Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
• • 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
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
  • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • 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
  • C09B57/00—Other synthetic dyes of known constitution
• • 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
  • C09B57/00—Other synthetic dyes of known constitution
  • C09B57/02—Coumarine dyes
• • 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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
  • H10F39/10—Integrated devices
  • H10F39/12—Image sensors
  • H10F39/18—Complementary metal-oxide-semiconductor [CMOS] image sensors; Photodiode array image sensors
  • H10F39/182—Colour image sensors

Definitions

• the present invