica particles are planarly linked.
  • spherical in “spherical silica” means that it may be substantially spherical, and may be deformed within the scope of the effects of the present invention. For example, it includes a shape having unevenness on the surface and a flat shape having a long axis in a predetermined direction.
  • a plurality of spherical silica particles are linked in a beaded manner means a structure in which a plurality of spherical silica particles are linked in a linear and/or branched form. For example, as shown in FIG.
  • the structure in which "a plurality of spherical silica particles are linked in a beaded shape” includes not only a structure in which a ring is connected, but also a chain-like structure having an end. It also includes structures with
  • "a plurality of spherical silica particles are planarly connected” means a structure in which a plurality of spherical silica particles are connected to each other on substantially the same plane. It should be noted that “substantially the same plane” means not only the same plane, but also the vertical deviation from the same plane. For example, the vertical deviation may be within a range of 50% or less of the particle diameter of the spherical silica.
  • the beaded silica preferably has a ratio D 1 /D 2 of 3 or more between the average particle diameter D 1 measured by the dynamic light scattering method and the average particle diameter D 2 obtained by the following formula (1). Although there is no particular upper limit for D 1 /D 2 , it is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less. Favorable optical properties can be exhibited by setting D 1 /D 2 within such a range.
  • the value of D 1 /D 2 in beaded silica is also an index of the degree of connection of spherical silica.
  • D2 2720/S (1)
  • D 2 is the average particle size of beaded silica in units of nm
  • S is the specific surface area of beaded silica measured by the nitrogen adsorption method in units of m 2 /g. be.
  • the average particle size D2 of beaded silica can be regarded as an average particle size approximate to the primary particles of spherical silica.
  • the average particle diameter D2 is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more, and particularly preferably 7 nm or more.
  • the upper limit is preferably 100 nm or less, more preferably 80 nm or less, even more preferably 70 nm or less, even more preferably 60 nm or less, and particularly preferably 50 nm or less.
  • the average particle diameter D2 can be substituted by the equivalent circle diameter (D0) in the projected image of the spherical portion measured by a transmission electron microscope (TEM). Unless otherwise specified, the average particle diameter of 50 or more particles is evaluated as the number average of 50 or more particles.
  • D0 equivalent circle diameter
  • TEM transmission electron microscope
  • the average particle diameter D1 of beaded silica can be regarded as the number average particle diameter of secondary particles in which a plurality of spherical silica particles are aggregated. Therefore, the relationship D 1 >D 2 usually holds.
  • the average particle diameter D1 is preferably 25 nm or more, more preferably 30 nm or more, and particularly preferably 35 nm or more.
  • the upper limit is preferably 1000 nm or less, more preferably 700 nm or less, even more preferably 500 nm or less, and particularly preferably 300 nm or less.
  • Measurement of the average particle diameter D1 of the beaded silica is performed using a dynamic light scattering particle size distribution analyzer (Nikkiso Nanotrac Wave-EX150 [trade name]) unless otherwise specified.
  • the procedure is as follows. A dispersion liquid of beaded silica is put into a 20 ml sample bottle, and diluted with toluene so that the solid content concentration becomes 0.2% by mass. The sample solution after dilution is irradiated with ultrasonic waves of 40 kHz for 1 minute and immediately used for the test. A 2 ml measurement quartz cell is used at a temperature of 25° C., data is taken in 10 times, and the obtained "number average” is taken as the average particle size. For other detailed conditions, etc., refer to the description of JISZ8828:2013 "Particle Size Analysis-Dynamic Light Scattering Method" as necessary. Five samples are prepared for each level and the average value is adopted.
  • the beaded silica it is preferable that a plurality of spherical silica particles having an average particle diameter of 1 to 80 nm are connected via a connecting material.
  • the upper limit of the average particle size of spherical silica is preferably 70 nm or less, more preferably 60 nm or less, and even more preferably 50 nm or less.
  • the lower limit of the average particle size of spherical silica is preferably 3 nm or more, more preferably 5 nm or more, and even more preferably 7 nm or more.
  • the average particle size of spherical silica is determined from the equivalent circle diameter in the projected image of the spherical portion measured by a transmission electron microscope (TEM).
  • Metal oxide-containing silica can be used as a connecting material for connecting spherical silica particles.
  • metal oxides include oxides of metals selected from Ca, Mg, Sr, Ba, Zn, Sn, Pb, Ni, Co, Fe, Al, In, Y, and Ti.
  • metal oxide-containing silica include reaction products and mixtures of these metal oxides and silica (SiO 2 ).
  • the connecting member the description of International Publication No. WO 2000/015552 can be considered, and the content thereof is incorporated herein.
  • the number of spherical silica connections in beaded silica is preferably 3 or more, more preferably 5 or more.
  • the upper limit is preferably 1000 or less, more preferably 800 or less, even more preferably 500 or less.
  • the number of linkages of spherical silica can be measured by TEM.
  • beaded silica spherical silica whose surface is treated with hexamethyldisilazane or the like may be used.
  • Silica particles may be used in the form of a particle liquid (sol).
  • examples of media for dispersing silica particles include alcohols (e.g., methanol, ethanol, isopropanol), ethylene glycol, glycol ethers (e.g., propylene glycol monomethyl ether), glycol ether acetates (e.g., propylene glycol monomethyl ether acetate), and the like. be.
  • Solvent A1, solvent A2, etc., which will be described later, can also be used.
  • the particle liquid (sol) preferably has a SiO 2 concentration of 5 to 40% by mass.
  • silica sol described in Japanese Patent No. 4328935 can be used.
  • a commercial product can also be used as the particle liquid (sol) of beaded silica.
  • Nissan Chemical Co., Ltd. "Snowtex OUP”, “Snowtex UP”, “IPA-ST-UP”, “Snowtex PS-M”, “Snowtex PS-MO”, “Snowtex PS- S”, “Snowtex PS-SO”, "Fine Cataloid F-120” manufactured by Catalysts & Chemicals Co., Ltd., and "Quatron PL” manufactured by Fuso Chemical Industry Co., Ltd., and the like.
  • a commercial product can also be used as the particle liquid of silica particles with a hollow structure.
  • "Sururia 4110" manufactured by Nikki Shokubai Kasei Co., Ltd. can be used.
  • the content of inorganic particles in the composition is preferably 4% by mass or more, more preferably 6% by mass or more, and even more preferably 7% by mass or more.
  • the upper limit is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 11% by mass or less.
  • the content of inorganic particles in the total solid content of the composition is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and 60% by mass or more. It is more preferably at least 70% by mass, and particularly preferably at least 70% by mass.
  • the upper limit can be 99.95% by mass or less, 99.9% by mass or less, 99% by mass or less, or 95% by mass or less.
  • the content of silica particles in the composition is preferably 4% by mass or more, more preferably 6% by mass or more, and preferably 7% by mass or more. More preferred.
  • the upper limit is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 11% by mass or less.
  • the content of silica particles in the total solid content of the composition is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and 60% by mass or more. It is more preferably at least 70% by mass, and particularly preferably at least 70% by mass.
  • the upper limit can be 99.95% by mass or less, 99.9% by mass or less, 99% by mass or less, or 95% by mass or less. If the content of the silica particles is within the above range, it is easy to obtain a film with a low refractive index, a high antireflection effect, and suppressed defects. Further, when pattern formation is not performed, or when pattern formation is performed by an etching method, the content of silica particles in the total solid content of the composition is preferably high, for example, 95% by mass or more, preferably 97% by mass. The above is more preferable, and 99% by mass or more is even more preferable.
  • composition of the second aspect contains the silicone-based surfactant A (specific silicone-based surfactant) described above.
  • Specific silicone-based surfactants include materials described as specific silicone-based surfactants that can be included in the composition of the first aspect.
  • the content of the specific silicone-based surfactant in the composition is preferably 1 to 1000 mass ppm.
  • the lower limit is preferably 0.5 mass ppm or more, and preferably 1 mass ppm or more.
  • the upper limit is preferably 750 mass ppm or less, more preferably 500 mass ppm or less.
  • composition of the second aspect may contain a surfactant (other surfactant) other than the specific silicone-based surfactant.
  • Other surfactants include those materials described as other surfactants that the composition of the first aspect can contain.
  • the content of other surfactants in the composition is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and even more preferably 250 mass ppm or less.
  • the lower limit can be, for example, 1 ppm by mass or more.
  • the content of the other surfactant is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and 25 parts by mass or less with respect to 100 parts by mass of the specific silicone surfactant. is more preferable.
  • the lower limit can be, for example, 1 part by mass or more. It is also preferred that the composition of the second aspect does not contain other surfactants.
  • the composition of the second aspect contains a solvent.
  • the solvent include organic solvents and water, and it is preferable to include at least the organic solvent.
  • organic solvents include aliphatic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, amide solvents, sulfoxide solvents, and aromatic solvents. Examples include solvents.
  • the content of the solvent in the composition is preferably 70-99% by mass.
  • the upper limit is preferably 93% by mass or less, more preferably 92% by mass or less, and even more preferably 90% by mass or less.
  • the lower limit is preferably 75% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more. Only 1 type may be used for a solvent and 2 or more types may be used for it. When two or more types are used, the total amount thereof is preferably within the above range.
  • the composition of the second aspect contains silica particles
  • the boiling point of the solvent is the value at 1 atmosphere (0.1 MPa).
  • the boiling point of solvent A1 is preferably 200°C or higher, more preferably 210°C or higher, and more preferably 220°C or higher.
  • the boiling point of solvent A1 is preferably 270° C. or lower, more preferably 265° C. or lower.
  • the viscosity of solvent A1 is preferably 10 mPa ⁇ s or less, more preferably 7 mPa ⁇ s or less, and more preferably 4 mPa ⁇ s or less.
  • the lower limit of the viscosity of solvent A1 is preferably 1.0 mPa ⁇ s or more, more preferably 1.4 mPa ⁇ s or more, and even more preferably 1.8 mPa ⁇ s or more from the viewpoint of coating properties. .
  • the molecular weight of solvent A1 is preferably 100 or more, more preferably 130 or more, still more preferably 140 or more, and particularly preferably 150 or more.
  • the upper limit is preferably 300 or less, more preferably 290 or less, even more preferably 280 or less, and particularly preferably 270 or less, from the viewpoint of coatability.
  • Solvent A1 preferably has a solubility parameter of 8.5 to 13.3 (cal/cm 3 ) 0.5 .
  • the upper limit is preferably 12.5 (cal/cm 3 ) 0.5 or less, more preferably 11.5 (cal/cm 3 ) 0.5 or less, and 10.5 (cal/cm 3 ) ) is more preferably 0.5 or less.
  • the lower limit is preferably 8.7 (cal/cm 3 ) 0.5 or more, more preferably 8.9 (cal/cm 3 ) 0.5 or more, and 9.1 (cal/cm 3 ) is more preferably 0.5 or more. If the solubility parameter of solvent A1 is within the above range, high affinity with silica particles can be obtained, and excellent coatability can be easily obtained. Note that 1 (cal/cm 3 ) 0.5 is 2.0455 MPa 0.5 . Solvent solubility parameters are values calculated by HSPiP.
  • the Hansen solubility parameter is used as the solubility parameter of the solvent. Specifically, a value calculated using the Hansen solubility parameter software "HSPiP 5.0.09" is used.
  • the solvent A1 is preferably an aprotic solvent.
  • an aprotic solvent as solvent A1, aggregation of silica particles during film formation can be more effectively suppressed.
  • Solvent A1 is preferably an ether-based solvent or an ester-based solvent, more preferably an ester-based solvent. Moreover, the ester-based solvent used as the solvent A1 is preferably a compound that does not contain a hydroxyl group or a terminal alkoxy group.
  • the solvent A1 is preferably at least one selected from alkylenediol diacetates and cyclic carbonates because it has a high affinity with silica particles and is likely to have excellent coatability.
  • Alkylene diol diacetates include propylene glycol diacetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate and the like.
  • Cyclic carbonates include propylene carbonate and ethylene carbonate.
  • solvent A1 examples include propylene carbonate (boiling point 240°C), ethylene carbonate (boiling point 260°C), propylene glycol diacetate (boiling point 190°C), dipropylene glycol methyl-n-propyl ether (boiling point 203°C), Propylene glycol methyl ether acetate (boiling point 213°C), 1,4-butanediol diacetate (boiling point 232°C), 1,3-butylene glycol diacetate (boiling point 232°C), 1,6-hexanediol diacetate (boiling point 260°C) ° C.), diethylene glycol monoethyl ether acetate (boiling point 217° C.), diethylene glycol monobutyl ether acetate (boiling point 247° C.), triacetin (boiling point 260° C.), dipropylene glycol
  • the solvent used in the composition of the second aspect preferably contains 3% by mass or more of the solvent A1, more preferably 4% by mass or more, and 5% by mass or more. It is more preferable that the According to this aspect, the effects of the present invention described above are likely to be obtained remarkably.
  • the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less. According to this aspect, it is easy to obtain a film with good surface properties. Only one kind of solvent A1 may be used, or two or more kinds thereof may be used in combination. When the composition of the second aspect contains two or more solvents A1, it is preferable that the total of them is within the above range.
  • the solvent used in the composition of the second aspect preferably further contains solvent A2 having a boiling point of 110°C or higher and lower than 190°C. According to this aspect, the drying property of the composition can be moderately increased to effectively suppress the occurrence of wavy coating unevenness, and a film with a good surface condition can be easily formed.
  • the boiling point of solvent A2 is preferably 115°C or higher, more preferably 120°C or higher, and more preferably 130°C or higher.
  • the boiling point of solvent A2 is preferably 170° C. or lower, more preferably 150° C. or lower. If the boiling point of the solvent A2 is within the above range, the effects described above are likely to be obtained more remarkably.
  • the molecular weight of solvent A2 is preferably 100 or more, more preferably 130 or more, even more preferably 140 or more, and even more preferably 150 or more, because the above-described effects are likely to be obtained more remarkably. is particularly preferred.
  • the upper limit is preferably 300 or less, more preferably 290 or less, even more preferably 280 or less, and particularly preferably 270 or less, from the viewpoint of coatability.
  • Solvent A2 preferably has a solubility parameter of 9.0 to 11.4 (cal/cm 3 ) 0.5 .
  • the upper limit is preferably 11.0 (cal/cm 3 ) 0.5 or less, more preferably 10.6 (cal/cm 3 ) 0.5 or less, and 10.2 (cal/cm 3 ) ) is more preferably 0.5 or less.
  • the lower limit is preferably 9.2 (cal/cm 3 ) 0.5 or more, more preferably 9.4 (cal/cm 3 ) 0.5 or more, and 9.6 (cal/cm 3 ) ) is more preferably 0.5 or more. If the solubility parameter of solvent A2 is within the above range, high affinity with silica particles can be obtained, and excellent coatability can be easily obtained.
  • the absolute value of the difference between the solubility parameter of solvent A1 and the solubility parameter of solvent A2 is preferably 0.01 to 1.1 (cal/cm 3 ) 0.5 .
  • the upper limit is preferably 0.9 (cal/cm 3 ) 0.5 or less, more preferably 0.7 (cal/cm 3 ) 0.5 or less, and 0.5 (cal/cm 3 ) is more preferably 0.5 or less.
  • the lower limit is preferably 0.03 (cal/cm 3 ) 0.5 or more, more preferably 0.05 (cal/cm 3 ) 0.5 or more, and 0.08 (cal/cm 3 ) ) is more preferably 0.5 or more.
  • the solvent A2 is preferably at least one selected from ether-based solvents and ester-based solvents, more preferably includes at least an ester-based solvent, and still more preferably includes an ether-based solvent and an ester-based solvent.
  • Specific examples of solvent A2 include cyclohexanol acetate (boiling point 173°C), dipropylene glycol dimethyl ether (boiling point 175°C), butyl acetate (boiling point 126°C), ethylene glycol monomethyl ether acetate (boiling point 145°C), and propylene glycol monomethyl ether.
  • the content of solvent A2 is preferably 500 to 5000 parts by mass with respect to 100 parts by mass of solvent A1.
  • the upper limit is preferably 4500 parts by mass or less, more preferably 4000 parts by mass or less, and even more preferably 3500 parts by mass or less.
  • the lower limit is preferably 600 parts by mass or more, more preferably 700 parts by mass or more, and even more preferably 750 parts by mass or more.
  • the content of solvent A2 in the total amount of solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
  • the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.
  • the content of the solvent A2 is within the above range, the effects of the present invention are likely to be obtained more remarkably. Only one kind of solvent A2 may be used, or two or more kinds thereof may be used in combination. When the composition of the second aspect contains two or more solvents A2, the total is preferably within the above range.
  • the solvent used in the composition of the second aspect preferably contains the solvent A1 and the solvent A2 in a total content of 62% by mass or more, more preferably 72% by mass or more, and 82% by mass. % or more is more preferable.
  • the upper limit can be 100% by mass, 96% by mass or less, or 92% by mass or less.
  • the solvent used in the composition of the second aspect preferably further contains at least one solvent A3 selected from methanol, ethanol and 2-propyl alcohol. According to this aspect, high affinity with silica particles can be obtained, and excellent coatability can be easily obtained.
  • the solvent used in the composition of the second aspect further contains solvent A3, the content of solvent A3 in the total amount of solvent is preferably 0.1 to 10% by mass.
  • the upper limit is preferably 8% by mass or less, more preferably 6% by mass or less, and even more preferably 4% by mass or less.
  • the lower limit is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. If the content of the solvent A3 is within the above range, the above effects can be obtained more remarkably. Only one kind of solvent A3 may be used, or two or more kinds thereof may be used in combination. When the composition contains two or more solvents A3, it is preferable that the total is within the above range.
  • the solvent used in the composition of the second aspect preferably further contains water. According to this aspect, high affinity with silica particles can be obtained, and excellent coatability can be easily obtained.
  • the content of water in the total amount of the solvent is preferably 0.1 to 5% by mass.
  • the upper limit is preferably 4% by mass or less, more preferably 2.5% by mass or less, and even more preferably 1.5% by mass or less.
  • the lower limit is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. If the content of water is within the above range, the effects described above are likely to be obtained more remarkably.
  • the solvent used in the composition of the second aspect contains the above solvent A3 and water.
  • High affinity with silica particles can be obtained, and excellent coatability can be easily obtained.
  • the total content of solvent A3 and water in the total amount of solvent is preferably 0.2 to 15% by mass.
  • the upper limit is preferably 12% by mass or less, more preferably 9% by mass or less, and even more preferably 6% by mass or less.
  • the lower limit is preferably 0.4% by mass or more, more preferably 0.7% by mass or more, and even more preferably 1.5% by mass or more. If the total content of solvent A3 and water is within the above range, the above-described effects can be obtained more remarkably.
  • the solvent used in the composition of the second aspect can further contain solvent A4 with a boiling point of over 280°C.
  • solvent A4 with a boiling point of over 280°C.
  • the upper limit of the boiling point of solvent A4 is preferably 400° C. or lower, more preferably 380° C. or lower, and even more preferably 350° C. or lower.
  • Solvent A4 is preferably at least one selected from ether-based solvents and ester-based solvents. Specific examples of solvent A4 include polyethylene glycol monomethyl ether.
  • the content of solvent A4 in the total amount of solvent is preferably 0.5 to 15% by mass.
  • the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less.
  • the lower limit is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more.
  • the solvent used in the composition of the second aspect does not substantially contain solvent A4.
  • substantially free of solvent A4" means that the content of solvent A4 in the total amount of solvent is 0.1% by mass or less, preferably 0.05% by mass or less, and 0.1% by mass or less. It is more preferably 01% by mass or less, and more preferably not contained.
  • the solvent used in the composition of the second aspect may contain solvents (other solvents) other than solvent A1, solvent A2, solvent A3, solvent A4 and water described above, but other solvents are substantially It is preferable not to contain in Note that "substantially free of other solvents" means that the content of other solvents in the total amount of solvents is 0.1% by mass or less, preferably 0.05% by mass or less, It is more preferably 0.01% by mass or less, and more preferably not contained.
  • the content of compounds having a molecular weight (weight average molecular weight in the case of a polymer) exceeding 300 is preferably 10% by mass or less, and is 8% by mass or less. is more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less. According to this aspect, more excellent coatability can be easily obtained, and a film having an excellent surface condition can be easily obtained.
  • the solvent used in the composition of the second aspect preferably contains 10% by mass or less, more preferably 8% by mass or less, of compounds having a viscosity of more than 10 mPa s at 25°C. It is more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less. According to this aspect, more excellent coatability can be easily obtained, and a film having an excellent surface condition can be easily obtained.
  • the composition of the second aspect can contain a curable compound.
  • the curable compound include materials such as the resins and polymerizable monomers described as the curable compound that can be included in the composition of the first aspect.
  • the curable compound preferably contains a resin.
  • the content of the curable compound in the composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more.
  • the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.
  • the content of the curable compound in the total solid content of the composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
  • the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. Only 1 type may be used for a sclerosing
  • the total amount thereof is preferably within the above range. It is also preferred that the composition of the second aspect is free of polymerizable monomers. According to this aspect, it is easy to form a film with a lower refractive index. Furthermore, it is easy to form a film with a small haze.
  • the composition of the second aspect can contain a photoinitiator.
  • Photoinitiators include the materials described as photoinitiators that the composition of the first aspect can contain.
  • the content of the photopolymerization initiator in the composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more.
  • the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less.
  • the content of the photopolymerization initiator in the total solid content of the composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and more preferably 20% by mass or less. Only one kind of photopolymerization initiator may be used, or two or more kinds thereof may be used.
  • the total amount thereof is preferably within the above range. It is also preferred that the composition of the second aspect does not contain a photoinitiator. According to this aspect, it is easy to form a film with a lower refractive index. Furthermore, it is easy to form a film with a small haze.
  • composition of the second aspect can contain a silane coupling agent.
  • Silane coupling agents include materials described as silane coupling agents that the composition of the first aspect can include.
  • the content of the silane coupling agent in the total solid content of the composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and particularly preferably 0.1% by mass or more.
  • the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. 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 thereof is preferably within the above range. It is also preferred that the composition of the second aspect does not contain a silane coupling agent.
  • Black color material>> The composition of the second aspect can contain a black colorant.
  • Black colorants include the materials described as black colorants that the composition of the first aspect can contain.
  • the content of the black colorant in the total solid content of the composition is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less. It is also preferred that the composition of the second aspect does not substantially contain a black colorant. In addition, when the composition does not substantially contain a black colorant, it means that the content of the black colorant in the total solid content of the composition is 0.1% by mass or less, and 0.05 % by mass or less, and more preferably contains no black colorant.
  • the composition of the second aspect can contain a chromatic colorant.
  • the chromatic colorant includes the materials described as the chromatic colorant that the composition of the first aspect can contain.
  • the content of the chromatic coloring material in the total solid content of the composition is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less. It is also preferred that the composition of the second aspect does not substantially contain a chromatic colorant. In addition, when the composition does not substantially contain a chromatic colorant, it means that the content of the chromatic colorant in the total solid content of the composition is 0.1% by mass or less. It is preferably 0.05% by mass or less, and more preferably does not contain a chromatic coloring material.
  • composition of the second aspect may optionally contain ultraviolet absorbers, antioxidants, latent antioxidants, polymerization inhibitors, sensitizers, fillers, thermosetting accelerators, plasticizers and other auxiliary agents.
  • ultraviolet absorbers for example, conductive particles, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.
  • conductive particles, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc. may be contained.
  • These materials include the materials described as being capable of being included in the composition of the first aspect described above.
  • the storage container for the 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 resins and a bottle with a 7-layer structure of 6 types of resins for the purpose of suppressing the contamination of raw materials and coloring compositions. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351.
  • the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the composition, and suppressing deterioration of components.
  • compositions of the present invention can be prepared by admixing the aforementioned ingredients.
  • the composition may be produced by simultaneously dissolving and/or dispersing all the components in a solvent, or if necessary, each component may be appropriately prepared as two or more solutions or dispersions.
  • a composition may be produced by mixing these at the time of use (at the time of application).
  • a process of dispersing the pigment is included in the production of the 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.
  • 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.
  • Beads used for dispersion can be zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, glass, or combinations thereof.
  • an inorganic compound having a Mohs hardness of 2 or more can be used.
  • the composition may contain 1 to 10000 ppm of the beads.
  • any filter that has been conventionally used for filtration or the like can be used without particular limitation.
  • fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF)
  • polyamide resins such as nylon (eg nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high-molecular-weight polyolefin resin) and other materials.
  • PP polypropylene
  • nylon including high density polypropylene
  • nylon including high density polypropylene
  • the pore size of the filter is preferably 0.01-7.0 ⁇ m, more preferably 0.01-3.0 ⁇ m, and even more preferably 0.05-0.5 ⁇ m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably.
  • the pore size value of the filter reference can be made to the filter manufacturer's nominal value.
  • Various filters provided by Nippon Pall Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used as filters. .
  • fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers.
  • Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.
  • filters When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed. In addition, the filter can be appropriately selected according to the hydrophilicity/hydrophobicity of the composition.
  • the membrane of the invention is a membrane obtained from the composition of the invention as 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. Also, the film of the present invention can be used as a light-shielding film, a partition wall, and the like.
  • 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, and even more preferably 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more.
  • the film of the present invention When 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 1100 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 characteristics 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 density (OD) per 1.5 ⁇ m film thickness in the wavelength range of 400 to 1100 nm of the film is preferably 2.5 or more, and preferably 3.0. It is more preferable to be above.
  • the upper limit is not particularly limited, it is generally preferably 10 or less.
  • the reflectance of the film is preferably less than 8%, more preferably less than 6%, and even more preferably less than 4%.
  • the lower limit is preferably 0% or more.
  • the light-shielding film is used in portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as multi-function printers and scanners; industrial equipment such as automated teller machines), high-speed cameras, and equipment with personal authentication functions using face image authentication or biometric authentication; vehicle-mounted camera equipment; medical cameras such as endoscopes, capsule endoscopes, and catheters equipment; and space equipment such as biosensors, biosensors, military reconnaissance cameras, stereo map cameras, weather and ocean observation cameras, land resource exploration cameras and exploration cameras for space astronomy and deep space targets; It can be used for optical filters and modules used.
  • OA Office Automation
  • industrial equipment such as automated teller machines
  • high-speed cameras and equipment with personal authentication functions using face image authentication or biometric authentication
  • vehicle-mounted camera equipment medical cameras such as endoscopes, capsule endoscopes, and catheters equipment
  • space equipment such as biosensors, biosensors, military reconnaissance cameras, stereo map cameras, weather and ocean observation cameras, land resource exploration cameras and exploration cameras
  • the light-shielding film can also be used for applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes).
  • Micro LEDs and micro OLEDs include, for example, examples described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890.
  • the light shielding film can also be used for a quantum dot sensor.
  • Quantum dot sensors include, for example, examples described in US2012/37789 and WO2008/131313.
  • the refractive index of the film of the present invention for light having a wavelength of 633 nm is preferably 1.4 or less, more preferably 1.35 or less, and 1.3 or less. It is more preferably 1.27 or less.
  • the value of the said refractive index is a value in the measurement temperature of 25 degreeC.
  • the membrane of the present invention can be produced through the step of coating the composition of the present invention on 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 composition layer on a support using the composition of the present invention, patternwise exposing the composition layer, and developing the unexposed portion of the composition layer. and removing to form a pattern. If necessary, a step of baking the composition layer (pre-baking step) and a step of baking the developed pattern (post-baking step) may be provided.
  • the composition of the present invention is used to form the composition layer on the 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 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 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 composition layer is exposed in a pattern (exposure step).
  • the 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 exposure is performed by repeating light irradiation and rest in short-time (for example, millisecond level or less) cycles.
  • the irradiation amount is, for example, preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2 .
  • the oxygen concentration at the time of exposure can be selected as appropriate.
  • 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 composition layer is removed by development to form a pattern.
  • the development and removal of the unexposed portion of the composition layer can be performed using a developer.
  • the unexposed portion of the 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 composition layer after development while rotating the support on which the 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.
  • 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 steps of forming a composition layer on a support using the composition of the present invention, curing the entire composition layer to form a cured product layer, and forming a cured product layer. a step of forming a photoresist layer on the layer; a step of exposing the photoresist layer in a pattern and then developing it to form a resist pattern; and a step of dry etching.
  • 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.
  • FIG. 2 is a side cross-sectional view showing one embodiment of the structure of the present invention
  • FIG. 3 is a plan view of the support member in the same structure viewed from directly above.
  • the structure 100 of the present invention includes a support 11, partitions 12 provided on the support 11, and regions on the support 11 partitioned by the partitions 12. and a pixel 14 provided.
  • pixels include colored pixels, transparent pixels, pixels of a near-infrared transmission filter layer, and pixels of a near-infrared cut filter layer.
  • Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
  • the type of support 11 is not particularly limited.
  • Substrates silicon wafers, silicon carbide wafers, silicon nitride wafers, sapphire wafers, glass wafers, etc.
  • a substrate for a solid-state imaging device on which a photodiode is formed, or the like can also be used.
  • an underlying layer may be provided for improving the adhesion with the upper layer, preventing diffusion of substances, or flattening the surface.
  • partition walls 12 are formed on the support 11 .
  • the partition walls 12 are formed in a grid pattern in a plan view seen from directly above the support 11 .
  • the shape of the region partitioned by the partitions 12 on the support 11 (hereinafter also referred to as the shape of the opening of the partition) is a square, but the shape of the opening of the partition is It is not particularly limited, and may be, for example, rectangular, circular, elliptical, or polygonal.
  • the partition wall 12 can be formed using the composition of the present invention (preferably the composition of the second aspect). Specifically, it can be formed through a step of forming a composition layer using the composition of the present invention and a step of forming a pattern on the composition layer by photolithography or dry etching.
  • the width W1 of the partition walls 12 is preferably 20 to 500 nm.
  • the lower limit is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more.
  • the upper limit is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less.
  • the height H1 of the partition wall 12 is preferably 200 nm or more, more preferably 300 nm or more, and even more preferably 400 nm or more.
  • the upper limit is preferably the thickness of the pixel 14 x 200% or less, more preferably the thickness of the pixel 14 x 150% or less, and still more preferably substantially the same as the thickness of the pixel 14 .
  • the ratio of height to width (height/width) of the partition walls 12 is preferably 1-100, more preferably 5-50, even more preferably 5-30.
  • Pixels 14 are formed in regions (openings of the partition walls) on the support 11 and partitioned by the partition walls 12 .
  • the width L1 of the pixel 14 can be appropriately selected depending on the application. For example, it is preferably 500 to 2000 nm, more preferably 500 to 1500 nm, even more preferably 500 to 1000 nm.
  • the height (thickness) H2 of the pixel 14 can be appropriately selected depending on the application. For example, it is preferably 300 to 1000 nm, more preferably 300 to 800 nm, even more preferably 300 to 600 nm.
  • the height H2 of the pixels 14 is preferably 50 to 150%, more preferably 70 to 130%, and even more preferably 90 to 110% of the height H1 of the partition walls 12.
  • a protective layer is provided on the surface of the partition wall.
  • a protective layer By providing a protective layer on the surfaces of the partition walls 12, the adhesion between the partition walls 12 and the pixels 14 can be improved.
  • Various inorganic materials and organic materials can be used as the material of the protective layer. Examples of organic materials include acrylic resins, polystyrene resins, polyimide resins, organic SOG (Spin On Glass) resins, and the like. It can also be formed using a composition containing a compound having an ethylenically unsaturated bond-containing group.
  • the structure of the present invention can be preferably used for optical filters, optical sensors, image display devices, and the like.
  • 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 may have a light shielding film.
  • a color filter, a near-infrared transmission filter, a near-infrared cut filter, or the like may be formed in the openings of the light-shielding film formed on the support.
  • 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.
  • Each pixel included in the optical filter preferably has high flatness.
  • the pixel surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example.
  • the surface roughness of a pixel can be measured using, for example, AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco.
  • the contact angle of water on the pixel can be appropriately set to a preferable value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT-A type (manufactured by Kyowa Interface Science Co., Ltd.).
  • the volume resistance value of the pixel is high.
  • the volume resistance value of the pixel is preferably 10 9 ⁇ cm or more, more preferably 10 11 ⁇ cm or more.
  • the upper limit is not specified, it is preferably 10 14 ⁇ cm or less, for example.
  • the volume resistance value of the pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest).
  • the film thickness of the light shielding film is preferably 5 ⁇ m or less, more preferably 2.5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and even more preferably 1 ⁇ m or more.
  • a protective layer may be provided on the surface of the film of the present invention.
  • the protective layer By providing the protective layer, it is possible to impart various functions such as blocking oxygen, reducing reflection, making the film hydrophilic and hydrophobic, and blocking light of a specific wavelength (ultraviolet rays, near-infrared rays, etc.).
  • the thickness of the protective layer is preferably 0.01-10 ⁇ m, more preferably 0.1-5 ⁇ m.
  • Examples of the method of forming the protective layer include a method of applying a protective layer-forming composition, a chemical vapor deposition method, and a method of adhering a molded resin with an adhesive.
  • Components constituting the protective layer include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, and polyimides.
  • the protective layer preferably contains a polyol resin, SiO 2 and Si 2 N 4 .
  • the protective layer preferably contains a (meth)acrylic resin and a fluororesin.
  • the protective layer contains organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index modifiers, antioxidants, adhesion agents, additives such as surfactants. may contain.
  • organic/inorganic fine particles include polymeric fine particles (eg, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like.
  • a known absorber can be used as the absorber for light of a specific wavelength.
  • the content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the protective layer.
  • the protective layer the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.
  • optical sensor of the present invention comprises the membrane of the present invention as described above.
  • optical sensors include solid-state imaging devices.
  • the configuration of the solid-state imaging device is not particularly limited as long as it functions as a solid-state imaging device.
  • a plurality of photodiodes and transfer electrodes made of polysilicon or the like are provided on the substrate, forming the light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal-oxide semiconductor) image sensor, etc.). and a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. and a color filter on the device protective film.
  • CCD charge-coupled device
  • CMOS complementary metal-oxide semiconductor
  • the color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.
  • the partition wall preferably has a lower refractive index than each color pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478, JP-A-2014-179577, and International Publication No. 2018/043654.
  • an ultraviolet absorption layer may be provided in the structure of the solid-state imaging device to improve light resistance.
  • Imaging devices equipped with solid-state imaging devices can be used not only for digital cameras and electronic devices (mobile phones, etc.) having imaging functions, but also for vehicle-mounted cameras and monitoring cameras.
  • the image display device of the present invention includes 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).
  • 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)".
  • the present invention can be applied to liquid crystal display devices of various systems described in the above-mentioned "next generation liquid crystal display technology”.
  • dispersion liquid A mixed liquid obtained by mixing raw materials 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). Then, dispersion treatment was carried out using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reduction mechanism under conditions of a pressure of 2000 kg/cm 2 and a flow rate of 500 g/min. This dispersing treatment was repeated 10 times to obtain a dispersion. Numerical values indicating compounding amounts in the table below are parts by mass. In addition, the numerical value of the compounding quantity of a dispersing agent is a numerical value by solid content conversion.
  • PR122 C.I. I. Pigment Red 122 (red pigment) PR254: C.I. I. Pigment Red 254 (red pigment)
  • PG7 C.I. I. Pigment Green 7 (green pigment)
  • PG36 C.I. I. Pigment Green 36 (green pigment)
  • PB15:3 C.I. I. Pigment Blue 15:3 (blue pigment)
  • PB15:4 C.I. I. Pigment Blue 15:4 (blue pigment)
  • PB15:6 C.I. I. Pigment Blue 15:6 (blue pigment)
  • PB16 C.I. I. Pigment Blue 16 (blue pigment)
  • PY139 C.I. I.
  • Pigment Yellow 139 (yellow pigment) PY150: C.I. I. Pigment Yellow 150 (yellow pigment) PV23: C.I. I. Pigment Violet 23 (purple pigment)
  • TiON Titanium nitride (black pigment) TiO2-1: TTO-51 (manufactured by Ishihara Sangyo Co., Ltd., titanium oxide, white pigment)
  • TiO2-2 MPT-141 (manufactured by Ishihara Sangyo Co., Ltd., titanium oxide, white pigment)
  • Pigment A compound having the following structure (near-infrared absorbing pigment, iC 8 H 17 and iC 10 H 21 portions are isomer mixtures with different carbon numbers and branching positions)
  • D-1 Resin having the following structure (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.
  • D-2 Resin having the following structure
  • D-3 Resin having the following structure (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.
  • D-4 Resin shown below (weight average molecular weight 8000, acid value 37 mgKOH/g, ethylenically unsaturated bond-containing group value 0.22 mmol/g)
  • composition ⁇ Production of composition> The raw materials shown in the table below were mixed and filtered using Nippon Pall's DFA4201NIEY (0.45 ⁇ m nylon filter) to produce a composition. Numerical values indicating compounding amounts in the following table are parts by mass.
  • Dispersions 1 to 21 Dispersions 1 to 21 described above
  • Silica particle liquid 1 A propylene glycol monomethyl ether solution (silica particles This is a silica particle liquid prepared by adding 3.0 g of trimethylmethoxysilane as a hydrophobizing agent to 100.0 g of a solution having a concentration of 20% by mass and reacting the mixture at 20° C. for 6 hours.
  • the average particle diameter of the spherical silica was obtained by calculating the number average of the equivalent circle diameters in the projected images of the spherical portions of 50 spherical silica particles measured by a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • Dye 1 compound having the following structure (weight average molecular weight 9000)
  • M-1 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
  • M-2 Aronix TO-2349 (manufactured by Toagosei Co., Ltd.)
  • M-3 NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • B-1 Resin having the following structure (numerical values attached to the main chain are molar ratios; weight average molecular weight: 11,000)
  • B-2 Resin having the following structure (numerical values attached to the main chain are molar ratios. Weight average molecular weight: 19000. Solid content: 40%)
  • the kinematic viscosity was measured using an Ubbelohde viscometer. Further, the surface tension was measured using a solution having a solid concentration of 1000 mass ppm prepared by dissolving each surfactant in PGMEA as a measurement sample. The temperature of this measurement sample was adjusted to 25° C., and a surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) was used as a measuring device, and the plate method using a platinum plate was used for measurement.
  • a surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.
  • a composition for forming a base layer (CT-4000L, manufactured by FUJIFILM Electronic Materials Co., Ltd.) is applied so that the dry film thickness is 0.1 ⁇ m, After drying, heat treatment was performed at 220° C. for 5 minutes to form an underlayer.
  • each composition is applied using a spin coater so that the film thickness after prebaking is 0.6 ⁇ m, and heat-treated for 120 seconds using a hot plate at 100 ° C. (pre-baking) was performed.
  • an i-line stepper exposure apparatus (FPA-3000i5+, manufactured by Canon Inc.) was used to expose the entire surface of the glass wafer to light with a wavelength of 365 nm at an exposure dose of 500 mJ/cm 2 .
  • the glass wafer having the exposed film was subjected to heat treatment (post-baking) using a hot plate at 200° C. for 300 seconds to form a film.
  • the transmittance in the wavelength range of 400 to 1100 nm was measured using a spectrophotometer (U-4150, manufactured by Hitachi, Ltd.) for the glass wafer on which the film was formed.
  • the color mixture evaluation composition was applied using a spin coater so that the film thickness after prebaking was 0.6 ⁇ m, and heat treatment (prebaking) was performed using a hot plate at 100° C. for 120 seconds.
  • the composition of Comparative Example 3-1 was used as the composition for color mixture evaluation.
  • the composition of Comparative Example 1-1 was used as a composition for color mixing evaluation.
  • the glass wafer was placed on a horizontal rotating table of a spin/shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and an alkaline developer (CD-2060, manufactured by Fuji Film Electronic Materials Co., Ltd.) was used. ) at 23° C. for 60 seconds.
  • a spin/shower developing machine DW-30 type, manufactured by Chemitronics Co., Ltd.
  • an alkaline developer CD-2060, manufactured by Fuji Film Electronic Materials Co., Ltd.
  • the transmittance of the film before and after the color mixing test The maximum value of the difference was evaluated, and color mixture was evaluated according to the following criteria.
  • Transmittance difference
  • the example was able to suppress the occurrence of color mixture more than the comparative example.

Abstract

This composition contains a curable compound, a silicone-based surfactant A, and a solvent. Regarding the silicone-based surfactant A, when the silicone-based surfactant A is dissolved in propylene glycol monomethyl ether acetate to prepare a solution having a solid content concentration of 1000 mass ppm, the surface tension of the solution at 25°C is 26 mN/m or more. The film, the optical filter, the optical sensor, the image display apparatus, and the structural body according to the present invention use said composition.

Description

組成物、膜、光学フィルタ、光学センサ、画像表示装置および構造体Compositions, films, optical filters, optical sensors, image display devices and structures
　本発明は、シリコーン系界面活性剤を含む組成物に関する。また、本発明は、膜、光学フィルタ、光学センサ、画像表示装置および構造体に関する。 The present invention relates to a composition containing a silicone-based surfactant. The present invention also relates to films, optical filters, optical sensors, image display devices and structures.
　カラーフィルタなどの光学フィルタを備えた光学センサの、光学フィルタなどの製造に用いられる組成物には、界面活性剤を含む組成物が用いられている。 A composition containing a surfactant is used in the composition used to manufacture optical filters such as color filters for optical sensors.
　特許文献１には、（Ａ）着色剤、（Ｂ）分散剤、（Ｃ）溶剤、（Ｄ）バインダー樹脂、及び（Ｅ）光重合開始剤を含有する着色樹脂組成物であって、（Ｂ）分散剤が、所定の繰り返し単位を有する分散剤（ｂ）を含有し、更に、着色樹脂組成物が、（Ｆ）界面活性剤を全固形分中に０．０１質量％以上含有する着色樹脂組成物に関する発明が開示されている。 Patent Document 1 discloses a colored resin composition containing (A) a colorant, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator, wherein (B ) The dispersant contains a dispersant (b) having a predetermined repeating unit, and the colored resin composition contains (F) a surfactant in the total solid content of 0.01% by mass or more. Inventions relating to compositions are disclosed.
特開２０１８－１３２５５４号公報JP 2018-132554 A
　光学センサや画像表示装置などに用いられている光学フィルタは、一般的に複数の種類の画素を有している。このような光学フィルタは、１種類目の画素形成用組成物を用いて１種類目の画素を形成したのち、２種類目以降の画素形成用組成物を用いて２種類目以降の画素を順次形成して製造される。 Optical filters used in optical sensors and image display devices generally have multiple types of pixels. In such an optical filter, after forming the first type of pixels using the first type of pixel-forming composition, the second and subsequent types of pixels are sequentially formed using the second and subsequent types of pixel-forming compositions. Manufactured by forming.
　また、近年では、光学フィルタにおける各色の画素を隔壁で区画された空間に設ける試みも検討されている。このような光学フィルタは、例えば、支持体上に各画素を区画する隔壁を形成したのち、隔壁間に各種類の画素を順次形成して製造される。 In recent years, attempts have also been made to provide pixels of each color in an optical filter in a space partitioned by partition walls. Such an optical filter is manufactured, for example, by forming partition walls for partitioning each pixel on a support, and then sequentially forming each type of pixel between the partition walls.
　光学フィルタなどの製造プロセスにおいては、混色の発生を抑制することが求められている。このため、混色が生じにくい膜を形成可能な組成物が求められており、近年においては、上記性能のさらなる向上が求められている。 In the manufacturing process of optical filters, etc., it is required to suppress the occurrence of color mixture. Therefore, there is a demand for a composition capable of forming a film in which color mixing is less likely to occur, and in recent years, there has been a demand for further improvement in the above performance.
　よって、本発明の目的は、混色の抑制された膜を形成可能な組成物を提供することにある。また、本発明の目的は、膜、光学フィルタ、光学センサ、画像表示装置および構造体を提供することにある。 Accordingly, an object of the present invention is to provide a composition capable of forming a film in which color mixing is suppressed. Another object of the present invention is to provide a film, an optical filter, an optical sensor, an image display device and a structure.
　本発明は以下を提供する。
　＜１＞　硬化性化合物と、
　シリコーン系界面活性剤Ａと、
　溶剤と、を含み、
　上記シリコーン系界面活性剤Ａは、上記シリコーン系界面活性剤Ａをプロピレングリコールモノメチルエーテルアセテートに溶解させて固形分濃度１０００質量ｐｐｍの溶液を調製した際に、上記溶液の２５℃における表面張力が２６ｍＮ／ｍ以上である、
　組成物。
　＜２＞　上記硬化性化合物は、樹脂と、重合性モノマーを含み、
　上記組成物は、更に光重合開始剤を含む、＜１＞に記載の組成物。
　＜３＞　更に、色材を含む、＜１＞または＜２＞に記載の組成物。
　＜４＞　無機粒子と、
　シリコーン系界面活性剤Ａと、
　溶剤と、を含み、
　上記シリコーン系界面活性剤Ａは、上記シリコーン系界面活性剤Ａをプロピレングリコールモノメチルエーテルアセテートに溶解させて固形分濃度１０００質量ｐｐｍの溶液を調製した際に、上記溶液の２５℃における表面張力が２６ｍＮ／ｍ以上である、
　組成物。
　＜５＞　上記無機粒子は、シリカ粒子を含む、＜４＞に記載の組成物。
　＜６＞　上記シリカ粒子は、複数個の球状シリカが数珠状に連結した形状のシリカ粒子、複数個の球状シリカが平面的に連結した形状のシリカ粒子、および、中空構造のシリカ粒子から選ばれる少なくとも１種を含む、＜５＞に記載の組成物。
　＜７＞　上記組成物の全固形分中における上記無機粒子の含有量が２０質量％以上である、＜４＞～＜６＞のいずれか１つに記載の組成物。
　＜８＞　上記シリコーン系界面活性剤Ａの水酸基価が８０ｍｇＫＯＨ／ｇ以上である、＜１＞～＜７＞のいずれか１つに記載の組成物。
　＜９＞　上記シリコーン系界面活性剤Ａの２５℃における動粘度が４０ｍｍ２／ｓ以下である、＜１＞～＜８＞のいずれか１つに記載の組成物。
　＜１０＞　上記シリコーン系界面活性剤Ａは、カルビノール変性ジアルキルポリシロキサンである、＜１＞～＜９＞のいずれか１つに記載の組成物。
　＜１１＞　上記シリコーン系界面活性剤Ａは、アルキレンオキシ基とヒドロキシ基を有するジメチルポリシロキサンである、＜１＞～＜１０＞のいずれか１つに記載の組成物。
　＜１２＞　上記組成物中における上記シリコーン系界面活性剤Ａの含有量が１～１０００質量ｐｐｍである、＜１＞～＜１１＞のいずれか１つに記載の組成物。
　＜１３＞　＜１＞～＜１２＞のいずれか１つに記載の組成物を用いて得られる膜。
　＜１４＞　＜１３＞に記載の膜を有する光学フィルタ。
　＜１５＞　＜１３＞に記載の膜を有する光学センサ。
　＜１６＞　＜１３＞に記載の膜を有する画像表示装置。
　＜１７＞　支持体と、
　上記支持体上に設けられた＜４＞に記載の組成物を用いて得られる隔壁と、
　上記隔壁で区画された領域に設けられた画素と、
　を有する構造体。 The present invention provides the following.
<1> a curable compound,
a silicone-based surfactant A;
including a solvent and
The silicone surfactant A has a surface tension of 26 mN at 25° C. when a solution having a solid concentration of 1000 ppm by mass is prepared by dissolving the silicone surfactant A in propylene glycol monomethyl ether acetate. / m or more,
Composition.
<2> The curable compound contains a resin and a polymerizable monomer,
The composition according to <1>, further comprising a photopolymerization initiator.
<3> The composition according to <1> or <2>, further comprising a colorant.
<4> inorganic particles,
a silicone-based surfactant A;
including a solvent and
The silicone surfactant A has a surface tension of 26 mN at 25° C. when a solution having a solid concentration of 1000 ppm by mass is prepared by dissolving the silicone surfactant A in propylene glycol monomethyl ether acetate. / m or more,
Composition.
<5> The composition according to <4>, wherein the inorganic particles include silica particles.
<6> The silica particles are selected from silica particles having a shape in which a plurality of spherical silicas are connected in a beaded shape, silica particles having a shape in which a plurality of spherical silicas are connected in a plane, and silica particles having a hollow structure. The composition according to <5>, comprising at least one.
<7> The composition according to any one of <4> to <6>, wherein the content of the inorganic particles in the total solid content of the composition is 20% by mass or more.
<8> The composition according to any one of <1> to <7>, wherein the silicone surfactant A has a hydroxyl value of 80 mgKOH/g or more.
<9> The composition according to any one of <1> to <8>, wherein the silicone surfactant A has a kinematic viscosity at 25° C. of 40 mm 2 /s or less.
<10> The composition according to any one of <1> to <9>, wherein the silicone surfactant A is a carbinol-modified dialkylpolysiloxane.
<11> The composition according to any one of <1> to <10>, wherein the silicone surfactant A is a dimethylpolysiloxane having an alkyleneoxy group and a hydroxy group.
<12> The composition according to any one of <1> to <11>, wherein the content of the silicone surfactant A in the composition is 1 to 1000 mass ppm.
<13> A film obtained using the composition according to any one of <1> to <12>.
<14> An optical filter comprising the film according to <13>.
<15> An optical sensor comprising the film according to <13>.
<16> An image display device comprising the film according to <13>.
<17> a support;
Partition walls obtained using the composition according to <4> provided on the support;
pixels provided in regions partitioned by the partition walls;
A struct with
　本発明によれば、混色の抑制された膜を形成可能な組成物、膜、光学フィルタ、光学センサ、画像表示装置および構造体を提供することができる。 According to the present invention, it is possible to provide a composition, a film, an optical filter, an optical sensor, an image display device, and a structure capable of forming a film with suppressed color mixing.
複数個の球状シリカが数珠状に連結した形状のシリカ粒子を模式的に示す拡大図である。FIG. 2 is an enlarged view schematically showing silica particles having a shape in which a plurality of spherical silica particles are connected in a beaded shape. 本発明の構造体の一実施形態を示す側断面図である。1 is a side sectional view showing one embodiment of a structure of the present invention; FIG. 同構造体における支持体の真上方向からみた平面図である。It is the top view seen from just above the support body in the same structure.
　以下において、本発明の内容について詳細に説明する。
　本明細書において、「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において、「（メタ）アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「（メタ）アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「（メタ）アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
　本明細書において、近赤外線とは、波長７００～２５００ｎｍの光をいう。
　本明細書において、構造式中のＭｅはメチル基を表し、Ｅｔはエチル基を表し、Ｂｕはブチル基を表し、Ｐｈはフェニル基を表す。
　本明細書において、重量平均分子量および数平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）法により測定したポリスチレン換算値である。
　本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。
　本明細書において、顔料とは、溶剤に対して溶解しにくい色材を意味する。
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。 The contents of the present invention will be described in detail below.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.
In the description of a group (atomic group) in the present specification, 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. For example, 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).
As used herein, the term "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.
In the present specification, "(meth)acrylate" represents both or either acrylate and methacrylate, "(meth)acryl" represents both or either acrylic and methacrylic, and "(meth) ) acryloyl” refers to acryloyl and/or methacryloyl.
As used herein, near-infrared light refers to light with a wavelength of 700 to 2500 nm.
In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent.
As used herein, the term "pigment" means a coloring material that is difficult to dissolve in a solvent.
As used herein, 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. .
＜組成物＞
　本発明の第１の態様の組成物は、
　硬化性化合物と、
　シリコーン系界面活性剤Ａと、
　溶剤と、を含み、
　上記シリコーン系界面活性剤Ａは、シリコーン系界面活性剤Ａをプロピレングリコールモノメチルエーテルアセテートに溶解させて固形分濃度１０００質量ｐｐｍの溶液を調製した際に、上記溶液の２５℃における表面張力が２６ｍＮ／ｍ以上であることを特徴とする。 <Composition>
The composition of the first aspect of the invention comprises
a curable compound;
a silicone-based surfactant A;
including a solvent and
The silicone surfactant A has a surface tension of 26 mN/ m or more.
　また、本発明の第２の態様の組成物は、
　無機粒子と、
　シリコーン系界面活性剤Ａと、
　溶剤と、を含み、
　上記シリコーン系界面活性剤Ａは、シリコーン系界面活性剤Ａをプロピレングリコールモノメチルエーテルアセテートに溶解させて固形分濃度１０００質量ｐｐｍの溶液を調製した際に、上記溶液の２５℃における表面張力が２６ｍＮ／ｍ以上であることを特徴とする。 Also, the composition of the second aspect of the present invention is
inorganic particles;
a silicone-based surfactant A;
including a solvent and
The silicone surfactant A has a surface tension of 26 mN/ m or more.
　本発明の組成物によれば、混色の抑制された膜を形成することができる。このような効果が得られる理由は以下によるものであると推測される。本発明の組成物は、上記シリコーン系界面活性剤Ａを含むことにより、得られる膜表面の水との親和性を高めることができると推測される。このため、例えば、本発明の組成物を用いてパターンなどの膜を形成した後、この膜と隣接する位置に、他の画素形成用組成物などを用いて他の画素などを形成する場合において、現像液やリンス液によって膜表面から他の画素形成用組成物の付着物が除去されやすく、その結果、膜表面に他の画素形成用組成物の残渣などが生じにくくできると推測される。このため、本発明の組成物は、混色の抑制された膜を形成することができたと推測される。 According to the composition of the present invention, a film with suppressed color mixing can be formed. The reason why such an effect is obtained is presumed to be as follows. It is presumed that the composition of the present invention can enhance the affinity of the surface of the obtained film for water by containing the silicone-based surfactant A. For this reason, for example, after forming a film such as a pattern using the composition of the present invention, in a position adjacent to this film, using another pixel-forming composition or the like, another pixel or the like is formed. It is presumed that deposits of other pixel-forming compositions are easily removed from the film surface by the developer or rinse solution, and as a result, residues of other pixel-forming compositions are less likely to be left on the film surface. For this reason, it is presumed that the composition of the present invention was able to form a film in which color mixing was suppressed.
　本発明の組成物は、光学センサ用または画像表示装置用の組成物であることが好ましく、光学センサ用の組成物であることがより好ましい。より具体的には、本発明の組成物は、光学センサや画像表示装置などに用いられる光学フィルタや隔壁等の形成用の組成物として好ましく用いることができる。
　例えば、第１の態様の組成物は、光学フィルタ形成用の組成物として好ましく用いられる。
　また、第２の態様の組成物は、隔壁形成用の組成物として好ましく用いられる。特に、無機粒子としてシリカ粒子を用いた場合においては、屈折率の小さい膜を形成することができるので、隔壁形成用の組成物として好ましく用いられる。 The composition of the present invention is preferably a composition for optical sensors or image display devices, and more preferably a composition for optical sensors. More specifically, the composition of the present invention can be preferably used as a composition for forming optical filters, partition walls, and the like used in optical sensors, image display devices, and the like.
For example, the composition of the first aspect is preferably used as a composition for forming optical filters.
Moreover, the composition of the second aspect is preferably used as a composition for forming partition walls. In particular, when silica particles are used as the inorganic particles, a film having a small refractive index can be formed, so that it is preferably used as a composition for forming partition walls.
　光学フィルタとしては、カラーフィルタ、近赤外線透過フィルタ、近赤外線カットフィルタなどが挙げられ、カラーフィルタであることが好ましい。 Examples of optical filters include color filters, near-infrared transmission filters, and near-infrared cut filters, with color filters being preferred.
　カラーフィルタとしては、特定の波長の光を透過させる着色画素を有するフィルタが挙げられ、赤色画素、青色画素、緑色画素、黄色画素、シアン色画素及びマゼンタ色画素から選ばれる少なくとも１種の着色画素を有するフィルタであることが好ましい。カラーフィルタは、有彩色色材を含む組成物を用いて形成することができる。 Examples of color filters include filters having colored pixels that transmit light of a specific wavelength, and at least one colored pixel selected from red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, and magenta pixels. Preferably, the filter has A color filter can be formed using a composition containing a chromatic colorant.
　近赤外線カットフィルタとしては、極大吸収波長が波長７００～１８００ｎｍの範囲に存在するフィルタが挙げられる。近赤外線カットフィルタの極大吸収波長は、波長７００～１３００ｎｍの範囲に存在することが好ましく、波長７００～１１００ｎｍの範囲に存在することがより好ましい。また、近赤外線カットフィルタの波長４００～６５０ｎｍの全範囲での透過率は７０％以上であることが好ましく、８０％以上であることがより好ましく、９０％以上であることが更に好ましい。また、波長７００～１８００ｎｍの範囲の少なくとも１点での透過率は２０％以下であることが好ましい。また、近赤外線カットフィルタの極大吸収波長における吸光度Ａｍａｘと、波長５５０ｎｍにおける吸光度Ａ５５０との比である吸光度Ａｍａｘ／吸光度Ａ５５０は、２０～５００であることが好ましく、５０～５００であることがより好ましく、７０～４５０であることが更に好ましく、１００～４００であることが特に好ましい。近赤外線カットフィルタは、近赤外線吸収色材を含む組成物を用いて形成することができる。 Examples of near-infrared cut filters include filters having a maximum absorption wavelength in the wavelength range of 700 to 1800 nm. The maximum absorption wavelength of the near-infrared cut filter preferably exists in the wavelength range of 700 to 1300 nm, more preferably in the wavelength range of 700 to 1100 nm. The transmittance of the near-infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Also, the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less. In addition, absorbance Amax/absorbance A550, which is the ratio of absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter and 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 composition containing a near-infrared absorbing colorant.
　近赤外線透過フィルタは、近赤外線の少なくとも一部を透過させるフィルタである。近赤外線透過フィルタは、可視光の少なくとも一部を遮光し、近赤外線の少なくとも一部を透過させるフィルタであることが好ましい。近赤外線透過フィルタとしては、波長４００～６４０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１１００～１３００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である分光特性を満たしているフィルタなどが好ましく挙げられる。近赤外線透過フィルタは、以下の（１）～（５）のいずれかの分光特性を満たしているフィルタであることが好ましい。
　（１）：波長４００～６４０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長８００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。
　（２）：波長４００～７５０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長９００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。
　（３）：波長４００～８３０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１０００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。
　（４）：波長４００～９５０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１１００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。
　（５）：波長４００～１０５０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１２００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。 A near-infrared transmission filter is a filter that transmits at least part of near-infrared rays. The near-infrared transmission filter is preferably a filter that blocks at least part of visible light and transmits at least part of near-infrared light. The near-infrared transmission filter has a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm, and has a transmittance in the wavelength range of 1100 to 1300 nm. Filters satisfying spectral characteristics with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) are preferred. The near-infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (5).
(1): 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).
(2): 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).
(3): 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).
(4): 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).
(5): 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).
　隔壁としては、例えば、固体撮像素子の撮像エリア上に画素を形成する際に、隣接する画素同士を区画するために用いられる隔壁などが挙げられる。画素としては、着色画素、透明画素、近赤外線透過フィルタ層の画素および近赤外線カットフィルタ層の画素などが挙げられる。一例として、画素同士を区画するグリッド構造を形成するための隔壁が挙げられる。その例としては、特開２０１２－２２７４７８号公報、特開２０１０－２３２５３７号公報、特開２００９－１１１２２５号公報、特開２０１７－０２８２４１号公報の図１、特開２０１６－２０１５２４号公報の図４Ｄなどに記載された構造が挙げられる。また、カラーフィルタ、近赤外線透過フィルタ、近赤外線カットフィルタなどの光学フィルタの周辺の額縁構造を形成するための隔壁などが挙げられる。その例としては、特開２０１４－０４８５９６号公報に記載された構造を挙げることができ、この内容は本明細書に組み込まれる。 Examples of partition walls include partition walls used for partitioning adjacent pixels when pixels are formed on an imaging area of a solid-state imaging device. Examples of pixels include colored pixels, transparent pixels, pixels of a near-infrared transmission filter layer, and pixels of a near-infrared cut filter layer. One example is partition walls for forming a grid structure that partitions pixels. Examples thereof include JP 2012-227478, JP 2010-232537, JP 2009-111225, FIG. 1 of JP 2017-028241, FIG. 4D of JP 2016-201524 and the like. Other examples include partition walls for forming a frame structure around optical filters such as color filters, near-infrared transmission filters, and near-infrared cut filters. An example thereof is the structure described in JP-A-2014-048596, the content of which is incorporated herein.
　本発明の組成物は、遮光膜形成用の組成物として用いることもできる。本発明の組成物を、遮光膜形成用の組成物として用いる場合には、本発明の組成物は、色材として黒色色材を含むことが好ましく、黒色顔料を含むことがより好ましい。 The composition of the present invention can also be used as a composition for forming a light shielding film. When the composition of the present invention is used as a composition for forming a light-shielding film, the composition of the present invention preferably contains a black colorant as a colorant, and more preferably contains a black pigment.
　本発明の組成物を遮光膜形成用の組成物として用いる場合、本発明の組成物を用いて形成される膜は、４００～１１００ｎｍの波長領域における膜厚１．５μｍあたりの光学濃度（ＯＤ：Ｏｐｔｉｃａｌ　Ｄｅｎｓｉｔｙ）が、２．５以上であることが好ましく、３．０以上であることがより好ましい。なお、上限値は特に制限されないが、一般に１０以下が好ましい。なお、本明細書において、４００～１１００ｎｍの波長領域における膜厚１．５μｍあたりの光学濃度が２．５以上であるとは、波長４００～１１００ｎｍの全域において、膜厚１．５μｍあたりの光学濃度が２．５以上であることを意味する。 When the composition of the present invention is used as a composition for forming a light-shielding film, the film formed using the composition of the present invention has an optical density (OD: Optical Density) is preferably 2.5 or more, more preferably 3.0 or more. Although the upper limit is not particularly limited, generally 10 or less is preferable. In this specification, the optical density per 1.5 μm film thickness in the wavelength region of 400 to 1100 nm is 2.5 or more, which means that the optical density per 1.5 μm film thickness is 2.5 or more in the entire wavelength range of 400 to 1100 nm. is 2.5 or more.
　また、上記膜の反射率は、８％未満が好ましく、６％未満がより好ましく、４％未満が更に好ましい。下限は、０％以上が好ましい。反射率とは、日本分光株式会社製分光器Ｖ７２００（商品名）ＶＡＲユニットを用いて角度５°の入射角で波長４００～１１００ｎｍの光を入射し、得られた反射率スペクトルより求められる。具体的には、波長４００～１１００ｎｍの範囲で最大反射率を示した波長の光の反射率を、膜の反射率とする。 Also, the reflectance of the film is preferably less than 8%, more preferably less than 6%, and even more preferably less than 4%. The lower limit is preferably 0% or more. The reflectance is determined from the reflectance spectrum obtained by using a spectroscope V7200 (trade name) VAR unit manufactured by JASCO Corporation to irradiate light with a wavelength of 400 to 1100 nm at an incident angle of 5°. Specifically, the reflectance of the light having the maximum reflectance in the wavelength range of 400 to 1100 nm is taken as the reflectance of the film.
　本発明の組成物は、フォトリソグラフィ法でのパターン形成用の組成物であることも好ましい。この態様によれば、微細なサイズの画素を容易に形成することができる。例えば、エチレン性不飽和結合含有基を有する成分（例えば、エチレン性不飽和結合含有基を有する樹脂やエチレン性不飽和結合含有基を有するモノマー）と、光重合開始剤とを含有する組成物は、フォトリソグラフィ法でのパターン形成用の組成物として好ましく用いることができる。フォトリソグラフィ法でのパターン形成用の組成物は、更にアルカリ可溶性樹脂を含むことも好ましい。 The composition of the present invention is also preferably a composition for pattern formation by photolithography. According to this aspect, fine-sized pixels can be easily formed. For example, a composition containing a component having an ethylenically unsaturated bond-containing group (e.g., a resin having an ethylenically unsaturated bond-containing group or a monomer having an ethylenically unsaturated bond-containing group) and a photopolymerization initiator is , can be preferably used as a composition for pattern formation in photolithography. It is also preferable that the composition for pattern formation by photolithography further contains an alkali-soluble resin.
　組成物の固形分濃度は、５～３０質量％であることが好ましい。下限は、７．５質量％以上が好ましく、１０質量％以上がより好ましい。上限は、２５質量％以下が好ましく、２０質量％以下がより好ましい。 The solid content concentration of the composition is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less.
　以下、本発明の組成物に用いられる各成分について説明する。
［第１の態様の組成物］
＜＜硬化性化合物＞＞
　第１の態様の組成物は硬化性化合物を含有する。硬化性化合物としては、重合性化合物、樹脂等が挙げられる。樹脂は、非重合性の樹脂（重合性基を有さない樹脂）であってもよく、重合性の樹脂（重合性基を有する樹脂）であってもよい。重合性基としては、エチレン性不飽和結合含有基および環状エーテル基などが挙げられる。エチレン性不飽和結合含有基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基などが挙げられる。環状エーテル基としては、エポキシ基、オキセタニル基などが挙げられ、エポキシ基が好ましい。エポキシ基は、脂環式エポキシ基であってもよい。なお、脂環式エポキシ基とは、エポキシ環と飽和炭化水素環とが縮合した環状構造を有する１価の官能基のことを意味する。 Each component used in the composition of the present invention is described below.
[Composition of the first aspect]
<<Curable compound>>
The composition of the first aspect contains a curable compound. Examples of the curable compound include polymerizable compounds and resins. The resin may be a non-polymerizable resin (a resin having no polymerizable group) or a polymerizable resin (a resin having a polymerizable group). Polymerizable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred. The epoxy group may be a cycloaliphatic epoxy group. The alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
　硬化性化合物としては、樹脂を少なくとも含むものを用いることが好ましい。また、本発明の組成物をフォトリソグラフィ用の組成物とする場合には、硬化性化合物として、樹脂（好ましくは酸基を有する樹脂）と、重合性モノマー（モノマータイプの重合性化合物）とを用いることが好ましく、樹脂（好ましくは酸基を有する樹脂）と、エチレン性不飽和結合含有基を有する重合性モノマー（モノマータイプの重合性化合物）とを用いることがより好ましい。 As the curable compound, it is preferable to use one containing at least a resin. Further, when the composition of the present invention is used as a composition for photolithography, a resin (preferably a resin having an acid group) and a polymerizable monomer (monomer-type polymerizable compound) are used as the curable compound. It is preferable to use a resin (preferably a resin having an acid group) and a polymerizable monomer (monomer-type polymerizable compound) having an ethylenically unsaturated bond-containing group is more preferably used.
（重合性化合物）
　重合性化合物としては、エチレン性不飽和結合含有基を有する化合物および環状エーテル基を有する化合物等が挙げられる。エチレン性不飽和結合含有基を有する化合物はラジカル重合性化合物として好ましく用いることができる。また、環状エーテル基を有する化合物は、カチオン重合性化合物として好ましく用いることができる。 (Polymerizable compound)
Examples of the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group and compounds having a cyclic ether group. A compound having an ethylenically unsaturated bond-containing group can be preferably used as a radically polymerizable compound. A compound having a cyclic ether group can also be preferably used as a cationically polymerizable compound.
　樹脂タイプの重合性化合物としては、重合性基を有する繰り返し単位を含む樹脂などが挙げられる。 Examples of resin-type polymerizable compounds include resins containing repeating units having polymerizable groups.
　モノマータイプの重合性化合物（重合性モノマー）の分子量は、２０００未満であることが好ましく、１５００以下であることがより好ましい。重合性モノマーの分子量の下限は１００以上であることが好ましく、２００以上であることがより好ましい。樹脂タイプの重合性化合物の重量平均分子量（Ｍｗ）は、２０００～２００００００であることが好ましい。重量平均分子量の上限は、１００００００以下であることが好ましく、５０００００以下であることがより好ましい。重量平均分子量の下限は、３０００以上であることが好ましく、５０００以上であることがより好ましい。 The molecular weight of the monomer type polymerizable compound (polymerizable monomer) is preferably less than 2000, more preferably 1500 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 or more. The weight average molecular weight (Mw) of the resin-type polymerizable compound is preferably 2,000 to 2,000,000. The upper limit of the weight average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit of the weight average molecular weight is preferably 3000 or more, more preferably 5000 or more.
　重合性モノマーとしてのエチレン性不飽和結合含有基を有する化合物は、３～１５官能の（メタ）アクリレート化合物であることが好ましく、３～６官能の（メタ）アクリレート化合物であることがより好ましい。具体例としては、特開２００９－２８８７０５号公報の段落番号００９５～０１０８、特開２０１３－０２９７６０号公報の段落０２２７、特開２００８－２９２９７０号公報の段落番号０２５４～０２５７、特開２０１３－２５３２２４号公報の段落番号００３４～００３８、特開２０１２－２０８４９４号公報の段落番号０４７７、特開２０１７－０４８３６７号公報、特許第６０５７８９１号公報、特許第６０３１８０７号公報、特開２０１７－１９４６６２号公報に記載されている化合物が挙げられ、これらの内容は本明細書に組み込まれる。 The compound having an ethylenically unsaturated bond-containing group as a polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound. Specific 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-2013-253224. Paragraph numbers 0034 to 0038 of the publication, paragraph number 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, JP 6031807, JP 2017-194662 and the contents of which are incorporated herein.
　エチレン性不飽和結合含有基を有する化合物としては、ジペンタエリスリトールトリ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、ＮＫエステルＡ－ＤＰＨ－１２Ｅ；新中村化学工業（株）製）、およびこれらの化合物の（メタ）アクリロイル基がエチレングリコールおよび／またはプロピレングリコール残基を介して結合している構造の化合物（例えば、サートマー社から市販されている、ＳＲ４５４、ＳＲ４９９）などが挙げられる。また、エチレン性不飽和結合含有基を有する化合物としては、ジグリセリンＥＯ（エチレンオキシド）変性（メタ）アクリレート（市販品としてはＭ－４６０；東亞合成製）、ペンタエリスリトールテトラアクリレート（新中村化学工業（株）製、ＮＫエステルＡ－ＴＭＭＴ）、１，６－ヘキサンジオールジアクリレート（日本化薬（株）製、ＫＡＹＡＲＡＤ　ＨＤＤＡ）、ＲＰ－１０４０（日本化薬（株）製）、アロニックスＴＯ－２３４９（東亞合成（株）製）、ＮＫオリゴＵＡ－７２００（新中村化学工業（株）製）、８ＵＨ－１００６、８ＵＨ－１０１２（大成ファインケミカル（株）製）、ライトアクリレートＰＯＢ－Ａ０（共栄社化学（株）製）などを用いることもできる。 Examples of compounds having an ethylenically unsaturated bond-containing group include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetra(meth)acrylate (commercially available). KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate ) Acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and the (meth)acryloyl groups of these compounds are ethylene glycol and / Or a compound having a structure linked via a propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer). Examples of compounds having an ethylenically unsaturated bond-containing group include diglycerin EO (ethylene oxide)-modified (meth)acrylate (commercially available as M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (Shin-Nakamura Chemical Industry ( 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 Nippon Kayaku Co., Ltd.) Toagosei Co., Ltd.), NK Oligo UA-7200 (Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (Taisei Fine Chemical Co., Ltd.), Light acrylate POB-A0 (Kyoeisha Chemical Co., Ltd. ) made) etc. can also be used.
　また、エチレン性不飽和結合含有基を有する化合物としては、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキシド変性トリ（メタ）アクリレート、トリメチロールプロパンエチレンオキシド変性トリ（メタ）アクリレート、イソシアヌル酸エチレンオキシド変性トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートなどの３官能の（メタ）アクリレート化合物を用いることも好ましい。３官能の（メタ）アクリレート化合物の市販品としては、アロニックスＭ－３０９、Ｍ－３１０、Ｍ－３２１、Ｍ－３５０、Ｍ－３６０、Ｍ－３１３、Ｍ－３１５、Ｍ－３０６、Ｍ－３０５、Ｍ－３０３、Ｍ－４５２、Ｍ－４５０（東亞合成（株）製）、ＮＫエステル　Ａ９３００、Ａ－ＧＬＹ－９Ｅ、Ａ－ＧＬＹ－２０Ｅ、Ａ－ＴＭＭ－３、Ａ－ＴＭＭ－３Ｌ、Ａ－ＴＭＭ－３ＬＭ－Ｎ、Ａ－ＴＭＰＴ、ＴＭＰＴ（新中村化学工業（株）製）、ＫＡＹＡＲＡＤ　ＧＰＯ－３０３、ＴＭＰＴＡ、ＴＨＥ－３３０、ＴＰＡ－３３０、ＰＥＴ－３０（日本化薬（株）製）などが挙げられる。 Examples of compounds having an ethylenically unsaturated bond-containing group include trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, and ethylene oxide isocyanurate. It is also preferable to use trifunctional (meth)acrylate compounds such as modified tri(meth)acrylate and pentaerythritol tri(meth)acrylate. Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) etc.
　エチレン性不飽和結合含有基を有する化合物は、更に、カルボキシ基、スルホ基、リン酸基等の酸基を有していてもよい。このような化合物の市販品としては、アロニックスＭ－３０５、Ｍ－５１０、Ｍ－５２０、アロニックスＴＯ－２３４９（東亞合成（株）製）等が挙げられる。 A compound having an ethylenically unsaturated bond-containing group may further have an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group. Commercially available products of such compounds include Aronix M-305, M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
　エチレン性不飽和結合含有基を有する化合物としては、カプロラクトン構造を有する化合物を用いることもできる。カプロラクトン構造を有する化合物については、特開２０１３－２５３２２４号公報の段落００４２～００４５の記載を参酌することができ、この内容は本明細書に組み込まれる。カプロラクトン構造を有する化合物は、例えば、日本化薬（株）からシリーズとして市販されている、ＤＰＣＡ－２０、ＤＰＣＡ－３０、ＤＰＣＡ－６０、ＤＰＣＡ－１２０等が挙げられる。 A compound having a caprolactone structure can also be used as the compound having an ethylenically unsaturated bond-containing group. For compounds having a caprolactone structure, the descriptions in paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, the contents of which are incorporated herein. Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as a series from Nippon Kayaku Co., Ltd.
　エチレン性不飽和結合含有基を有する化合物としては、エチレン性不飽和結合含有基とアルキレンオキシ基を有する化合物を用いることもできる。このような化合物は、エチレン性不飽和結合含有基と、エチレンオキシ基および／またはプロピレンオキシ基とを有する化合物であることが好ましく、エチレン性不飽和結合含有基とエチレンオキシ基とを有する化合物であることがより好ましく、エチレンオキシ基を４～２０個有する３～６官能（メタ）アクリレート化合物であることがさらに好ましい。市販品としては、例えばサートマー社製のエチレンオキシ基を４個有する４官能（メタ）アクリレートであるＳＲ－４９４、日本化薬（株）製のイソブチレンオキシ基を３個有する３官能（メタ）アクリレートであるＫＡＹＡＲＡＤ　ＴＰＡ－３３０などが挙げられる。 A compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used as the compound having an ethylenically unsaturated bond-containing group. Such a compound is preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and/or a propyleneoxy group, and is a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group. More preferably, it is a tri- to hexa-functional (meth)acrylate compound having 4 to 20 ethyleneoxy groups. Commercially available products include, for example, SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer Co., Ltd., and a trifunctional (meth)acrylate having three isobutyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. KAYARAD TPA-330, etc.
　エチレン性不飽和結合含有基を有する化合物としては、フルオレン骨格を有する重合性化合物を用いることもできる。市販品としては、オグソールＥＡ－０２００、ＥＡ－０３００（大阪ガスケミカル（株）製、フルオレン骨格を有する（メタ）アクリレートモノマー）などが挙げられる。 A polymerizable compound having a fluorene skeleton can also be used as the compound having an ethylenically unsaturated bond-containing group. Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).
　エチレン性不飽和結合含有基を有する化合物としては、トルエンなどの環境規制物質を実質的に含まない化合物を用いることも好ましい。このような化合物の市販品としては、ＫＡＹＡＲＡＤ　ＤＰＨＡ　ＬＴ、ＫＡＹＡＲＡＤ　ＤＰＥＡ－１２　ＬＴ（日本化薬（株）製）などが挙げられる。 As the compound having an ethylenically unsaturated bond-containing group, it is also preferable to use a compound such as toluene that does not substantially contain environmentally regulated substances. Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
　エチレン性不飽和結合含有基を有する化合物としては、ＵＡ－７２００（新中村化学工業（株）製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００、ＬＩＮＣ－２０２ＵＡ（共栄社化学（株）製）、８ＵＨ－１００６、８ＵＨ－１０１２（以上、大成ファインケミカル（株）製）、ライトアクリレートＰＯＢ－Ａ０（共栄社化学（株）製）などを用いることも好ましい。 Examples of compounds having an ethylenically unsaturated bond-containing group include UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA- 306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 ( Kyoeisha Chemical Co., Ltd.) and the like are also preferably used.
　環状エーテル基を有する化合物としては、エポキシ基を有する化合物、オキセタニル基を有する化合物などが挙げられ、エポキシ基を有する化合物であることが好ましい。エポキシ基を有する化合物としては、１分子内にエポキシ基を１～１００個有する化合物が挙げられる。エポキシ基の数の上限は、例えば、１０個以下とすることもでき、５個以下とすることもできる。エポキシ基の数の下限は、２個以上が好ましい。 Compounds having a cyclic ether group include compounds having an epoxy group, compounds having an oxetanyl group, and the like, and compounds having an epoxy group are preferred. Compounds having an epoxy group include compounds having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably two or more.
　環状エーテル基を有する化合物は、低分子化合物（例えば分子量１０００未満）でもよいし、高分子化合物（ｍａｃｒｏｍｏｌｅｃｕｌｅ）（例えば、分子量１０００以上、ポリマーの場合は、重量平均分子量が１０００以上）でもよい。環状エーテル基の重量平均分子量は、２００～１０００００が好ましく、５００～５００００がより好ましい。重量平均分子量の上限は、１００００以下が好ましく、５０００以下がより好ましく、３０００以下が更に好ましい。 A compound having a cyclic ether group may be a low-molecular compound (for example, a molecular weight of less than 1000) or a macromolecule (for example, a molecular weight of 1000 or more, and 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.
　環状エーテル基を有する化合物としては、特開２０１３－０１１８６９号公報の段落番号００３４～００３６に記載された化合物、特開２０１４－０４３５５６号公報の段落番号０１４７～０１５６に記載された化合物、特開２０１４－０８９４０８号公報の段落番号００８５～００９２に記載された化合物、特開２０１７－１７９１７２号公報に記載された化合物を用いることもできる。 As the compound having a cyclic ether group, compounds described in paragraph numbers 0034 to 0036 of JP-A-2013-011869, compounds described in paragraph numbers 0147-0156 of JP-A-2014-043556, JP 2014 The compounds described in paragraphs 0085 to 0092 of JP-A-089408 and the compounds described in JP-A-2017-179172 can also be used.
　環状エーテル基を有する化合物の市販品としては、デナコール　ＥＸ－２１２Ｌ、ＥＸ－２１２、ＥＸ－２１４Ｌ、ＥＸ－２１４、ＥＸ－２１６Ｌ、ＥＸ－２１６、ＥＸ－３２１Ｌ、ＥＸ－３２１、ＥＸ－８５０Ｌ、ＥＸ－８５０（以上、ナガセケムテックス（株）製）、ＡＤＥＫＡ　ＲＥＳＩＮ　ＥＰ－４０００Ｓ、ＥＰ－４００３Ｓ、ＥＰ－４０１０Ｓ、ＥＰ－４０１１Ｓ（以上、（株）ＡＤＥＫＡ製）、ＮＣ－２０００、ＮＣ－３０００、ＮＣ－７３００、ＸＤ－１０００、ＥＰＰＮ－５０１、ＥＰＰＮ－５０２（以上、（株）ＡＤＥＫＡ製）、セロキサイド２０２１Ｐ、セロキサイド２０８１、セロキサイド２０８３、セロキサイド２０８５、ＥＨＰＥ３１５０、ＥＰＯＬＥＡＤ　ＰＢ　３６００、ＰＢ　４７００（以上、（株）ダイセル製）、サイクロマーＰ　ＡＣＡ　２００Ｍ、ＡＣＡ　２３０ＡＡ、ＡＣＡ　Ｚ２５０、ＡＣＡ　Ｚ２５１、ＡＣＡ　Ｚ３００、ＡＣＡ　Ｚ３２０（以上、（株）ダイセル製）、ｊＥＲ１０３１Ｓ、ｊＥＲ１５７Ｓ６５、ｊＥＲ１５２、ｊＥＲ１５４、ｊＥＲ１５７Ｓ７０（以上、三菱ケミカル（株）製）、アロンオキセタンＯＸＴ－１２１、ＯＸＴ－２２１、ＯＸ－ＳＱ、ＰＮＯＸ（以上、東亞合成（株）製）、アデカグリシロール　ＥＤ－５０５（（株）ＡＤＥＫＡ製、エポキシ基含有モノマー）、マープルーフＧ－０１５０Ｍ、Ｇ－０１０５ＳＡ、Ｇ－０１３０ＳＰ、Ｇ－０２５０ＳＰ、Ｇ－１００５Ｓ、Ｇ－１００５ＳＡ、Ｇ－１０１０Ｓ、Ｇ－２０５０Ｍ、Ｇ－０１１００、Ｇ－０１７５８（日油（株）製、エポキシ基含有ポリマー）、ＯＸＴ－１０１、ＯＸＴ－１２１、ＯＸＴ－２１２、ＯＸＴ－２２１（以上、東亞合成（株）製、オキセタニル基含有モノマー）、ＯＸＥ－１０、ＯＸＥ－３０（以上、大阪有機化学工業（株）製、オキセタニル基含有モノマー）などが挙げられる。 Commercially available compounds having a cyclic ether group include Denacol EX-212L, EX-212, EX-214L, EX-214, EX-216L, EX-216, EX-321L, EX-321, EX-850L, EX -850 (manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC -7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (manufactured by ADEKA Corporation) Daicel), Cychromer P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (manufactured by Daicel Co., Ltd.), jER1031S, jER157S65, jER152, jER154, jER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.) ), Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.), ADEKA GLYCIROL ED-505 (manufactured by ADEKA Co., Ltd., epoxy group-containing monomer), Proof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation, epoxy group containing polymer), OXT-101, OXT-121, OXT-212, OXT-221 (manufactured by Toagosei Co., Ltd., oxetanyl group-containing monomer), OXE-10, OXE-30 (above, Osaka Organic Chemical Industry ( Co., Ltd., oxetanyl group-containing monomer), and the like.
（樹脂）
　本発明の組成物は、硬化性化合物として樹脂を用いることができる。硬化性化合物は、樹脂を少なくとも含むものを用いることが好ましい。樹脂は、例えば、顔料等を組成物中で分散させる用途や、バインダーの用途で配合される。なお、主に顔料等を組成物中で分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外を目的として樹脂を使用することもできる。なお、重合性基を有する樹脂は、重合性化合物にも該当する。 (resin)
The composition of the present invention can use a resin as a curable compound. It is preferable to use a curable compound containing at least a resin. The resin is blended, for example, for dispersing a pigment or the like in the composition or for a binder. A resin that is mainly used to disperse a pigment or the like in a composition is also called a dispersant. However, such uses of the resin are only examples, and the resin can be used for purposes other than such uses. A resin having a polymerizable group also corresponds to a polymerizable compound.
　樹脂の重量平均分子量は、３０００～２００００００が好ましい。上限は、１００００００以下が好ましく、５０００００以下がより好ましい。下限は、４０００以上が好ましく、５０００以上がより好ましい。 The weight average molecular weight of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.
　樹脂としては、（メタ）アクリル樹脂、エポキシ樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂、酢酸ビニル樹脂、ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、ポリウレタン樹脂、ポリウレア樹脂などが挙げられる。これらの樹脂から１種を単独で使用してもよく、２種以上を混合して使用してもよい。環状オレフィン樹脂としては、耐熱性向上の観点からノルボルネン樹脂が好ましい。ノルボルネン樹脂の市販品としては、例えば、ＪＳＲ（株）製のＡＲＴＯＮシリーズ（例えば、ＡＲＴＯＮ　Ｆ４５２０）などが挙げられる。また、樹脂としては、国際公開第２０１６／０８８６４５号の実施例に記載された樹脂、特開２０１７－０５７２６５号公報に記載された樹脂、特開２０１７－０３２６８５号公報に記載された樹脂、特開２０１７－０７５２４８号公報に記載された樹脂、特開２０１７－０６６２４０号公報に記載された樹脂、特開２０１７－１６７５１３号公報に記載された樹脂、特開２０１７－１７３７８７号公報に記載された樹脂、特開２０１７－２０６６８９号公報の段落番号００４１～００６０に記載された樹脂、特開２０１８－０１０８５６号公報の段落番号００２２～００７１に記載された樹脂、特開２０１６－２２２８９１号公報に記載されたブロックポリイソシアネート樹脂、特開２０２０－１２２０５２号公報に記載された樹脂、特開２０２０－１１１６５６号公報に記載された樹脂、特開２０２０－１３９０２１号公報に記載された樹脂、特開２０１７－１３８５０３号公報に記載の主鎖に環構造を有する構成単位と側鎖にビフェニル基を有する構成単位とを含む樹脂を用いることもできる。また、樹脂としては、フルオレン骨格を有する樹脂を好ましく用いることもできる。フルオレン骨格を有する樹脂については、米国特許出願公開第２０１７／０１０２６１０号明細書の記載を参酌でき、この内容は本明細書に組み込まれる。また、樹脂としては、特開２０２０－１８６３７３号公報の段落０１９９～０２３３に記載の樹脂、特開２０２０－１８６３２５号公報に記載のアルカリ可溶性樹脂、韓国公開特許第１０－２０２０－００７８３３９号公報に記載の式１で表される樹脂を用いることもできる。 Examples of resins include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, Polyamide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, and the like. One of these resins may be used alone, or two or more may be mixed and used. As the cyclic olefin resin, norbornene resin is preferable from the viewpoint of improving heat resistance. Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (for example, ARTON F4520). Further, as the resin, the resin described in the examples of International Publication No. 2016/088645, the resin described in JP-A-2017-057265, the resin described in JP-A-2017-032685, JP Resins described in JP-A-2017-075248, resins described in JP-A-2017-066240, resins described in JP-A-2017-167513, resins described in JP-A-2017-173787, Resins described in paragraph numbers 0041 to 0060 of JP-A-2017-206689, resins described in paragraph numbers 0022-0071 of JP-A-2018-010856, blocks described in JP-A-2016-222891 Polyisocyanate resin, resin described in JP-A-2020-122052, resin described in JP-A-2020-111656, resin described in JP-A-2020-139021, JP-A-2017-138503 A resin containing a structural unit having a ring structure in its main chain and a structural unit having a biphenyl group in its side chain as described in 1) can also be used. As the resin, a resin having a fluorene skeleton can also be preferably used. Regarding the resin having a fluorene skeleton, the description of US Patent Application Publication No. 2017/0102610 can be referred to, the content of which is incorporated herein. In addition, as the resin, the resin described in paragraphs 0199 to 0233 of JP-A-2020-186373, the alkali-soluble resin described in JP-A-2020-186325, and the Korean Patent Publication No. 10-2020-0078339. A resin represented by the formula 1 can also be used.
　樹脂として、酸基を有する樹脂を用いることが好ましい。酸基としては、例えば、カルボキシ基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられる。これら酸基は、１種のみであってもよいし、２種以上であってもよい。酸基を有する樹脂は、例えば、アルカリ可溶性樹脂として用いることができる。酸基を有する樹脂の酸価は、３０～５００ｍｇＫＯＨ／ｇが好ましい。下限は、５０ｍｇＫＯＨ／ｇ以上が好ましく、７０ｍｇＫＯＨ／ｇ以上がより好ましい。上限は、４００ｍｇＫＯＨ／ｇ以下が好ましく、２００ｍｇＫＯＨ／ｇ以下がより好ましく、１５０ｍｇＫＯＨ／ｇ以下が更に好ましく、１２０ｍｇＫＯＨ／ｇ以下が最も好ましい。 It is preferable to use a resin having an acid group as the resin. Examples of acid groups include carboxy groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. Only one kind of these acid groups may be used, or two or more kinds thereof may be used. A resin having an acid group can be used, for example, as an alkali-soluble resin. The acid value of the resin having acid groups is preferably 30-500 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more. The upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.
　樹脂としては、式（ＥＤ１）で示される化合物および／または式（ＥＤ２）で表される化合物（以下、これらの化合物を「エーテルダイマー」と称することもある。）由来の繰り返し単位を含む樹脂を含むことも好ましい。 As the resin, a resin containing a repeating unit derived from a compound represented by the formula (ED1) and/or a compound represented by the formula (ED2) (hereinafter, these compounds may be referred to as an "ether dimer"). It is also preferred to include
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（ＥＤ１）中、Ｒ１およびＲ２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１～２５の炭化水素基を表す。
Figure JPOXMLDOC01-appb-C000002
 　式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。式（ＥＤ２）の具体例としては、特開２０１０－１６８５３９号公報の記載を参酌できる。 In formula (ED1), 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.
Figure JPOXMLDOC01-appb-C000002
 In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description in JP-A-2010-168539 can be referred to.
　エーテルダイマーの具体例については、特開２０１３－０２９７６０号公報の段落番号０３１７を参酌することができ、この内容は本明細書に組み込まれる。 For specific examples of ether dimers, paragraph number 0317 of JP-A-2013-029760 can be referred to, the content of which is incorporated herein.
　樹脂としては、重合性基を有する樹脂を用いることも好ましい。重合性基は、エチレン性不飽和結合含有基および環状エーテル基が挙げられる。 As the resin, it is also preferable to use a resin having a polymerizable group. Polymerizable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.
　また、樹脂として、式（Ｅｐ－１）で表される繰り返し単位および式（Ｅｐ－２）で表される繰り返し単位から選ばれる少なくとも１種の繰り返し単位（以下、繰り返し単位Ｅｐともいう）を有する樹脂（以下、樹脂Ｅｐともいう）を用いることもできる。上記樹脂Ｅｐは、式（Ｅｐ－１）で表される繰り返し単位および式（Ｅｐ－２）で表される繰り返し単位のうち、いずれか一方の繰り返し単位のみを含んでいてもよく、式（Ｅｐ－１）で表される繰り返し単位と式（Ｅｐ－２）で表される繰り返し単位のそれぞれを含んでいてもよい。両方の繰り返し単位を含む場合、式（Ｅｐ－１）で表される繰り返し単位と式（Ｅｐ－２）で表される繰り返し単位との比率は、モル比で、式（Ｅｐ－１）で表される繰り返し単位：式（Ｅｐ－２）で表される繰り返し単位＝５：９５～９５：５であることが好ましく、１０：９０～９０：１０であることがより好ましく、２０：８０～８０：２０であることが更に好ましい。
Figure JPOXMLDOC01-appb-C000003
 Further, as the resin, at least one type of 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). A resin (hereinafter also referred to as resin Ep) can also be used. The resin Ep may contain only one of the repeating units represented by the formula (Ep-1) and the repeating unit represented by the formula (Ep-2). -1) and the repeating unit represented by formula (Ep-2) may be included. 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.
Figure JPOXMLDOC01-appb-C000003
　式（Ｅｐ－１）、（Ｅｐ－２）中、Ｌ１は単結合または２価の連結基を表し、Ｒ１は水素原子または置換基を表す。Ｒ１が表す置換基としては、アルキル基およびアリール基が挙げられ、アルキル基であることが好ましい。アルキル基の炭素数は１～１０が好ましく、１～５がより好ましく、１～３が更に好ましい。Ｒ１は、水素原子またはメチル基であることが好ましい。Ｌ１が表す２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基）、－ＮＨ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－Ｓ－およびこれらの２以上を組み合わせてなる基が挙げられる。アルキレン基は、直鎖状、分岐状、及び、環状のいずれでもよく、直鎖状または分岐状が好ましい。また、アルキレン基は、置換基を有していてもよく、無置換であってもよい。置換基としては、ヒドロキシ基、アルコキシ基などが挙げられる。 In formulas (Ep-1) and (Ep-2), L 1 represents a single bond or a divalent linking group, and 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. Moreover, the alkylene group may have a substituent or may be unsubstituted. A hydroxy group, an alkoxy group, etc. are mentioned as a substituent.
　樹脂Ｅｐ中における上記繰り返し単位Ｅｐの含有量は、樹脂Ｅｐの全繰り返し単位中１～１００モル％であることが好ましい。上限は９０モル％以下であることが好ましく、８０モル％以下であることがより好ましい。下限は、２モル％以上が好ましく、３モル％以上がより好ましい。 The content of the repeating unit Ep in the resin Ep is preferably 1 to 100 mol% of all repeating units in the resin Ep. The upper limit is preferably 90 mol % or less, more preferably 80 mol % or less. The lower limit is preferably 2 mol % or more, more preferably 3 mol % or more.
　樹脂Ｅｐは、上記繰り返し単位Ｅｐの他に他の繰り返し単位を有していてもよい。他の繰り返し単位としては、酸基を有する繰り返し単位、エチレン性不飽和結合含有基を有する繰り返し単位などが挙げられる。 The resin Ep may have other repeating units in addition to the repeating unit Ep. Other repeating units include a repeating unit having an acid group, a repeating unit having an ethylenically unsaturated bond-containing group, and the like.
　酸基としては、フェノール性ヒドロキシ基、カルボキシ基、スルホ基、リン酸基が挙げられ、フェノール性ヒドロキシ基またはカルボキシ基であることが好ましく、カルボキシ基であることがより好ましい。 The acid group includes a phenolic hydroxy group, a carboxy group, a sulfo group, and a phosphoric acid group, preferably a phenolic hydroxy group or a carboxy group, more preferably a carboxy group.
　エチレン性不飽和結合含有基としては、ビニル基、スチレン基、（メタ）アリル基、（メタ）アクリロイル基等が挙げられる。 Examples of ethylenically unsaturated bond-containing groups include vinyl groups, styrene groups, (meth)allyl groups, and (meth)acryloyl groups.
　樹脂Ｅｐが酸基を有する繰り返し単位を含む場合、樹脂Ｅｐ中における酸基を有する繰り返し単位の含有量は、樹脂Ｅｐの全繰り返し単位中５～８５モル％であることが好ましい。上限は６０モル％以下であることが好ましく、４０モル％以下であることがより好ましい。下限は、８モル％以上が好ましく、１０モル％以上がより好ましい。 When the resin Ep contains a repeating unit having an acid group, the content of the repeating unit having an acid group in the resin Ep is preferably 5 to 85 mol% of all repeating units in the resin Ep. The upper limit is preferably 60 mol % or less, more preferably 40 mol % or less. The lower limit is preferably 8 mol% or more, more preferably 10 mol% or more.
　樹脂Ｅｐがエチレン性不飽和結合含有基を有する繰り返し単位を含む場合、樹脂Ｅｐ中におけるエチレン性不飽和結合含有基を有する繰り返し単位の含有量は、樹脂Ｅｐの全繰り返し単位中１～６５モル％であることが好ましい。上限は４５モル％以下であることが好ましく、３０モル％以下であることがより好ましい。下限は、２モル％以上が好ましく、３モル％以上がより好ましい。 When the resin Ep contains a repeating unit having an ethylenically unsaturated bond-containing group, the content of the repeating unit having an ethylenically unsaturated bond-containing group in the resin Ep is 1 to 65 mol% of the total repeating units of the resin Ep. is preferably The upper limit is preferably 45 mol % or less, more preferably 30 mol % or less. The lower limit is preferably 2 mol % or more, more preferably 3 mol % or more.
　樹脂Ｅｐは、更に芳香族炭化水素環を有する繰り返し単位を含むことが好ましい。芳香族炭化水素環としては、ベンゼン環またはナフタレン環であることが好ましく、ベンゼン環であることが好ましい。芳香族炭化水素環は置換基を有していてもよい。置換基としては、アルキル基などが挙げられる。環状エーテル基を有する樹脂が、芳香族炭化水素環を有する繰り返し単位を含む場合、芳香族炭化水素環を有する繰り返し単位の含有量は、環状エーテル基を有する樹脂の全繰り返し単位中１～６５モル％であることが好ましい。上限は４５モル％以下であることが好ましく、３０モル％以下であることがより好ましい。下限は、２モル％以上が好ましく、３モル％以上がより好ましい。芳香族炭化水素環を有する繰り返し単位としては、ビニルトルエン、ベンジル（メタ）アクリレートなどの芳香族炭化水素環を有する単官能の重合性化合物由来の繰り返し単位が挙げられる。 The resin Ep preferably further contains a repeating unit having an aromatic hydrocarbon ring. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The aromatic hydrocarbon ring may have a substituent. An alkyl group etc. are mentioned as a substituent. When the resin having a cyclic ether group contains a repeating unit having an aromatic hydrocarbon ring, the content of the repeating unit having an aromatic hydrocarbon ring is 1 to 65 mol in all repeating units of the resin having a cyclic ether group. %. The upper limit is preferably 45 mol % or less, more preferably 30 mol % or less. The lower limit is preferably 2 mol % or more, more preferably 3 mol % or more. Repeating units having an aromatic hydrocarbon ring include repeating units derived from monofunctional polymerizable compounds having an aromatic hydrocarbon ring, such as vinyl toluene and benzyl (meth)acrylate.
　樹脂としては、式（Ｘ）で表される化合物由来の繰り返し単位を含む樹脂を用いることも好ましい。
Figure JPOXMLDOC01-appb-C000004
 　式中、Ｒ１は水素原子またはメチル基を表し、Ｒ２１およびＲ２２はそれぞれ独立してアルキレン基を表し、ｎは０～１５の整数を表す。Ｒ２１およびＲ２２が表すアルキレン基の炭素数は１～１０であることが好ましく、１～５であることがより好ましく、１～３であることが更に好ましく、２または３であることが特に好ましい。ｎは０～５の整数であることが好ましく、０～４の整数であることがより好ましく、０～３の整数であることが更に好ましい。 As the resin, it is also preferable to use a resin containing a repeating unit derived from the compound represented by formula (X).
Figure JPOXMLDOC01-appb-C000004
 In the formula, R 1 represents a hydrogen atom or a methyl group, R 21 and R 22 each independently represent an alkylene group, and 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 is preferably an integer of 0-5, more preferably an integer of 0-4, even more preferably an integer of 0-3.
　式（Ｘ）で表される化合物としては、パラクミルフェノールのエチレンオキサイドまたはプロピレンオキサイド変性（メタ）アクリレートなどが挙げられる。市販品としては、アロニックスＭ－１１０（東亞合成（株）製）などが挙げられる。 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.).
　樹脂としては、芳香族カルボキシ基を有する樹脂（以下、樹脂Ａｃともいう）を用いることも好ましい。樹脂Ａｃにおいて、芳香族カルボキシ基は繰り返し単位の主鎖に含まれていてもよく、繰り返し単位の側鎖に含まれていてもよい。芳香族カルボキシ基は繰り返し単位の主鎖に含まれていることが好ましい。なお、本明細書において、芳香族カルボキシ基とは、芳香族環にカルボキシ基が１個以上結合した構造の基のことである。芳香族カルボキシ基において、芳香族環に結合したカルボキシ基の数は、１～４個であることが好ましく、１～２個であることがより好ましい。 As the resin, it is also preferable to use a resin having an aromatic carboxy group (hereinafter also referred to as resin Ac). In 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. In this specification, an aromatic carboxy group is a group having a structure in which one or more carboxy groups are bonded to an aromatic ring. In the aromatic carboxy group, the number of carboxy groups bonded to the aromatic ring is preferably 1-4, more preferably 1-2.
　本発明の組成物は分散剤としての樹脂を含有することが好ましい。分散剤としては、酸性分散剤（酸性樹脂）、塩基性分散剤（塩基性樹脂）が挙げられる。ここで、酸性分散剤（酸性樹脂）とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤（酸性樹脂）としては、酸基の量と塩基性基の量の合計量を１００モル％としたときに、酸基の量が７０モル％以上である樹脂が好ましい。酸性分散剤（酸性樹脂）が有する酸基は、カルボキシ基が好ましい。酸性分散剤（酸性樹脂）の酸価は、１０～１０５ｍｇＫＯＨ／ｇが好ましい。また、塩基性分散剤（塩基性樹脂）とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤（塩基性樹脂）としては、酸基の量と塩基性基の量の合計量を１００モル％としたときに、塩基性基の量が５０モル％を超える樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミノ基が好ましい。 The composition of the present invention preferably contains a resin as a dispersant. Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups. As the acidic dispersant (acidic resin), a resin having an acid group content of 70 mol % or more is preferable when the total amount of the acid group and the basic group is 100 mol %. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g. Further, a basic dispersant (basic resin) represents a resin in which the amount of basic groups is greater than the amount of acid groups. As the basic dispersant (basic resin), a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and basic groups is 100 mol %. The basic group possessed by the basic dispersant is preferably an amino group.
　分散剤として用いる樹脂は、グラフト樹脂であることも好ましい。グラフト樹脂の詳細については、特開２０１２－２５５１２８号公報の段落番号００２５～００９４の記載を参酌でき、この内容は本明細書に組み込まれる。 The resin used as the dispersant is also preferably a graft resin. For details of the graft resin, reference can be made to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
　分散剤として用いる樹脂は、主鎖及び側鎖の少なくとも一方に窒素原子を含むポリイミン系分散剤であることも好ましい。ポリイミン系分散剤としては、ｐＫａ１４以下の官能基を有する部分構造を有する主鎖と、原子数４０～１００００の側鎖とを有し、かつ主鎖及び側鎖の少なくとも一方に塩基性窒素原子を有する樹脂が好ましい。塩基性窒素原子は、塩基性を呈する窒素原子であれば特に制限はない。ポリイミン系分散剤については、特開２０１２－２５５１２８号公報の段落番号０１０２～０１６６の記載を参酌でき、この内容は本明細書に組み込まれる。 The resin used as the dispersant is also preferably a polyimine-based dispersant containing nitrogen atoms in at least one of its main chain and side chains. 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. Regarding the polyimine-based dispersant, the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
　分散剤として用いる樹脂は、コア部に複数個のポリマー鎖が結合した構造の樹脂であることも好ましい。このような樹脂としては、例えば、デンドリマー（星型ポリマーを含む）が挙げられる。また、デンドリマーの具体例としては、特開２０１３－０４３９６２号公報の段落番号０１９６～０２０９に記載された高分子化合物Ｃ－１～Ｃ－３１などが挙げられる。 The resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core. Such 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.
　分散剤として用いる樹脂は、エチレン性不飽和結合含有基を側鎖に有する繰り返し単位を含む樹脂であることも好ましい。エチレン性不飽和結合含有基を側鎖に有する繰り返し単位の含有量は、樹脂の全繰り返し単位中１０モル％以上であることが好ましく、１０～８０モル％であることがより好ましく、２０～７０モル％であることが更に好ましい。 The resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain. The content of repeating units having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70, of the total repeating units of the resin. More preferably, it is mol %.
　また、分散剤として、特開２０１８－０８７９３９号公報に記載された樹脂、特許第６４３２０７７号公報の段落番号０２１９～０２２１に記載されたブロック共重合体（ＥＢ－１）～（ＥＢ－９）、国際公開第２０１６／１０４８０３号に記載のポリエステル側鎖を有するポリエチレンイミン、国際公開第２０１９／１２５９４０号に記載のブロック共重合体、特開２０２０－０６６６８７号公報に記載のアクリルアミド構造単位を有するブロックポリマー、特開２０２０－０６６６８８号公報に記載のアクリルアミド構造単位を有するブロックポリマー、国際公開第２０１６／１０４８０３号に記載の分散剤などを用いることもできる。 Further, as a dispersant, resins described in JP-A-2018-087939, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, Polyethyleneimine having a polyester side chain described in International Publication No. 2016/104803, a block copolymer described in International Publication No. 2019/125940, a block polymer having an acrylamide structural unit described in JP-A-2020-066687 , a block polymer having an acrylamide structural unit described in JP-A-2020-066688, a dispersant described in WO 2016/104803, and the like can also be used.
　分散剤は、市販品としても入手可能であり、そのような具体例としては、ビックケミー社製のＤｉｓｐｅｒｂｙｋシリーズ（例えば、Ｄｉｓｐｅｒｂｙｋ－１１１、１６１、２００１など）、日本ルーブリゾール（株）製のソルスパースシリーズ（例えば、ソルスパース２００００、７６５００など）、味の素ファインテクノ（株）製のアジスパーシリーズ等が挙げられる。また、特開２０１２－１３７５６４号公報の段落番号０１２９に記載された製品、特開２０１７－１９４６６２号公報の段落番号０２３５に記載された製品を分散剤として用いることもできる。 Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like. In addition, the product described in paragraph number 0129 of JP-A-2012-137564 and the product described in paragraph number 0235 of JP-A-2017-194662 can also be used as a dispersant.
　組成物の全固形分中における硬化性化合物の含有量は、１～７０質量％であることが好ましい。下限は、２質量％以上であることが好ましく、３質量％以上であることがより好ましく、５質量％以上であることが更に好ましい。上限は、６５質量％以下であることが好ましく、６０質量％以下であることがより好ましい。本発明の組成物は、硬化性化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。硬化性化合物を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the curable compound in the total solid content of the composition is preferably 1 to 70% by mass. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less. The composition of the present invention may contain only one kind of curable compound, or may contain two or more kinds. When two or more curable compounds are included, the total amount thereof is preferably within the above range.
　本発明の組成物が硬化性化合物として重合性化合物を含む場合、重合性化合物の含有量は、組成物の全固形分中１～７０質量％であることが好ましい。下限は、２質量％以上であることが好ましく、３質量％以上であることがより好ましく、５質量％以上であることが更に好ましい。上限は、６５質量％以下であることが好ましく、６０質量％以下であることがより好ましい。本発明の組成物は、重合性化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。重合性化合物を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 When the composition of the present invention contains a polymerizable compound as a curable compound, the content of the polymerizable compound is preferably 1 to 70% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less. The composition of the present invention may contain only one polymerizable compound, or may contain two or more polymerizable compounds. When two or more polymerizable compounds are included, the total amount thereof is preferably within the above range.
　本発明の組成物が硬化性化合物として重合性モノマーを含む場合、重合性モノマーの含有量は、組成物の全固形分中１～５０質量％であることが好ましい。下限は、２質量％以上であることが好ましく、３質量％以上であることがより好ましく、５質量％以上であることが更に好ましい。上限は、３５質量％以下であることが好ましく、３０質量％以下であることがより好ましく、２０質量％以下であることが更に好ましい。本発明の組成物は、重合性モノマーを１種のみ含んでいてもよいし、２種以上含んでいてもよい。重合性モノマーを２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 When the composition of the present invention contains a polymerizable monomer as a curable compound, the content of the polymerizable monomer is preferably 1 to 50% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. The composition of the present invention may contain only one polymerizable monomer, or may contain two or more polymerizable monomers. When two or more polymerizable monomers are included, the total amount thereof is preferably within the above range.
　本発明の組成物が硬化性化合物として樹脂を含む場合、樹脂の含有量は、組成物の全固形分中１～７０質量％であることが好ましい。下限は、２質量％以上であることが好ましく、３質量％以上であることがより好ましく、５質量％以上であることが更に好ましい。上限は、６５質量％以下であることが好ましく、６０質量％以下であることがより好ましい。
　また、酸基を有する樹脂の含有量は、組成物の全固形分中１～７０質量％であることが好ましい。下限は、２質量％以上であることが好ましく、３質量％以上であることがより好ましく、５質量％以上であることが更に好ましい。上限は、６５質量％以下であることが好ましく、６０質量％以下であることがより好ましい。
　また、アルカリ可溶性樹脂の含有量は、組成物の全固形分中１～７０質量％であることが好ましい。下限は、２質量％以上であることが好ましく、３質量％以上であることがより好ましく、５質量％以上であることが更に好ましい。上限は、６５質量％以下であることが好ましく、６０質量％以下であることがより好ましい。
　本発明の組成物が分散剤としての樹脂を含有する場合、分散剤としての樹脂の含有量は、組成物の全固形分中０．１～３０質量％が好ましい。上限は、２５質量％以下が好ましく、２０質量％以下が更に好ましい。下限は、０．５質量％以上が好ましく、１質量％以上が更に好ましい。また、分散剤としての樹脂の含有量は、顔料１００質量部に対して、１～１００質量部が好ましい。上限は、８０質量部以下であることが好ましく、７０質量部以下であることがより好ましく、６０質量部以下であることが更に好ましい。下限は、５質量部以上であることが好ましく、１０質量部以上であることがより好ましく、２０質量部以上であることが更に好ましい。
　本発明の組成物は、樹脂を１種のみ含んでいてもよいし、２種以上含んでいてもよい。樹脂を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 When the composition of the present invention contains a resin as a curable compound, the content of the resin is preferably 1 to 70% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
Moreover, the content of the resin having an acid group is preferably 1 to 70% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
Also, the content of the alkali-soluble resin is preferably 1 to 70% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
When the composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant is preferably 0.1 to 30% by mass based on the total solid content of the composition. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. Also, the content of the resin as a dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the pigment. The upper limit is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less. The lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more.
The composition of the present invention may contain only one resin, or may contain two or more resins. When two or more resins are included, the total amount thereof is preferably within the above range.
＜＜シリコーン系界面活性剤Ａ（特定シリコーン系界面活性剤）＞＞
　第１の態様の組成物は、以下に示す特定の表面張力を示すシリコーン系界面活性剤Ａ（以下、特定シリコーン系界面活性剤）を含む。この特定シリコーン系界面活性剤は、プロピレングリコールモノメチルエーテルアセテートに溶解させて固形分濃度１０００質量ｐｐｍの溶液を調製した際に、上記溶液の２５℃における表面張力が２６ｍＮ／ｍ以上を示すものである。上記溶液の表面張力は、２６．５ｍＮ／ｍ以上であることが好ましく、２７ｍＮ／ｍ以上であることがより好ましく、２７．２ｍＮ／ｍ以上であることが更に好ましい。上限は、２８ｍＮ／ｍ以下であることが好ましい。 <<Silicone Surfactant A (Specific Silicone Surfactant)>>
The composition of the first aspect contains a silicone-based surfactant A (hereinafter referred to as a specific silicone-based surfactant) exhibiting a specific surface tension shown below. When this specific silicone-based surfactant is dissolved in propylene glycol monomethyl ether acetate to prepare a solution with a solid content concentration of 1000 ppm by mass, the solution exhibits a surface tension of 26 mN / m or more at 25 ° C. . The surface tension of the solution is preferably 26.5 mN/m or more, more preferably 27 mN/m or more, and even more preferably 27.2 mN/m or more. The upper limit is preferably 28 mN/m or less.
　なお、本明細書において、シリコーン系界面活性剤とは、主鎖にシロキサン結合を含む繰り返し単位を有する化合物であって、一分子内に疎水部と親水部とを含む化合物のことである。 In this specification, a silicone-based surfactant is a compound having a repeating unit containing a siloxane bond in its main chain and containing a hydrophobic part and a hydrophilic part in one molecule.
　特定シリコーン系界面活性剤は、フッ素原子を含まない化合物であることが好ましい。この態様によれば、表面張力の均一性が上がりやすく本発明の効果がより顕著に得られやすい。 The specific silicone-based surfactant is preferably a compound containing no fluorine atoms. According to this aspect, the uniformity of the surface tension is likely to be improved, and the effects of the present invention are likely to be obtained more remarkably.
　特定シリコーン系界面活性剤の水酸基価は８０ｍｇＫＯＨ／ｇ以上であることが好ましく、９０ｍｇＫＯＨ／ｇ以上であることがより好ましく、１００ｍｇＫＯＨ／ｇ以上であることが更に好ましく、１１０ｍｇＫＯＨ／ｇ以上であることが特に好ましい。特定シリコーン系界面活性剤の水酸基価が８０ｍｇＫＯＨ／ｇ以上であれば、膜表面の水との親和性をより高めることができる。特定シリコーン系界面活性剤の水酸基価の上限は、界面活性剤としての機能の観点から２００ｍｇＫＯＨ／ｇ以下であることが好ましく、１９０ｍｇＫＯＨ／ｇ以下であることがより好ましく、１８０ｍｇＫＯＨ／ｇ以下であることが更に好ましい。 The hydroxyl value of the specific silicone surfactant is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more, still more preferably 100 mgKOH/g or more, and preferably 110 mgKOH/g or more. Especially preferred. If the hydroxyl value of the specific silicone-based surfactant is 80 mgKOH/g or more, the affinity of the film surface for water can be further enhanced. The upper limit of the hydroxyl value of the specific silicone surfactant is preferably 200 mgKOH/g or less, more preferably 190 mgKOH/g or less, and 180 mgKOH/g or less from the viewpoint of the function as a surfactant. is more preferred.
　特定シリコーン系界面活性剤の２５℃における動粘度は、４０ｍｍ２／ｓ以下であることが好ましく、３８ｍｍ２／ｓ以下であることがより好ましく、３６ｍｍ２／ｓ以下であることが更に好ましい。特定シリコーン系界面活性剤の動粘度が４０ｍｍ２／ｓ以下であれば、流動性が高いので、本発明の組成物を用いて形成して得られる膜表面の流動性を高めることができる。このため、本発明の組成物を用いて形成した膜と隣接する位置に他の画素形成用組成物などを用いて他の画素などを形成する場合において、膜表面の流動性が高いことから、現像液やリンス液によって膜最表層を他の画素形成用組成物の付着物とともに除去することができると推測され、その結果、膜表面に他の画素形成用組成物の残渣などが生じにくくなり、混色の発生をより効果的に抑制することができる。
　特定シリコーン系界面活性剤の動粘度の下限は界面活性剤の機能観点から１０ｍｍ２／ｓ以上であることが好ましく、１５ｍｍ２／ｓ以上であることがより好ましく、２０ｍｍ２／ｓ以上であることが更に好ましく、２５ｍｍ２／ｓ以上であることが特に好ましい。 The kinematic viscosity at 25° C. of the specific silicone surfactant is preferably 40 mm 2 /s or less, more preferably 38 mm 2 /s or less, even more preferably 36 mm 2 /s or less. If the kinematic viscosity of the specific silicone-based surfactant is 40 mm 2 /s or less, the fluidity is high, so the fluidity of the film surface obtained by using the composition of the present invention can be enhanced. Therefore, when another pixel is formed using another pixel-forming composition at a position adjacent to the film formed using the composition of the present invention, the fluidity of the film surface is high. It is presumed that the outermost layer of the film can be removed together with deposits of other pixel-forming compositions by the developer or rinse solution, and as a result, residues of other pixel-forming compositions are less likely to occur on the film surface. , the occurrence of color mixture can be more effectively suppressed.
The lower limit of the kinematic viscosity of the specific silicone-based surfactant is preferably 10 mm 2 /s or more, more preferably 15 mm 2 /s or more, and 20 mm 2 /s or more from the viewpoint of the function of the surfactant. is more preferable, and 25 mm 2 /s or more is particularly preferable.
　特定シリコーン系界面活性剤の重量平均分子量は、５００～３００００であることが好ましい。 The weight-average molecular weight of the specific silicone-based surfactant is preferably 500-30,000.
　特定シリコーン系界面活性剤は、変性ポリシロキサンであることが好ましい。変性ポリシロキサンとしては、ポリシロキサンの側鎖および／または末端に置換基を導入した構造の化合物が挙げられる。置換基としては、アミノ基、エポキシ基、脂環式エポキシ基、ヒドロキシ基、メルカプト基、カルボキシ基、脂肪酸エステル基および脂肪酸アミド基から選ばれる官能基を含む基、並びに、ポリエーテル鎖を含む基が挙げられ、ヒドロキシ基を含む基であることが好ましく、アルキレンオキシ基とヒドロキシ基を有する基であることがより好ましい。 The specific silicone-based surfactant is preferably modified polysiloxane. Examples of modified polysiloxane include compounds having a structure in which substituents are introduced into the side chains and/or terminals of polysiloxane. Examples of substituents include groups containing functional groups selected from amino groups, epoxy groups, alicyclic epoxy groups, hydroxyl groups, mercapto groups, carboxy groups, fatty acid ester groups and fatty acid amide groups, and groups containing polyether chains. and is preferably a group containing a hydroxy group, more preferably a group having an alkyleneoxy group and a hydroxy group.
　ヒドロキシ基を含む基は、式（Ｇ－１）で表される基または式（Ｇ－２）で表される基であることが好ましい。
　－ＬＧ１－（ＯＲＧ１）ｍ１ＯＨ　　　・・・（Ｇ－１）
　－ＬＧ１－（ＲＧ１Ｏ）ｍ１Ｈ　　　・・・（Ｇ－２） The group containing a hydroxy group is preferably a group represented by formula (G-1) or a group represented by formula (G-2).
-L G1 -(OR G1 ) m1 OH (G-1)
-L G1 -(R G1 O) m1 H (G-2)
　式（Ｇ－１）および式（Ｇ－２）中、ＬＧ１は単結合または２価の連結基を表す。ＬＧ１が表す２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基、より好ましくは１～６のアルキレン基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基、より好ましくは６～１２のアリーレン基）、－ＮＨ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－Ｓ－およびこれらの２以上を組み合わせてなる基が挙げられる。 In formulas (G-1) and (G-2), LG1 represents a single bond or a divalent linking group. The divalent linking group represented by L G1 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms). , more preferably 6 to 12 arylene groups), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S- and two or more of these A group formed by combination is mentioned.
　式（Ｇ－１）および式（Ｇ－２）中、ｍ１は０または１以上の整数を表し、１～１０の整数であることが好ましく、１～５の整数であることがより好ましい。 In formulas (G-1) and (G-2), m1 represents an integer of 0 or 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5.
　式（Ｇ－１）および式（Ｇ－２）中、ＲＧ１は、アルキレン基を表す。アルキレン基の炭素数は１～１０が好ましく、１～５がより好ましく、１～３が更に好ましく、２または３が特に好ましい。ＲＧ１が表すアルキレン基は、直鎖または分岐のいずれでもよい。ｍ１個のＲＧ１が表すアルキレン基は同一であってもよく、異なっていてもよい。 In formulas (G-1) and (G-2), R G1 represents an alkylene group. The number of carbon atoms in the alkylene group is preferably 1-10, more preferably 1-5, still more preferably 1-3, and particularly preferably 2 or 3. The alkylene group represented by R G1 may be linear or branched. The alkylene groups represented by m1 R G1 may be the same or different.
　ポリエーテル鎖を含む基としては、下記式（Ｇ－１１）で表される基および式（Ｇ－１２）で表される基が挙げられる。 Groups containing polyether chains include groups represented by the following formula (G-11) and groups represented by formula (G-12).
　－ＬＧ１１－（ＲＧ１１Ｏ）ｍ２ＲＧ１２　　　・・・（Ｇ－１１）
　－ＬＧ１１－（ＯＲＧ１１）ｍ２ＯＲＧ１２　　　・・・（Ｇ－１２） -L G11 -(R G11 O) m2 R G12 (G-11)
-L G11 -(OR G11 ) m2 OR G12 ...(G-12)
　式（Ｇ－１１）および式（Ｇ－１２）中、ＬＧ１１は単結合または２価の連結基を表す。ＬＧ１１が表す２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基、より好ましくは１～６のアルキレン基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基、より好ましくは６～１２のアリーレン基）、－ＮＨ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－Ｓ－およびこれらの２以上を組み合わせてなる基が挙げられる。 In formulas (G-11) and (G-12), LG11 represents a single bond or a divalent linking group. The divalent linking group represented by L G11 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms). , more preferably 6 to 12 arylene groups), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S- and two or more of these A group formed by combination is mentioned.
　式（Ｇ－１１）および式（Ｇ－１２）中、ｍ２は２以上の数を表し、２～２００が好ましい。 In formulas (G-11) and (G-12), m2 represents a number of 2 or more, preferably 2-200.
　式（Ｇ－１１）および式（Ｇ－１２）中、ＲＧ１１は、アルキレン基を表す。アルキレン基の炭素数は１～１０が好ましく、１～５がより好ましく、１～３が更に好ましく、２または３が特に好ましい。ＲＧ１１が表すアルキレン基は、直鎖または分岐のいずれでもよい。ｍ２個のＲＧ１１が表すアルキレン基は同一であってもよく、異なっていてもよい。 In formulas (G-11) and (G-12), R G11 represents an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms. The alkylene group represented by R G11 may be linear or branched. The alkylene groups represented by m2 R G11 may be the same or different.
　式（Ｇ－１１）および式（Ｇ－１２）中、ＲＧ１２はアルキル基又はアリール基を表す。ＲＧ１２が表すアルキル基の炭素数は１～１０が好ましく、１～５がより好ましく、１～３が更に好ましい。アルキル基は直鎖または分岐のいずれでもよい。ＲＧ１２が表すアリール基の炭素数は６～２０が好ましく、６～１０がより好ましい。 In formulas (G-11) and (G-12), R G12 represents an alkyl group or an aryl group. The number of carbon atoms in the alkyl group represented by R 1 G12 is preferably 1-10, more preferably 1-5, even more preferably 1-3. Alkyl groups may be straight or branched. The aryl group represented by R G12 preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
　特定シリコーン系界面活性剤は、カルビノール変性ポリシロキサンであることが好ましく、カルビノール変性ジアルキルポリシロキサンであることがより好ましい。また、特定シリコーン系界面活性剤は、アルキレンオキシ基とヒドロキシ基を有するジメチルポリシロキサンであることが好ましい。 The specific silicone-based surfactant is preferably carbinol-modified polysiloxane, more preferably carbinol-modified dialkylpolysiloxane. Moreover, the specific silicone-based surfactant is preferably dimethylpolysiloxane having an alkyleneoxy group and a hydroxy group.
　特定シリコーン系界面活性剤は、式（Ｓｉ－１）または式（Ｓｉ－２）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000005
 The specific silicone surfactant is preferably a compound represented by formula (Si-1) or formula (Si-2).
Figure JPOXMLDOC01-appb-C000005
　式（Ｓｉ－１）中、ＲＳ１～ＲＳ７はそれぞれ独立してアルキル基又はアリール基を表し、
　ＸＳ１は、上述した式（Ｇ－１）で表される基または式（Ｇ－２）で表される基を表し、
　ｎ１は、２～２００の数を表す。 In formula (Si-1), R S1 to R S7 each independently represent an alkyl group or an aryl group,
X S1 represents a group represented by the above formula (G-1) or a group represented by formula (G-2),
n1 represents a number from 2 to 200;
　式（Ｓｉ－２）中、ＲＳ１１～ＲＳ１６はそれぞれ独立してアルキル基又はアリール基を表し、
　ＸＳ１１およびＸＳ１２はそれぞれ独立して上述した式（Ｇ－１）で表される基または式（Ｇ－２）で表される基を表し、
　ｎ１１は、２～２００の数を表す。 In formula (Si-2), R S11 to R S16 each independently represent an alkyl group or an aryl group;
X S11 and X S12 each independently represent a group represented by formula (G-1) or a group represented by formula (G-2),
n11 represents a number from 2 to 200;
　式（Ｓｉ－１）のＲＳ１～ＲＳ７が表すアルキル基および式（Ｓｉ－２）のＲＳ１１～ＲＳ１６が表すアルキル基の炭素数は１～１０が好ましく、１～５がより好ましく、１～３が更に好ましく、１が特に好ましい。上記アルキル基は直鎖または分岐のいずれでもよいが、直鎖であることが好ましい。
　式（Ｓｉ－１）のＲＳ１～ＲＳ７が表すアリール基および式（Ｓｉ－２）のＲＳ１１～ＲＳ１６が表すアリール基の炭素数は６～２０が好ましく、６～１２がより好ましく、６であることが特に好ましい。
　ＲＳ１～ＲＳ７、ＲＳ１１～ＲＳ１６はメチル基またはフェニル基であることが好ましく、メチル基であることがより好ましい。 The number of carbon atoms in the alkyl group represented by R S1 to R S7 in formula (Si-1) and the alkyl group represented by R S11 to R S16 in formula (Si-2) is preferably 1 to 10, more preferably 1 to 5. 1 to 3 are more preferred, and 1 is particularly preferred. The above alkyl group may be linear or branched, but preferably linear.
The number of carbon atoms in the aryl group represented by R S1 to R S7 in formula (Si-1) and the aryl group represented by R S11 to R S16 in formula (Si-2) is preferably 6 to 20, more preferably 6 to 12. 6 is particularly preferred.
R S1 to R S7 and R S11 to R S16 are preferably methyl groups or phenyl groups, more preferably methyl groups.
　ｎ１およびｎ１１は、１～１００の数であることが好ましい。 n1 and n11 are preferably numbers from 1 to 100.
　特定シリコーン系界面活性剤の具体例としては、後述する実施例に記載の化合物が挙げられる。 Specific examples of specific silicone-based surfactants include the compounds described in the examples below.
　組成物中における特定シリコーン系界面活性剤の含有量は、１～１０００質量ｐｐｍであることが好ましい。下限は、０．５質量ｐｐｍ以上であることが好ましく、１質量ｐｐｍ以上であることが好ましい。上限は、７５０質量ｐｐｍ以下であることが好ましく、５００質量ｐｐｍ以下であることがより好ましい。 The content of the specific silicone-based surfactant in the composition is preferably 1 to 1000 mass ppm. The lower limit is preferably 0.5 mass ppm or more, and preferably 1 mass ppm or more. The upper limit is preferably 750 mass ppm or less, more preferably 500 mass ppm or less.
＜＜他の界面活性剤＞＞
　第１の態様の組成物は、上述した特定シリコーン系界面活性剤以外の界面活性剤（以下、他の界面活性剤ともいう）を含有してもよい。他の界面活性剤としては、フッ素系界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、アニオン性界面活性剤などが挙げられる。また、上述した特定シリコーン系界面活性剤以外のシリコーン系界面活性剤を他の界面活性剤として用いることもできる。 <<Other surfactants>>
The composition of the first aspect may contain a surfactant (hereinafter also referred to as another surfactant) other than the specific silicone surfactant described above. Other surfactants include fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and the like. Moreover, silicone-based surfactants other than the above-mentioned specific silicone-based surfactants can also be used as other surfactants.
　フッ素系界面活性剤としては、特開２０１４－０４１３１８号公報の段落番号００６０～００６４（対応する国際公開第２０１４／０１７６６９号の段落番号００６０～００６４）等に記載の界面活性剤、特開２０１１－１３２５０３号公報の段落番号０１１７～０１３２に記載の界面活性剤、特開２０２０－００８６３４号公報に記載の界面活性剤が挙げられ、これらの内容は本明細書に組み込まれる。フッ素系界面活性剤の市販品としては、例えば、メガファックＦ－１７１、Ｆ－１７２、Ｆ－１７３、Ｆ－１７６、Ｆ－１７７、Ｆ－１４１、Ｆ－１４２、Ｆ－１４３、Ｆ－１４４、Ｆ－４３７、Ｆ－４７５、Ｆ－４７７、Ｆ－４７９、Ｆ－４８２、Ｆ－５５４、Ｆ－５５５－Ａ、Ｆ－５５６、Ｆ－５５７、Ｆ－５５８、Ｆ－５５９、Ｆ－５６０、Ｆ－５６１、Ｆ－５６５、Ｆ－５６３、Ｆ－５６８、Ｆ－５７５、Ｆ－７８０、ＥＸＰ、ＭＦＳ－３３０、Ｒ－０１、Ｒ－４０、Ｒ－４０－ＬＭ、Ｒ－４１、Ｒ－４１－ＬＭ、ＲＳ－４３、Ｒ－４３、ＴＦ－１９５６、ＲＳ－９０、Ｒ－９４、ＲＳ－７２－Ｋ、ＤＳ－２１（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、ＦＣ４３１、ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、ＳＣ－１０１、ＳＣ－１０３、ＳＣ－１０４、ＳＣ－１０５、ＳＣ－１０６８、ＳＣ－３８１、ＳＣ－３８３、Ｓ－３９３、ＫＨ－４０（以上、ＡＧＣ（株）製）、ＰｏｌｙＦｏｘ　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（以上、ＯＭＮＯＶＡ社製）、フタージェント２０８Ｇ、２１５Ｍ、２４５Ｆ、６０１ＡＤ、６０１ＡＤＨ２、６０２Ａ、６１０ＦＭ、７１０ＦＬ、７１０ＦＭ、７１０ＦＳ、ＦＴＸ－２１８（以上、（株）ＮＥＯＳ製）等が挙げられる。 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- Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-132503 and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein. Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 and F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560 , F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-01, R-40, R-40-LM, R-41, R -41-LM, RS-43, R-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH- 40 (manufactured by AGC), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), Futergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS , FTX-218 (manufactured by NEOS Corporation) and the like.
　フッ素系界面活性剤は、フッ素原子を含有する官能基を持つ分子構造を有し、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、ＤＩＣ（株）製のメガファックＤＳシリーズ（化学工業日報（２０１６年２月２２日）、日経産業新聞（２０１６年２月２３日））、例えば、メガファックＤＳ－２１が挙げられる。 The fluorosurfactant has a molecular structure with a functional group containing a fluorine atom, and an acrylic compound in which the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied is also suitable. Available. Examples of such 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.
　フッ素系界面活性剤は、フッ素化アルキル基またはフッ素化アルキレンエーテル基を有するフッ素原子含有ビニルエーテル化合物と、親水性のビニルエーテル化合物との重合体を用いることも好ましい。このようなフッ素系界面活性剤は、特開２０１６－２１６６０２号公報に記載されたフッ素系界面活性剤が挙げられ、この内容は本明細書に組み込まれる。 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. Such fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.
　フッ素系界面活性剤は、ブロックポリマーを用いることもできる。フッ素系界面活性剤は、フッ素原子を有する（メタ）アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができる。また、特開２０１０－０３２６９８号公報の段落番号００１６～００３７に記載されたフッ素含有界面活性剤や、下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
Figure JPOXMLDOC01-appb-C000006
 　上記の化合物の重量平均分子量は、好ましくは３０００～５００００であり、例えば、１４０００である。上記の化合物中、繰り返し単位の割合を示す％はモル％である。 A block polymer can also be used as the fluorosurfactant. The fluorosurfactant has 2 or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) (meta). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. Further, 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.
Figure JPOXMLDOC01-appb-C000006
 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%.
　また、フッ素系界面活性剤は、エチレン性不飽和結合含有基を側鎖に有する含フッ素重合体を用いることもできる。具体例としては、特開２０１０－１６４９６５号公報の段落番号００５０～００９０および段落番号０２８９～０２９５に記載された化合物、ＤＩＣ（株）製のメガファックＲＳ－１０１、ＲＳ－１０２、ＲＳ－７１８Ｋ、ＲＳ－７２－Ｋ等が挙げられる。また、フッ素系界面活性剤は、特開２０１５－１１７３２７号公報の段落番号００１５～０１５８に記載の化合物を用いることもできる。 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. Further, as the fluorosurfactant, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
　また、国際公開第２０２０／０８４８５４号に記載の界面活性剤を、炭素数６以上のパーフルオロアルキル基を有する界面活性剤の代替として用いることも、環境規制の観点から好ましい。 It is also preferable from the viewpoint of environmental regulations to use the surfactant described in International Publication No. 2020/084854 as a substitute for the surfactant having a perfluoroalkyl group with 6 or more carbon atoms.
　また、式（ｆｉ－１）で表される含フッ素イミド塩化合物を界面活性剤として用いることも好ましい。
Figure JPOXMLDOC01-appb-C000007
 　式（ｆｉ－１）中、ｍは１または２を表し、ｎは１～４の整数を表し、ａは１または２を表し、Ｘａ＋はａ価の金属イオン、第１級アンモニウムイオン、第２級アンモニウムイオン、第３級アンモニウムイオン、第４級アンモニウムイオンまたはＮＨ４ ＋を表す。 It is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant.
Figure JPOXMLDOC01-appb-C000007
 In the formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, a represents 1 or 2, X a + is a valent metal ion, primary ammonium ion, Represents secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH4 + .
　ノニオン性界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（ＢＡＳＦ社製）、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（ＢＡＳＦ社製）、ソルスパース２００００（日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（富士フイルム和光純薬（株）製）、パイオニンＤ－６１１２、Ｄ－６１１２－Ｗ、Ｄ－６３１５（竹本油脂（株）製）、オルフィンＥ１０１０、サーフィノール１０４、４００、４４０（日信化学工業（株）製）などが挙げられる。 Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm Wa Kojunyaku Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Oil Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.) ) and the like.
　カチオン性界面活性剤としては、テトラアルキルアンモニウム塩、アルキルアミン塩、ベンザルコニウム塩、アルキルピリジウム塩、イミダゾリウム塩等が挙げられる。具体例としては、ジヒドロキシエチルステアリルアミン、２－ヘプタデセニル－ヒドロキシエチルイミダゾリン、ラウリルジメチルベンジルアンモニウムクロライド、セチルピリジニウムクロライド、ステアラミドメチルピリジウムクロライド等が挙げられる。 Cationic surfactants include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridium salts, imidazolium salts, and the like. Specific examples include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, stearamidomethylpyridinium chloride and the like.
　アニオン性界面活性剤としては、ドデシルベンゼンスルホン酸、ドデシルベンゼンスルホン酸ナトリウム、ラウリル硫酸ナトリウム、アルキルジフェニルエーテルジスルホン酸ナトリウム、アルキルナフタレンスルホン酸ナトリウム、ジアルキルスルホコハク酸ナトリウム、ステアリン酸ナトリウム、オレイン酸カリウム、ナトリウムジオクチルスルホサクシネート、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルエーテ硫酸ナトリウム、ポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウム、ジアルキルスルホコハク酸ナトリウム、ステアリン酸ナトリウム、オレイン酸ナトリウム、ｔ－オクチルフェノキシエトキシポリエトキシエチル硫酸ナトリウム塩等が挙げられる。 Anionic surfactants include dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyletherdisulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl Sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, t-octylphenoxyethoxypolyethoxyethyl sodium sulfate and the like.
　組成物中における他の界面活性剤の含有量は、１０００質量ｐｐｍ以下であることが好ましく、５００質量ｐｐｍ以下であることがより好ましく、２５０質量ｐｐｍ以下であることが更に好ましい。下限は、例えば、１質量ｐｐｍ以上とすることができる。
　また、他の界面活性剤の含有量は、特定シリコーン系界面活性剤の１００質量部に対して１００質量部以下であることが好ましく、５０質量部以下であることがより好ましく、２５質量部以下であることが更に好ましい。下限は、例えば、１質量部以上とすることができる。
　本発明の組成物は他の界面活性剤を含有しないことも好ましい。 The content of other surfactants in the composition is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and even more preferably 250 mass ppm or less. The lower limit can be, for example, 1 ppm by mass or more.
In addition, the content of the other surfactant is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and 25 parts by mass or less with respect to 100 parts by mass of the specific silicone surfactant. is more preferable. The lower limit can be, for example, 1 part by mass or more.
It is also preferred that the compositions of the present invention do not contain other surfactants.
＜＜溶剤＞＞
　第１の態様の組成物は、溶剤を含有する。溶剤としては、水および有機溶剤が挙げられる。溶剤の種類は、各成分の溶解性や組成物の塗布性を満足すれば基本的には特に制限はない。有機溶剤としては、脂肪族炭化水素系溶剤、ハロゲン化炭化水素系溶剤、アルコール系溶剤、エーテル系溶剤、エステル系溶剤、ケトン系溶剤、ニトリル系溶剤、アミド系溶剤、スルホキシド系溶剤、芳香族系溶剤などが挙げられる。これらの詳細については、国際公開第２０１５／１６６７７９号の段落番号０２２３を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤も好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、ジクロロメタン、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、２－ペンタノン、３－ペンタノン、４－ヘプタノン、シクロヘキサノン、２－メチルシクロヘキサノン、３－メチルシクロヘキサノン、４－メチルシクロヘキサノン、シクロヘプタノン、シクロオクタノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、プロピレングリコールジアセテート、３－メトキシブタノール、メチルエチルケトン、ガンマブチロラクトン、スルホラン、アニソール、１，４－ジアセトキシブタン、ジエチレングリコールモノエチルエーテルアセタート、二酢酸ブタン－１，３－ジイル、ジプロピレングリコールメチルエーテルアセタート、ジアセトンアルコール（別名としてダイアセトンアルコール、４－ヒドロキシ－４－メチル－２－ペンタノン）、２－メトキシプロピルアセテート、２－メトキシ－１－プロパノール、イソプロピルアルコールなどが挙げられる。ただし有機溶剤としての芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン等）は、環境面等の理由により低減したほうがよい場合がある（例えば、有機溶剤全量に対して、５０質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）以下とすることもでき、１０質量ｐｐｍ以下とすることもでき、１質量ｐｐｍ以下とすることもできる）。 <<Solvent>>
The composition of the first aspect contains a solvent. Solvents include water and organic solvents. The type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. Examples of organic solvents include aliphatic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, amide solvents, sulfoxide solvents, and aromatic solvents. Examples include solvents. For these details, reference can be made to paragraph 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. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxy butanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropyl alcohol and the like. However, 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 mass ppm or less, or 1 mass ppm or less).
　本発明においては、金属含有量の少ない有機溶剤を用いることが好ましい。有機溶剤の金属含有量は、例えば、１０質量ｐｐｂ（ｐａｒｔｓ　ｐｅｒ　ｂｉｌｌｉｏｎ）以下であることが好ましい。必要に応じて質量ｐｐｔ（ｐａｒｔｓ　ｐｅｒ　ｔｒｉｌｌｉｏｎ）レベルの有機溶剤を用いてもよく、そのような有機溶剤は、例えば、東洋合成社が提供している（化学工業日報、２０１５年１１月１３日）。 In the present invention, it is preferable to use an organic solvent with a low metal content. 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 ppt (parts per trillion) level by mass may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015). .
　有機溶剤から金属等の不純物を除去する方法としては、例えば、蒸留（分子蒸留や薄膜蒸留等）やフィルタを用いたろ過を挙げることができる。ろ過に用いるフィルタのフィルタ孔径としては、１０μｍ以下が好ましく、５μｍ以下がより好ましく、３μｍ以下が更に好ましい。フィルタの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。 Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
　有機溶剤は、異性体（原子数が同じであるが構造が異なる化合物）が含まれていてもよい。また、異性体は、１種のみが含まれていてもよいし、複数種含まれていてもよい。 The organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers may be contained.
　有機溶剤中の過酸化物の含有率が０．８ｍｍｏｌ／Ｌ以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。 The content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.
　組成物中における溶剤の含有量は、１０～９５質量％であることが好ましく、２０～９０質量％であることがより好ましく、３０～９０質量％であることが更に好ましい。
　本発明の組成物は、溶剤を１種のみ含んでいてもよいし、２種以上含んでいてもよい。溶剤を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The solvent content in the composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, even more preferably 30 to 90% by mass.
The composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are included, the total amount thereof is preferably within the above range.
＜＜色材＞＞
　第１の態様の組成物は色材を含有することが好ましい。このような組成物は、光学フィルタ形成用（より詳しくは、光学フィルタの画素形成用）の組成物として好ましく用いることができる。 <<coloring material>>
The composition of the first aspect preferably contains a coloring material. Such a composition can be preferably used as a composition for forming optical filters (more specifically, for forming pixels of optical filters).
　色材としては白色色材、黒色色材、有彩色色材、近赤外線吸収色材が挙げられる。なお、本明細書において、白色色材には純白色のみならず、白に近い明るい灰色（例えば灰白色、薄灰色など）の色材も含まれる。 Examples of colorants include white colorants, black colorants, chromatic colorants, and near-infrared absorbing colorants. In this specification, 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.).
　色材は、有彩色色材、黒色色材、及び近赤外線吸収色材よりなる群から選ばれる少なくとも１種を含むことが好ましく、有彩色色材及び黒色色材よりなる群から選ばれる少なくとも１種を含むことがより好ましく、有彩色色材を含むことが更に好ましい。 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 at least one selected from the group consisting of a chromatic colorant and a black colorant. It is more preferable to contain a seed, and it is still more preferable to contain a chromatic coloring material.
　また、色材は、２種以上の有彩色色材と近赤外線吸収色材とを含むことも好ましい。また、２種以上の有彩色色材の組み合わせで黒色を形成していてもよい。また、色材は、黒色色材と近赤外線吸収色材とを含むことも好ましい。これらの態様によれば、本発明の組成物を、近赤外線透過フィルタ形成用の組成物として好ましく用いることができる。２種以上の有彩色色材の組み合わせで黒色を形成する色材の組み合わせについては、特開２０１３－０７７００９号公報、特開２０１４－１３０３３８号公報、国際公開第２０１５／１６６７７９号等を参照できる。 Also, the colorant preferably contains two or more chromatic colorants and a near-infrared absorbing colorant. Moreover, black may be formed by a combination of two or more chromatic colorants. Also, the colorant preferably contains a black colorant and a near-infrared absorbing colorant. According to these aspects, the composition of the present invention can be preferably used as a composition for forming a near-infrared transmission filter. For combinations of colorants that form black by combining two or more chromatic colorants, reference can be made to JP-A-2013-077009, JP-A-2014-130338, International Publication No. 2015/166779, and the like.
　色材は、顔料であってもよく、染料であってもよいが、顔料であることが好ましい。顔料の平均一次粒子径は、１～２００ｎｍが好ましい。下限は５ｎｍ以上が好ましく、１０ｎｍ以上がより好ましい。上限は、１８０ｎｍ以下が好ましく、１５０ｎｍ以下がより好ましく、１００ｎｍ以下が更に好ましい。なお、本明細書において、顔料の一次粒子径は、顔料の一次粒子を透過型電子顕微鏡により観察し、得られた画像写真から求めることができる。具体的には、顔料の一次粒子の投影面積を求め、それに対応する円相当直径を顔料の一次粒子径として算出する。また、本明細書における平均一次粒子径は、４００個の顔料の一次粒子についての一次粒子径の算術平均値とする。また、顔料の一次粒子とは、凝集のない独立した粒子をいう。 The coloring material may be a pigment or a dye, but is preferably a pigment. 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. In addition, in this specification, 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. Further, 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. Further, the primary particles of the pigment refer to independent particles without agglomeration.
（有彩色色材）
　有彩色色材としては、波長４００～７００ｎｍの範囲に極大吸収波長を有する色材が挙げられる。例えば、緑色色材、赤色色材、黄色色材、紫色色材、青色色材、オレンジ色色材などが挙げられる。 (chromatic colorant)
Examples of 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.
　緑色色材としては、フタロシアニン化合物およびスクアリリウム化合物が挙げられ、フタロシアニン化合物であることが好ましい。また、緑色色材は顔料であることが好ましい。緑色色材の具体例としては、Ｃ．Ｉ．ピグメントグリーン７，１０，３６，３７，５８，５９，６２，６３，６４，６５，６６等の緑色顔料が挙げられる。また、緑色色材として、１分子中のハロゲン原子数が平均１０～１４個であり、臭素原子数が平均８～１２個であり、塩素原子数が平均２～５個であるハロゲン化亜鉛フタロシアニン顔料を用いることもできる。具体例としては、国際公開第２０１５／１１８７２０号に記載の化合物が挙げられる。また、緑色色材として中国特許出願第１０６９０９０２７号明細書に記載の化合物、国際公開第２０１２／１０２３９５号に記載のリン酸エステルを配位子として有するフタロシアニン化合物、特開２０１９－００８０１４号公報に記載のフタロシアニン化合物、特開２０１８－１８００２３号公報に記載のフタロシアニン化合物、特開２０１９－０３８９５８号公報に記載の化合物、特開２０２０－０７０４２６号公報に記載のアルミニウムフタロシアニン化合物、特開２０２０－０７６９９５号公報に記載のコアシェル型色素、特表２０２０－５０４７５８号公報に記載のジアリールメタン化合物などを用いることもできる。 Examples of green colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. Also, the green colorant is preferably a pigment. 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. Further, as a green colorant, a halogenated zinc phthalocyanine having an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 Pigments can also be used. Specific examples include compounds described in International Publication No. 2015/118720. In addition, as a green colorant, the compound described in Chinese Patent Application No. 106909027, the phthalocyanine compound having a phosphoric acid ester as a ligand described in WO 2012/102395, described in JP 2019-008014. The 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.
　緑色色材は、Ｃ．Ｉ．ピグメントグリーン７，３６，５８，５９，６２，６３が好ましく、Ｃ．Ｉ．ピグメントグリーン７，３６，５８，５９がより好ましい。 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 and 59 are more preferred.
　赤色色材としては、ジケトピロロピロール化合物、アントラキノン化合物、アゾ化合物、ナフトール化合物、アゾメチン化合物、キサンテン化合物、キナクリドン化合物、ペリレン化合物、チオインジゴ化合物などが挙げられ、ジケトピロロピロール化合物、アントラキノン化合物、アゾ化合物であることが好ましく、ジケトピロロピロール化合物であることがより好ましい。また、赤色色材は顔料であることが好ましい。赤色色材の具体例としては、Ｃ．Ｉ．（カラーインデックス）ピグメントレッド１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２６９，２７０，２７２，２７９，２９１，２９４，２９５，２９６，２９７等の赤色顔料が挙げられる。また、赤色色材として、特開２０１７－２０１３８４号公報に記載の構造中に少なくとも１つの臭素原子が置換したジケトピロロピロール化合物、特許第６２４８８３８号の段落番号００１６～００２２に記載のジケトピロロピロール化合物、国際公開第２０１２／１０２３９９号に記載のジケトピロロピロール化合物、国際公開第２０１２／１１７９６５号に記載のジケトピロロピロール化合物、特開２０２０－０８５９４７号公報に記載の臭素化ジケトピロロピロール化合物、特開２０１２－２２９３４４号公報に記載のナフトールアゾ化合物、特許第６５１６１１９号公報に記載の赤色色材、特許第６５２５１０１号公報に記載の赤色色材、特開２０２０－０９０６３２号公報の段落番号０２２９に記載の臭素化ジケトピロロピロール化合物、韓国公開特許第１０－２０１９－０１４０７４１号公報に記載のアントラキノン化合物、韓国公開特許第１０－２０１９－０１４０７４４号公報に記載のアントラキノン化合物、特開２０２０－０７９３９６号公報に記載のペリレン化合物、特開２０２０－０８３９８２号公報に記載のペリレン化合物、特開２０１８－０３５３４５号公報に記載のキサンテン化合物、特開２０２０－０６６７０２号公報の段落番号００２５～００４１に記載のジケトピロロピロール化合物などを用いることもできる。また、赤色色材として、芳香族環に対して、酸素原子、硫黄原子または窒素原子が結合した基が導入された芳香族環基がジケトピロロピロール骨格に結合した構造を有する化合物を用いることもできる。赤色色材として、Ｌｕｍｏｇｅｎ　Ｆ　Ｏｒａｎｇｅ　２４０（ＢＡＳＦ製、赤色顔料、ペリレン顔料）を用いることもできる。 Examples of red colorants 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. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, 297 and other red pigments. Further, as 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. 6248838 Pyrrole compounds, diketopyrrolopyrrole compounds described in WO 2012/102399, diketopyrrolopyrrole compounds described in WO 2012/117965, brominated diketopyrrolo described in JP 2020-085947 Pyrrole compound, naphthol azo compound described in JP-A-2012-229344, red colorant described in JP-A-6516119, red colorant described in JP-A-6525101, paragraph of JP-A-2020-090632 Brominated diketopyrrolopyrrole compound described in No. 0229, anthraquinone compound described in Korean Patent Publication No. 10-2019-0140741, anthraquinone compound 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. In addition, as a red colorant, a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton is used. can also Lumogen F Orange 240 (manufactured by BASF, red pigment, perylene pigment) can also be used as the red colorant.
　赤色色材は、Ｃ．Ｉ．ピグメントレッド１２２，１７７，１７９，２５４，２５５，２６４，２６９，２７２，２９１が好ましく、Ｃ．Ｉ．ピグメントレッド２５４，２６４，２７２がより好ましい。 The red coloring material is C.I. I. Pigment Red 122, 177, 179, 254, 255, 264, 269, 272 and 291 are preferred, and C.I. I. Pigment Red 254, 264, 272 are more preferred.
　黄色色材としては、アゾ化合物、アゾメチン化合物、イソインドリン化合物、プテリジン化合物、キノフタロン化合物およびペリレン化合物などが挙げられる。黄色色材は、顔料であることが好ましく、アゾ顔料、アゾメチン顔料、イソインドリン顔料、プテリジン顔料、キノフタロン顔料またはペリレン顔料であることがより好ましく、アゾ顔料またはアゾメチン顔料であることがより好ましい。黄色色材の具体例としては、Ｃ．Ｉ．ピグメントイエロー１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４，２１５，２２８，２３１，２３２，２３３，２３４，２３５，２３６等の黄色顔料が挙げられる。 Examples of yellow colorants 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 more preferably an azo pigment or an azomethine pigment. Specific examples of the yellow coloring material include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236 and other yellow pigments.
　また、黄色色材として、下記構造のアゾバルビツール酸ニッケル錯体を用いることもできる。
Figure JPOXMLDOC01-appb-C000008
 As a yellow colorant, a nickel azobarbiturate complex having the following structure can also be used.
Figure JPOXMLDOC01-appb-C000008
　また、黄色色材として、特開２０１７－２０１００３号公報に記載の化合物、特開２０１７－１９７７１９号公報に記載の化合物、特開２０１７－１７１９１２号公報の段落番号００１１～００６２、０１３７～０２７６に記載の化合物、特開２０１７－１７１９１３号公報の段落番号００１０～００６２、０１３８～０２９５に記載の化合物、特開２０１７－１７１９１４号公報の段落番号００１１～００６２、０１３９～０１９０に記載の化合物、特開２０１７－１７１９１５号公報の段落番号００１０～００６５、０１４２～０２２２に記載の化合物、特開２０１３－０５４３３９号公報の段落番号００１１～００３４に記載のキノフタロン化合物、特開２０１４－０２６２２８号公報の段落番号００１３～００５８に記載のキノフタロン化合物、特開２０１８－０６２６４４号公報に記載のイソインドリン化合物、特開２０１８－２０３７９８号公報に記載のキノフタロン化合物、特開２０１８－０６２５７８号公報に記載のキノフタロン化合物、特許第６４３２０７６号公報に記載のキノフタロン化合物、特開２０１８－１５５８８１号公報に記載のキノフタロン化合物、特開２０１８－１１１７５７号公報に記載のキノフタロン化合物、特開２０１８－０４０８３５号公報に記載のキノフタロン化合物、特開２０１７－１９７６４０号公報に記載のキノフタロン化合物、特開２０１６－１４５２８２号公報に記載のキノフタロン化合物、特開２０１４－０８５５６５号公報に記載のキノフタロン化合物、特開２０１４－０２１１３９号公報に記載のキノフタロン化合物、特開２０１３－２０９６１４号公報に記載のキノフタロン化合物、特開２０１３－２０９４３５号公報に記載のキノフタロン化合物、特開２０１３－１８１０１５号公報に記載のキノフタロン化合物、特開２０１３－０６１６２２号公報に記載のキノフタロン化合物、特開２０１３－０３２４８６号公報に記載のキノフタロン化合物、特開２０１２－２２６１１０号公報に記載のキノフタロン化合物、特開２００８－０７４９８７号公報に記載のキノフタロン化合物、特開２００８－０８１５６５号公報に記載のキノフタロン化合物、特開２００８－０７４９８６号公報に記載のキノフタロン化合物、特開２００８－０７４９８５号公報に記載のキノフタロン化合物、特開２００８－０５０４２０号公報に記載のキノフタロン化合物、特開２００８－０３１２８１号公報に記載のキノフタロン化合物、特公昭４８－０３２７６５号公報に記載のキノフタロン化合物、特開２０１９－００８０１４号公報に記載のキノフタロン化合物、特許第６６０７４２７号公報に記載のキノフタロン化合物、韓国公開特許第１０－２０１４－００３４９６３号公報に記載の化合物、特開２０１７－０９５７０６号公報に記載の化合物、台湾特許出願公開第２０１９２０４９５号公報に記載の化合物、特許第６６０７４２７号公報に記載の化合物、特開２０２０－０３３５２５号公報に記載の化合物、特開２０２０－０３３５２４号公報に記載の化合物、特開２０２０－０３３５２３号公報に記載の化合物、特開２０２０－０３３５２２号公報に記載の化合物、特開２０２０－０３３５２１号公報に記載の化合物、国際公開第２０２０／０４５２００号に記載の化合物、国際公開第２０２０／０４５１９９号に記載の化合物、国際公開第２０２０／０４５１９７号に記載の化合物、特開２０２０－０９３９９４号公報に記載のアゾ化合物、国際公開第２０２０／１０５３４６号に記載のペリレン化合物、特表２０２０－５１７７９１号公報に記載のキノフタロン化合物、下記式（ＱＰ１）で表される化合物、下記式（ＱＰ２）で表される化合物を用いることもできる。また、これらの化合物を多量体化したものも、色価向上の観点から好ましく用いられる。
Figure JPOXMLDOC01-appb-C000009
 Further, as the yellow colorant, compounds described in JP-A-2017-201003, compounds described in JP-A-2017-197719, paragraph numbers 0011-0062, 0137-0276 of JP-A-2017-171912 Compounds described in paragraph numbers 0010 to 0062 and 0138 to 0295 of JP-A-2017-171913, compounds described in paragraph numbers 0011-0062 and 0139-0190 of JP-A-2017-171914, JP 2017 Compounds described in paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A-171915, quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP-A-2013-054339, paragraph numbers 0013- of JP-A-2014-026228 0058, the isoindoline compound described in JP-A-2018-062644, the quinophthalone compound described in JP-A-2018-203798, the quinophthalone compound described in JP-A-2018-062578, and the patent No. 6432076. Quinophthalone compounds described in JP-A-2018-155881, quinophthalone compounds described in JP-A-2018-111757, quinophthalone compounds described in JP-A-2018-040835, JP-A-2017 -Quinophthalone compounds described in JP-A-197640, quinophthalone compounds described in JP-A-2016-145282, quinophthalone compounds described in JP-A-2014-085565, quinophthalone compounds described in JP-A-2014-021139, in particular Quinophthalone compounds described in JP-A-2013-209614, quinophthalone compounds described in JP-A-2013-209435, quinophthalone compounds described in JP-A-2013-181015, quinophthalone compounds described in JP-A-2013-061622 , the quinophthalone compound described in JP-A-2013-032486, the quinophthalone compound described in JP-A-2012-226110, the quinophthalone compound described in JP-A-2008-074987, the JP-A-2008-081565. Quinophthalone compounds, quinophthalone compounds described in JP-A-2008-074986, quinophthalone compounds described in JP-A-2008-074985, quinophthalone compounds described in JP-A-2008-050420, JP-A-2 008-031281, the quinophthalone compound described in JP-B-48-032765, the quinophthalone compound described in JP-A-2019-008014, the quinophthalone compound described in Japanese Patent No. 6607427, the Korean publication Compounds described in Patent No. 10-2014-0034963, compounds described in JP 2017-095706, compounds described in Taiwan Patent Application Publication No. 201920495, compounds described in Patent No. 6607427, Compounds described in JP-A-2020-033525, compounds described in JP-A-2020-033524, compounds described in JP-A-2020-033523, compounds described in JP-A-2020-033522, JP-A-2020 - compound described in WO 2020/045200, compound described in WO 2020/045199, compound described in WO 2020/045197, JP 2020-093994 Azo compound described in the publication, a perylene compound described in International Publication No. 2020/105346, a quinophthalone compound described in JP 2020-517791, a compound represented by the following formula (QP1), the following formula (QP2) A compound represented by can also be used. Moreover, those obtained by polymerizing these compounds are also preferably used from the viewpoint of improving the color value.
Figure JPOXMLDOC01-appb-C000009
　式（ＱＰ１）中、Ｘ１～Ｘ１６は各々独立に水素原子又はハロゲン原子を表し、Ｚ１は炭素数１～３のアルキレン基を表す。式（ＱＰ１）で表される化合物の具体例としては、特許第６４４３７１１号公報の段落番号００１６に記載されている化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000010
 In formula (QP1), X 1 to X 16 each independently represent a hydrogen atom or a halogen atom, and Z 1 represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by formula (QP1) include compounds described in paragraph 0016 of Japanese Patent No. 6443711.
Figure JPOXMLDOC01-appb-C000010
　式（ＱＰ２）中、Ｙ１～Ｙ３は、それぞれ独立にハロゲン原子を示す。ｎ、ｍは０～６の整数、ｐは０～５の整数を表す。（ｎ＋ｍ）は１以上である。式（ＱＰ２）で表される化合物の具体例としては、特許６４３２０７７号公報の段落番号００４７～００４８に記載されている化合物が挙げられる。 In formula (QP2), 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.
　黄色色材は、Ｃ．Ｉ．ピグメントイエロー１１７，１２９，１３８，１３９，１５０，１８５が好ましい。 The yellow coloring material is C.I. I. Pigment Yellow 117, 129, 138, 139, 150 and 185 are preferred.
　オレンジ色色材しては、Ｃ．Ｉ．ピグメントオレンジ２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等のオレンジ色顔料が挙げられる。 As an orange colorant, 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.
　紫色色材としては、Ｃ．Ｉ．ピグメントバイオレット１，１９，２３，２７，３２，３７，４２，６０，６１等の紫色顔料が挙げられる。 As a purple coloring material, C.I. I. Purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61 are included.
　青色色材としては、Ｃ．Ｉ．ピグメントブルー１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，２９，６０，６４，６６，７９，８０，８７，８８等が挙げられる。また、青色色材として、リン原子を有するアルミニウムフタロシアニン化合物を用いることもできる。具体例としては、特開２０１２－２４７５９１号公報の段落番号００２２～００３０、特開２０１１－１５７４７８号公報の段落番号００４７に記載の化合物が挙げられる。 As a blue colorant, 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. be done. 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.
　有彩色色材には染料を用いることもできる。染料としては特に制限はなく、公知の染料が使用できる。例えば、ピラゾールアゾ系、アニリノアゾ系、トリアリールメタン系、アントラキノン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ベンゾピラン系、インジゴ系、ピロメテン系等の染料が挙げられる。 Dyes can also be used as chromatic colorants. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes can be used.
　有彩色色材には色素多量体を用いることもできる。色素多量体は、有機溶剤に溶解して用いられる染料であることが好ましい。また、色素多量体は、粒子を形成していてもよい。色素多量体が粒子である場合は通常溶剤に分散した状態で用いられる。粒子状態の色素多量体は、例えば乳化重合によって得ることができ、特開２０１５－２１４６８２号公報に記載されている化合物および製造方法が具体例として挙げられる。色素多量体は、一分子中に、色素構造を２以上有するものであり、色素構造を３以上有することが好ましい。上限は、特に限定はないが、１００以下とすることもできる。一分子中に有する複数の色素構造は、同一の色素構造であってもよく、異なる色素構造であってもよい。色素多量体の重量平均分子量（Ｍｗ）は、２０００～５００００が好ましい。下限は、３０００以上がより好ましく、６０００以上がさらに好ましい。上限は、３００００以下がより好ましく、２００００以下がさらに好ましい。色素多量体は、特開２０１１－２１３９２５号公報、特開２０１３－０４１０９７号公報、特開２０１５－０２８１４４号公報、特開２０１５－０３０７４２号公報、国際公開第２０１６／０３１４４２号等に記載されている化合物を用いることもできる。 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.
　有彩色色材には、特表２０２０－５０４７５８号公報に記載のジアリールメタン化合物、韓国公開特許第１０－２０２０－００２８１６０号公報に記載されたトリアリールメタン染料ポリマー、特開２０２０－１１７６３８号公報に記載のキサンテン化合物、国際公開第２０２０／１７４９９１号に記載のフタロシアニン化合物、特開２０２０－１６０２７９号公報に記載のイソインドリン化合物又はそれらの塩、韓国公開特許第１０－２０２０－００６９４４２号公報に記載の式１で表される化合物、韓国公開特許第１０－２０２０－００６９７３０号公報に記載の式１で表される化合物、韓国公開特許第１０－２０２０－００６９０７０号公報に記載の式１で表される化合物、韓国公開特許第１０－２０２０－００６９０６７号公報に記載の式１で表される化合物、韓国公開特許第１０－２０２０－００６９０６２号公報に記載の式１で表される化合物、特許第６８０９６４９号に記載のハロゲン化亜鉛フタロシアニン顔料、特開２０２０－１８０１７６号公報に記載のイソインドリン化合物を用いることができる。有彩色色材は、ロタキサンであってもよく、色素骨格はロタキサンの環状構造に使用されていてもよく、棒状構造に使用されていてもよく、両方の構造に使用されていてもよい。 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. 10-2020-0069067, compounds represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069062, Patent No. 6809649 and the isoindoline compound described in JP-A-2020-180176. 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.
　有彩色色材は、２種以上組み合わせて用いてもよい。
　また、有彩色色材を２種以上組み合わせて用いる場合、２種以上の有彩色色材の組み合わせで黒色を形成していてもよい。そのような組み合わせとしては、例えば以下の（１）～（７）の態様が挙げられる。
（１）赤色色材と青色色材とを含有する態様。
（２）赤色色材と青色色材と黄色色材とを含有する態様。
（３）赤色色材と青色色材と黄色色材と紫色色材とを含有する態様。
（４）赤色色材と青色色材と黄色色材と紫色色材と緑色色材とを含有する態様。
（５）赤色色材と青色色材と黄色色材と緑色色材とを含有する態様。
（６）赤色色材と青色色材と緑色色材とを含有する態様。
（７）黄色色材と紫色色材とを含有する態様。 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).
(1) A mode containing a red colorant and a blue colorant.
(2) A mode containing a red colorant, a blue colorant, and a yellow colorant.
(3) A mode containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant.
(4) A mode containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.
(5) A mode containing a red colorant, a blue colorant, a yellow colorant, and a green colorant.
(6) A mode containing a red colorant, a blue colorant, and a green colorant.
(7) A mode containing a yellow colorant and a purple colorant.
（白色色材）
　白色色材としては、酸化チタン、チタン酸ストロンチウム、チタン酸バリウム、酸化亜鉛、酸化マグネシウム、酸化ジルコニウム、酸化アルミニウム、硫酸バリウム、シリカ、タルク、マイカ、水酸化アルミニウム、ケイ酸カルシウム、ケイ酸アルミニウム、硫化亜鉛などの無機顔料（白色顔料）が挙げられる。白色顔料は、チタン原子を有する粒子が好ましく、酸化チタンがより好ましい。また、白色顔料は、波長５８９ｎｍの光に対する屈折率が２．１０以上の粒子であることが好ましい。前述の屈折率は、２．１０～３．００であることが好ましく、２．５０～２．７５であることがより好ましい。 (white colorant)
White colorants include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, Examples include inorganic pigments (white pigments) such as zinc sulfide. The white pigment is preferably particles containing titanium atoms, more preferably titanium oxide. Further, 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.
　また、白色顔料は「酸化チタン　物性と応用技術　清野学著　１３～４５ページ　１９９１年６月２５日発行、技報堂出版発行」に記載の酸化チタンを用いることもできる。 In addition, the white pigment can also use the titanium oxide described in "Titanium Oxide Physical Properties and Application Techniques Manabu Seino, Pages 13-45, June 25, 1991, published by Gihodo Publishing".
　白色顔料は、単一の無機物からなるものだけでなく、他の素材と複合させた粒子を用いてもよい。例えば、内部に空孔や他の素材を有する粒子、コア粒子に無機粒子を多数付着させた粒子、ポリマー粒子からなるコア粒子と無機ナノ微粒子からなるシェル層とからなるコア及びシェル複合粒子を用いることが好ましい。上記ポリマー粒子からなるコア粒子と無機ナノ微粒子からなるシェル層とからなるコア及びシェル複合粒子としては、例えば、特開２０１５－０４７５２０号公報の段落番号００１２～００４２の記載を参酌することができ、この内容は本明細書に組み込まれる。 The white pigment is not only made of a single inorganic substance, but also particles combined with other materials may be used. For example, particles having voids or other materials inside, particles in which a large number of inorganic particles are attached to a core particle, 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. For 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.
　白色顔料は、中空無機粒子を用いることもできる。中空無機粒子とは、内部に空洞を有する構造の無機粒子であり、外殻に包囲された空洞を有する無機粒子のことを言う。中空無機粒子としては、特開２０１１－０７５７８６号公報、国際公開第２０１３／０６１６２１号、特開２０１５－１６４８８１号公報などに記載された中空無機粒子が挙げられ、これらの内容は本明細書に組み込まれる。 Hollow inorganic particles can also be used as the white pigment. A hollow inorganic particle is an inorganic particle having a structure having a cavity inside, and refers to an inorganic particle having a cavity surrounded by an outer shell. Examples of hollow inorganic particles include hollow inorganic particles described in JP 2011-075786, WO 2013/061621, JP 2015-164881, etc., the contents of which are incorporated herein. be
（黒色色材）
　黒色色材としては特に限定されず、公知のものを用いることができる。黒色色材は顔料（黒色顔料）であることが好ましい。なお、本明細書において、黒色色材は、波長４００～７００ｎｍの全ての範囲にわたって吸収を示す色材を意味する。例えば、無機黒色色材としては、カーボンブラック、チタンブラック、グラファイト等が挙げられ、カーボンブラック、チタンブラックが好ましく、チタンブラックがより好ましい。チタンブラックとは、チタン原子を含有する黒色粒子であり、低次酸化チタンや酸窒化チタンが好ましい。チタンブラックは、分散性向上、凝集性抑制などの目的で必要に応じ、表面を修飾することが可能である。例えば、酸化珪素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化マグネシウム、又は、酸化ジルコニウムでチタンブラックの表面を被覆することが可能である。また、特開２００７－３０２８３６号公報に表されるような撥水性物質での処理も可能である。黒色色材として、カラーインデックス（Ｃ．Ｉ．）Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　１，７を用いることもできる。チタンブラックは、個々の粒子の一次粒子径及び平均一次粒子径のいずれもが小さいことが好ましい。具体的には、平均一次粒子径が１０～４５ｎｍであることが好ましい。チタンブラックは、分散物として用いることもできる。例えば、チタンブラック粒子とシリカ粒子とを含み、分散物中のＳｉ原子とＴｉ原子との含有比が０．２０～０．５０の範囲に調整した分散物などが挙げられる。上記分散物については、特開２０１２－１６９５５６号公報の段落００２０～０１０５の記載を参酌でき、この内容は本明細書に組み込まれる。チタンブラックの市販品の例としては、チタンブラック１０Ｓ、１２Ｓ、１３Ｒ、１３Ｍ、１３Ｍ－Ｃ、１３Ｒ－Ｎ、１３Ｍ－Ｔ（商品名：三菱マテリアル（株）製）、ティラック（Ｔｉｌａｃｋ）Ｄ（商品名：赤穂化成（株）製）などが挙げられる。 (black colorant)
The black colorant is not particularly limited, and known ones can be used. The black colorant is preferably a pigment (black pigment). In this specification, the black colorant means a colorant that exhibits absorption over the entire wavelength range of 400 to 700 nm. For example, 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. For example, it is possible to coat the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, treatment with a water-repellent substance as disclosed in Japanese Patent Laid-Open No. 2007-302836 is also possible. Color index (C.I.) Pigment Black 1, 7 can also be used as the black colorant. Titanium black preferably has a small primary particle size and an average primary particle size of individual particles. Specifically, the average primary particle size is preferably 10 to 45 nm. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms and Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50, may be mentioned. Regarding the dispersion, the description in paragraphs 0020 to 0105 of JP-A-2012-169556 can be referred to, and the contents thereof are incorporated herein. 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.
　有機黒色色材としては、ビスベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物、アゾ化合物などが挙げられ、ビスベンゾフラノン化合物、ペリレン化合物が好ましい。ビスベンゾフラノン化合物としては、特表２０１０－５３４７２６号公報、特表２０１２－５１５２３３号公報、特表２０１２－５１５２３４号公報、国際公開第２０１４／２０８３４８号、特表２０１５－５２５２６０号公報などに記載の化合物が挙げられ、例えば、ＢＡＳＦ社製の「Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ」として入手可能である。ペリレン化合物としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　３１、３２などが挙げられる。アゾメチン化合物としては、特開平０１－１７０６０１号公報、特開平０２－０３４６６４号公報などに記載の化合物が挙げられ、例えば、大日精化社製の「クロモファインブラックＡ１１０３」として入手できる。また、有機黒色色材としては、特開２０１７－２２６８２１号公報の段落００１６～００２０に記載のペリレンブラック（Ｌｕｍｏｇｅｎ　Ｂｌａｃｋ　ＦＫ４２８０等）を使用しても良い。 Examples of organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. As the 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. As a perylene compound, C.I. I. Pigment Black 31, 32 and the like. Examples of the azomethine compound include compounds described in JP-A-01-170601, JP-A-02-034664, and the like. As the organic black colorant, perylene black (Lumogen Black FK4280, etc.) described in paragraphs 0016 to 0020 of JP-A-2017-226821 may be used.
（近赤外線吸収色材）
　近赤外線吸収色材は、波長７００ｎｍを超え１４００ｎｍ以下の範囲に極大吸収波長が存在する化合物であることが好ましい。近赤外線吸収色材の極大吸収波長は、１２００ｎｍ以下であることが好ましく、１０００ｎｍ以下であることがより好ましく、９５０ｎｍ以下であることが更に好ましい。近赤外線吸収色材は、波長５５０ｎｍにおける吸光度Ａ５５０と極大吸収波長における吸光度Ａｍａｘとの比であるＡ５５０／Ａｍａｘが０．１以下であることが好ましく、０．０５以下であることがより好ましく、０．０３以下であることが更に好ましく、０．０２以下であることが特に好ましい。下限は、特に限定はないが、例えば、０．０００１以上とすることができ、０．０００５以上とすることもできる。近赤外線吸収色材は、顔料であってもよく、染料であってもよいが、顔料であることが好ましく、有機顔料であることがより好ましい。 (Near-infrared absorption colorant)
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. It is more preferably 0.03 or less, and particularly preferably 0.02 or less. The lower limit is not particularly limited, but can be, for example, 0.0001 or more, and can also be 0.0005 or more. The near-infrared absorbing colorant may be a pigment or a dye, preferably a pigment, more preferably an organic pigment.
　近赤外線吸収色材としては、特に限定はないが、ピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物、クアテリレン化合物、メロシアニン化合物、クロコニウム化合物、オキソノール化合物、イミニウム化合物、ジチオール化合物、トリアリールメタン化合物、ピロメテン化合物、アゾメチン化合物、アントラキノン化合物、ジベンゾフラノン化合物、ジチオレン金属錯体等が挙げられる。ピロロピロール化合物としては、特開２００９－２６３６１４号公報の段落番号００１６～００５８に記載の化合物、特開２０１１－０６８７３１号公報の段落番号００３７～００５２に記載の化合物、国際公開第２０１５／１６６８７３号の段落番号００１０～００３３に記載の化合物などが挙げられる。スクアリリウム化合物としては、特開２０１１－２０８１０１号公報の段落番号００４４～００４９に記載の化合物、特許第６０６５１６９号公報の段落番号００６０～００６１に記載の化合物、国際公開第２０１６／１８１９８７号の段落番号００４０に記載の化合物、特開２０１５－１７６０４６号公報に記載の化合物、国際公開第２０１６／１９０１６２号の段落番号００７２に記載の化合物、特開２０１６－０７４６４９号公報の段落番号０１９６～０２２８に記載の化合物、特開２０１７－０６７９６３号公報の段落番号０１２４に記載の化合物、国際公開第２０１７／１３５３５９号に記載の化合物、特開２０１７－１１４９５６号公報に記載の化合物、特許６１９７９４０号公報に記載の化合物、国際公開第２０１６／１２０１６６号に記載の化合物などが挙げられる。シアニン化合物としては、特開２００９－１０８２６７号公報の段落番号００４４～００４５に記載の化合物、特開２００２－１９４０４０号公報の段落番号００２６～００３０に記載の化合物、特開２０１５－１７２００４号公報に記載の化合物、特開２０１５－１７２１０２号公報に記載の化合物、特開２００８－０８８４２６号公報に記載の化合物、国際公開第２０１６／１９０１６２号の段落番号００９０に記載の化合物、特開２０１７－０３１３９４号公報に記載の化合物などが挙げられる。クロコニウム化合物としては、特開２０１７－０８２０２９号公報に記載の化合物が挙げられる。イミニウム化合物としては、例えば、特表２００８－５２８７０６号公報に記載の化合物、特開２０１２－０１２３９９号公報に記載の化合物、特開２００７－０９２０６０号公報に記載の化合物、国際公開第２０１８／０４３５６４号の段落番号００４８～００６３に記載の化合物が挙げられる。フタロシアニン化合物としては、特開２０１２－０７７１５３号公報の段落番号００９３に記載の化合物、特開２００６－３４３６３１号公報に記載のオキシチタニウムフタロシアニン、特開２０１３－１９５４８０号公報の段落番号００１３～００２９に記載の化合物、特許第６０８１７７１号公報に記載のバナジウムフタロシアニン化合物、国際公開第２０２０／０７１４７０号に記載の化合物が挙げられる。ナフタロシアニン化合物としては、特開２０１２－０７７１５３号公報の段落番号００９３に記載の化合物が挙げられる。ジチオレン金属錯体としては、特許第５７３３８０４号公報に記載の化合物が挙げられる。 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 Examples include reelmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, and dithiolene metal complexes. As the 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. Compounds described in, compounds described in JP-A-2015-176046, compounds described in paragraph No. 0072 of WO 2016/190162, compounds described in paragraph Nos. 0196 to 0228 of JP-A-2016-074649 , the compound described in paragraph number 0124 of JP 2017-067963, the compound described in WO 2017/135359, the compound described in JP 2017-114956, the compound described in Patent 6197940, Examples include compounds described in International Publication No. 2016/120166. As the cyanine compound, compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, compounds described in paragraphs 0026-0030 of JP-A-2002-194040, and JP-A-2015-172004. The compound, the compound described in JP-A-2015-172102, the compound described in JP-A-2008-088426, the compound described in paragraph number 0090 of WO 2016/190162, JP-A-2017-031394 and the like compounds described in. Examples of croconium compounds include compounds described in JP-A-2017-082029. As the iminium compound, for example, compounds described in JP-A-2008-528706, compounds described in JP-A-2012-012399, compounds described in JP-A-2007-092060, International Publication No. 2018/043564 and the compounds described in paragraphs 0048 to 0063 of. Examples of the phthalocyanine compound include compounds described in paragraph number 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraph numbers 0013 to 0029 of JP-A-2013-195480. compounds, vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, 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.
　また、近赤外線吸収色材としては、特開２０１７－１９７４３７号公報に記載のスクアリリウム化合物、特開２０１７－０２５３１１号公報に記載のスクアリリウム化合物、国際公開第２０１６／１５４７８２号に記載のスクアリリウム化合物、特許第５８８４９５３号公報に記載のスクアリリウム化合物、特許第６０３６６８９号公報に記載のスクアリリウム化合物、特許第５８１０６０４号公報に記載のスクアリリウム化合物、国際公開第２０１７／２１３０４７号の段落番号００９０～０１０７に記載のスクアリリウム化合物、特開２０１８－０５４７６０号公報の段落番号００１９～００７５に記載のピロール環含有化合物、特開２０１８－０４０９５５号公報の段落番号００７８～００８２に記載のピロール環含有化合物、特開２０１８－００２７７３号公報の段落番号００４３～００６９に記載のピロール環含有化合物、特開２０１８－０４１０４７号公報の段落番号００２４～００８６に記載のアミドα位に芳香環を有するスクアリリウム化合物、特開２０１７－１７９１３１号公報に記載のアミド連結型スクアリリウム化合物、特開２０１７－１４１２１５号公報に記載のピロールビス型スクアリリウム骨格又はクロコニウム骨格を有する化合物、特開２０１７－０８２０２９号公報に記載されたジヒドロカルバゾールビス型のスクアリリウム化合物、特開２０１７－０６８１２０号公報の段落番号００２７～０１１４に記載の非対称型の化合物、特開２０１７－０６７９６３号公報に記載されたピロール環含有化合物（カルバゾール型）、特許第６２５１５３０号公報に記載されたフタロシアニン化合物、特開２０２０－０７５９５９号公報に記載されたスクアリリウム化合物、 韓国公開特許第１０－２０１９－０１３５２１７号公報に記載の銅錯体などを用いることもできる。 Further, as 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. 2017/213047 , Pyrrole ring-containing compounds described in paragraph numbers 0019 to 0075 of JP-A-2018-054760, pyrrole ring-containing compounds described in paragraph numbers 0078-0082 of JP-A-2018-040955, JP-A-2018-002773 A pyrrole ring-containing compound described in paragraph numbers 0043 to 0069 of JP-A-2018-041047, a squarylium compound having an aromatic ring at the amide α-position described in paragraph numbers 0024-0086 of JP-A-2017-179131. 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.
　組成物の全固形分中における色材の含有量は２０～８０質量％であることが好ましい。下限は、３０質量％以上であることが好ましく、４０質量％以上であることがより好ましく、５０質量％以上であることが更に好ましい。上限は、７５質量％以下であることが好ましく、７０質量％以下であることがより好ましい。
　本発明の組成物は、色材を１種のみ含んでいてもよいし、２種以上含んでいてもよい。色材を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the coloring material in the total solid content of the 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 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.
＜光重合開始剤＞＞
　第１の態様の組成物は光重合開始剤を含有することができる。硬化性化合物として重合性モノマーを用いた場合には、光重合開始剤を含有することが好ましい。光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する化合物が好ましい。光重合開始剤は、光ラジカル重合開始剤であることが好ましい。 <Photoinitiator>>
The composition of the first aspect can contain a photoinitiator. When a polymerizable monomer is used as the curable compound, it 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.
　光重合開始剤としては、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物など）、アシルホスフィン化合物、ヘキサアリールビイミダゾール化合物、オキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、α－ヒドロキシケトン化合物、α－アミノケトン化合物などが挙げられる。光重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、ヘキサアリールビイミダゾール化合物、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン－ベンゼン－鉄錯体、ハロメチルオキサジアゾール化合物および３－アリール置換クマリン化合物であることが好ましく、オキシム化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、および、アシルホスフィン化合物から選ばれる化合物であることがより好ましく、オキシム化合物であることが更に好ましい。また、光重合開始剤としては、特開２０１４－１３０１７３号公報の段落００６５～０１１１に記載された化合物、特許第６３０１４８９号公報に記載された化合物、ＭＡＴＥＲＩＡＬ　ＳＴＡＧＥ　３７～６０ｐ，ｖｏｌ．１９，Ｎｏ．３，２０１９に記載されたパーオキサイド系光重合開始剤、国際公開第２０１８／２２１１７７号に記載の光重合開始剤、国際公開第２０１８／１１０１７９号に記載の光重合開始剤、特開２０１９－０４３８６４号公報に記載の光重合開始剤、特開２０１９－０４４０３０号公報に記載の光重合開始剤、特開２０１９－１６７３１３号公報に記載の過酸化物系開始剤、特開２０２０－０５５９９２号公報に記載のオキサゾリジン基を有するアミノアセトフェノン系開始剤、特開２０１３－１９０４５９号公報に記載のオキシム系光重合開始剤、特開２０２０－１７２６１９号公報に記載の重合体、国際公開第２０２０／１５２１２０号に記載の式１で表される化合物などが挙げられ、これらの内容は本明細書に組み込まれる。 Examples of 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, α-hydroxyketone compounds, α-aminoketone compounds and the like. From the viewpoint of exposure sensitivity, photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-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, α-hydroxyketones compounds, α-aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds. Further, as the photopolymerization initiator, compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3, the peroxide photopolymerization initiator described in 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiator described in JP-A-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, the peroxide-based initiator described in JP-A-2020-055992. An aminoacetophenone-based initiator having an oxazolidine group described, an oxime-based photopolymerization initiator described in JP-A-2013-190459, a polymer described in JP-A-2020-172619, and International Publication No. 2020/152120. and the compounds of Formula 1 described, the contents of which are incorporated herein.
　ヘキサアリールビイミダゾール化合物の具体例としては、２，２’，４－トリス（２－クロロフェニル）－５－（３，４－ジメトキシフェニル）－４，５－ジフェニル－１，１’－ビイミダゾールなどが挙げられる。 Specific examples of hexaarylbiimidazole compounds include 2,2′,4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1′-biimidazole, etc. is mentioned.
　α－ヒドロキシケトン化合物の市販品としては、Ｏｍｎｉｒａｄ　１８４、Ｏｍｎｉｒａｄ　１１７３、Ｏｍｎｉｒａｄ　２９５９、Ｏｍｎｉｒａｄ　１２７（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、Ｉｒｇａｃｕｒｅ　１８４、Ｉｒｇａｃｕｒｅ　１１７３、Ｉｒｇａｃｕｒｅ　２９５９、Ｉｒｇａｃｕｒｅ　１２７（以上、ＢＡＳＦ社製）などが挙げられる。α－アミノケトン化合物の市販品としては、Ｏｍｎｉｒａｄ　９０７、Ｏｍｎｉｒａｄ　３６９、Ｏｍｎｉｒａｄ　３６９Ｅ、Ｏｍｎｉｒａｄ　３７９ＥＧ（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、Ｉｒｇａｃｕｒｅ　９０７、Ｉｒｇａｃｕｒｅ　３６９、Ｉｒｇａｃｕｒｅ　３６９Ｅ、Ｉｒｇａｃｕｒｅ　３７９ＥＧ（以上、ＢＡＳＦ社製）などが挙げられる。アシルホスフィン化合物の市販品としては、Ｏｍｎｉｒａｄ　８１９、Ｏｍｎｉｒａｄ　ＴＰＯ（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、Ｉｒｇａｃｕｒｅ　８１９、Ｉｒｇａｃｕｒｅ　ＴＰＯ（以上、ＢＡＳＦ社製）などが挙げられる。 Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above company) and the like. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by Irgacure 369E, Irgacure 379EG). made), etc. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).
　オキシム化合物としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－０８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１６５３－１６６０）に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１５６－１６２）に記載の化合物、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年、ｐｐ．２０２－２３２）に記載の化合物、特開２０００－０６６３８５号公報に記載の化合物、特表２００４－５３４７９７号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、特開２０１７－０１９７６６号公報に記載の化合物、特許第６０６５５９６号公報に記載の化合物、国際公開第２０１５／１５２１５３号に記載の化合物、国際公開第２０１７／０５１６８０号に記載の化合物、特開２０１７－１９８８６５号公報に記載の化合物、国際公開第２０１７／１６４１２７号の段落番号００２５～００３８に記載の化合物、国際公開第２０１３／１６７５１５号に記載の化合物などが挙げられる。オキシム化合物の具体例としては、３－ベンゾイルオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オン、１－［４－（フェニルチオ）フェニル］－３－シクロヘキシル－プロパン－１，２－ジオン－２－（Ｏ－アセチルオキシム）などが挙げられる。市販品としては、Ｉｒｇａｃｕｒｅ　ＯＸＥ０１、Ｉｒｇａｃｕｒｅ　ＯＸＥ０２、Ｉｒｇａｃｕｒｅ　ＯＸＥ０３、Ｉｒｇａｃｕｒｅ　ＯＸＥ０４（以上、ＢＡＳＦ社製）、ＴＲ－ＰＢＧ－３０４、ＴＲ－ＰＢＧ－３２７（トロンリー社製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－０１４０５２号公報に記載の光重合開始剤２）が挙げられる。また、オキシム化合物としては、着色性が無い化合物や、透明性が高く変色し難い化合物を用いることも好ましい。市販品としては、アデカアークルズＮＣＩ－７３０、ＮＣＩ－８３１、ＮＣＩ－９３０（以上、（株）ＡＤＥＫＡ製）などが挙げられる。 Examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No. 2015 / 152153, compounds described in WO 2017/051680, compounds described in JP 2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017/164127, Examples include compounds described in International Publication No. 2013/167515. Specific examples of 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. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (manufactured by BASF), TR-PBG-304, TR-PBG-327 (manufactured by Tronly), and Adeka Optomer N-1919 (manufactured by Tronly). ) manufactured by ADEKA, photopolymerization initiator 2) described in JP-A-2012-014052. As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Corporation).
　光重合開始剤としては、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開２０１４－１３７４６６号公報に記載の化合物、特許第６６３６０８１号公報に記載の化合物、韓国公開特許第１０－２０１６－０１０９４４４号公報に記載の化合物が挙げられる。 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.
　光重合開始剤としては、カルバゾール環の少なくとも１つのベンゼン環がナフタレン環となった骨格を有するオキシム化合物を用いることもできる。そのようなオキシム化合物の具体例としては、国際公開第２０１３／０８３５０５号に記載の化合物が挙げられる。 As the photopolymerization initiator, 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.
　光重合開始剤としては、フッ素原子を有するオキシム化合物を用いることもできる。フッ素原子を有するオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載の化合物、特表２０１４－５００８５２号公報に記載の化合物２４、３６～４０、特開２０１３－１６４４７１号公報に記載の化合物（Ｃ－３）などが挙げられる。 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.
　光重合開始剤としては、ニトロ基を有するオキシム化合物を用いることができる。ニトロ基を有するオキシム化合物は、二量体とすることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開２０１３－１１４２４９号公報の段落番号００３１～００４７、特開２０１４－１３７４６６号公報の段落番号０００８～００１２、００７０～００７９に記載されている化合物、特許４２２３０７１号公報の段落番号０００７～００２５に記載されている化合物、アデカアークルズＮＣＩ－８３１（（株）ＡＤＥＫＡ製）が挙げられる。 An oxime compound having a nitro group can be used as the photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.
　光重合開始剤としては、ベンゾフラン骨格を有するオキシム化合物を用いることもできる。具体例としては、国際公開第２０１５／０３６９１０号に記載されているＯＥ－０１～ＯＥ－７５が挙げられる。 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.
　光重合開始剤としては、カルバゾール骨格にヒドロキシ基を有する置換基が結合したオキシム化合物を用いることもできる。このような光重合開始剤としては国際公開第２０１９／０８８０５５号に記載された化合物などが挙げられる。 As the photopolymerization initiator, 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.
　光重合開始剤としては、芳香族環に電子求引性基が導入された芳香族環基ＡｒＯＸ１を有するオキシム化合物（以下、オキシム化合物ＯＸともいう）を用いることもできる。上記芳香族環基ＡｒＯＸ１が有する電子求引性基としては、アシル基、ニトロ基、トリフルオロメチル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、シアノ基が挙げられ、アシル基およびニトロ基が好ましく、耐光性に優れた膜を形成しやすいという理由からアシル基であることがより好ましく、ベンゾイル基であることが更に好ましい。ベンゾイル基は、置換基を有していてもよい。置換基としては、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシ基、アルキル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルケニル基、アルキルスルファニル基、アリールスルファニル基、アシル基またはアミノ基であることが好ましく、アルキル基、アルコキシ基、アリール基、アリールオキシ基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基またはアミノ基であることがより好ましく、アルコキシ基、アルキルスルファニル基またはアミノ基であることが更に好ましい。 As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used. Examples of the electron-withdrawing group possessed by the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferred, an acyl group is more preferred, and a benzoyl group is even more preferred because a film having excellent light resistance can be easily formed. A benzoyl group may have a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group. A sulfanyl group or an amino group is more preferred.
　オキシム化合物ＯＸは、式（ＯＸ１）で表される化合物および式（ＯＸ２）で表される化合物から選ばれる少なくとも１種であることが好ましく、式（ＯＸ２）で表される化合物であることがより好ましい。
Figure JPOXMLDOC01-appb-C000011
 　式中、ＲＸ１は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アシルオキシ基、アミノ基、ホスフィノイル基、カルバモイル基またはスルファモイル基を表し、
　ＲＸ２は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシルオキシ基またはアミノ基を表し、
　ＲＸ３～ＲＸ１４は、それぞれ独立して水素原子または置換基を表す；
　ただし、ＲＸ１０～ＲＸ１４のうち少なくとも一つは、電子求引性基である。 The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
Figure JPOXMLDOC01-appb-C000011
 In the formula, R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group,
R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl represents a sulfonyl group, an acyloxy group or an amino group,
R X3 to R X14 each independently represent a hydrogen atom or a substituent;
However, at least one of R X10 to R X14 is an electron-withdrawing group.
　電子求引性基としては、アシル基、ニトロ基、トリフルオロメチル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、シアノ基が挙げられ、アシル基およびニトロ基が好ましく、耐光性に優れた膜を形成しやすいという理由からアシル基であることがより好ましく、ベンゾイル基であることが更に好ましい。 Examples of electron-withdrawing groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups, with acyl groups and nitro groups being preferred. An acyl group is more preferred, and a benzoyl group is even more preferred, because a film having excellent properties can be easily formed.
　上記式において、ＲＸ１２が電子求引性基であり、ＲＸ１０、ＲＸ１１、ＲＸ１３、ＲＸ１４は水素原子であることが好ましい。 In the above formula, R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 and R X14 are preferably hydrogen atoms.
　オキシム化合物ＯＸの具体例としては、特許第４６００６００号公報の段落番号００８３～０１０５に記載の化合物が挙げられる。 Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.
　本発明において好ましく使用されるオキシム化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of oxime compounds preferably used in the present invention are shown below, but the present invention is not limited to these.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　オキシム化合物は、波長３５０～５００ｎｍの範囲に極大吸収波長を有する化合物が好ましく、波長３６０～４８０ｎｍの範囲に極大吸収波長を有する化合物がより好ましい。また、オキシム化合物の波長３６５ｎｍ又は波長４０５ｎｍにおけるモル吸光係数は、感度の観点から、高いことが好ましく、１０００～３０００００であることがより好ましく、２０００～３０００００であることが更に好ましく、５０００～２０００００であることが特に好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 The oxime compound is preferably a compound having a maximum absorption wavelength in 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. Further, 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).
　光重合開始剤としては、Ｉｒｇａｃｕｒｅ　ＯＸＥ０１（ＢＡＳＦ社製）および／またはＩｒｇａｃｕｒｅ　ＯＸＥ０２（ＢＡＳＦ社製）と、Ｏｍｎｉｒａｄ　２９５９（ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）とを組み合わせて用いることも好ましい。 As a photopolymerization initiator, it is also preferable to use a combination of Irgacure OXE01 (manufactured by BASF) and/or Irgacure OXE02 (manufactured by BASF) and Omnirad 2959 (manufactured by IGM Resins B.V.).
　光重合開始剤としては、２官能あるいは３官能以上の光ラジカル重合開始剤を用いてもよい。そのような光ラジカル重合開始剤を用いることにより、光ラジカル重合開始剤の１分子から２つ以上のラジカルが発生するため、良好な感度が得られる。また、非対称構造の化合物を用いた場合においては、結晶性が低下して溶剤などへの溶解性が向上して、経時で析出しにくくなり、組成物の経時安定性を向上させることができる。２官能あるいは３官能以上の光ラジカル重合開始剤の具体例としては、特表２０１０－５２７３３９号公報、特表２０１１－５２４４３６号公報、国際公開第２０１５／００４５６５号、特表２０１６－５３２６７５号公報の段落番号０４０７～０４１２、国際公開第２０１７／０３３６８０号の段落番号００３９～００５５に記載されているオキシム化合物の２量体、特表２０１３－５２２４４５号公報に記載されている化合物（Ｅ）および化合物（Ｇ）、国際公開第２０１６／０３４９６３号に記載されているＣｍｐｄ１～７、特表２０１７－５２３４６５号公報の段落番号０００７に記載されているオキシムエステル類光開始剤、特開２０１７－１６７３９９号公報の段落番号００２０～００３３に記載されている光開始剤、特開２０１７－１５１３４２号公報の段落番号００１７～００２６に記載されている光重合開始剤（Ａ）、特許第６４６９６６９号公報に記載されているオキシムエステル光開始剤などが挙げられる。 As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation becomes difficult over time, and the stability over time of the 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. 2015/004565, and Japanese Patent Publication No. 2016-532675. Paragraph numbers 0407 to 0412, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compounds described in JP-A-2013-522445 ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP 2017-523465, JP 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, described in Japanese Patent No. 6469669 and oxime ester photoinitiators.
　組成物の全固形分中における光重合開始剤の含有量は０．１～２０質量％が好ましい。下限は、０．５質量％以上が好ましく、１質量％以上がより好ましい。上限は、１５質量％以下が好ましく、１０質量％以下がより好ましい。
　本発明の組成物は、光重合開始剤を１種のみ含んでいてもよいし、２種以上含んでいてもよい。光重合開始剤を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the photopolymerization initiator in the total solid content of the 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.
The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more photopolymerization initiators are included, the total amount thereof preferably falls within the above range.
＜＜顔料誘導体＞＞
　第１の態様の組成物は顔料誘導体を含有することができる。顔料誘導体は例えば分散助剤として用いられる。顔料誘導体としては、色素骨格に酸基または塩基性基が結合した構造を有する化合物が挙げられる。 <<Pigment derivative>>
The composition of the first aspect can contain 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.
　顔料誘導体を構成する色素骨格としては、キノリン色素骨格、ベンゾイミダゾロン色素骨格、ベンゾイソインドール色素骨格、ベンゾチアゾール色素骨格、イミニウム色素骨格、スクアリリウム色素骨格、クロコニウム色素骨格、オキソノール色素骨格、ピロロピロール色素骨格、ジケトピロロピロール色素骨格、アゾ色素骨格、アゾメチン色素骨格、フタロシアニン色素骨格、ナフタロシアニン色素骨格、アントラキノン色素骨格、キナクリドン色素骨格、ジオキサジン色素骨格、ペリノン色素骨格、ペリレン色素骨格、チオインジゴ色素骨格、イソインドリン色素骨格、イソインドリノン色素骨格、キノフタロン色素骨格、イミニウム色素骨格、ジチオール色素骨格、トリアリールメタン色素骨格、ピロメテン色素骨格等が挙げられる。 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. skeleton, diketopyrrolopyrrole dye skeleton, azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, quinacridone dye skeleton, dioxazine dye skeleton, perinone dye skeleton, perylene dye skeleton, thioindigo dye skeleton, Isoindoline dye skeletons, isoindolinone dye skeletons, quinophthalone dye skeletons, iminium dye skeletons, dithiol dye skeletons, triarylmethane dye skeletons, pyrromethene dye skeletons, and the like can be mentioned.
　酸基としては、カルボキシ基、スルホ基、リン酸基、ボロン酸基、カルボン酸アミド基、スルホン酸アミド基、イミド酸基及びこれらの塩等が挙げられる。塩を構成する原子または原子団としては、アルカリ金属イオン（Ｌｉ＋、Ｎａ＋、Ｋ＋など）、アルカリ土類金属イオン（Ｃａ２＋、Ｍｇ２＋など）、アンモニウムイオン、イミダゾリウムイオン、ピリジニウムイオン、ホスホニウムイオンなどが挙げられる。カルボン酸アミド基としては、－ＮＨＣＯＲＸ１で表される基が好ましい。スルホン酸アミド基としては、－ＮＨＳＯ２ＲＸ２で表される基が好ましい。イミド酸基としては、－ＳＯ２ＮＨＳＯ２ＲＸ３、－ＣＯＮＨＳＯ２ＲＸ４、－ＣＯＮＨＣＯＲＸ５または－ＳＯ２ＮＨＣＯＲＸ６で表される基が好ましく、－ＳＯ２ＮＨＳＯ２ＲＸ３がより好ましい。ＲＸ１～ＲＸ６は、それぞれ独立に、アルキル基またはアリール基を表す。ＲＸ１～ＲＸ６が表すアルキル基及びアリール基は、置換基を有してもよい。置換基としてはハロゲン原子であることが好ましく、フッ素原子であることがより好ましい。 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. As the carboxylic acid amide group, a group represented by —NHCOR X1 is preferable. As the 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.
　塩基性基としては、アミノ基、ピリジニル基およびその塩、アンモニウム基の塩、並びにフタルイミドメチル基が挙げられる。塩を構成する原子または原子団としては、水酸化物イオン、ハロゲンイオン、カルボン酸イオン、スルホン酸イオン、フェノキシドイオンなどが挙げられる。 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.
　顔料誘導体は、可視透明性に優れた顔料誘導体（以下、透明顔料誘導体ともいう）を用いることもできる。透明顔料誘導体の４００～７００ｎｍの波長領域におけるモル吸光係数の最大値（εｍａｘ）は３０００Ｌ・ｍｏｌ－１・ｃｍ－１以下であることが好ましく、１０００Ｌ・ｍｏｌ－１・ｃｍ－１以下であることがより好ましく、１００Ｌ・ｍｏｌ－１・ｃｍ－１以下であることがさらに好ましい。εｍａｘの下限は、例えば１Ｌ・ｍｏｌ－１・ｃｍ－１以上であり、１０Ｌ・ｍｏｌ－１・ｃｍ－１以上でもよい。 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 (εmax) 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 εmax is, for example, 1 L·mol −1 ·cm −1 or more, and may be 10 L·mol −1 ·cm −1 or more.
　顔料誘導体の具体例としては、特開昭５６－１１８４６２号公報に記載の化合物、特開昭６３－２６４６７４号公報に記載の化合物、特開平０１－２１７０７７号公報に記載の化合物、特開平０３－００９９６１号公報に記載の化合物、特開平０３－０２６７６７号公報に記載の化合物、特開平０３－１５３７８０号公報に記載の化合物、特開平０３－０４５６６２号公報に記載の化合物、特開平０４－２８５６６９号公報に記載の化合物、特開平０６－１４５５４６号公報に記載の化合物、特開平０６－２１２０８８号公報に記載の化合物、特開平０６－２４０１５８号公報に記載の化合物、特開平１０－０３００６３号公報に記載の化合物、特開平１０－１９５３２６号公報に記載の化合物、国際公開第２０１１／０２４８９６号の段落番号００８６～００９８に記載の化合物、国際公開第２０１２／１０２３９９号の段落番号００６３～００９４に記載の化合物、国際公開第２０１７／０３８２５２号の段落番号００８２に記載の化合物、特開２０１５－１５１５３０号公報の段落番号０１７１に記載の化合物、特開２０１１－２５２０６５号公報の段落番号０１６２～０１８３に記載の化合物、特開２００３－０８１９７２号公報に記載の化合物、特許第５２９９１５１号公報に記載の化合物、特開２０１５－１７２７３２号公報に記載の化合物、特開２０１４－１９９３０８号公報に記載の化合物、特開２０１４－０８５５６２号公報に記載の化合物、特開２０１４－０３５３５１号公報に記載の化合物、特開２００８－０８１５６５号公報に記載の化合物、特開２０１９－１０９５１２号公報に記載の化合物、特開２０１９－１３３１５４号公報に記載の化合物、国際公開第２０２０／００２１０６号に記載のチオール連結基を有するジケトピロロピロール化合物、特開２０１８－１６８２４４号公報に記載のベンゾイミダゾロン化合物又はそれらの塩が挙げられる。 Specific examples of pigment derivatives include 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, compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, compounds 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, JP 2011-252065 described in paragraphs 0162 to 0183 Compounds, compounds described in JP-A-2003-081972, compounds described in Patent No. 5299151, compounds described in JP-A-2015-172732, compounds described in JP-A-2014-199308, JP Compounds described in 2014-085562, compounds described in JP-A-2014-035351, compounds described in JP-A-2008-081565, compounds described in JP-A-2019-109512, JP-A-2019- Compounds described in 133154, diketopyrrolopyrrole compounds having a thiol linking group described in WO 2020/002106, benzimidazolone compounds described in JP 2018-168244 or salts thereof. .
　顔料誘導体の含有量は、上述した顔料１００質量部に対して１～３０質量部が好ましく、３～２０質量部が更に好ましい。また、顔料誘導体と色材との合計の含有量は、組成物の全固形分中３５質量％以上であることが好ましく、４０質量％以上がより好ましく、４５質量％以上が更に好ましく、５０質量％以上が特に好ましい。上限は、７０質量％以下が好ましく、６５質量％以下がより好ましい。本発明の組成物は、顔料誘導体を１種のみ含んでいてもよいし、２種以上含んでいてもよい。顔料誘導体を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。顔料誘導体を２種以上含むことで、組成物の分散安定性をより向上できる。また、可視透明性に優れた顔料誘導体を用いることで、耐熱試験や耐光試験後の膜の色の変化を抑制することができ、耐熱性、耐光性が更に優れる。また、色素骨格を有する顔料誘導体と、可視透明性に優れた顔料誘導体を併用することで、分散安定性と、耐熱性と、耐光性をより高い水準で並立させることができる。 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 above pigment. Further, 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 composition. % or more is particularly preferred. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less. The 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. By containing two or more pigment derivatives, the dispersion stability of the composition can be further improved. In addition, by using 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. Further, by using a pigment derivative having a pigment skeleton and a pigment derivative excellent in visible transparency, dispersion stability, heat resistance, and light resistance can all be achieved at a higher level.
＜＜ポリアルキレンイミン＞＞
　第１の態様の組成物は、ポリアルキレンイミンを含有することもできる。ポリアルキレンイミンは例えば顔料の分散助剤として用いられる。分散助剤とは、組成物中において顔料の分散性を高めるための素材のことである。ポリアルキレンイミンとは、アルキレンイミンを開環重合したポリマーであって、２級アミノ基を少なくとも有するポリマーである。ポリアルキレンイミンは、２級アミノ基の他に、１級アミノ基や３級アミノ基を含んでいてもよい。ポリアルキレンイミンは、１級アミノ基と、２級アミノ基と、３級アミノ基とをそれぞれ含む分岐構造を有するポリマーであることが好ましい。アルキレンイミンの炭素数は２～６が好ましく、２～４がより好ましく、２または３であることが更に好ましく、２であることが特に好ましい。 <<Polyalkyleneimine>>
The composition of the first aspect can also contain a polyalkyleneimine. Polyalkyleneimines are used, for example, as dispersing aids for pigments. A dispersing aid is a material that enhances the dispersibility of the pigment in the composition. A polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine and has at least a secondary amino group. The polyalkyleneimine may contain a primary amino group or a tertiary amino group in addition to the secondary amino group. The polyalkyleneimine is preferably a polymer having a branched structure each containing a primary amino group, a secondary amino group and a tertiary amino group. The number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2.
　ポリアルキレンイミンの分子量は、２００以上であることが好ましく、２５０以上であることがより好ましい。上限は、１０００００以下であることが好ましく、５００００以下であることがより好ましく、１００００以下であることが更に好ましく、２０００以下であることが特に好ましい。なお、ポリアルキレンイミンの分子量の値について、構造式から分子量が計算できる場合は、ポリアルキレンイミンの分子量は構造式から計算した値である。一方、特定アミン化合物の分子量が構造式から計算できない、あるいは、計算が困難な場合には、沸点上昇法で測定した数平均分子量の値を用いる。また、沸点上昇法でも測定できない、あるいは、測定が困難な場合は、粘度法で測定した数平均分子量の値を用いる。また、粘度法でも測定できない、あるいは、粘度法での測定が困難な場合は、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）法により測定したポリスチレン換算値での数平均分子量の値を用いる。 The molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less. Regarding the value of the molecular weight of the polyalkyleneimine, when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, when the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used. When the boiling point elevation method cannot be used or the measurement is difficult, the value of the number average molecular weight measured by the viscosity method is used. In addition, when measurement by the viscosity method is not possible or measurement by the viscosity method is difficult, the value of the number average molecular weight in terms of polystyrene measured by the GPC (gel permeation chromatography) method is used.
　ポリアルキレンイミンのアミン価は５ｍｍｏｌ／ｇ以上であることが好ましく、１０ｍｍｏｌ／ｇ以上であることがより好ましく、１５ｍｍｏｌ／ｇ以上であることが更に好ましい。 The amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
　アルキレンイミンの具体例としては、エチレンイミン、プロピレンイミン、１，２－ブチレンイミン、２，３－ブチレンイミンなどが挙げられ、エチレンイミンまたはプロピレンイミンであることが好ましく、エチレンイミンであることがより好ましい。ポリアルキレンイミンは、ポリエチレンイミンであることが特に好ましい。また、ポリエチレンイミンは、１級アミノ基を、１級アミノ基と２級アミノ基と３級アミノ基との合計に対して１０モル％以上含むことが好ましく、２０モル％以上含むことがより好ましく、３０モル％以上含むことが更に好ましい。ポリエチレンイミンの市販品としては、エポミンＳＰ－００３、ＳＰ－００６、ＳＰ－０１２、ＳＰ－０１８、ＳＰ－２００、Ｐ－１０００（以上、（株）日本触媒製）などが挙げられる。 Specific examples of alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine and the like, preferably ethyleneimine or propyleneimine, more preferably ethyleneimine. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. In addition, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more, of the primary amino group with respect to the total of the primary amino group, the secondary amino group and the tertiary amino group. , more preferably 30 mol % or more. Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, P-1000 (manufactured by Nippon Shokubai Co., Ltd.).
　組成物の全固形分中におけるポリアルキレンイミンの含有量は０．１～５質量％であることが好ましい。下限は０．２質量％以上であることが好ましく、０．５質量％以上であることがより好ましく、１質量％以上であることが更に好ましい。上限は４．５質量％以下であることが好ましく、４質量％以下であることがより好ましく、３質量％以下であることが更に好ましい。また、ポリアルキレンイミンの含有量は、顔料１００質量部に対して０．５～２０質量部であることが好ましい。下限は０．６質量部以上であることが好ましく、１質量部以上であることがより好ましく、２質量部以上であることが更に好ましい。上限は１０質量部以下であることが好ましく、８質量部以下であることがより好ましい。ポリアルキレンイミンは、１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合はそれらの合計量が上記範囲であることが好ましい。 The content of polyalkyleneimine in the total solid content of the composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. Also, the content of the polyalkyleneimine is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. Only one kind of polyalkyleneimine may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
＜＜硬化促進剤＞＞
　第１の態様の組成物は、硬化促進剤を含有することができる。硬化促進剤としては、チオール化合物、メチロール化合物、アミン化合物、ホスホニウム塩化合物、アミジン塩化合物、アミド化合物、塩基発生剤、イソシアネート化合物、アルコキシシラン化合物、オニウム塩化合物などが挙げられる。硬化促進剤の具体例としては、国際公開第２０１８／０５６１８９号の段落番号００９４～００９７に記載の化合物、特開２０１５－０３４９６３号公報の段落番号０２４６～０２５３に記載の化合物、特開２０１３－０４１１６５号公報の段落番号０１８６～０２５１に記載の化合物、特開２０１４－０５５１１４号公報に記載のイオン性化合物、特開２０１２－１５０１８０号公報の段落番号００７１～００８０に記載の化合物、特開２０１１－２５３０５４号公報に記載のエポキシ基を有するアルコキシシラン化合物、特許第５７６５０５９号公報の段落番号００８５～００９２に記載の化合物、特開２０１７－０３６３７９号公報に記載のカルボキシ基含有エポキシ硬化剤などが挙げられる。組成物の全固形分中における硬化促進剤の含有量は０．３～８．９質量％であることが好ましく、０．８～６．４質量％であることがより好ましい。硬化促進剤は、１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合はそれらの合計量が上記範囲であることが好ましい。 <<Curing accelerator>>
The composition of the first aspect can 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. Specific examples of 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 paragraph numbers 0186 to 0251 of the publication, ionic compounds described in JP 2014-055114, compounds described in paragraph numbers 0071 to 0080 of JP 2012-150180, JP 2011-253054 Alkoxysilane compounds having an epoxy group described in JP-A-2005-200557, 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 composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass. Only one curing accelerator may be used, or two or more curing accelerators may be used. When two or more types are used, the total amount thereof is preferably within the above range.
＜＜紫外線吸収剤＞＞
　第１の態様の組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤としては、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物などが挙げられる。このような化合物の具体例としては、特開２００９－２１７２２１号公報の段落番号００３８～００５２、特開２０１２－２０８３７４号公報の段落番号００５２～００７２、特開２０１３－０６８８１４号公報の段落番号０３１７～０３３４、特開２０１６－１６２９４６号公報の段落番号００６１～００８０に記載された化合物が挙げられ、これらの内容は本明細書に組み込まれる。紫外線吸収剤の市販品としては、例えば、ＵＶ－５０３（大東化学（株）製）、ＢＡＳＦ社製のＴｉｎｕｖｉｎシリーズ、Ｕｖｉｎｕｌ（ユビナール）シリーズ、住化ケムテックス（株）製のＳｕｍｉｓｏｒｂシリーズなどが挙げられる。また、ベンゾトリアゾール化合物としては、ミヨシ油脂製のＭＹＵＡシリーズ（化学工業日報、２０１６年２月１日）が挙げられる。また、紫外線吸収剤は、特許第６２６８９６７号公報の段落番号００４９～００５９に記載された化合物、国際公開第２０１６／１８１９８７号の段落番号００５９～００７６に記載された化合物、国際公開第２０２０／１３７８１９号に記載されたチオアリール基置換ベンゾトリアゾール型紫外線吸収剤を用いることもできる。組成物の全固形分中における紫外線吸収剤の含有量は、０．０１～１０質量％であることが好ましく、０．０１～５質量％であることがより好ましい。紫外線吸収剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、それらの合計量が上記範囲となることが好ましい。 <<Ultraviolet absorber>>
The composition of the first aspect can contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, paragraph numbers 0317-0317 of JP-A-2013-068814. 0334, and compounds described in paragraphs 0061 to 0080 of JP-A-2016-162946, the contents of which are incorporated herein. Examples of commercially available UV absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.), Tinuvin series and Uvinul series manufactured by BASF, and Sumisorb series manufactured by Sumika Chemtex Co., Ltd. . Moreover, as a benzotriazole compound, the MYUA series made from Miyoshi oil and fats (Chemical Daily, February 1, 2016) is mentioned. In addition, the ultraviolet absorber is a compound described in paragraph numbers 0049 to 0059 of Japanese Patent No. 6268967, a compound described in paragraph numbers 0059 to 0076 of WO 2016/181987, and WO 2020/137819. A thioaryl group-substituted benzotriazole-type ultraviolet absorber described in can also be used. The content of the ultraviolet absorber in the total solid content of the composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more are used, the total amount thereof is preferably within the above range.
＜＜重合禁止剤＞＞
　第１の態様の組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔｅｒｔ－ブチルカテコール、ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシアミン塩（アンモニウム塩、第一セリウム塩等）が挙げられる。中でも、ｐ－メトキシフェノールが好ましい。組成物の全固形分中における重合禁止剤の含有量は、０．０００１～５質量％であることが好ましい。重合禁止剤は、１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合はそれらの合計量が上記範囲であることが好ましい。 <<polymerization inhibitor>>
The composition of the first aspect can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the composition is preferably 0.0001 to 5% by mass. Only 1 type may be used for a polymerization inhibitor and 2 or more types may be used for it. When two or more types are used, the total amount thereof is preferably within the above range.
＜＜シランカップリング剤＞＞
　第１の態様の組成物は、シランカップリング剤を含有することができる。本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、ケイ素原子に直結し、加水分解反応及び縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基としては、例えば、ビニル基、（メタ）アリル基、（メタ）アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基、フェニル基などが挙げられ、アミノ基、（メタ）アクリロイル基およびエポキシ基が好ましい。シランカップリング剤の具体例としては、Ｎ－β－アミノエチル－γ－アミノプロピルメチルジメトキシシラン（信越化学工業（株）製、商品名　ＫＢＭ－６０２）、Ｎ－β－アミノエチル－γ－アミノプロピルトリメトキシシラン（信越化学工業（株）製、商品名　ＫＢＭ－６０３）、Ｎ－β－アミノエチル－γ－アミノプロピルトリエトキシシラン（信越化学工業（株）製、商品名　ＫＢＥ－６０２）、γ－アミノプロピルトリメトキシシラン（信越化学工業（株）製、商品名　ＫＢＭ－９０３）、γ－アミノプロピルトリエトキシシラン（信越化学工業（株）製、商品名　ＫＢＥ－９０３）、３－メタクリロキシプロピルメチルジメトキシシラン（信越化学工業（株）製、商品名　ＫＢＭ－５０２）、３－メタクリロキシプロピルトリメトキシシラン（信越化学工業（株）製、商品名　ＫＢＭ－５０３）等がある。また、シランカップリング剤の具体例については、特開２００９－２８８７０３号公報の段落番号００１８～００３６に記載の化合物、特開２００９－２４２６０４号公報の段落番号００５６～００６６に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。組成物の全固形分中におけるシランカップリング剤の含有量は、０．０１～１５．０質量％であることが好ましく、０．０５～１０．０質量％であることがより好ましい。シランカップリング剤は、１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合はそれらの合計量が上記範囲であることが好ましい。 <<Silane coupling agent>>
The composition of the first aspect can contain a silane coupling agent. In the present invention, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, 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. Specific examples of the silane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-amino propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxy Propylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503), and the like. Further, specific examples of the silane coupling agent 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 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 thereof is preferably within the above range.
＜＜酸化防止剤＞＞
　第１の態様の組成物は、酸化防止剤を含有することができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位（オルト位）に置換基を有する化合物が好ましい。前述の置換基としては炭素数１～２２の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス［２－［［２，４，８，１０－テトラキス（１，１－ジメチルエチル）ジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－６－イル］オキシ］エチル］アミン、トリス［２－［（４，６，９，１１－テトラ－ｔｅｒｔ－ブチルジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－２－イル）オキシ］エチル］アミン、亜リン酸エチルビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ　ＡＯ－２０、アデカスタブ　ＡＯ－３０、アデカスタブ　ＡＯ－４０、アデカスタブ　ＡＯ－５０、アデカスタブ　ＡＯ－５０Ｆ、アデカスタブ　ＡＯ－６０、アデカスタブ　ＡＯ－６０Ｇ、アデカスタブ　ＡＯ－８０、アデカスタブ　ＡＯ－３３０（以上、（株）ＡＤＥＫＡ製）などが挙げられる。また、酸化防止剤は、特許第６２６８９６７号公報の段落番号００２３～００４８に記載された化合物、国際公開第２０１７／００６６００号に記載された化合物、国際公開第２０１７／１６４０２４号に記載された化合物、韓国公開特許第１０－２０１９－００５９３７１号公報に記載された化合物を使用することもできる。組成物の全固形分中における酸化防止剤の含有量は、０．０１～２０質量％であることが好ましく、０．３～１５質量％であることがより好ましい。酸化防止剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合はそれらの合計量が上記範囲であることが好ましい。 <<Antioxidant>>
The composition of the first aspect 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. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like. In addition, antioxidants are compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, compounds described in WO 2017/164024, Compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used. The content of the antioxidant in the total solid content of the composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
＜＜その他成分＞＞
　第１の態様の組成物は、必要に応じて、増感剤、フィラー、熱硬化促進剤、可塑剤及びその他の助剤類（例えば、導電性粒子、消泡剤、難燃剤、レベリング剤、剥離促進剤、香料、表面張力調整剤、連鎖移動剤など）を含有してもよい。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開２０１２－００３２２５号公報の段落番号０１８３以降（対応する米国特許出願公開第２０１３／００３４８１２号明細書の段落番号０２３７）の記載、特開２００８－２５００７４号公報の段落番号０１０１～０１０４、０１０７～０１０９等の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、第１の態様の組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、１００～２５０℃で加熱するか、又は酸／塩基触媒存在下で８０～２００℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第２０１４／０２１０２３号、国際公開第２０１７／０３０００５号、特開２０１７－００８２１９号公報に記載された化合物が挙げられる。潜在酸化防止剤の市販品としては、アデカアークルズＧＰＡ－５００１（（株）ＡＤＥＫＡ製）等が挙げられる。 <<Other Ingredients>>
The composition of the first aspect may optionally contain sensitizers, 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. The composition of the first aspect may also contain latent antioxidants, if desired. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
　第１の態様の組成物は、耐光性改良剤を含んでもよい。耐光性改良剤としては、特開２０１７－１９８７８７号公報の段落番号００３６～００３７に記載の化合物、特開２０１７－１４６３５０号公報の段落番号００２９～００３４に記載の化合物、特開２０１７－１２９７７４号公報の段落番号００３６～００３７、００４９～００５２に記載の化合物、特開２０１７－１２９６７４号公報の段落番号００３１～００３４、００５８～００５９に記載の化合物、特開２０１７－１２２８０３号公報の段落番号００３６～００３７、００５１～００５４に記載の化合物、国際公開第２０１７／１６４１２７号の段落番号００２５～００３９に記載の化合物、特開２０１７－１８６５４６号公報の段落番号００３４～００４７に記載の化合物、特開２０１５－０２５１１６号公報の段落番号００１９～００４１に記載の化合物、特開２０１２－１４５６０４号公報の段落番号０１０１～０１２５に記載の化合物、特開２０１２－１０３４７５号公報の段落番号００１８～００２１に記載の化合物、特開２０１１－２５７５９１号公報の段落番号００１５～００１８に記載の化合物、特開２０１１－１９１４８３号公報の段落番号００１７～００２１に記載の化合物、特開２０１１－１４５６６８号公報の段落番号０１０８～０１１６に記載の化合物、特開２０１１－２５３１７４号公報の段落番号０１０３～０１５３に記載の化合物などが挙げられる。 The composition of the first aspect may contain a light resistance improver. As the light resistance improver, compounds described in paragraph numbers 0036 to 0037 of JP-A-2017-198787, compounds described in paragraph numbers 0029-0034 of JP-A-2017-146350, JP-A-2017-129774 Compounds described in paragraph numbers 0036 to 0037, 0049 to 0052 of JP 2017-129674 JP 2017-129674 paragraph numbers 0031 to 0034, 0058 to 0059 compounds described in JP 2017-122803 paragraph numbers 0036 to 0037 , compounds described in 0051 to 0054, compounds described in paragraph numbers 0025 to 0039 of WO 2017/164127, compounds described in paragraph numbers 0034 to 0047 of JP 2017-186546, JP 2015-025116 Compounds described in paragraph numbers 0019 to 0041 of JP-A-2012-145604, compounds described in paragraph numbers 0101-0125 of JP-A-2012-103475, compounds described in paragraph numbers 0018-0021 of JP-A-2012-103475, in particular Compounds described in paragraphs 0015 to 0018 of JP 2011-257591, compounds described in paragraphs 0017 to 0021 of JP 2011-191483, described in paragraphs 0108 to 0116 of JP 2011-145668 and compounds described in paragraph numbers 0103 to 0153 of JP-A-2011-253174.
　環境規制の観点から、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩の使用が規制されることがある。本発明の組成物において、上記した化合物の含有率を小さくする場合、パーフルオロアルキルスルホン酸（特にパーフルオロアルキル基の炭素数が６～８のパーフルオロアルキルスルホン酸）及びその塩、並びにパーフルオロアルキルカルボン酸（特にパーフルオロアルキル基の炭素数が６～８のパーフルオロアルキルカルボン酸）及びその塩の含有率は、組成物の全固形分に対して、０．０１ｐｐｂ～１，０００ｐｐｂの範囲であることが好ましく、０．０５ｐｐｂ～５００ｐｐｂの範囲であることがより好ましく、０．１ｐｐｂ～３００ｐｐｂの範囲であることが更に好ましい。本発明の組成物は、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩を実質的に含まなくてもよい。例えば、パーフルオロアルキルスルホン酸及びその塩の代替となりうる化合物、並びにパーフルオロアルキルカルボン酸及びその塩の代替となりうる化合物を用いることで、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩を実質的に含まない組成物を選択してもよい。規制化合物の代替となりうる化合物としては、例えば、パーフルオロアルキル基の炭素数の違いによって規制対象から除外された化合物が挙げられる。ただし、上記した内容は、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩の使用を妨げるものではない。本発明の組成物は、許容される最大の範囲内で、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩を含んでもよい。 From the perspective of environmental regulations, the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts may be regulated. In the composition of the present invention, when the content of the above compounds is reduced, perfluoroalkylsulfonic acid (especially perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and salts thereof, and perfluoro The content of alkylcarboxylic acid (especially perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is in the range of 0.01ppb to 1,000ppb relative to the total solid content of the composition. , more preferably in the range of 0.05 ppb to 500 ppb, even more preferably in the range of 0.1 ppb to 300 ppb. The composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts. For example, by using 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. Examples of compounds that can substitute for regulated compounds include compounds that are excluded from the scope of regulation due to differences in the number of carbon atoms in perfluoroalkyl groups. However, the above content does not prevent the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts. The compositions of the present invention may contain perfluoroalkylsulfonic acids and their salts and perfluoroalkylcarboxylic acids and their salts within the maximum permissible range.
［第２の態様の組成物］
＜＜無機粒子＞＞
　第２の態様の組成物は無機粒子を含む。無機粒子としては、シリカ粒子、酸化チタン粒子、チタン酸ストロンチウム粒子、チタン酸バリウム粒子、酸化亜鉛粒子、酸化マグネシウム粒子、酸化ジルコニウム粒子、酸化アルミニウム粒子、硫酸バリウム粒子、水酸化アルミニウム粒子、ケイ酸カルシウム粒子、ケイ酸アルミニウム粒子、硫化亜鉛粒子などが挙げられ、シリカ粒子であることが好ましい。無機粒子としてシリカ粒子を用いた組成物は、隔壁形成用の組成物として好ましく用いられる。 [Composition of the second aspect]
<<Inorganic particles>>
The composition of the second aspect comprises inorganic particles. Examples of inorganic particles include silica particles, titanium oxide particles, strontium titanate particles, barium titanate particles, zinc oxide particles, magnesium oxide particles, zirconium oxide particles, aluminum oxide particles, barium sulfate particles, aluminum hydroxide particles, and calcium silicate. particles, aluminum silicate particles, zinc sulfide particles, etc., and silica particles are preferred. A composition using silica particles as inorganic particles is preferably used as a composition for forming partition walls.
　シリカ粒子としては、複数個の球状シリカが数珠状に連結した形状のシリカ粒子、複数個の球状シリカが平面的に連結した形状のシリカ粒子、中空構造のシリカ粒子、中実シリカ粒子などが挙げられる。中実シリカ粒子の市販品としては、例えば、ＰＬ－２Ｌ－ＩＰＡ（扶桑化学工業（株）製）などが挙げられる。 Examples of silica particles include silica particles in which a plurality of spherical silica particles are connected in a beaded shape, silica particles in which a plurality of spherical silica particles are connected in a plane, silica particles with a hollow structure, solid silica particles, and the like. be done. Commercially available solid silica particles include, for example, PL-2L-IPA (manufactured by Fuso Chemical Industry Co., Ltd.).
　シリカ粒子は、より屈折率の小さい膜を形成しやすいという理由から、複数個の球状シリカが数珠状に連結した形状のシリカ粒子、複数個の球状シリカが平面的に連結した形状のシリカ粒子および中空構造のシリカ粒子が好ましく、複数個の球状シリカが数珠状に連結した形状のシリカ粒子および複数個の球状シリカが平面的に連結した形状のシリカ粒子が好ましい。以下、複数個の球状シリカが数珠状に連結した形状のシリカ粒子と複数個の球状シリカが平面的に連結した形状のシリカ粒子とをあわせて数珠状シリカともいう。なお、複数個の球状シリカが数珠状に連結した形状のシリカ粒子は、複数個の球状シリカが平面的に連結した形状を有していてもよい。 Since silica particles tend to form a film with a smaller refractive index, silica particles having a shape in which a plurality of spherical silicas are linked in a beaded shape, silica particles having a shape in which a plurality of spherical silicas are planarly linked, and Silica particles having a hollow structure are preferred, and silica particles having a shape in which a plurality of spherical silica particles are linked in a beaded shape and silica particles in a shape in which a plurality of spherical silica particles are planarly linked are preferable. Hereinafter, a silica particle having a shape in which a plurality of spherical silica particles are linked in a beaded shape and a silica particle having a shape in which a plurality of spherical silica particles are planarly linked are collectively referred to as beaded silica. The silica particles having a shape in which a plurality of spherical silica particles are linked in a beaded shape may have a shape in which a plurality of spherical silica particles are planarly linked.
　なお、本明細書において「球状シリカ」における「球状」とは、実質的に球形であれば良く、本発明の効果を奏する範囲で、変形していてもよい意味である。例えば、表面に凹凸を有する形状や、所定の方向に長軸を有する扁平形状も含む意味である。また、「複数個の球状シリカが数珠状に連結されている」とは、複数個の球状シリカ同士が直鎖状および／または分岐した形で繋がった構造を意味する。例えば、図１に示すように、複数個の球状シリカ１同士が、これよりも外径の小さい接合部２で連結された構造が挙げられる。また、本発明において、「複数個の球状シリカが数珠状に連結されている」構造としては、リング状につながった形態をなしている構造のみならず、末端を有する鎖状の形態をなしている構造も含まれる。また、「複数個の球状シリカが平面的に連結されている」とは、複数個の球状シリカ同士が、略同一平面上において連結された構造を意味する。なお、「略同一平面」とは同一平面である場合のみならず、同一平面から上下にずれていてもよい意味である。例えば、球状シリカの粒子径の５０％以下の範囲で上下にずれていてもよい。 In this specification, the term "spherical" in "spherical silica" means that it may be substantially spherical, and may be deformed within the scope of the effects of the present invention. For example, it includes a shape having unevenness on the surface and a flat shape having a long axis in a predetermined direction. In addition, "a plurality of spherical silica particles are linked in a beaded manner" means a structure in which a plurality of spherical silica particles are linked in a linear and/or branched form. For example, as shown in FIG. 1, there is a structure in which a plurality of spherical silica particles 1 are connected to each other by a joint portion 2 having an outer diameter smaller than that of the spherical silica particles. In addition, in the present invention, the structure in which "a plurality of spherical silica particles are linked in a beaded shape" includes not only a structure in which a ring is connected, but also a chain-like structure having an end. It also includes structures with In addition, "a plurality of spherical silica particles are planarly connected" means a structure in which a plurality of spherical silica particles are connected to each other on substantially the same plane. It should be noted that "substantially the same plane" means not only the same plane, but also the vertical deviation from the same plane. For example, the vertical deviation may be within a range of 50% or less of the particle diameter of the spherical silica.
　数珠状シリカは、動的光散乱法により測定された平均粒子径Ｄ１と下記式（１）により得られる平均粒子径Ｄ２との比Ｄ１／Ｄ２が３以上であることが好ましい。Ｄ１／Ｄ２の上限は特にないが、１０００以下であることが好ましく、８００以下であることがより好ましく、５００以下であることが更に好ましい。Ｄ１／Ｄ２をこのような範囲とすることにより、良好な光学特性を発現することができる。なお、数珠状シリカにおけるＤ１／Ｄ２の値は、球状シリカのつながり度合の指標でもある。
　Ｄ２＝２７２０／Ｓ　　　・・・（１）
　式中、Ｄ２は数珠状シリカの平均粒子径であって、単位はｎｍであり、Ｓは、窒素吸着法により測定された数珠状シリカの比表面積であって、単位はｍ２／ｇである。 The beaded silica preferably has a ratio D 1 /D 2 of 3 or more between the average particle diameter D 1 measured by the dynamic light scattering method and the average particle diameter D 2 obtained by the following formula (1). Although there is no particular upper limit for D 1 /D 2 , it is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less. Favorable optical properties can be exhibited by setting D 1 /D 2 within such a range. The value of D 1 /D 2 in beaded silica is also an index of the degree of connection of spherical silica.
D2 =2720/S (1)
In the formula, D 2 is the average particle size of beaded silica in units of nm, and S is the specific surface area of beaded silica measured by the nitrogen adsorption method in units of m 2 /g. be.
　数珠状シリカの上記平均粒子径Ｄ２は、球状シリカの一次粒子に近似する平均粒子径とみなすことができる。平均粒子径Ｄ２は１ｎｍ以上であることが好ましく、３ｎｍ以上であることがより好ましく、５ｎｍ以上であることが更に好ましく、７ｎｍ以上であることが特に好ましい。上限としては、１００ｎｍ以下であることが好ましく、８０ｎｍ以下であることがより好ましく、７０ｎｍ以下であることが更に好ましく、６０ｎｍ以下であることがより一層好ましく、５０ｎｍ以下であることが特に好ましい。 The average particle size D2 of beaded silica can be regarded as an average particle size approximate to the primary particles of spherical silica. The average particle diameter D2 is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more, and particularly preferably 7 nm or more. The upper limit is preferably 100 nm or less, more preferably 80 nm or less, even more preferably 70 nm or less, even more preferably 60 nm or less, and particularly preferably 50 nm or less.
　平均粒子径Ｄ２は、透過型電子顕微鏡（ＴＥＭ）によって測定した球状部分の投影像における円相当直径（Ｄ０）で代用することができる。円相当直径による平均粒子径はとくに断らない限り、５０個以上の粒子の数平均で評価する。 The average particle diameter D2 can be substituted by the equivalent circle diameter (D0) in the projected image of the spherical portion measured by a transmission electron microscope (TEM). Unless otherwise specified, the average particle diameter of 50 or more particles is evaluated as the number average of 50 or more particles.
　数珠状シリカの上記平均粒子径Ｄ１は、複数の球状シリカがまとまった二次粒子の数平均粒子径とみなすことができる。したがって、通常、Ｄ１＞Ｄ２の関係が成り立つ。平均粒子径Ｄ１は、２５ｎｍ以上であることが好ましく、３０ｎｍ以上であることがより好ましく、３５ｎｍ以上であることが特に好ましい。上限としては、１０００ｎｍ以下であることが好ましく、７００ｎｍ以下であることがより好ましく、５００ｎｍ以下であることがさらに好ましく、３００ｎｍ以下であることが特に好ましい。 The average particle diameter D1 of beaded silica can be regarded as the number average particle diameter of secondary particles in which a plurality of spherical silica particles are aggregated. Therefore, the relationship D 1 >D 2 usually holds. The average particle diameter D1 is preferably 25 nm or more, more preferably 30 nm or more, and particularly preferably 35 nm or more. The upper limit is preferably 1000 nm or less, more preferably 700 nm or less, even more preferably 500 nm or less, and particularly preferably 300 nm or less.
　数珠状シリカの上記平均粒子径Ｄ１の測定は、特に断らない限り、動的光散乱式粒径分布測定装置（日機装製　ナノトラック　Ｎａｎｏｔｒａｃ　Ｗａｖｅ－ＥＸ１５０［商品名］）を用いて行う。手順は以下のとおりである。数珠状シリカの分散液を２０ｍｌサンプル瓶に分取し、トルエンにより固形分濃度が０．２質量％になるように希釈調整する。希釈後の試料溶液は、４０ｋＨｚの超音波を１分間照射し、その直後に試験に使用する。温度２５℃で２ｍｌの測定用石英セルを使用してデータ取り込みを１０回行い、得られた「数平均」を平均粒子径とする。その他の詳細な条件等は必要によりＪＩＳＺ８８２８：２０１３「粒子径解析－動的光散乱法」の記載を参照する。１水準につき５つの試料を作製しその平均値を採用する。 Measurement of the average particle diameter D1 of the beaded silica is performed using a dynamic light scattering particle size distribution analyzer (Nikkiso Nanotrac Wave-EX150 [trade name]) unless otherwise specified. The procedure is as follows. A dispersion liquid of beaded silica is put into a 20 ml sample bottle, and diluted with toluene so that the solid content concentration becomes 0.2% by mass. The sample solution after dilution is irradiated with ultrasonic waves of 40 kHz for 1 minute and immediately used for the test. A 2 ml measurement quartz cell is used at a temperature of 25° C., data is taken in 10 times, and the obtained "number average" is taken as the average particle size. For other detailed conditions, etc., refer to the description of JISZ8828:2013 "Particle Size Analysis-Dynamic Light Scattering Method" as necessary. Five samples are prepared for each level and the average value is adopted.
　数珠状シリカは、平均粒子径１～８０ｎｍの球状シリカが、連結材を介して複数個連結していることが好ましい。球状シリカの平均粒子径の上限としては、７０ｎｍ以下であることが好ましく、６０ｎｍ以下であることがより好ましく、５０ｎｍ以下であることが更に好ましい。また、球状シリカの平均粒子径の下限としては、３ｎｍ以上であることが好ましく、５ｎｍ以上であることがより好ましく、７ｎｍ以上であることが更に好ましい。なお、本発明において球状シリカの平均粒子径の値は、透過型電子顕微鏡（ＴＥＭ）によって測定した球状部分の投影像における円相当直径から求められる平均粒子径の値を用いる。 As for the beaded silica, it is preferable that a plurality of spherical silica particles having an average particle diameter of 1 to 80 nm are connected via a connecting material. The upper limit of the average particle size of spherical silica is preferably 70 nm or less, more preferably 60 nm or less, and even more preferably 50 nm or less. The lower limit of the average particle size of spherical silica is preferably 3 nm or more, more preferably 5 nm or more, and even more preferably 7 nm or more. In the present invention, the average particle size of spherical silica is determined from the equivalent circle diameter in the projected image of the spherical portion measured by a transmission electron microscope (TEM).
　球状シリカ同士を連結する連結材としては、金属酸化物含有シリカが挙げられる。金属酸化物としては、例えば、Ｃａ、Ｍｇ、Ｓｒ、Ｂａ、Ｚｎ、Ｓｎ、Ｐｂ、Ｎｉ、Ｃｏ、Ｆｅ、Ａｌ、Ｉｎ、Ｙ、Ｔｉから選ばれる金属の酸化物などが挙げられる。金属酸化物含有シリカとしては、これらの金属酸化物とシリカ（ＳｉＯ２）との反応物、混合物などが挙げられる。連結材については、国際公開第２０００／０１５５５２号の記載を参酌でき、この内容は本明細書に組み込まれる。 Metal oxide-containing silica can be used as a connecting material for connecting spherical silica particles. Examples of metal oxides include oxides of metals selected from Ca, Mg, Sr, Ba, Zn, Sn, Pb, Ni, Co, Fe, Al, In, Y, and Ti. Examples of metal oxide-containing silica include reaction products and mixtures of these metal oxides and silica (SiO 2 ). Regarding the connecting member, the description of International Publication No. WO 2000/015552 can be considered, and the content thereof is incorporated herein.
　数珠状シリカにおける球状シリカの連結数としては、３個以上が好ましく、５個以上がより好ましい。上限は、１０００個以下が好ましく、８００個以下がより好ましく、５００個以下が更に好ましい。球状シリカの連結数は、ＴＥＭで測定できる。 The number of spherical silica connections in beaded silica is preferably 3 or more, more preferably 5 or more. The upper limit is preferably 1000 or less, more preferably 800 or less, even more preferably 500 or less. The number of linkages of spherical silica can be measured by TEM.
　数珠状シリカとしては、球状シリカの表面をヘキサメチルジシラザンなどで表面処理したものを用いてもよい。 As the beaded silica, spherical silica whose surface is treated with hexamethyldisilazane or the like may be used.
　シリカ粒子は、粒子液（ゾル）の状態で用いてもよい。シリカ粒子を分散させる媒体としては、アルコール（例えば、メタノール、エタノール、イソプロパノール）、エチレングリコール、グリコールエーテル（例えば、プロピレングリコールモノメチルエーテル）、グリコールエーテルアセテート（例えば、プロピレングリコールモノメチルエーテルアセテート）等が例示される。また、後述する溶剤Ａ１、溶剤Ａ２などを用いることもできる。粒子液（ゾル）において、ＳｉＯ２濃度は５～４０質量％であることが好ましい。 Silica particles may be used in the form of a particle liquid (sol). Examples of media for dispersing silica particles include alcohols (e.g., methanol, ethanol, isopropanol), ethylene glycol, glycol ethers (e.g., propylene glycol monomethyl ether), glycol ether acetates (e.g., propylene glycol monomethyl ether acetate), and the like. be. Solvent A1, solvent A2, etc., which will be described later, can also be used. The particle liquid (sol) preferably has a SiO 2 concentration of 5 to 40% by mass.
　数珠状シリカの粒子液としては、例えば特許第４３２８９３５号公報に記載されているシリカゾル等を使用することができる。また、数珠状シリカの粒子液（ゾル）は市販品を用いることもできる。例えば、日産化学（株）製の「スノーテックス　ＯＵＰ」、「スノーテックス　ＵＰ」、「ＩＰＡ－ＳＴ－ＵＰ」、「スノーテックス　ＰＳ－Ｍ」、「スノーテックス　ＰＳ－ＭＯ」、「スノーテックス　ＰＳ－Ｓ」、「スノーテックス　ＰＳ－ＳＯ」、触媒化成工業株式会社製の「ファインカタロイドＦ－１２０」、扶桑化学工業（株）製の「クォートロンＰＬ」などが挙げられる。 As the particle liquid of beaded silica, for example, silica sol described in Japanese Patent No. 4328935 can be used. A commercial product can also be used as the particle liquid (sol) of beaded silica. For example, Nissan Chemical Co., Ltd. "Snowtex OUP", "Snowtex UP", "IPA-ST-UP", "Snowtex PS-M", "Snowtex PS-MO", "Snowtex PS- S", "Snowtex PS-SO", "Fine Cataloid F-120" manufactured by Catalysts & Chemicals Co., Ltd., and "Quatron PL" manufactured by Fuso Chemical Industry Co., Ltd., and the like.
　また、中空構造のシリカ粒子の粒子液も市販品を用いることもできる。例えば、日揮触媒化成（株）製の「スルーリア４１１０」などが挙げられる。 In addition, a commercial product can also be used as the particle liquid of silica particles with a hollow structure. For example, "Sururia 4110" manufactured by Nikki Shokubai Kasei Co., Ltd. can be used.
　組成物中における無機粒子の含有量は４質量％以上であることが好ましく、６質量％以上であることがより好ましく、７質量％以上であることが更に好ましい。上限は１５質量％以下であることが好ましく、１３質量％以下であることがより好ましく、１１質量％以下であることが更に好ましい。また、組成物の全固形分中における無機粒子の含有量は、２０質量％以上であることが好ましく、４０質量％以上であることがより好ましく、５０質量％以上であることが更に好ましく、６０質量％以上であることがより一層好ましく、７０質量％以上であることが特に好ましい。上限は、９９．９５質量％以下とすることができ、９９．９質量％以下とすることもでき、９９質量％以下とすることもでき、９５質量％以下とすることもできる。 The content of inorganic particles in the composition is preferably 4% by mass or more, more preferably 6% by mass or more, and even more preferably 7% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 11% by mass or less. In addition, the content of inorganic particles in the total solid content of the composition is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and 60% by mass or more. It is more preferably at least 70% by mass, and particularly preferably at least 70% by mass. The upper limit can be 99.95% by mass or less, 99.9% by mass or less, 99% by mass or less, or 95% by mass or less.
　無機粒子としてシリカ粒子を用いる場合には、組成物中におけるシリカ粒子の含有量は４質量％以上であることが好ましく、６質量％以上であることがより好ましく、７質量％以上であることが更に好ましい。上限は１５質量％以下であることが好ましく、１３質量％以下であることがより好ましく、１１質量％以下であることが更に好ましい。また、組成物の全固形分中におけるシリカ粒子の含有量は、２０質量％以上であることが好ましく、４０質量％以上であることがより好ましく、５０質量％以上であることが更に好ましく、６０質量％以上であることがより一層好ましく、７０質量％以上であることが特に好ましい。上限は、９９．９５質量％以下とすることができ、９９．９質量％以下とすることもでき、９９質量％以下とすることもでき、９５質量％以下とすることもできる。シリカ粒子の含有量が上記範囲であれば、低屈折率で反射防止効果が高く、欠陥の抑制された膜が得られやすい。また、パターン形成を行わない場合や、エッチング法でパターン形成する場合においては、組成物の全固形分中におけるシリカ粒子の含有量は高いことが好ましく、例えば９５質量％以上が好ましく、９７質量％以上がより好ましく、９９質量％以上が更に好ましい。 When silica particles are used as inorganic particles, the content of silica particles in the composition is preferably 4% by mass or more, more preferably 6% by mass or more, and preferably 7% by mass or more. More preferred. The upper limit is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 11% by mass or less. In addition, the content of silica particles in the total solid content of the composition is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and 60% by mass or more. It is more preferably at least 70% by mass, and particularly preferably at least 70% by mass. The upper limit can be 99.95% by mass or less, 99.9% by mass or less, 99% by mass or less, or 95% by mass or less. If the content of the silica particles is within the above range, it is easy to obtain a film with a low refractive index, a high antireflection effect, and suppressed defects. Further, when pattern formation is not performed, or when pattern formation is performed by an etching method, the content of silica particles in the total solid content of the composition is preferably high, for example, 95% by mass or more, preferably 97% by mass. The above is more preferable, and 99% by mass or more is even more preferable.
＜＜シリコーン系界面活性剤Ａ（特定シリコーン系界面活性剤）＞＞
　第２の態様の組成物は、上述したシリコーン系界面活性剤Ａ（特定シリコーン系界面活性剤）を含有する。特定シリコーン系界面活性剤としては、第１の態様の組成物が含むことができる特定シリコーン系界面活性剤として説明した素材が挙げられる。 <<Silicone Surfactant A (Specific Silicone Surfactant)>>
The composition of the second aspect contains the silicone-based surfactant A (specific silicone-based surfactant) described above. Specific silicone-based surfactants include materials described as specific silicone-based surfactants that can be included in the composition of the first aspect.
　組成物中における特定シリコーン系界面活性剤の含有量は、１～１０００質量ｐｐｍであることが好ましい。下限は、０．５質量ｐｐｍ以上であることが好ましく、１質量ｐｐｍ以上であることが好ましい。上限は、７５０質量ｐｐｍ以下であることが好ましく、５００質量ｐｐｍ以下であることがより好ましい。 The content of the specific silicone-based surfactant in the composition is preferably 1 to 1000 mass ppm. The lower limit is preferably 0.5 mass ppm or more, and preferably 1 mass ppm or more. The upper limit is preferably 750 mass ppm or less, more preferably 500 mass ppm or less.
＜＜他の界面活性剤＞＞
　第２の態様の組成物は、特定シリコーン系界面活性剤以外の界面活性剤（他の界面活性剤）を含有してもよい。他の界面活性剤としては、第１の態様の組成物が含むことができる他の界面活性剤として説明した素材が挙げられる。 <<Other surfactants>>
The composition of the second aspect may contain a surfactant (other surfactant) other than the specific silicone-based surfactant. Other surfactants include those materials described as other surfactants that the composition of the first aspect can contain.
　組成物中における他の界面活性剤の含有量は、１０００質量ｐｐｍ以下であることが好ましく、５００質量ｐｐｍ以下であることがより好ましく、２５０質量ｐｐｍ以下であることが更に好ましい。下限は、例えば、１質量ｐｐｍ以上とすることができる。
　また、他の界面活性剤の含有量は、特定シリコーン系界面活性剤の１００質量部に対して１００質量部以下であることが好ましく、５０質量部以下であることがより好ましく、２５質量部以下であることが更に好ましい。下限は、例えば、１質量部以上とすることができる。
　第２の態様の組成物は他の界面活性剤を含有しないことも好ましい。 The content of other surfactants in the composition is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and even more preferably 250 mass ppm or less. The lower limit can be, for example, 1 ppm by mass or more.
In addition, the content of the other surfactant is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and 25 parts by mass or less with respect to 100 parts by mass of the specific silicone surfactant. is more preferable. The lower limit can be, for example, 1 part by mass or more.
It is also preferred that the composition of the second aspect does not contain other surfactants.
＜＜溶剤＞＞
　第２の態様の組成物は溶剤を含有する。溶剤として、有機溶剤および水が挙げられ、有機溶剤を少なくとも含むことが好ましい。有機溶剤としては、脂肪族炭化水素系溶剤、ハロゲン化炭化水素系溶剤、アルコール系溶剤、エーテル系溶剤、エステル系溶剤、ケトン系溶剤、ニトリル系溶剤、アミド系溶剤、スルホキシド系溶剤、芳香族系溶剤などが挙げられる。 <<Solvent>>
The composition of the second aspect contains a solvent. Examples of the solvent include organic solvents and water, and it is preferable to include at least the organic solvent. Examples of organic solvents include aliphatic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, amide solvents, sulfoxide solvents, and aromatic solvents. Examples include solvents.
　組成物中における溶剤の含有量は、７０～９９質量％であることが好ましい。上限は９３質量％以下であることが好ましく、９２質量％以下であることがより好ましく、９０質量％以下であることが更に好ましい。下限は７５質量％以上であることが好ましく、８０質量％以上であることがより好ましく、８５質量％以上であることが更に好ましい。溶剤は、１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合はそれらの合計量が上記範囲であることが好ましい。 The content of the solvent in the composition is preferably 70-99% by mass. The upper limit is preferably 93% by mass or less, more preferably 92% by mass or less, and even more preferably 90% by mass or less. The lower limit is preferably 75% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more. Only 1 type may be used for a solvent and 2 or more types may be used for it. When two or more types are used, the total amount thereof is preferably within the above range.
　第２の態様の組成物がシリカ粒子を含む場合には、溶剤として、沸点が１９０℃以上２８０℃以下の溶剤Ａ１を含むものを用いることが好ましい。なお、本明細書において溶剤の沸点は１気圧（０．１ＭＰａ）での値である。 When the composition of the second aspect contains silica particles, it is preferable to use a solvent containing solvent A1 having a boiling point of 190°C or higher and 280°C or lower. In this specification, the boiling point of the solvent is the value at 1 atmosphere (0.1 MPa).
　溶剤Ａ１の沸点は、２００℃以上であることが好ましく、２１０℃以上であることがより好ましく、２２０℃以上であることがより好ましい。また、溶剤Ａ１の沸点は、２７０℃以下であることが好ましく、２６５℃以下であることが更に好ましい。 The boiling point of solvent A1 is preferably 200°C or higher, more preferably 210°C or higher, and more preferably 220°C or higher. The boiling point of solvent A1 is preferably 270° C. or lower, more preferably 265° C. or lower.
　溶剤Ａ１の粘度は、１０ｍＰａ・ｓ以下であることが好ましく、７ｍＰａ・ｓ以下であることがより好ましく、４ｍＰａ・ｓ以下であることがより好ましい。溶剤Ａ１の粘度の下限は、塗布性の観点から１．０ｍＰａ・ｓ以上であることが好ましく、１．４ｍＰａ・ｓ以上であることがより好ましく、１．８ｍＰａ・ｓ以上であることが更に好ましい。 The viscosity of solvent A1 is preferably 10 mPa·s or less, more preferably 7 mPa·s or less, and more preferably 4 mPa·s or less. The lower limit of the viscosity of solvent A1 is preferably 1.0 mPa·s or more, more preferably 1.4 mPa·s or more, and even more preferably 1.8 mPa·s or more from the viewpoint of coating properties. .
　溶剤Ａ１の分子量は、１００以上であることが好ましく、１３０以上であることがより好ましく、１４０以上であることが更に好ましく、１５０以上であることが特に好ましい。上限は、塗布性の観点から３００以下であることが好ましく、２９０以下であることがより好ましく、２８０以下であることが更に好ましく、２７０以下であることが特に好ましい。 The molecular weight of solvent A1 is preferably 100 or more, more preferably 130 or more, still more preferably 140 or more, and particularly preferably 150 or more. The upper limit is preferably 300 or less, more preferably 290 or less, even more preferably 280 or less, and particularly preferably 270 or less, from the viewpoint of coatability.
　溶剤Ａ１の溶解度パラメータは、８．５～１３．３（ｃａｌ／ｃｍ３）０．５であることが好ましい。上限は、１２．５（ｃａｌ／ｃｍ３）０．５以下であることが好ましく、１１．５（ｃａｌ／ｃｍ３）０．５以下であることがより好ましく、１０．５（ｃａｌ／ｃｍ３）０．５以下であることが更に好ましい。下限は、８．７（ｃａｌ／ｃｍ３）０．５以上であることが好ましく、８．９（ｃａｌ／ｃｍ３）０．５以上であることがより好ましく、９．１（ｃａｌ／ｃｍ３）０．５以上であることが更に好ましい。溶剤Ａ１の溶解度パラメータが上記範囲であれば、シリカ粒子との高い親和性が得られ、優れた塗布性が得られやすい。なお、１（ｃａｌ／ｃｍ３）０．５は、２．０４５５ＭＰａ０．５である。また、溶剤の溶解度パラメータは、ＨＳＰiＰで計算した値である。 Solvent A1 preferably has a solubility parameter of 8.5 to 13.3 (cal/cm 3 ) 0.5 . The upper limit is preferably 12.5 (cal/cm 3 ) 0.5 or less, more preferably 11.5 (cal/cm 3 ) 0.5 or less, and 10.5 (cal/cm 3 ) ) is more preferably 0.5 or less. The lower limit is preferably 8.7 (cal/cm 3 ) 0.5 or more, more preferably 8.9 (cal/cm 3 ) 0.5 or more, and 9.1 (cal/cm 3 ) is more preferably 0.5 or more. If the solubility parameter of solvent A1 is within the above range, high affinity with silica particles can be obtained, and excellent coatability can be easily obtained. Note that 1 (cal/cm 3 ) 0.5 is 2.0455 MPa 0.5 . Solvent solubility parameters are values calculated by HSPiP.
　なお、本明細書において、溶剤の溶解度パラメータは、ハンセン溶解度パラメータを用いる。具体的には、ハンセン溶解度パラメータ・ソフトウエア「ＨＳＰｉＰ　５．０．０９」を用いて算出される値を用いる。 In this specification, the Hansen solubility parameter is used as the solubility parameter of the solvent. Specifically, a value calculated using the Hansen solubility parameter software "HSPiP 5.0.09" is used.
　溶剤Ａ１は、非プロトン性溶剤であることが好ましい。溶剤Ａ１として非プロトン性溶剤を用いることで、製膜時でのシリカ粒子の凝集をより効果的に抑制できる。 The solvent A1 is preferably an aprotic solvent. By using an aprotic solvent as solvent A1, aggregation of silica particles during film formation can be more effectively suppressed.
　溶剤Ａ１は、エーテル系溶剤及びエステル系溶剤が好ましく、エステル系溶剤がより好ましい。また、溶剤Ａ１として用いられるエステル系溶剤は、ヒドロキシ基や、末端アルコキシ基を含まない化合物であることが好ましい。 Solvent A1 is preferably an ether-based solvent or an ester-based solvent, more preferably an ester-based solvent. Moreover, the ester-based solvent used as the solvent A1 is preferably a compound that does not contain a hydroxyl group or a terminal alkoxy group.
　溶剤Ａ１は、シリカ粒子との高い親和性が得られ、優れた塗布性が得られやすいという理由から、アルキレンジオールジアセテートおよび環状カルボナートから選ばれる少なくとも１種であることが好ましい。アルキレンジオールジアセテートとしては、プロピレングリコールジアセテート、１，４－ブタンジオールジアセテート、１，３－ブチレングリコールジアセテート、１，６－ヘキサンジオールジアセテートなどが挙げられる。環状カルボナートとしては、炭酸プロピレン、炭酸エチレンなどが挙げられる。 The solvent A1 is preferably at least one selected from alkylenediol diacetates and cyclic carbonates because it has a high affinity with silica particles and is likely to have excellent coatability. Alkylene diol diacetates include propylene glycol diacetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate and the like. Cyclic carbonates include propylene carbonate and ethylene carbonate.
　溶剤Ａ１の具体例としては、炭酸プロピレン（沸点２４０℃）、炭酸エチレン（沸点２６０℃）、プロピレングリコールジアセテート（沸点１９０℃）、ジプロピレングリコールメチル－ｎ－プロピルエーテル（沸点２０３℃）、ジプロピレングリコールメチルエーテルアセテート（沸点２１３℃）、１，４－ブタンジオールジアセテート（沸点２３２℃）、１，３－ブチレングリコールジアセテート（沸点２３２℃）、１，６－ヘキサンジオールジアセテート（沸点２６０℃）、ジエチレングリコールモノエチルエーテルアセテート（沸点２１７℃）、ジエチレングリコールモノブチルエーテルアセテート（沸点２４７℃）、トリアセチン（沸点２６０℃）、ジプロピレングリコ－ルモノメチルエ－テル（沸点１９０℃）、ジエチレングリコールモノエチルエーテル（沸点２０２℃）、ジプロピレングリコールモノプロピルエ－テル（沸点２１２℃）、ジプロピレングリコールモノブチルエ－テル（沸点２２９℃）、トリプロピレングリコールモノメチルエーテル（沸点２４２℃）、トリプロピレングリコールモノブチルエーテル（沸点２７４℃）などが挙げられる。 Specific examples of solvent A1 include propylene carbonate (boiling point 240°C), ethylene carbonate (boiling point 260°C), propylene glycol diacetate (boiling point 190°C), dipropylene glycol methyl-n-propyl ether (boiling point 203°C), Propylene glycol methyl ether acetate (boiling point 213°C), 1,4-butanediol diacetate (boiling point 232°C), 1,3-butylene glycol diacetate (boiling point 232°C), 1,6-hexanediol diacetate (boiling point 260°C) ° C.), diethylene glycol monoethyl ether acetate (boiling point 217° C.), diethylene glycol monobutyl ether acetate (boiling point 247° C.), triacetin (boiling point 260° C.), dipropylene glycol monomethyl ether (boiling point 190° C.), diethylene glycol monoethyl ether (boiling point 202°C), dipropylene glycol monopropyl ether (boiling point 212°C), dipropylene glycol monobutyl ether (boiling point 229°C), tripropylene glycol monomethyl ether (boiling point 242°C), tripropylene glycol monobutyl ether (boiling point 274°C) and the like.
　第２の態様の組成物に用いられる溶剤は、上記溶剤Ａ１を３質量％以上含有するものであることが好ましく、４質量％以上含有するものであることがより好ましく、５質量％以上含有するものであることが更に好ましい。この態様によれば、上述した本発明の効果が顕著に得られやすい。上限は、２０質量％以下であることが好ましく、１５質量％以下であることがより好ましく、１２質量％以下であることが更に好ましい。この態様によれば、面性状の良い膜が得られやすい。溶剤Ａ１は１種のみであってもよく、２種以上を併用してもよい。第２の態様の組成物が溶剤Ａ１を２種以上含む場合は、それらの合計が上記範囲であることが好ましい。 The solvent used in the composition of the second aspect preferably contains 3% by mass or more of the solvent A1, more preferably 4% by mass or more, and 5% by mass or more. It is more preferable that the According to this aspect, the effects of the present invention described above are likely to be obtained remarkably. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less. According to this aspect, it is easy to obtain a film with good surface properties. Only one kind of solvent A1 may be used, or two or more kinds thereof may be used in combination. When the composition of the second aspect contains two or more solvents A1, it is preferable that the total of them is within the above range.
　第２の態様の組成物に用いられる溶剤は、更に、沸点が１１０℃以上１９０℃未満の溶剤Ａ２を含有することが好ましい。この態様によれば、組成物の乾燥性を適度に高めて波状の塗布ムラの発生を効果的に抑制でき、面状の良好な膜を形成しやすい。 The solvent used in the composition of the second aspect preferably further contains solvent A2 having a boiling point of 110°C or higher and lower than 190°C. According to this aspect, the drying property of the composition can be moderately increased to effectively suppress the occurrence of wavy coating unevenness, and a film with a good surface condition can be easily formed.
　溶剤Ａ２の沸点は、１１５℃以上であることが好ましく、１２０℃以上であることがより好ましく、１３０℃以上であることがより好ましい。また、溶剤Ａ２の沸点は、１７０℃以下であることが好ましく、１５０℃以下であることが更に好ましい。溶剤Ａ２の沸点が上記範囲であれば、上述した効果がより顕著に得られやすい。 The boiling point of solvent A2 is preferably 115°C or higher, more preferably 120°C or higher, and more preferably 130°C or higher. The boiling point of solvent A2 is preferably 170° C. or lower, more preferably 150° C. or lower. If the boiling point of the solvent A2 is within the above range, the effects described above are likely to be obtained more remarkably.
　溶剤Ａ２の分子量は、上述した効果がより顕著に得られやすいという理由から、１００以上であることが好ましく、１３０以上であることがより好ましく、１４０以上であることが更に好ましく、１５０以上であることが特に好ましい。上限は、塗布性の観点から３００以下であることが好ましく、２９０以下であることがより好ましく、２８０以下であることが更に好ましく、２７０以下であることが特に好ましい。 The molecular weight of solvent A2 is preferably 100 or more, more preferably 130 or more, even more preferably 140 or more, and even more preferably 150 or more, because the above-described effects are likely to be obtained more remarkably. is particularly preferred. The upper limit is preferably 300 or less, more preferably 290 or less, even more preferably 280 or less, and particularly preferably 270 or less, from the viewpoint of coatability.
　溶剤Ａ２の溶解度パラメータは、９．０～１１．４（ｃａｌ／ｃｍ３）０．５であることが好ましい。上限は、１１．０（ｃａｌ／ｃｍ３）０．５以下であることが好ましく、１０．６（ｃａｌ／ｃｍ３）０．５以下であることがより好ましく、１０．２（ｃａｌ／ｃｍ３）０．５以下であることが更に好ましい。下限は、９．２（ｃａｌ／ｃｍ３）０．５以上であることが好ましく、９．４（ｃａｌ／ｃｍ３）０．５以上であることがより好ましく、９．６（ｃａｌ／ｃｍ３）０．５以上であることが更に好ましい。溶剤Ａ２の溶解度パラメータが上記範囲であれば、シリカ粒子との高い親和性が得られ、優れた塗布性が得られやすい。また、溶剤Ａ１の溶解度パラメータと溶剤Ａ２の溶解度パラメータとの差の絶対値は、０．０１～１．１（ｃａｌ／ｃｍ３）０．５であることが好ましい。上限は、０．９（ｃａｌ／ｃｍ３）０．５以下であることが好ましく、０．７（ｃａｌ／ｃｍ３）０．５以下であることがより好ましく、０．５（ｃａｌ／ｃｍ３）０．５以下であることが更に好ましい。下限は、０．０３（ｃａｌ／ｃｍ３）０．５以上であることが好ましく、０．０５（ｃａｌ／ｃｍ３）０．５以上であることがより好ましく、０．０８（ｃａｌ／ｃｍ３）０．５以上であることが更に好ましい。 Solvent A2 preferably has a solubility parameter of 9.0 to 11.4 (cal/cm 3 ) 0.5 . The upper limit is preferably 11.0 (cal/cm 3 ) 0.5 or less, more preferably 10.6 (cal/cm 3 ) 0.5 or less, and 10.2 (cal/cm 3 ) ) is more preferably 0.5 or less. The lower limit is preferably 9.2 (cal/cm 3 ) 0.5 or more, more preferably 9.4 (cal/cm 3 ) 0.5 or more, and 9.6 (cal/cm 3 ) ) is more preferably 0.5 or more. If the solubility parameter of solvent A2 is within the above range, high affinity with silica particles can be obtained, and excellent coatability can be easily obtained. The absolute value of the difference between the solubility parameter of solvent A1 and the solubility parameter of solvent A2 is preferably 0.01 to 1.1 (cal/cm 3 ) 0.5 . The upper limit is preferably 0.9 (cal/cm 3 ) 0.5 or less, more preferably 0.7 (cal/cm 3 ) 0.5 or less, and 0.5 (cal/cm 3 ) is more preferably 0.5 or less. The lower limit is preferably 0.03 (cal/cm 3 ) 0.5 or more, more preferably 0.05 (cal/cm 3 ) 0.5 or more, and 0.08 (cal/cm 3 ) ) is more preferably 0.5 or more.
　溶剤Ａ２は、エーテル系溶剤及びエステル系溶剤から選ばれる少なくとも１種であることが好ましく、エステル系溶剤を少なくとも含むことがより好ましく、エーテル系溶剤及びエステル系溶剤を含むことが更に好ましい。溶剤Ａ２の具体例としては、シクロヘキサノールアセテート（沸点１７３℃）、ジプロピレングリコールジメチルエーテル（沸点１７５℃）、ブチルアセテート（沸点１２６℃）、エチレングリコールモノメチルエーテルアセテート（沸点１４５℃）、プロピレングリコールモノメチルエーテルアセテート（沸点１４６℃）、３－メトキシブチルアセテート（沸点１７１℃）、プロピレングリコールモノメチルエーテル（沸点１２０℃）、３－メトキシブタノール（沸点１６１℃）、プロピレングリコールモノプロピルエ－テル（沸点１５０℃）、プロピレングリコールモノブチルエ－テル（沸点１７０℃）、エチレングリコールモノブチルエーテルアセテート（沸点１８８℃）などが挙げられ、シリカ粒子との高い親和性が得られ、優れた塗布性が得られやすいという理由からプロピレングリコールモノメチルエーテルアセテートを少なくとも含むことが好ましい。 The solvent A2 is preferably at least one selected from ether-based solvents and ester-based solvents, more preferably includes at least an ester-based solvent, and still more preferably includes an ether-based solvent and an ester-based solvent. Specific examples of solvent A2 include cyclohexanol acetate (boiling point 173°C), dipropylene glycol dimethyl ether (boiling point 175°C), butyl acetate (boiling point 126°C), ethylene glycol monomethyl ether acetate (boiling point 145°C), and propylene glycol monomethyl ether. Acetate (boiling point 146°C), 3-methoxybutyl acetate (boiling point 171°C), propylene glycol monomethyl ether (boiling point 120°C), 3-methoxybutanol (boiling point 161°C), propylene glycol monopropyl ether (boiling point 150°C) , propylene glycol monobutyl ether (boiling point 170 ° C.), ethylene glycol monobutyl ether acetate (boiling point 188 ° C.), etc., which have a high affinity with silica particles and are easy to obtain excellent coating properties. to propylene glycol monomethyl ether acetate.
　第２の態様の組成物に用いられる溶剤が溶剤Ａ２を含有する場合、溶剤Ａ２の含有量は、溶剤Ａ１の１００質量部に対して５００～５０００質量部であることが好ましい。上限は４５００質量部以下であることが好ましく、４０００質量部以下であることがより好ましく、３５００質量部以下であることが更に好ましい。下限は６００質量部以上であることが好ましく、７００質量部以上であることがより好ましく、７５０質量部以上であることが更に好ましい。また、溶剤全量中における溶剤Ａ２の含有量は、５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７０質量％以上であることが更に好ましい。上限は９５質量％以下であることが好ましく、９０質量％以下であることがより好ましく、８５質量％以下であることが更に好ましい。溶剤Ａ２の含有量が上記範囲であれば、本発明の効果がより顕著に得られやすい。溶剤Ａ２は１種のみであってもよく、２種以上を併用してもよい。第２の態様の組成物が溶剤Ａ２を２種以上含む場合は、それらの合計が上記範囲であることが好ましい。 When the solvent used in the composition of the second aspect contains solvent A2, the content of solvent A2 is preferably 500 to 5000 parts by mass with respect to 100 parts by mass of solvent A1. The upper limit is preferably 4500 parts by mass or less, more preferably 4000 parts by mass or less, and even more preferably 3500 parts by mass or less. The lower limit is preferably 600 parts by mass or more, more preferably 700 parts by mass or more, and even more preferably 750 parts by mass or more. The content of solvent A2 in the total amount of solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. If the content of the solvent A2 is within the above range, the effects of the present invention are likely to be obtained more remarkably. Only one kind of solvent A2 may be used, or two or more kinds thereof may be used in combination. When the composition of the second aspect contains two or more solvents A2, the total is preferably within the above range.
　また、第２の態様の組成物に用いられる溶剤は、溶剤Ａ１と溶剤Ａ２とを合計で６２質量％以上含有するものであることが好ましく、７２質量％以上であることがより好ましく、８２質量％以上であることが更に好ましい。上限は、１００質量％とすることもでき、９６質量％以下とすることもでき、９２質量％以下とすることもできる。 Further, the solvent used in the composition of the second aspect preferably contains the solvent A1 and the solvent A2 in a total content of 62% by mass or more, more preferably 72% by mass or more, and 82% by mass. % or more is more preferable. The upper limit can be 100% by mass, 96% by mass or less, or 92% by mass or less.
　第２の態様の組成物に用いられる溶剤は、更にメタノール、エタノールおよび２－プロピルアルコールから選ばれる少なくとも１種の溶剤Ａ３を含有することも好ましい。この態様によれば、シリカ粒子との高い親和性が得られ、優れた塗布性が得られやすい。第２の態様の組成物に用いられる溶剤が更に溶剤Ａ３を含有する場合、溶剤全量中における溶剤Ａ３の含有量は、０．１～１０質量％であることが好ましい。上限は８質量％以下であることが好ましく、６質量％以下であることがより好ましく、４質量％以下であることが更に好ましい。下限は０．３質量％以上であることが好ましく、０．５質量％以上であることがより好ましく、１質量％以上であることが更に好ましい。溶剤Ａ３の含有量が上記範囲であれば、上述した効果がより顕著に得られやすい。溶剤Ａ３は１種のみであってもよく、２種以上を併用してもよい。組成物が溶剤Ａ３を２種以上含む場合は、それらの合計が上記範囲であることが好ましい。 The solvent used in the composition of the second aspect preferably further contains at least one solvent A3 selected from methanol, ethanol and 2-propyl alcohol. According to this aspect, high affinity with silica particles can be obtained, and excellent coatability can be easily obtained. When the solvent used in the composition of the second aspect further contains solvent A3, the content of solvent A3 in the total amount of solvent is preferably 0.1 to 10% by mass. The upper limit is preferably 8% by mass or less, more preferably 6% by mass or less, and even more preferably 4% by mass or less. The lower limit is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. If the content of the solvent A3 is within the above range, the above effects can be obtained more remarkably. Only one kind of solvent A3 may be used, or two or more kinds thereof may be used in combination. When the composition contains two or more solvents A3, it is preferable that the total is within the above range.
　第２の態様の組成物に用いられる溶剤は、更に水を含有することも好ましい。この態様によれば、シリカ粒子との高い親和性が得られ、優れた塗布性が得られやすい。第２の態様の組成物に用いられる溶剤が更に水を含有する場合、溶剤全量中における水の含有量は、０．１～５質量％であることが好ましい。上限は４質量％以下であることが好ましく、２．５質量％以下であることがより好ましく、１．５質量％以下であることが更に好ましい。下限は０．３質量％以上であることが好ましく、０．５質量％以上であることがより好ましく、１．０質量％以上であることが更に好ましい。水の含有量が上記範囲であれば、上述した効果がより顕著に得られやすい。 The solvent used in the composition of the second aspect preferably further contains water. According to this aspect, high affinity with silica particles can be obtained, and excellent coatability can be easily obtained. When the solvent used for the composition of the second aspect further contains water, the content of water in the total amount of the solvent is preferably 0.1 to 5% by mass. The upper limit is preferably 4% by mass or less, more preferably 2.5% by mass or less, and even more preferably 1.5% by mass or less. The lower limit is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. If the content of water is within the above range, the effects described above are likely to be obtained more remarkably.
　第２の態様の組成物に用いられる溶剤は上述した溶剤Ａ３と水とを含むことも好ましい。シリカ粒子との高い親和性が得られ、優れた塗布性が得られやすい。第２の態様の組成物に用いられる溶剤が溶剤Ａ３と水とを含む場合、溶剤全量中における溶剤Ａ３と水の合計の含有量は、０．２～１５質量％であることが好ましい。上限は１２質量％以下であることが好ましく、９質量％以下であることがより好ましく、６質量％以下であることが更に好ましい。下限は０．４質量％以上であることが好ましく、０．７質量％以上であることがより好ましく、１．５質量％以上であることが更に好ましい。溶剤Ａ３と水との合計の含有量が上記範囲であれば、上述した効果がより顕著に得られやすい。 It is also preferable that the solvent used in the composition of the second aspect contains the above solvent A3 and water. High affinity with silica particles can be obtained, and excellent coatability can be easily obtained. When the solvent used in the composition of the second aspect contains solvent A3 and water, the total content of solvent A3 and water in the total amount of solvent is preferably 0.2 to 15% by mass. The upper limit is preferably 12% by mass or less, more preferably 9% by mass or less, and even more preferably 6% by mass or less. The lower limit is preferably 0.4% by mass or more, more preferably 0.7% by mass or more, and even more preferably 1.5% by mass or more. If the total content of solvent A3 and water is within the above range, the above-described effects can be obtained more remarkably.
　第２の態様の組成物に用いられる溶剤は、更に、沸点が２８０℃を超える溶剤Ａ４を含有することができる。この態様によれば、組成物の乾燥性を適度に高めて波状の塗布ムラの発生を効果的に抑制でき、面状の良好な膜を形成しやすい。溶剤Ａ４の沸点の上限は、４００℃以下であることが好ましく、３８０℃以下であることがより好ましく、３５０℃以下であることが更に好ましい。溶剤Ａ４は、エーテル系溶剤及びエステル系溶剤から選ばれる少なくとも１種であることが好ましい。溶剤Ａ４の具体例としては、ポリエチレングリコールモノメチルエーテルなどが挙げられる。第２の態様の組成物に用いられる溶剤が更に溶剤Ａ４を含有する場合、溶剤全量中における溶剤Ａ４の含有量は、０．５～１５質量％であることが好ましい。上限は１０質量％以下であることが好ましく、８質量％以下であることがより好ましく、６質量％以下であることが更に好ましい。下限は１質量％以上であることが好ましく、１．５質量％以上であることがより好ましく、２質量％以上であることが更に好ましい。また、第２の態様の組成物に用いられる溶剤は、溶剤Ａ４を実質的に含有しないことも好ましい。なお、溶剤Ａ４を実質的に含有しないとは、溶剤全量中における溶剤Ａ４の含有量が０．１質量％以下であることを意味し、０．０５質量％以下であることが好ましく、０．０１質量％以下であることが更に好ましく、含有しないことが更に好ましい。 The solvent used in the composition of the second aspect can further contain solvent A4 with a boiling point of over 280°C. According to this aspect, the drying property of the composition can be moderately increased to effectively suppress the occurrence of wavy coating unevenness, and a film with a good surface condition can be easily formed. The upper limit of the boiling point of solvent A4 is preferably 400° C. or lower, more preferably 380° C. or lower, and even more preferably 350° C. or lower. Solvent A4 is preferably at least one selected from ether-based solvents and ester-based solvents. Specific examples of solvent A4 include polyethylene glycol monomethyl ether. When the solvent used in the composition of the second aspect further contains solvent A4, the content of solvent A4 in the total amount of solvent is preferably 0.5 to 15% by mass. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more. It is also preferred that the solvent used in the composition of the second aspect does not substantially contain solvent A4. Note that "substantially free of solvent A4" means that the content of solvent A4 in the total amount of solvent is 0.1% by mass or less, preferably 0.05% by mass or less, and 0.1% by mass or less. It is more preferably 01% by mass or less, and more preferably not contained.
　第２の態様の組成物に用いられる溶剤は、上述した溶剤Ａ１、溶剤Ａ２、溶剤Ａ３、溶剤Ａ４および水以外の溶剤（他の溶剤）を含有してもよいが、他の溶剤を実質的に含有しないことが好ましい。なお、他の溶剤を実質的に含有しないとは、溶剤全量中における他の溶剤の含有量が０．１質量％以下であることを意味し、０．０５質量％以下であることが好ましく、０．０１質量％以下であることが更に好ましく、含有しないことが更に好ましい。 The solvent used in the composition of the second aspect may contain solvents (other solvents) other than solvent A1, solvent A2, solvent A3, solvent A4 and water described above, but other solvents are substantially It is preferable not to contain in Note that "substantially free of other solvents" means that the content of other solvents in the total amount of solvents is 0.1% by mass or less, preferably 0.05% by mass or less, It is more preferably 0.01% by mass or less, and more preferably not contained.
　第２の態様の組成物に用いられる溶剤は、分子量（高分子の場合は、重量平均分子量）が３００を超える化合物の含有量が１０質量％以下であることが好ましく、８質量％以下であることがより好ましく、５質量％以下であることが更に好ましく、３質量％以下であることがより一層好ましく、１質量％以下であることが特に好ましい。この態様によれば、より優れた塗布性が得られやすく、面状に優れた膜が得られやすい。 In the solvent used in the composition of the second aspect, the content of compounds having a molecular weight (weight average molecular weight in the case of a polymer) exceeding 300 is preferably 10% by mass or less, and is 8% by mass or less. is more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less. According to this aspect, more excellent coatability can be easily obtained, and a film having an excellent surface condition can be easily obtained.
　第２の態様の組成物に用いられる溶剤は、２５℃での粘度が１０ｍＰａ・ｓを超える化合物の含有量が１０質量％以下であることが好ましく、８質量％以下であることがより好ましく、５質量％以下であることが更に好ましく、３質量％以下であることがより一層好ましく、１質量％以下であることが特に好ましい。この態様によれば、より優れた塗布性が得られやすく、面状に優れた膜が得られやすい。 The solvent used in the composition of the second aspect preferably contains 10% by mass or less, more preferably 8% by mass or less, of compounds having a viscosity of more than 10 mPa s at 25°C. It is more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less. According to this aspect, more excellent coatability can be easily obtained, and a film having an excellent surface condition can be easily obtained.
＜＜硬化性化合物＞＞
　第２の態様の組成物は硬化性化合物を含有することができる。硬化性化合物としては、第１の態様の組成物が含むことができる硬化性化合物として説明した樹脂や重合性モノマーなどの素材が挙げられる。硬化性化合物は、樹脂を含むものであることが好ましい。 <<Curable compound>>
The composition of the second aspect can contain a curable compound. Examples of the curable compound include materials such as the resins and polymerizable monomers described as the curable compound that can be included in the composition of the first aspect. The curable compound preferably contains a resin.
　組成物中における硬化性化合物の含有量は、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上が更に好ましい。上限は、１０質量％以下が好ましく、５質量％以下がより好ましく、３質量％以下が更に好ましい。また、組成物の全固形分中における硬化性化合物の含有量は、０．１質量％以上が好ましく、０．５質量％以上がより好ましく、１質量％以上が更に好ましい。上限は、３０質量％以下が好ましく、２０質量％以下がより好ましく、１０質量％以下が更に好ましい。硬化性化合物は、１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合はそれらの合計量が上記範囲であることが好ましい。
　第２の態様の組成物は重合性モノマーを含まないことも好ましい。この態様によれば、より屈折率の低い膜を形成しやすい。更には、ヘイズの小さい膜を形成しやすい。 The content of the curable compound in the composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. The content of the curable compound in the total solid content of the composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. Only 1 type may be used for a sclerosing|hardenable compound, and 2 or more types may be used for it. When two or more types are used, the total amount thereof is preferably within the above range.
It is also preferred that the composition of the second aspect is free of polymerizable monomers. According to this aspect, it is easy to form a film with a lower refractive index. Furthermore, it is easy to form a film with a small haze.
＜＜光重合開始剤＞＞
　第２の態様の組成物は、光重合開始剤を含有することができる。光重合開始剤としては、第１の態様の組成物が含むことができる光重合開始剤として説明した素材が挙げられる。 <<Photoinitiator>>
The composition of the second aspect can contain a photoinitiator. Photoinitiators include the materials described as photoinitiators that the composition of the first aspect can contain.
　組成物中における光重合開始剤の含有量は、０．１質量％以上が好ましく、０．２質量％以上がより好ましく、０．５質量％以上が更に好ましい。上限は、１０質量％以下が好ましく、５質量％以下がより好ましく、３質量％以下がより好ましい。また、組成物の全固形分中における光重合開始剤の含有量は、１質量％以上が好ましく、２質量％以上がより好ましく、５質量％以上が更に好ましい。上限は、３０質量％以下が好ましく、２５質量％以下がより好ましく、２０質量％以下がより好ましい。光重合開始剤は、１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合はそれらの合計量が上記範囲であることが好ましい。
　第２の態様の組成物は、光重合開始剤を含まないことも好ましい。この態様によれば、より屈折率の低い膜を形成しやすい。更には、ヘイズの小さい膜を形成しやすい。 The content of the photopolymerization initiator in the composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less. Moreover, the content of the photopolymerization initiator in the total solid content of the composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and more preferably 20% by mass or less. Only one kind of photopolymerization initiator may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
It is also preferred that the composition of the second aspect does not contain a photoinitiator. According to this aspect, it is easy to form a film with a lower refractive index. Furthermore, it is easy to form a film with a small haze.
＜＜シランカップリング剤＞＞
　第２の態様の組成物は、シランカップリング剤を含有することができる。シランカップリング剤としては、第１の態様の組成物が含むことができるシランカップリング剤として説明した素材が挙げられる。 <<Silane coupling agent>>
The composition of the second aspect can contain a silane coupling agent. Silane coupling agents include materials described as silane coupling agents that the composition of the first aspect can include.
　組成物の全固形分中におけるシランカップリング剤の含有量は、０．００１質量％以上が好ましく、０．０１質量％以上がより好ましく、０．１質量％以上が特に好ましい。上限は、２０質量％以下が好ましく、１０質量％以下がより好ましく、５質量％以下が特に好ましい。シランカップリング剤は、１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合はそれらの合計量が上記範囲であることが好ましい。
　第２の態様の組成物は、シランカップリング剤を含まないことも好ましい。 The content of the silane coupling agent in the total solid content of the composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. 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 thereof is preferably within the above range.
It is also preferred that the composition of the second aspect does not contain a silane coupling agent.
＜＜黒色色材＞＞
　第２の態様の組成物は、黒色色材を含有することができる。黒色色材としては、第１の態様の組成物が含むことができる黒色色材として説明した素材が挙げられる。 <<Black color material>>
The composition of the second aspect can contain a black colorant. Black colorants include the materials described as black colorants that the composition of the first aspect can contain.
　組成物の全固形分中における黒色色材の含有量は、１０質量％以下が好ましく、５質量％以下がより好ましく、１質量％以下が特に好ましい。
　第２の態様の組成物は、黒色色材を実質的に含まないことも好ましい。なお、組成物が黒色色材を実質的に含まない場合とは、組成物の全固形分中における黒色色材の含有量が、０．１質量％以下であることを意味し、０．０５質量％以下であることが好ましく、黒色色材を含有しないことがより好ましい。 The content of the black colorant in the total solid content of the composition is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less.
It is also preferred that the composition of the second aspect does not substantially contain a black colorant. In addition, when the composition does not substantially contain a black colorant, it means that the content of the black colorant in the total solid content of the composition is 0.1% by mass or less, and 0.05 % by mass or less, and more preferably contains no black colorant.
＜＜有彩色色材＞＞
　第２の態様の組成物は、有彩色色材を含有することができる。有彩色色材としては、第１の態様の組成物が含むことができる有彩色色材として説明した素材が挙げられる。 << Chromatic color material >>
The composition of the second aspect can contain a chromatic colorant. The chromatic colorant includes the materials described as the chromatic colorant that the composition of the first aspect can contain.
　組成物の全固形分中における有彩色色材の含有量は、１０質量％以下が好ましく、５質量％以下がより好ましく、１質量％以下が特に好ましい。
　第２の態様の組成物は、有彩色色材を実質的に含まないことも好ましい。なお、組成物が有彩色色材を実質的に含まない場合とは、組成物の全固形分中における有彩色色材の含有量が、０．１質量％以下であることを意味し、０．０５質量％以下であることが好ましく、有彩色色材を含有しないことがより好ましい。 The content of the chromatic coloring material in the total solid content of the composition is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less.
It is also preferred that the composition of the second aspect does not substantially contain a chromatic colorant. In addition, when the composition does not substantially contain a chromatic colorant, it means that the content of the chromatic colorant in the total solid content of the composition is 0.1% by mass or less. It is preferably 0.05% by mass or less, and more preferably does not contain a chromatic coloring material.
＜＜その他成分＞＞
　第２の態様の組成物は、必要に応じて、紫外線吸収剤、酸化防止剤、潜在酸化防止剤、重合禁止剤、増感剤、フィラー、熱硬化促進剤、可塑剤及びその他の助剤類（例えば、導電性粒子、消泡剤、難燃剤、レベリング剤、剥離促進剤、香料、表面張力調整剤、連鎖移動剤など）を含有してもよい。これらの素材は、上述した第１の態様の組成物が含むことができるものとして説明した素材が挙げられる。 <<Other Ingredients>>
The composition of the second aspect may optionally contain ultraviolet absorbers, antioxidants, latent antioxidants, polymerization inhibitors, sensitizers, fillers, thermosetting accelerators, plasticizers and other auxiliary agents. (For example, conductive particles, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.) may be contained. These materials include the materials described as being capable of being included in the composition of the first aspect described above.
＜収容容器＞
　本発明の組成物の収容容器としては、特に限定はなく、公知の収容容器を用いることができる。また、収容容器として、原材料や着色組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成する多層ボトルや６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。また、容器内壁は、容器内壁からの金属溶出を防ぎ、組成物の保存安定性を高めたり、成分変質を抑制するなど目的で、ガラス製やステンレス製などにすることも好ましい。 <Container>
The storage container for the composition of the present invention is not particularly limited, and known storage containers can be used. In addition, as a storage container, a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resins and a bottle with a 7-layer structure of 6 types of resins for the purpose of suppressing the contamination of raw materials and coloring compositions. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351. In addition, the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the composition, and suppressing deterioration of components.
＜組成物の製造方法＞
　本発明の組成物は、前述の成分を混合して製造できる。組成物の製造に際しては、全成分を同時に溶剤に溶解および／または分散して組成物を製造してもよいし、必要に応じて、各成分を適宜２つ以上の溶液または分散液としておいて、使用時（塗布時）にこれらを混合して組成物を製造してもよい。 <Method for producing composition>
The compositions of the present invention can be prepared by admixing the aforementioned ingredients. In the production of the composition, the composition may be produced by simultaneously dissolving and/or dispersing all the components in a solvent, or if necessary, each component may be appropriately prepared as two or more solutions or dispersions. A composition may be produced by mixing these at the time of use (at the time of application).
　また、組成物の製造に際して、顔料を分散させるプロセスを含むことが好ましい。顔料を分散させるプロセスにおいて、顔料の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断、キャビテーションなどが挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、ボールミル、ペイントシェーカー、マイクロフルイダイザー、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化、超音波分散などが挙げられる。またサンドミル（ビーズミル）における顔料の粉砕においては、径の小さいビーズを使用する、ビーズの充填率を大きくする事等により粉砕効率を高めた条件で処理することが好ましい。また、粉砕処理後にろ過、遠心分離などで粗粒子を除去することが好ましい。また、顔料を分散させるプロセスおよび分散機は、「分散技術大全集、株式会社情報機構発行、２００５年７月１５日」や「サスペンション（固／液分散系）を中心とした分散技術と工業的応用の実際　総合資料集、経営開発センター出版部発行、１９７８年１０月１０日」、特開２０１５－１５７８９３号公報の段落番号００２２に記載のプロセス及び分散機を好適に使用出来る。また顔料を分散させるプロセスにおいては、ソルトミリング工程にて粒子の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器、処理条件等は、例えば、特開２０１５－１９４５２１号公報、特開２０１２－０４６６２９号公報の記載を参酌できる。分散に使用するビーズとしては、ジルコニア、メノウ、石英、チタニア、タングステンカーバイト、窒化ケイ素、アルミナ、ステンレス鋼、ガラスまたはそれらの組み合わせを使用できる。また、モース硬度が２以上の無機化合物を使用できる。組成物中に上記ビーズが１～１００００ｐｐｍ含まれていてもよい。 In addition, it is preferable that a process of dispersing the pigment is included in the production of the composition. In the process of dispersing pigments, mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like. In pulverizing the pigment in a sand mill (bead mill), it is preferable to use beads with a small diameter or to increase the filling rate of the beads so as to increase the pulverization efficiency. Moreover, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, 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 Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. In the process of dispersing the pigment, 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. Beads used for dispersion can be zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, glass, or combinations thereof. Also, an inorganic compound having a Mohs hardness of 2 or more can be used. The composition may contain 1 to 10000 ppm of the beads.
　本発明の組成物の製造にあたり、異物の除去や欠陥の低減などの目的で、組成物をフィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているフィルタであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）等のフッ素樹脂、ナイロン（例えばナイロン－６、ナイロン－６，６）等のポリアミド系樹脂、ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度、超高分子量のポリオレフィン樹脂を含む）等の素材を用いたフィルタが挙げられる。これら素材の中でもポリプロピレン（高密度ポリプロピレンを含む）およびナイロンが好ましい。 　In the production of the composition of the present invention, it is preferable to filter the composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high-molecular-weight polyolefin resin) and other materials. Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.
　フィルタの孔径は、０．０１～７．０μｍが好ましく、０．０１～３．０μｍがより好ましく、０．０５～０．５μｍが更に好ましい。フィルタの孔径が上記範囲であれば、微細な異物をより確実に除去できる。フィルタの孔径値については、フィルタメーカーの公称値を参照することができる。フィルタは、日本ポール株式会社（ＤＦＡ４２０１ＮＸＥＹ、ＤＦＡ４２０１ＮＡＥＹ、ＤＦＡ４２０１Ｊ００６Ｐなど）、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）および株式会社キッツマイクロフィルタ等が提供する各種フィルタを用いることができる。 The pore size of the filter is preferably 0.01-7.0 μm, more preferably 0.01-3.0 μm, and even more preferably 0.05-0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For 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. .
　また、フィルタとしてファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。市販品としては、ロキテクノ社製のＳＢＰタイプシリーズ（ＳＢＰ００８など）、ＴＰＲタイプシリーズ（ＴＰＲ００２、ＴＰＲ００５など）、ＳＨＰＸタイプシリーズ（ＳＨＰＸ００３など）が挙げられる。 It is also preferable to use a fiber-like filter medium as the filter. Examples of fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.
　フィルタを使用する際、異なるフィルタ（例えば、第１のフィルタと第２のフィルタなど）を組み合わせてもよい。その際、各フィルタでのろ過は、１回のみでもよいし、２回以上行ってもよい。また、上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。また、第１のフィルタでのろ過は、分散液のみに対して行い、他の成分を混合した後で、第２のフィルタでろ過を行ってもよい。また組成物の親疎水性に合わせて、適宜フィルタを選択することができる。 When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed. In addition, the filter can be appropriately selected according to the hydrophilicity/hydrophobicity of the composition.
＜膜＞
　本発明の膜は、上述した本発明の組成物から得られる膜である。本発明の膜は、カラーフィルタ、近赤外線透過フィルタ、近赤外線カットフィルタなどの光学フィルタに用いることができる。また、本発明の膜は遮光膜、隔壁などに用いることもできる。 <Membrane>
The membrane of the invention is a membrane obtained from the composition of the invention as 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. Also, the film of the present invention can be used as a light-shielding film, a partition wall, and the like.
　本発明の膜の膜厚は、目的に応じて適宜調整できる。例えば、膜厚は、２０μｍ以下が好ましく、１０μｍ以下がより好ましく、５μｍ以下がさらに好ましい。膜厚の下限は、０．１μｍ以上が好ましく、０．２μｍ以上がより好ましく、０．３μｍ以上がさらに好ましい。 The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.
　本発明の膜をカラーフィルタとして用いる場合、本発明の膜は、緑色、赤色、青色、シアン色、マゼンタ色または黄色の色相を有することが好ましい。また、本発明の膜は、カラーフィルタの着色画素として好ましく用いることができる。着色画素としては、赤色画素、緑色画素、青色画素、マゼンタ色画素、シアン色画素、黄色画素などが挙げられる。 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.
　本発明の膜を近赤外線カットフィルタとして用いる場合、本発明の膜の極大吸収波長は、波長７００～１８００ｎｍの範囲に存在することが好ましく、波長７００～１３００ｎｍの範囲に存在することがより好ましく、波長７００～１１００ｎｍの範囲に存在することが更に好ましい。また、膜の波長４００～６５０ｎｍの全範囲での透過率は７０％以上であることが好ましく、８０％以上であることがより好ましく、９０％以上であることが更に好ましい。また、膜の波長７００～１８００ｎｍの範囲の少なくとも１点での透過率は２０％以下であることが好ましい。また、極大吸収波長における吸光度Ａｍａｘと、波長５５０ｎｍにおける吸光度Ａ５５０との比である吸光度Ａｍａｘ／吸光度Ａ５５０は、２０～５００であることが好ましく、５０～５００であることがより好ましく、７０～４５０であることが更に好ましく、１００～４００であることが特に好ましい。 When the film of the present invention is used as a near-infrared cut filter, 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 1100 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. Further, 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.
　本発明の膜を近赤外線透過フィルタとして用いる場合、本発明の膜は、例えば、以下の（ｉ１）～（ｉ５）のいずれかの分光特性を有することが好ましい。
　（ｉ１）：波長４００～６４０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長８００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。このような分光特性を有する膜は、波長４００～６４０ｎｍの範囲の光を遮光して、波長７５０ｎｍを超える光を透過させることができる。
　（ｉ２）：波長４００～７５０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長９００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。このような分光特性を有する膜は、波長４００～７５０ｎｍの範囲の光を遮光して、波長８５０ｎｍを超える光を透過させることができる。
　（ｉ３）：波長４００～８３０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１０００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。このような分光特性を有する膜は、波長４００～８３０ｎｍの範囲の光を遮光して、波長９５０ｎｍを超える光を透過させることができる。
　（ｉ４）：波長４００～９５０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１１００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。このような分光特性を有する膜は、波長４００～９５０ｎｍの範囲の光を遮光して、波長１０５０ｎｍを超える光を透過させることができる。
　（ｉ５）：波長４００～１０５０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１２００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。このような分光特性を有する膜は、波長４００～１０５０ｎｍの範囲の光を遮光して、波長１１５０ｎｍを超える光を透過させることができる。 When the film of the present invention is used as a near-infrared transmission filter, the film of the present invention preferably has, for example, any one of the following spectral characteristics (i1) to (i5).
(i1): 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). 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.
(i2): 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.
(i3): 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.
(i4): 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 characteristics can block light in the wavelength range of 400 to 950 nm and transmit light in the wavelength range of 1050 nm or more.
(i5): 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.
　本発明の膜を遮光膜として用いる場合、膜の４００～１１００ｎｍの波長領域における膜厚１．５μｍあたりの光学濃度（ＯＤ：Ｏｐｔｉｃａｌ　Ｄｅｎｓｉｔｙ）は、２．５以上であることが好ましく、３．０以上であることがより好ましい。上限値は特に制限されないが、一般に１０以下であることが好ましい。
　また、上記膜の反射率は、８％未満であることが好ましく、６％未満であることがより好ましく、４％未満であることが更に好ましい。下限は、０％以上であることが好ましい。 When the film of the present invention is used as a light-shielding film, the optical density (OD) per 1.5 μm film thickness in the wavelength range of 400 to 1100 nm of the film is preferably 2.5 or more, and preferably 3.0. It is more preferable to be above. Although the upper limit is not particularly limited, it is generally preferably 10 or less.
The reflectance of the film is preferably less than 8%, more preferably less than 6%, and even more preferably less than 4%. The lower limit is preferably 0% or more.
　遮光膜は、パーソナルコンピュータ、タブレット、携帯電話、スマートフォン及びデジタルカメラ等のポータブル機器；プリンタ複合機及びスキャナ等のＯＡ（Ｏｆｆｉｃｅ　Ａｕｔｏｍａｔｉｏｎ）機器；監視カメラ、バーコードリーダ、現金自動預け払い機（ＡＴＭ：ａｕｔｏｍａｔｅｄ　ｔｅｌｌｅｒ　ｍａｃｈｉｎｅ）、ハイスピードカメラ及び顔画像認証又は生体認証を使用した本人認証機能を有する機器等の産業用機器；車載用カメラ機器；内視鏡、カプセル内視鏡及びカテーテル等の医療用カメラ機器；並びに、生体センサ、バイオセンサ、軍事偵察用カメラ、立体地図用カメラ、気象及び海洋観測カメラ、陸地資源探査カメラ及び宇宙の天文及び深宇宙ターゲット用の探査カメラ等の宇宙用機器；等に使用される光学フィルタ及びモジュールに用いることができる。また、遮光膜は、マイクロＬＥＤ（Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）及びマイクロＯＬＥＤ（Ｏｒｇａｎｉｃ　Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）等の用途にも使用できる。マイクロＬＥＤ及びマイクロＯＬＥＤとしては、例えば、特表２０１５－５００５６２号公報及び特表２０１４－５３３８９０号公報に記載された例が挙げられる。また、遮光膜は、量子ドットセンサーに用いることもできる。量子ドットセンサーとしては、例えば、米国特許出願公開第２０１２／３７７８９号明細書及び国際公開第２００８／１３１３１３号に記載された例が挙げられる。 The light-shielding film is used in portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as multi-function printers and scanners; industrial equipment such as automated teller machines), high-speed cameras, and equipment with personal authentication functions using face image authentication or biometric authentication; vehicle-mounted camera equipment; medical cameras such as endoscopes, capsule endoscopes, and catheters equipment; and space equipment such as biosensors, biosensors, military reconnaissance cameras, stereo map cameras, weather and ocean observation cameras, land resource exploration cameras and exploration cameras for space astronomy and deep space targets; It can be used for optical filters and modules used. The light-shielding film can also be used for applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes). Micro LEDs and micro OLEDs include, for example, examples described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890. Moreover, the light shielding film can also be used for a quantum dot sensor. Quantum dot sensors include, for example, examples described in US2012/37789 and WO2008/131313.
　本発明の膜を隔壁として用いる場合、本発明の膜の波長６３３ｎｍの光の屈折率は、１．４以下であることが好ましく、１．３５以下であることがより好ましく、１．３以下であることが更に好ましく、１．２７以下であることがより一層好ましい。なお、上記屈折率の値は、測定温度２５℃での値である。 When the film of the present invention is used as a partition, the refractive index of the film of the present invention for light having a wavelength of 633 nm is preferably 1.4 or less, more preferably 1.35 or less, and 1.3 or less. It is more preferably 1.27 or less. In addition, the value of the said refractive index is a value in the measurement temperature of 25 degreeC.
＜膜の製造方法＞
　本発明の膜は、本発明の組成物を支持体に塗布する工程を経て製造できる。膜の製造方法においては、更にパターンを形成する工程を含むことが好ましい。パターンの形成方法としては、フォトリソグラフィ法、ドライエッチング法が挙げられ、フォトリソグラフィ法が好ましい。 <Method for producing membrane>
The membrane of the present invention can be produced through the step of coating the composition of the present invention on a support. Preferably, the film manufacturing method further includes the step of forming a pattern. Examples of the pattern forming method include a photolithography method and a dry etching method, and the photolithography method is preferable.
　フォトリソグラフィ法によるパターン形成は、本発明の組成物を用いて支持体上に組成物層を形成する工程と、組成物層をパターン状に露光する工程と、組成物層の未露光部を現像除去してパターンを形成する工程と、を含むことが好ましい。必要に応じて、組成物層をベークする工程（プリベーク工程）、および、現像されたパターンをベークする工程（ポストベーク工程）を設けてもよい。 Pattern formation by photolithography includes the steps of forming a composition layer on a support using the composition of the present invention, patternwise exposing the composition layer, and developing the unexposed portion of the composition layer. and removing to form a pattern. If necessary, a step of baking the composition layer (pre-baking step) and a step of baking the developed pattern (post-baking step) may be provided.
　組成物層を形成する工程では、本発明の組成物を用いて、支持体上に組成物層を形成する。支持体としては、特に限定は無く、用途に応じて適宜選択できる。例えば、ガラス基板、シリコン基板などが挙げられ、シリコン基板であることが好ましい。また、シリコン基板には、電荷結合素子（ＣＣＤ）、相補型金属酸化膜半導体（ＣＭＯＳ）、透明導電膜などが形成されていてもよい。また、シリコン基板には、各画素を隔離するブラックマトリクスが形成されている場合もある。また、シリコン基板には、上部の層との密着性改良、物質の拡散防止或いは基板表面の平坦化のために下地層が設けられていてもよい。 In the step of forming the composition layer, the composition of the present invention is used to form the composition layer on the 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. In some cases, the silicon substrate is formed with a black matrix that isolates each pixel. In addition, 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.
　組成物の塗布方法としては、公知の方法を用いることができる。例えば、滴下法（ドロップキャスト）；スリットコート法；スプレー法；ロールコート法；回転塗布法（スピンコーティング）；流延塗布法；スリットアンドスピン法；プリウェット法（例えば、特開２００９－１４５３９５号公報に記載されている方法）；インクジェット（例えば、オンデマンド方式、ピエゾ方式、サーマル方式）、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷などの各種印刷法；金型等を用いた転写法；ナノインプリント法などが挙げられる。インクジェットでの適用方法としては、特に限定されず、例えば「広がる・使えるインクジェット－特許に見る無限の可能性－、２００５年２月発行、住ベテクノリサーチ」に示された方法（特に１１５ページ～１３３ページ）や、特開２００３－２６２７１６号公報、特開２００３－１８５８３１号公報、特開２００３－２６１８２７号公報、特開２０１２－１２６８３０号公報、特開２００６－１６９３２５号公報などに記載の方法が挙げられる。また、組成物の塗布方法については、国際公開第２０１７／０３０１７４号、国際公開第２０１７／０１８４１９号の記載を参酌でき、これらの内容は本明細書に組み込まれる。 A known method can be used as a method for applying the composition. For example, dropping method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); methods described in publications); inkjet (e.g., on-demand method, piezo method, thermal method), 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. 133 page), and methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. mentioned. In addition, regarding the method of applying the composition, the descriptions in WO2017/030174 and WO2017/018419 can be referred to, and the contents thereof are incorporated herein.
　支持体上に形成した組成物層は、乾燥（プリベーク）してもよい。低温プロセスにより膜を製造する場合は、プリベークを行わなくてもよい。プリベークを行う場合、プリベーク温度は、１５０℃以下が好ましく、１２０℃以下がより好ましく、１１０℃以下が更に好ましい。下限は、例えば、５０℃以上とすることができ、８０℃以上とすることもできる。プリベーク時間は、１０～３００秒が好ましく、４０～２５０秒がより好ましく、８０～２２０秒がさらに好ましい。プリベークは、ホットプレート、オーブン等で行うことができる。 The 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. When pre-baking is performed, 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.
　次に、組成物層をパターン状に露光する（露光工程）。例えば、組成物層に対し、ステッパー露光機やスキャナ露光機などを用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン状に露光することができる。これにより、露光部分を硬化することができる。 Next, the composition layer is exposed in a pattern (exposure step). For example, the 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.
　露光に際して用いることができる放射線（光）としては、ｇ線、ｉ線等が挙げられる。また、波長３００ｎｍ以下の光（好ましくは波長１８０～３００ｎｍの光）を用いることもできる。波長３００ｎｍ以下の光としては、ＫｒＦ線（波長２４８ｎｍ）、ＡｒＦ線（波長１９３ｎｍ）などが挙げられ、ＫｒＦ線（波長２４８ｎｍ）が好ましい。また、３００ｎｍ以上の長波な光源も利用できる。 Radiation (light) that can be used 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.
　また、露光に際して、光を連続的に照射して露光してもよく、パルス的に照射して露光（パルス露光）してもよい。なお、パルス露光とは、短時間（例えば、ミリ秒レベル以下）のサイクルで光の照射と休止を繰り返して露光する方式の露光方法のことである。 In addition, when exposing, the light may be continuously irradiated and exposed, or may be irradiated and exposed in pulses (pulse exposure). Note that pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and rest in short-time (for example, millisecond level or less) cycles.
　照射量（露光量）は、例えば、０．０３～２．５Ｊ／ｃｍ２が好ましく、０．０５～１．０Ｊ／ｃｍ２がより好ましい。露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば、酸素濃度が１９体積％以下の低酸素雰囲気下（例えば、１５体積％、５体積％、または、実質的に無酸素）で露光してもよく、酸素濃度が２１体積％を超える高酸素雰囲気下（例えば、２２体積％、３０体積％、または、５０体積％）で露光してもよい。また、露光照度は適宜設定することが可能であり、通常１０００Ｗ／ｍ２～１０００００Ｗ／ｍ２（例えば、５０００Ｗ／ｍ２、１５０００Ｗ／ｍ２、または、３５０００Ｗ／ｍ２）の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度１０体積％で照度１００００Ｗ／ｍ２、酸素濃度３５体積％で照度２００００Ｗ／ｍ２などとすることができる。 The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2 . The oxygen concentration at the time of exposure can be selected as appropriate. 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). In addition, 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.
　次に、組成物層の未露光部を現像除去してパターンを形成する。組成物層の未露光部の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の組成物層が現像液に溶出し、光硬化した部分だけが残る。現像液の温度は、例えば、２０～３０℃が好ましい。現像時間は、２０～１８０秒が好ましい。また、残渣除去性を向上するため、現像液を６０秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返してもよい。 Next, the unexposed portion of the composition layer is removed by development to form a pattern. The development and removal of the unexposed portion of the composition layer can be performed using a developer. As a result, the unexposed portion of the 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.
　現像液は、有機溶剤、アルカリ現像液などが挙げられ、アルカリ現像液が好ましく用いられる。アルカリ現像液としては、アルカリ剤を純水で希釈したアルカリ性水溶液（アルカリ現像液）が好ましい。アルカリ剤としては、例えば、アンモニア、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、ジグリコールアミン、ジエタノールアミン、ヒドロキシアミン、エチレンジアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ－［５．４．０］－７－ウンデセンなどの有機アルカリ性化合物や、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウムなどの無機アルカリ性化合物が挙げられる。アルカリ剤は、分子量が大きい化合物の方が環境面および安全面で好ましい。アルカリ性水溶液のアルカリ剤の濃度は、０．００１～１０質量％が好ましく、０．０１～１質量％がより好ましい。また、現像液は、さらに界面活性剤を含有していてもよい。現像液は、移送や保管の便宜などの観点より、一旦濃縮液として製造し、使用時に必要な濃度に希釈してもよい。希釈倍率は特に限定されないが、例えば１．５～１００倍の範囲に設定することができる。また、現像後純水で洗浄（リンス）することも好ましい。また、リンスは、現像後の組成物層が形成された支持体を回転させつつ、現像後の組成物層へリンス液を供給して行うことが好ましい。また、リンス液を吐出させるノズルを支持体の中心部から支持体の周縁部に移動させて行うことも好ましい。この際、ノズルの支持体中心部から周縁部へ移動させるにあたり、ノズルの移動速度を徐々に低下させながら移動させてもよい。このようにしてリンスを行うことで、リンスの面内ばらつきを抑制できる。また、ノズルを支持体中心部から周縁部へ移動させつつ、支持体の回転速度を徐々に低下させても同様の効果が得られる。 The developer includes an organic solvent, an alkaline developer, etc., and an alkaline developer is preferably used. As the alkaline developer, an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable. Examples of alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. 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. Moreover, 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 composition layer after development while rotating the support on which the composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support. At this time, when moving the nozzle from the center of the support to the periphery, the moving speed of the nozzle may be gradually decreased. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. A similar effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the periphery.
　現像後、乾燥を施した後に追加露光処理や加熱処理（ポストベーク）を行うことが好ましい。追加露光処理やポストベークは、硬化を完全なものとするための現像後の硬化処理である。ポストベークにおける加熱温度は、例えば、１００～２４０℃が好ましく、２００～２４０℃がより好ましい。ポストベークは、現像後の膜を、上記条件になるようにホットプレートやコンベクションオーブン（熱風循環式乾燥機）、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。追加露光処理を行う場合、露光に用いられる光は、波長４００ｎｍ以下の光であることが好ましい。また、追加露光処理は、韓国公開特許第１０－２０１７－０１２２１３０号公報に記載された方法で行ってもよい。 After development, it is preferable to perform additional exposure processing and heat processing (post-baking) after drying. 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. . When the additional exposure process is performed, the light used for exposure preferably has a wavelength of 400 nm or less. Also, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
　ドライエッチング法でのパターン形成は、本発明の組成物を用いて支持体上に組成物層を形成し、この組成物層の全体を硬化させて硬化物層を形成する工程と、この硬化物層上にフォトレジスト層を形成する工程と、フォトレジスト層をパターン状に露光したのち、現像してレジストパターンを形成する工程と、このレジストパターンをマスクとして硬化物層に対してエッチングガスを用いてドライエッチングする工程と、を含むことが好ましい。フォトレジスト層の形成においては、更にプリベーク処理を施すことが好ましい。特に、フォトレジスト層の形成プロセスとしては、露光後の加熱処理、現像後の加熱処理（ポストベーク処理）を実施する形態が望ましい。ドライエッチング法でのパターン形成については、特開２０１３－０６４９９３号公報の段落番号００１０～００６７の記載を参酌でき、この内容は本明細書に組み込まれる。 Pattern formation by a dry etching method includes steps of forming a composition layer on a support using the composition of the present invention, curing the entire composition layer to form a cured product layer, and forming a cured product layer. a step of forming a photoresist layer on the layer; a step of exposing the photoresist layer in a pattern and then developing it to form a resist pattern; and a step of dry etching. In forming the photoresist layer, it is preferable to further perform a pre-baking process. In particular, as the formation process of the photoresist layer, a mode in which heat treatment after exposure and heat treatment (post-baking treatment) after development are performed is desirable. Regarding 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.
＜構造体＞
　次に、本発明の構造体について、図面を用いて説明する。図２は、本発明の構造体の一実施形態を示す側断面図であり、図３は、同構造体における支持体の真上方向からみた平面図である。図２、３に示すように、本発明の構造体１００は、支持体１１と、支持体１１上に設けられた隔壁１２と、支持体１１上であって、隔壁１２で区画された領域に設けられた画素１４と、を有する。画素としては、着色画素、透明画素、近赤外線透過フィルタ層の画素及び近赤外線カットフィルタ層の画素などが挙げられる。着色画素としては、赤色画素、緑色画素、青色画素、マゼンタ色画素、シアン色画素、黄色画素などが挙げられる。 <Structure>
Next, the structure of the present invention will be described with reference to the drawings. FIG. 2 is a side cross-sectional view showing one embodiment of the structure of the present invention, and FIG. 3 is a plan view of the support member in the same structure viewed from directly above. As shown in FIGS. 2 and 3, the structure 100 of the present invention includes a support 11, partitions 12 provided on the support 11, and regions on the support 11 partitioned by the partitions 12. and a pixel 14 provided. Examples of pixels include colored pixels, transparent pixels, pixels of a near-infrared transmission filter layer, and pixels of a near-infrared cut filter layer. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
　本発明の構造体において、支持体１１の種類としては特に限定はない。固体撮像素子などの各種電子デバイスなどで使用されている基板（シリコンウエハ、炭化ケイ素ウエハ、窒化ケイ素ウエハ、サファイアウエハ、ガラスウエハなど）を用いることができる。また、フォトダイオードが形成された固体撮像素子用基板などを用いることもできる。また、これらの基板上には、必要により、上部の層との密着性改良、物質の拡散防止あるいは表面の平坦化のために下地層が設けられていてもよい。 In the structure of the present invention, the type of support 11 is not particularly limited. Substrates (silicon wafers, silicon carbide wafers, silicon nitride wafers, sapphire wafers, glass wafers, etc.) used in various electronic devices such as solid-state imaging devices can be used. Further, a substrate for a solid-state imaging device on which a photodiode is formed, or the like can also be used. Further, on these substrates, if necessary, an underlying layer may be provided for improving the adhesion with the upper layer, preventing diffusion of substances, or flattening the surface.
　図２、３に示すように、支持体１１上には隔壁１２が形成されている。この実施形態においては、図３に示すように、隔壁１２は、支持体１１の真上方向から見た平面図において、格子状に形成されている。なお、この実施形態では、支持体１１上における隔壁１２によって区画された領域の形状（以下、隔壁の開口部の形状ともいう）は正方形状をなしているが、隔壁の開口部の形状は、特に限定されず、例えば、長方形状、円形状、楕円形状、または、多角形状等であっても良い。 As shown in FIGS. 2 and 3, partition walls 12 are formed on the support 11 . In this embodiment, as shown in FIG. 3, the partition walls 12 are formed in a grid pattern in a plan view seen from directly above the support 11 . In this embodiment, the shape of the region partitioned by the partitions 12 on the support 11 (hereinafter also referred to as the shape of the opening of the partition) is a square, but the shape of the opening of the partition is It is not particularly limited, and may be, for example, rectangular, circular, elliptical, or polygonal.
　隔壁１２は、本発明の組成物（好ましくは、第２の態様の組成物）を用いて形成することができる。具体的には、本発明の組成物を用いて組成物層を形成する工程と、組成物層をフォトリソグラフィ法又はドライエッチング法によりパターンを形成する工程を経て形成することができる。 The partition wall 12 can be formed using the composition of the present invention (preferably the composition of the second aspect). Specifically, it can be formed through a step of forming a composition layer using the composition of the present invention and a step of forming a pattern on the composition layer by photolithography or dry etching.
　隔壁１２の幅Ｗ１は、２０～５００ｎｍであることが好ましい。下限は、３０ｎｍ以上であることが好ましく、４０ｎｍ以上であることがより好ましく、５０ｎｍ以上であることが更に好ましい。上限は、３００ｎｍ以下であることが好ましく、２００ｎｍ以下であることがより好ましく、１００ｎｍ以下であることが更に好ましい。
　また、隔壁１２の高さＨ１は、２００ｎｍ以上であることが好ましく、３００ｎｍ以上であることがより好ましく、４００ｎｍ以上であることが更に好ましい。上限は、画素１４の厚さ×２００％以下であることが好ましく、画素１４の厚さ×１５０％以下であることがより好ましく、画素１４の厚さと実質的に同じであることが更に好ましい。
　隔壁１２の高さと幅の比（高さ／幅）は、１～１００であることが好ましく、５～５０であることがより好ましく、５～３０であることが更に好ましい。 The width W1 of the partition walls 12 is preferably 20 to 500 nm. The lower limit is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The upper limit is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less.
Moreover, the height H1 of the partition wall 12 is preferably 200 nm or more, more preferably 300 nm or more, and even more preferably 400 nm or more. The upper limit is preferably the thickness of the pixel 14 x 200% or less, more preferably the thickness of the pixel 14 x 150% or less, and still more preferably substantially the same as the thickness of the pixel 14 .
The ratio of height to width (height/width) of the partition walls 12 is preferably 1-100, more preferably 5-50, even more preferably 5-30.
　支持体１１上であって、隔壁１２で区画された領域（隔壁の開口部）には、画素１４が形成されている。 Pixels 14 are formed in regions (openings of the partition walls) on the support 11 and partitioned by the partition walls 12 .
　画素１４の幅Ｌ１は、用途により適宜選択できる。例えば、５００～２０００ｎｍであることが好ましく、５００～１５００ｎｍであることがより好ましく、５００～１０００ｎｍであることが更に好ましい。
　画素１４の高さ（厚さ）Ｈ２は、用途により適宜選択できる。例えば、３００～１０００ｎｍであることが好ましく、３００～８００ｎｍであることがより好ましく、３００～６００ｎｍであることが更に好ましい。また、画素１４の高さＨ２は、隔壁１２の高さＨ１の５０～１５０％であることが好ましく、７０～１３０％であることがより好ましく、９０～１１０％であることが更に好ましい。 The width L1 of the pixel 14 can be appropriately selected depending on the application. For example, it is preferably 500 to 2000 nm, more preferably 500 to 1500 nm, even more preferably 500 to 1000 nm.
The height (thickness) H2 of the pixel 14 can be appropriately selected depending on the application. For example, it is preferably 300 to 1000 nm, more preferably 300 to 800 nm, even more preferably 300 to 600 nm. The height H2 of the pixels 14 is preferably 50 to 150%, more preferably 70 to 130%, and even more preferably 90 to 110% of the height H1 of the partition walls 12.
　本発明の構造体において、隔壁の表面に保護層が設けられていることも好ましい。隔壁１２の表面に保護層を設けることで、隔壁１２と画素１４との密着性を向上させることができる。保護層の材質としては、種々の無機材料や有機材料を用いることができる。例えば、有機材料としては、アクリル系樹脂、ポリスチレン系樹脂、ポリイミド系樹脂、有機ＳＯＧ（Ｓｐｉｎ　Ｏｎ　Ｇｌａｓｓ）系樹脂などが挙げられる。また、エチレン性不飽和結合含有基を有する化合物を含む組成物を用いて形成することもできる。 In the structure of the present invention, it is also preferable that a protective layer is provided on the surface of the partition wall. By providing a protective layer on the surfaces of the partition walls 12, the adhesion between the partition walls 12 and the pixels 14 can be improved. Various inorganic materials and organic materials can be used as the material of the protective layer. Examples of organic materials include acrylic resins, polystyrene resins, polyimide resins, organic SOG (Spin On Glass) resins, and the like. It can also be formed using a composition containing a compound having an ethylenically unsaturated bond-containing group.
　本発明の構造体は、光学フィルタ、光学センサ、画像表示装置などに好ましく用いることができる。 The structure of the present invention can be preferably used for optical filters, optical sensors, image display devices, and the like.
＜光学フィルタ＞
　本発明の光学フィルタは、上述した本発明の膜を有する。光学フィルタの種類としては、光学フィルタとしては、カラーフィルタ、近赤外線透過フィルタ、近赤外線カットフィルタなどが挙げられ、カラーフィルタであることが好ましい。カラーフィルタとしては、カラーフィルタの着色画素として本発明の膜を有することが好ましい。
　また、光学フィルタは、隔壁により例えば格子状に仕切られた空間に、各画素が埋め込まれた構造を有していてもよい。
　また、光学フィルタは、遮光膜を有していてもよい。たとえば、支持体上に形成された遮光膜の開口部に、カラーフィルタ、近赤外線透過フィルタ、近赤外線カットフィルタなどが形成されていてもよい。
　本発明の光学フィルタは、固体撮像素子などの光学センサや画像表示装置などに用いることができる。 <Optical filter>
The optical filter of the present invention has the film of the present invention as described above. As for the type of optical filter, 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. As a color filter, it is preferable to have the film of the present invention as a colored pixel of the color filter.
Also, 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.
Also, the optical filter may have a light shielding film. For example, a color filter, a near-infrared transmission filter, a near-infrared cut filter, or the like may be formed in the openings of the light-shielding film formed on the support.
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.
　光学フィルタにおいて本発明の膜の膜厚は、目的に応じて適宜調整できる。光学フィルタに含まれる画素の膜厚は、５μｍ以下が好ましく、１μｍ以下がより好ましく、０．６μｍ以下がさらに好ましい。膜厚の下限は、０．１μｍ以上が好ましく、０．２μｍ以上がより好ましく、０．３μｍ以上がさらに好ましい。 In the optical filter, 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 μm or less, more preferably 1 μm or less, and even more preferably 0.6 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.
　光学フィルタに含まれる画素の幅は０．４～１０．０μｍであることが好ましい。下限は、０．４μｍ以上であることが好ましく、０．５μｍ以上であることがより好ましく、０．６μｍ以上であることが更に好ましい。上限は、５．０μｍ以下であることが好ましく、２．０μｍ以下であることがより好ましく、１．０μｍ以下であることが更に好ましく、０．８μｍ以下であることがより一層好ましい。また、画素のヤング率は０．５～２０ＧＰａであることが好ましく、２．５～１５ＧＰａがより好ましい。 The width of pixels included in the optical filter is preferably 0.4 to 10.0 μm. The lower limit is preferably 0.4 μm or more, more preferably 0.5 μm or more, and even more preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, even more preferably 1.0 μm or less, and even more preferably 0.8 μm or less. Also, the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
　光学フィルタに含まれる各画素は高い平坦性を有することが好ましい。具体的には、画素の表面粗さＲａは、１００ｎｍ以下であることが好ましく、４０ｎｍ以下であることがより好ましく、１５ｎｍ以下であることが更に好ましい。下限は規定されないが、例えば０．１ｎｍ以上であることが好ましい。画素の表面粗さは、例えばＶｅｅｃｏ社製のＡＦＭ（原子間力顕微鏡）　Ｄｉｍｅｎｓｉｏｎ３１００を用いて測定することができる。また、画素上の水の接触角は適宜好ましい値に設定することができるが、典型的には、５０～１１０°の範囲である。接触角は、例えば接触角計ＣＶ－ＤＴ・Ａ型（協和界面科学（株）製）を用いて測定できる。また、画素の体積抵抗値は高いことが好ましい。具体的には、画素の体積抵抗値は１０９Ω・ｃｍ以上であることが好ましく、１０１１Ω・ｃｍ以上であることがより好ましい。上限は規定されないが、例えば１０１４Ω・ｃｍ以下であることが好ましい。画素の体積抵抗値は、超高抵抗計５４１０（アドバンテスト社製）を用いて測定することができる。 Each pixel included in the optical filter preferably has high flatness. Specifically, the pixel surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example. The surface roughness of a pixel can be measured using, for example, AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco. Also, the contact angle of water on the pixel can be appropriately set to a preferable value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT-A type (manufactured by Kyowa Interface Science Co., Ltd.). Moreover, it is preferable that the volume resistance value of the pixel is high. Specifically, the volume resistance value of the pixel is preferably 10 9 Ω·cm or more, more preferably 10 11 Ω·cm or more. Although the upper limit is not specified, it is preferably 10 14 Ω·cm or less, for example. The volume resistance value of the pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest).
　また、光学フィルタが遮光膜を含む場合、遮光膜の膜厚は、５μｍ以下が好ましく、２．５μｍ以下がより好ましい。膜厚の下限は、０．１μｍ以上が好ましく、０．５μｍ以上がより好ましく、１μｍ以上がさらに好ましい。 Further, when the optical filter includes a light shielding film, the film thickness of the light shielding film is preferably 5 μm or less, more preferably 2.5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more.
　光学フィルタにおいては、本発明の膜の表面に保護層が設けられていてもよい。保護層を設けることで、酸素遮断化、低反射化、親疎水化、特定波長の光（紫外線、近赤外線等）の遮蔽等の種々の機能を付与することができる。保護層の厚さとしては、０．０１～１０μｍが好ましく、０．１～５μｍがより好ましい。保護層の形成方法としては、保護層形成用の組成物を塗布して形成する方法、化学気相蒸着法、成型した樹脂を接着材で貼りつける方法等が挙げられる。保護層を構成する成分としては、（メタ）アクリル樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂、ポリオール樹脂、ポリ塩化ビニリデン樹脂、メラミン樹脂、ウレタン樹脂、アラミド樹脂、ポリアミド樹脂、アルキド樹脂、エポキシ樹脂、変性シリコーン樹脂、フッ素樹脂、ポリアクリロニトリル樹脂、セルロース樹脂、Ｓｉ、Ｃ、Ｗ、Ａｌ２Ｏ３、Ｍｏ、ＳｉＯ２、Ｓｉ２Ｎ４などが挙げられ、これらの成分を二種以上含有しても良い。例えば、酸素遮断化を目的とした保護層の場合、保護層はポリオール樹脂と、ＳｉＯ２と、Ｓｉ２Ｎ４を含むことが好ましい。また、低反射化を目的とした保護層の場合、保護層は（メタ）アクリル樹脂とフッ素樹脂を含むことが好ましい。 In the optical filter, a protective layer may be provided on the surface of the film of the present invention. By providing the protective layer, it is possible to impart various functions such as blocking oxygen, reducing reflection, making the film hydrophilic and hydrophobic, and blocking light of a specific wavelength (ultraviolet rays, near-infrared rays, etc.). The thickness of the protective layer is preferably 0.01-10 μm, more preferably 0.1-5 μm. Examples of the method of forming the protective layer include a method of applying a protective layer-forming composition, a chemical vapor deposition method, and a method of adhering a molded resin with an adhesive. Components constituting the protective layer include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, and polyimides. Resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Resins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al 2 O 3 , Mo, SiO 2 , Si 2 N 4 and the like, and two or more of these components may be contained. For example, in the case of a protective layer intended to block oxygen, the protective layer preferably contains a polyol resin, SiO 2 and Si 2 N 4 . In the case of a protective layer intended to reduce reflection, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.
　保護層は、必要に応じて、有機・無機微粒子、特定波長の光（例えば、紫外線、近赤外線等）の吸収剤、屈折率調整剤、酸化防止剤、密着剤、界面活性剤等の添加剤を含有しても良い。有機・無機微粒子の例としては、例えば、高分子微粒子（例えば、シリコーン樹脂微粒子、ポリスチレン微粒子、メラミン樹脂微粒子）、酸化チタン、酸化亜鉛、酸化ジルコニウム、酸化インジウム、酸化アルミニウム、窒化チタン、酸窒化チタン、フッ化マグネシウム、中空シリカ、シリカ、炭酸カルシウム、硫酸バリウム等が挙げられる。特定波長の光の吸収剤は公知の吸収剤を用いることができる。これらの添加剤の含有量は適宜調整できるが、保護層の全質量に対して０．１～７０質量％が好ましく、１～６０質量％がさらに好ましい。 If necessary, the protective layer contains organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index modifiers, antioxidants, adhesion agents, additives such as surfactants. may contain. Examples of organic/inorganic fine particles include polymeric fine particles (eg, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like. A known absorber can be used as the absorber for light of a specific wavelength. The content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the protective layer.
　また、保護層としては、特開２０１７－１５１１７６号公報の段落番号００７３～００９２に記載の保護層を用いることもできる。 Further, as the protective layer, the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.
＜光学センサ＞
　本発明の光学センサは、上述した本発明の膜を含む。光学センサとしては、固体撮像素子などが挙げられる。固体撮像素子の構成としては、固体撮像素子として機能する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。 <Optical sensor>
The optical sensor of the present invention comprises the membrane of the present invention as described above. Examples of optical sensors include solid-state imaging devices. The configuration of the solid-state imaging device is not particularly limited as long as it functions as a solid-state imaging device.
　基板上に、固体撮像素子（ＣＣＤ（電荷結合素子）イメージセンサ、ＣＭＯＳ（相補型金属酸化膜半導体）イメージセンサ等）の受光エリアを構成する複数のフォトダイオードおよびポリシリコン等からなる転送電極を有し、フォトダイオードおよび転送電極上にフォトダイオードの受光部のみ開口した遮光膜を有し、遮光膜上に遮光膜全面およびフォトダイオード受光部を覆うように形成された窒化シリコン等からなるデバイス保護膜を有し、デバイス保護膜上に、カラーフィルタを有する構成である。更に、デバイス保護膜上であってカラーフィルタの下（基板に近い側）に集光手段（例えば、マイクロレンズ等。以下同じ）を有する構成や、カラーフィルタ上に集光手段を有する構成等であってもよい。また、カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各着色画素が埋め込まれた構造を有していてもよい。この場合の隔壁は各着色画素よりも低屈折率であることが好ましい。このような構造を有する撮像装置の例としては、特開２０１２－２２７４７８号公報、特開２０１４－１７９５７７号公報、国際公開第２０１８／０４３６５４号に記載の装置が挙げられる。また、特開２０１９－２１１５５９号公報の中で示しているように固体撮像素子の構造内に紫外線吸収層を設けて耐光性を改良してもよい。固体撮像素子を備えた撮像装置は、デジタルカメラや、撮像機能を有する電子機器（携帯電話等）の他、車載カメラや監視カメラ用としても用いることができる。 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. Furthermore, a configuration having a condensing means (for example, a microlens or the like; the same shall apply hereinafter) on the device protective film and below the color filter (on the side close to the substrate), or a configuration having a condensing means on the color filter, etc. There may be. Moreover, 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. In this case, the partition wall preferably has a lower refractive index than each color pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478, JP-A-2014-179577, and International Publication No. 2018/043654. Further, as disclosed in Japanese Patent Application Laid-Open No. 2019-211559, an ultraviolet absorption layer may be provided in the structure of the solid-state imaging device to improve light resistance. Imaging devices equipped with solid-state imaging devices can be used not only for digital cameras and electronic devices (mobile phones, etc.) having imaging functions, but also for vehicle-mounted cameras and monitoring cameras.
＜画像表示装置＞
　本発明の画像表示装置は、上述した本発明の膜を含む。画像表示装置としては、液晶表示装置や有機エレクトロルミネッセンス表示装置などが挙げられる。画像表示装置の定義や各画像表示装置の詳細については、例えば「電子ディスプレイデバイス（佐々木昭夫著、（株）工業調査会、１９９０年発行）」、「ディスプレイデバイス（伊吹順章著、産業図書（株）平成元年発行）」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術（内田龍男編集、（株）工業調査会、１９９４年発行）」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。 <Image display device>
The image display device of the present invention includes the film of the present invention described above. Examples of image display devices include liquid crystal display devices and organic 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). 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, and for example, the present invention can be applied to liquid crystal display devices of various systems described in the above-mentioned "next generation liquid crystal display technology".
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。なお、以下に示す構造式中のＰｈはフェニル基を表す。 The present invention will be described more specifically below with reference to examples. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. Ph in the structural formulas shown below represents a phenyl group.
＜分散液の製造＞
　下記表に記載の原料を混合した混合液を、ビーズミル（ジルコニアビーズ０．１ｍｍ径）を用いて３時間混合および分散した。次いで、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて圧力２０００ｋｇ／ｃｍ２および流量５００ｇ／ｍｉｎの条件の下、分散処理を行なった。この分散処理を全１０回繰り返して、分散液を得た。下記表に記載の配合量を示す数値は質量部である。なお、分散剤の配合量の数値は、固形分換算での数値である。 <Production of dispersion liquid>
A mixed liquid obtained by mixing raw materials 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). Then, dispersion treatment was carried out using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reduction mechanism under conditions of a pressure of 2000 kg/cm 2 and a flow rate of 500 g/min. This dispersing treatment was repeated 10 times to obtain a dispersion. Numerical values indicating compounding amounts in the table below are parts by mass. In addition, the numerical value of the compounding quantity of a dispersing agent is a numerical value by solid content conversion.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
　上記表に記載の原料のうち、略語で示した原料の詳細は以下の通りである。 Among the raw materials listed in the above table, the details of the raw materials indicated by abbreviations are as follows.
［粒子］
　ＰＲ１２２　：　Ｃ．Ｉ．ピグメントレッド１２２（赤色顔料）
　ＰＲ２５４　：　Ｃ．Ｉ．ピグメントレッド２５４（赤色顔料）
　ＰＧ７　：　Ｃ．Ｉ．ピグメントグリーン７（緑色顔料）
　ＰＧ３６　：　Ｃ．Ｉ．ピグメントグリーン３６（緑色顔料）
　ＰＢ１５：３　：　Ｃ．Ｉ．ピグメントブルー１５：３（青色顔料）
　ＰＢ１５：４　：　Ｃ．Ｉ．ピグメントブルー１５：４（青色顔料）
　ＰＢ１５：６　：　Ｃ．Ｉ．ピグメントブルー１５：６（青色顔料）
　ＰＢ１６　：　Ｃ．Ｉ．ピグメントブルー１６（青色顔料）
　ＰＹ１３９　：　Ｃ．Ｉ．ピグメントイエロー１３９（黄色顔料）
　ＰＹ１５０　：　Ｃ．Ｉ．ピグメントイエロー１５０（黄色顔料）
　ＰＶ２３　：　Ｃ．Ｉ．ピグメントバイオレット２３（紫色顔料）
　ＴｉＯＮ　：　窒化チタン（黒色顔料）
　ＴｉＯ２－１　：　ＴＴＯ－５１（石原産業（株）製、酸化チタン、白色顔料）
　ＴｉＯ２－２　：　ＭＰＴ－１４１（石原産業（株）製、酸化チタン、白色顔料）
　顔料Ａ：下記構造の化合物（近赤外線吸収顔料、ｉ－Ｃ８Ｈ１７とｉ－Ｃ１０Ｈ２１の部分は、炭素数と分岐位置違いの異性体混合物である）
Figure JPOXMLDOC01-appb-C000017
 [particle]
PR122: C.I. I. Pigment Red 122 (red pigment)
PR254: C.I. I. Pigment Red 254 (red pigment)
PG7: C.I. I. Pigment Green 7 (green pigment)
PG36: C.I. I. Pigment Green 36 (green pigment)
PB15:3: C.I. I. Pigment Blue 15:3 (blue pigment)
PB15:4: C.I. I. Pigment Blue 15:4 (blue pigment)
PB15:6: C.I. I. Pigment Blue 15:6 (blue pigment)
PB16: C.I. I. Pigment Blue 16 (blue pigment)
PY139: C.I. I. Pigment Yellow 139 (yellow pigment)
PY150: C.I. I. Pigment Yellow 150 (yellow pigment)
PV23: C.I. I. Pigment Violet 23 (purple pigment)
TiON: Titanium nitride (black pigment)
TiO2-1: TTO-51 (manufactured by Ishihara Sangyo Co., Ltd., titanium oxide, white pigment)
TiO2-2: MPT-141 (manufactured by Ishihara Sangyo Co., Ltd., titanium oxide, white pigment)
Pigment A: compound having the following structure (near-infrared absorbing pigment, iC 8 H 17 and iC 10 H 21 portions are isomer mixtures with different carbon numbers and branching positions)
Figure JPOXMLDOC01-appb-C000017
［顔料誘導体］
　Ｓｙｎ－１：下記構造の化合物
Figure JPOXMLDOC01-appb-C000018
 　Ｓｙｎ－２：下記構造の化合物
Figure JPOXMLDOC01-appb-C000019
 　Ｓｙｎ－３：下記構造の化合物
Figure JPOXMLDOC01-appb-C000020
 　Ｓｙｎ－４：下記構造の化合物
Figure JPOXMLDOC01-appb-C000021
 　Ｓｙｎ－５：下記構造の化合物
Figure JPOXMLDOC01-appb-C000022
 [Pigment derivative]
Syn-1: a compound having the following structure
Figure JPOXMLDOC01-appb-C000018
 Syn-2: a compound having the following structure
Figure JPOXMLDOC01-appb-C000019
 Syn-3: a compound having the following structure
Figure JPOXMLDOC01-appb-C000020
 Syn-4: a compound having the following structure
Figure JPOXMLDOC01-appb-C000021
 Syn-5: a compound having the following structure
Figure JPOXMLDOC01-appb-C000022
［分散剤］
　Ｄ－１：下記構造の樹脂（主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。重量平均分子量２４０００、酸価４７ｍｇＫＯＨ／ｇ）
Figure JPOXMLDOC01-appb-C000023
 　Ｄ－２：下記構造の樹脂
Figure JPOXMLDOC01-appb-C000024
 　Ｄ－３：下記構造の樹脂（主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。重量平均分子量２００００、酸価７０ｍｇＫＯＨ／ｇ）
Figure JPOXMLDOC01-appb-C000025
 　Ｄ－４：以下に示す樹脂（重量平均分子量８０００、酸価３７ｍｇＫＯＨ／ｇ、エチレン性不飽和結合含有基価０．２２ｍｍｏｌ／ｇ）
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
 [Dispersant]
D-1: Resin having the following structure (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 24000, acid value 47 mgKOH/g)
Figure JPOXMLDOC01-appb-C000023
 D-2: Resin having the following structure
Figure JPOXMLDOC01-appb-C000024
 D-3: Resin having the following structure (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: 20000, acid value: 70 mgKOH/g)
Figure JPOXMLDOC01-appb-C000025
 D-4: Resin shown below (weight average molecular weight 8000, acid value 37 mgKOH/g, ethylenically unsaturated bond-containing group value 0.22 mmol/g)
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
［溶剤］
　Ｓ－１：プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）
　Ｓ－２：シクロペンタノン
　Ｓ－３：プロピレングリコールモノメチルエーテル（ＰＧＭＥ）
　Ｓ－５：シクロヘキサノン [solvent]
S-1: Propylene glycol monomethyl ether acetate (PGMEA)
S-2: cyclopentanone S-3: propylene glycol monomethyl ether (PGME)
S-5: Cyclohexanone
＜組成物の製造＞
　下記表に記載の原料を混合し、日本ポール製ＤＦＡ４２０１ＮＩＥＹ（０．４５μｍナイロンフィルター）を用いてろ過を行って組成物を製造した。下記表に記載の配合量を示す数値は質量部である。 <Production of composition>
The raw materials shown in the table below were mixed and filtered using Nippon Pall's DFA4201NIEY (0.45 μm nylon filter) to produce a composition. Numerical values indicating compounding amounts in the following table are parts by mass.
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
　上記表に記載の原料のうち、略語で示した原料の詳細は以下の通りである。 Among the raw materials listed in the above table, the details of the raw materials indicated by abbreviations are as follows.
［分散液］
　分散液１～２１：上述した分散液１～２１
　シリカ粒子液１：平均粒子径１５ｎｍの球状シリカの複数個が金属酸化物含有シリカ（連結材）によって数珠状に連結された形状のシリカ粒子（数珠状シリカ）のプロピレングリコールモノメチルエーテル溶液（シリカ粒子濃度２０質量％）の１００．０ｇに疎水化処理剤としてトリメチルメトキシシランの３．０ｇを添加し、２０℃で６時間反応させて調製したシリカ粒子液である。なお、シリカ粒子液１において、球状シリカの平均粒子径は、透過型電子顕微鏡（ＴＥＭ）によって測定した５０個の球状シリカの球状部分の投影像における円相当直径の数平均を算出して求めた。また、シリカ粒子液１において、ＴＥＭ観察の方法で、複数個の球状シリカが数珠状に連結された形状のシリカ粒子を含むものであるかどうか調べた。 [Dispersion]
Dispersions 1 to 21: Dispersions 1 to 21 described above
Silica particle liquid 1: A propylene glycol monomethyl ether solution (silica particles This is a silica particle liquid prepared by adding 3.0 g of trimethylmethoxysilane as a hydrophobizing agent to 100.0 g of a solution having a concentration of 20% by mass and reacting the mixture at 20° C. for 6 hours. In the silica particle liquid 1, the average particle diameter of the spherical silica was obtained by calculating the number average of the equivalent circle diameters in the projected images of the spherical portions of 50 spherical silica particles measured by a transmission electron microscope (TEM). . Further, in the silica particle liquid 1, it was examined by a TEM observation method whether or not it contained silica particles having a shape in which a plurality of spherical silica particles were connected in a beaded shape.
［染料］
　染料１：下記構造の化合物（重量平均分子量９０００）
Figure JPOXMLDOC01-appb-C000037
 [dye]
Dye 1: compound having the following structure (weight average molecular weight 9000)
Figure JPOXMLDOC01-appb-C000037
［重合性モノマー］
　Ｍ－１：ＫＡＹＡＲＡＤ　ＤＰＨＡ（日本化薬（株）製）
　Ｍ－２：アロニックスＴＯ－２３４９（東亞合成（株）製）
　Ｍ－３：ＮＫエステル Ａ－ＤＰＨ－１２Ｅ（新中村化学工業（株）製） [Polymerizable Monomer]
M-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
M-2: Aronix TO-2349 (manufactured by Toagosei Co., Ltd.)
M-3: NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
［樹脂］
　Ｂ－１：下記構造の樹脂（主鎖に付記した数値はモル比である。重量平均分子量１１０００）
Figure JPOXMLDOC01-appb-C000038
 　Ｂ－２：下記構造の樹脂（主鎖に付記した数値はモル比である。重量平均分子量１９０００。固形分４０％）
Figure JPOXMLDOC01-appb-C000039
 [resin]
B-1: Resin having the following structure (numerical values attached to the main chain are molar ratios; weight average molecular weight: 11,000)
Figure JPOXMLDOC01-appb-C000038
 B-2: Resin having the following structure (numerical values attached to the main chain are molar ratios. Weight average molecular weight: 19000. Solid content: 40%)
Figure JPOXMLDOC01-appb-C000039
［光重合開始剤］
　Ｉ－１：下記構造の化合物（オキシム化合物）
Figure JPOXMLDOC01-appb-C000040
 　Ｉ－２：下記構造の化合物（オキシム化合物）
Figure JPOXMLDOC01-appb-C000041
 　Ｉ－３：下記構造の化合物（オキシム化合物）
Figure JPOXMLDOC01-appb-C000042
 　Ｉ－４：下記構造の化合物（オキシム化合物）
Figure JPOXMLDOC01-appb-C000043
 [Photoinitiator]
I-1: A compound having the following structure (oxime compound)
Figure JPOXMLDOC01-appb-C000040
 I-2: A compound having the following structure (oxime compound)
Figure JPOXMLDOC01-appb-C000041
 I-3: A compound having the following structure (oxime compound)
Figure JPOXMLDOC01-appb-C000042
 I-4: A compound having the following structure (oxime compound)
Figure JPOXMLDOC01-appb-C000043
［界面活性剤］
　Ｗ－１：下記構造の化合物（シリコーン系界面活性剤、水酸基価１２０ｍｇＫＯＨ／ｇ、２５℃における動粘度＝３５ｍｍ２／ｓ、２５℃における表面張力＝２７．６ｍＮ／ｍ）
　Ｗ－２：下記構造の化合物（シリコーン系界面活性剤、水酸基価１００ｍｇＫＯＨ／ｇ、２５℃における動粘度＝３８ｍｍ２／ｓ、２５℃における表面張力＝２７．１ｍＮ／ｍ）
　Ｗ－３：下記構造の化合物（シリコーン系界面活性剤、水酸基価８０ｍｇＫＯＨ／ｇ、２５℃における動粘度＝４０ｍｍ２／ｓ、２５℃における表面張力＝２６ｍＮ／ｍ）
Figure JPOXMLDOC01-appb-C000044
 [Surfactant]
W-1: compound having the following structure (silicone surfactant, hydroxyl value 120 mgKOH/g, kinematic viscosity at 25°C = 35 mm 2 /s, surface tension at 25°C = 27.6 mN/m)
W-2: Compound having the following structure (silicone surfactant, hydroxyl value 100 mgKOH/g, kinematic viscosity at 25°C = 38 mm 2 /s, surface tension at 25°C = 27.1 mN/m)
W-3: Compound having the following structure (silicone-based surfactant, hydroxyl value 80 mgKOH/g, kinematic viscosity at 25°C = 40 mm 2 /s, surface tension at 25°C = 26 mN/m)
Figure JPOXMLDOC01-appb-C000044
　ＣＷ－１：ＢＹＫ－３３０（ビックケミー社製、シリコーン系界面活性剤、２５℃における表面張力＝２５．１ｍＮ／ｍ）
　ＣＷ－２：フタージェント７１０ＦＭ（（株）ＮＥＯＳ製、フッ素系界面活性剤、２５℃における表面張力＝２４．３ｍＮ／ｍ） CW-1: BYK-330 (manufactured by BYK-Chemie, silicone surfactant, surface tension at 25°C = 25.1 mN/m)
CW-2: Futergent 710FM (manufactured by NEOS Co., Ltd., fluorine-based surfactant, surface tension at 25°C = 24.3 mN/m)
　なお、動粘度は、ウベローデ粘度計を用いて測定した。
　また、表面張力は、各界面活性剤をＰＧＭＥＡに溶解させて調製した固形分濃度１０００質量ｐｐｍの溶液を測定試料として測定した。この測定試料の温度を２５℃に調整し、測定装置として表面張力計ＣＢＶＰ－Ｚ（協和界面科学（株）製）を用い、白金プレートを用いたプレート法で測定した。 The kinematic viscosity was measured using an Ubbelohde viscometer.
Further, the surface tension was measured using a solution having a solid concentration of 1000 mass ppm prepared by dissolving each surfactant in PGMEA as a measurement sample. The temperature of this measurement sample was adjusted to 25° C., and a surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) was used as a measuring device, and the plate method using a platinum plate was used for measurement.
［溶剤］
　Ｓ－１、Ｓ－１１：プロピレングリコールモノメチルエーテルアセテート
　Ｓ－２：シクロペンタノン
　Ｓ－４：酢酸ブチル
　Ｓ－１２：１，４－ブタンジオールジアセテート
　Ｓ－１３：メタノール
　Ｓ－１４：エタノール
　Ｓ－１５：水 [solvent]
S-1, S-11: propylene glycol monomethyl ether acetate S-2: cyclopentanone S-4: butyl acetate S-12: 1,4-butanediol diacetate S-13: methanol S-14: ethanol S- 15: water
＜混色の評価＞
　直径８インチ（２０．３２ｃｍ）のガラスウエハ上に、乾燥膜厚が０．１μｍとなるように下地層形成用組成物（ＣＴ－４０００Ｌ、富士フイルムエレクトロニクスマテリアルズ（株）製）を塗布し、乾燥した後、２２０℃で５分間加熱処理を行い、下地層を形成した。
　次に、下地層を形成したガラスウエハ上に、各組成物をプリベーク後の膜厚が０．６μｍとなるようにスピンコーターを用いて塗布し、１００℃のホットプレートを用いて１２０秒間加熱処理（プリベーク）を行った。次いで、ｉ線ステッパー露光装置（ＦＰＡ－３０００ｉ５＋、Ｃａｎｏｎ（株）製）を使用して３６５ｎｍの波長の光を５００ｍＪ／ｃｍ２の露光量でガラスウエハ全面に照射して露光した。露光後の膜を有するガラスウエハを、２００℃で３００秒間、ホットプレートを用いて加熱処理（ポストベーク）を行い、膜を形成した。膜が形成されたガラスウエハについて、分光測定機（Ｕ－４１５０、（株）日立製作所製）を用いて、波長４００～１１００ｎｍの範囲の透過率を測定した。
　続いて、混色評価用組成物をプリベーク後の膜厚が０．６μｍとなるようにスピンコーターを用いて塗布し、１００℃のホットプレートを用いて１２０秒間加熱処理（プリベーク）を行った。
　なお、実施例１－１、１－２、１－３、比較例１－１、１－２については、混色評価用組成物として比較例３－１の組成物を用いた。
　また、実施例２－１～３１－１、実施例２－２～１３－２、実施例２－３～１３－３、比較例２－１～１３－１、比較例２－２～１３－２ついては、混色評価用組成物として比較例１－１の組成物を用いた。
　次いで、ガラスウエハをスピン・シャワー現像機（ＤＷ－３０型、（株）ケミトロニクス製）の水平回転テーブル上に載置し、アルカリ現像液（ＣＤ－２０６０、富士フイルムエレクトロニクスマテリアルズ（株）製）を用いて２３℃で６０秒間パドル現像した。次いで、パドル現像後のガラスウエハを、真空チャック方式で水平回転テーブルに固定し、回転装置によってガラスウエハを回転数５０ｒｐｍで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理（２３秒×２回）を行い、次いで、スピン乾燥を行い、次いで、２００℃で３００秒間、ホットプレートを用いて加熱処理（ポストベーク）を行い、混色評価用組成物を現像して混色試験を行った。混色試験後、再度膜が形成されたガラスウエハについて、分光測定機（Ｕ－４１５０、（株）日立製作所製）を用いて波長４００～１１００ｎｍの範囲の透過率を測定した。 <Evaluation of mixed colors>
On a glass wafer with a diameter of 8 inches (20.32 cm), a composition for forming a base layer (CT-4000L, manufactured by FUJIFILM Electronic Materials Co., Ltd.) is applied so that the dry film thickness is 0.1 μm, After drying, heat treatment was performed at 220° C. for 5 minutes to form an underlayer.
Next, on the glass wafer on which the underlayer is formed, each composition is applied using a spin coater so that the film thickness after prebaking is 0.6 μm, and heat-treated for 120 seconds using a hot plate at 100 ° C. (pre-baking) was performed. Then, an i-line stepper exposure apparatus (FPA-3000i5+, manufactured by Canon Inc.) was used to expose the entire surface of the glass wafer to light with a wavelength of 365 nm at an exposure dose of 500 mJ/cm 2 . The glass wafer having the exposed film was subjected to heat treatment (post-baking) using a hot plate at 200° C. for 300 seconds to form a film. The transmittance in the wavelength range of 400 to 1100 nm was measured using a spectrophotometer (U-4150, manufactured by Hitachi, Ltd.) for the glass wafer on which the film was formed.
Subsequently, the color mixture evaluation composition was applied using a spin coater so that the film thickness after prebaking was 0.6 μm, and heat treatment (prebaking) was performed using a hot plate at 100° C. for 120 seconds.
In Examples 1-1, 1-2, 1-3 and Comparative Examples 1-1 and 1-2, the composition of Comparative Example 3-1 was used as the composition for color mixture evaluation.
Also, Examples 2-1 to 31-1, Examples 2-2 to 13-2, Examples 2-3 to 13-3, Comparative Examples 2-1 to 13-1, Comparative Examples 2-2 to 13- 2, the composition of Comparative Example 1-1 was used as a composition for color mixing evaluation.
Next, the glass wafer was placed on a horizontal rotating table of a spin/shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and an alkaline developer (CD-2060, manufactured by Fuji Film Electronic Materials Co., Ltd.) was used. ) at 23° C. for 60 seconds. Next, the glass wafer after the paddle development was fixed on a horizontal rotary table by a vacuum chuck method, and while the glass wafer was rotated at a rotation speed of 50 rpm by a rotating device, pure water was sprayed from above the center of rotation in the form of a shower. Supply and rinse treatment (23 seconds × 2 times), then spin drying, and then heat treatment (post-baking) using a hot plate at 200 ° C. for 300 seconds to obtain a composition for color mixture evaluation. A color mixing test was performed after development. After the color mixing test, the transmittance in the wavelength range of 400 to 1100 nm was measured using a spectrophotometer (U-4150, manufactured by Hitachi, Ltd.) on the glass wafer on which the film was formed again.
　実施例１－１～７－１、９－１～３１－１、実施例１－２～７－２、９－２～１３－２、実施例１－３～７－３、９－３～１３－１、比較例１－１～７－１、９－１～１３－１、比較例１－２～７－２、９－２～１３－２については、混色試験前後の膜の透過率差の最大値を評価して、以下の基準で混色を評価した。
　透過率差＝｜混色試験前の膜の透過率－混色試験後の膜の透過率｜
　５：透過率差の最大値が１％以下である
　４：透過率差の最大値が１％を超え２％以下である
　３：透過率差の最大値が２％を超え３％以下である
　２：透過率差の最大値が３％を超え４％以下である
　１：透過率差の最大値が４％を超える Examples 1-1 to 7-1, 9-1 to 31-1, Examples 1-2 to 7-2, 9-2 to 13-2, Examples 1-3 to 7-3, 9-3 ~ For 13-1, Comparative Examples 1-1 to 7-1, 9-1 to 13-1, Comparative Examples 1-2 to 7-2, and 9-2 to 13-2, the transmittance of the film before and after the color mixing test The maximum value of the difference was evaluated, and color mixture was evaluated according to the following criteria.
Transmittance difference = | Transmittance of film before color mixing test - Transmittance of film after color mixing test |
5: The maximum value of the transmittance difference is 1% or less 4: The maximum value of the transmittance difference is more than 1% and 2% or less 3: The maximum value of the transmittance difference is more than 2% and 3% or less 2: The maximum value of transmittance difference is over 3% and 4% or less 1: The maximum value of transmittance difference is over 4%
　実施例８－１、８－２、８－３、比較例８－１、８～２については、混色試験前の透過率を基準とした、分光変動率を評価して、以下の基準で混色を評価した。
　分光変動率＝（１－混色試験後の膜の透過率／混色試験前の膜の透過率）ｘ１００で評価を実施した。
　５：分光変動率の最大値が１％以下である
　４：分光変動率の最大値が１％を超え２％以下である
　３：分光変動率の最大値が２％を超え３％以下である
　２：分光変動率の最大値が３％を超え４％以下である
　１：分光変動率の最大値が４％を超える For Examples 8-1, 8-2, 8-3, and Comparative Examples 8-1, 8-2, the spectral variation rate was evaluated based on the transmittance before the color mixing test, and the color mixing was performed according to the following criteria. evaluated.
The evaluation was performed using the spectral variation rate=(1−transmittance of film after color mixture test/transmittance of film before color mixture test)×100.
5: The maximum spectral variability is 1% or less 4: The maximum spectral variability is more than 1% and 2% or less 3: The maximum spectral variability is more than 2% and 3% or less 2: The maximum spectral variability exceeds 3% and is 4% or less 1: The maximum spectral variability exceeds 4%
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
　上記表に示すように、実施例は、比較例よりも混色の発生を抑制することができた。 As shown in the table above, the example was able to suppress the occurrence of color mixture more than the comparative example.
１１：支持体
１２：隔壁
１４：画素
１００：構造体 11: Support 12: Partition 14: Pixel 100: Structure

Claims (17)

  1. 　硬化性化合物と、
    　シリコーン系界面活性剤Ａと、
    　溶剤と、を含み、
    　前記シリコーン系界面活性剤Ａは、前記シリコーン系界面活性剤Ａをプロピレングリコールモノメチルエーテルアセテートに溶解させて固形分濃度１０００質量ｐｐｍの溶液を調製した際に、前記溶液の２５℃における表面張力が２６ｍＮ／ｍ以上である、
    　組成物。     a curable compound;
    a silicone-based surfactant A;
    including a solvent and
    The silicone surfactant A has a surface tension of 26 mN at 25° C. when a solution having a solid concentration of 1000 mass ppm is prepared by dissolving the silicone surfactant A in propylene glycol monomethyl ether acetate. / m or more,
    Composition.
  2. 　前記硬化性化合物は、樹脂と、重合性モノマーを含み、
    　前記組成物は、更に光重合開始剤を含む、請求項１に記載の組成物。     The curable compound contains a resin and a polymerizable monomer,
    2. The composition of claim 1, wherein said composition further comprises a photoinitiator.
  3. 　更に、色材を含む、請求項１または２に記載の組成物。 The composition according to claim 1 or 2, further comprising a coloring material.
  4. 　無機粒子と、
    　シリコーン系界面活性剤Ａと、
    　溶剤と、を含み、
    　前記シリコーン系界面活性剤Ａは、前記シリコーン系界面活性剤Ａをプロピレングリコールモノメチルエーテルアセテートに溶解させて固形分濃度１０００質量ｐｐｍの溶液を調製した際に、前記溶液の２５℃における表面張力が２６ｍＮ／ｍ以上である、
    　組成物。     inorganic particles;
    a silicone-based surfactant A;
    including a solvent and
    The silicone surfactant A has a surface tension of 26 mN at 25° C. when a solution having a solid concentration of 1000 mass ppm is prepared by dissolving the silicone surfactant A in propylene glycol monomethyl ether acetate. / m or more,
    Composition.
  5. 　前記無機粒子は、シリカ粒子を含む、請求項４に記載の組成物。 The composition according to claim 4, wherein the inorganic particles include silica particles.
  6. 　前記シリカ粒子は、複数個の球状シリカが数珠状に連結した形状のシリカ粒子、複数個の球状シリカが平面的に連結した形状のシリカ粒子、および、中空構造のシリカ粒子から選ばれる少なくとも１種を含む、請求項５に記載の組成物。 The silica particles are at least one selected from silica particles in which a plurality of spherical silica particles are linked in a beaded shape, silica particles in which a plurality of spherical silica particles are planarly linked, and silica particles with a hollow structure. 6. The composition of claim 5, comprising:
  7. 　前記組成物の全固形分中における前記無機粒子の含有量が２０質量％以上である、請求項４または５に記載の組成物。 The composition according to claim 4 or 5, wherein the content of the inorganic particles in the total solid content of the composition is 20% by mass or more.
  8. 　前記シリコーン系界面活性剤Ａの水酸基価が８０ｍｇＫＯＨ／ｇ以上である、請求項１または４に記載の組成物。 The composition according to claim 1 or 4, wherein the silicone surfactant A has a hydroxyl value of 80 mgKOH/g or more.
  9. 　前記シリコーン系界面活性剤Ａの２５℃における動粘度が４０ｍｍ２／ｓ以下である、請求項１または４に記載の組成物。 The composition according to claim 1 or 4, wherein the silicone surfactant A has a kinematic viscosity at 25°C of 40 mm 2 /s or less.
  10. 　前記シリコーン系界面活性剤Ａは、カルビノール変性ジアルキルポリシロキサンである、請求項１または４に記載の組成物。 The composition according to claim 1 or 4, wherein the silicone-based surfactant A is a carbinol-modified dialkylpolysiloxane.
  11. 　前記シリコーン系界面活性剤Ａは、アルキレンオキシ基とヒドロキシ基を有するジメチルポリシロキサンである、請求項１または４に記載の組成物。 The composition according to claim 1 or 4, wherein the silicone-based surfactant A is dimethylpolysiloxane having an alkyleneoxy group and a hydroxy group.
  12. 　前記組成物中における前記シリコーン系界面活性剤Ａの含有量が１～１０００質量ｐｐｍである、請求項１または４に記載の組成物。 The composition according to claim 1 or 4, wherein the content of the silicone-based surfactant A in the composition is 1 to 1000 mass ppm.
  13. 　請求項１または４に記載の組成物を用いて得られる膜。 A film obtained using the composition according to claim 1 or 4.
  14. 　請求項１３に記載の膜を有する光学フィルタ。 An optical filter having the film according to claim 13.
  15. 　請求項１３に記載の膜を有する光学センサ。 An optical sensor having the film according to claim 13.
  16. 　請求項１３に記載の膜を有する画像表示装置。 An image display device having the film according to claim 13.
  17. 　支持体と、
    　前記支持体上に設けられた請求項４に記載の組成物を用いて得られる隔壁と、
    　前記隔壁で区画された領域に設けられた画素と、
    　を有する構造体。     a support;
    partition walls obtained using the composition according to claim 4 provided on the support;
    pixels provided in regions partitioned by the partition walls;
    A struct with
PCT/JP2022/030851 2021-08-19 2022-08-15 Composition, film, optical filter, optical sensor, image display apparatus, and structural body WO2023022120A1 (en)

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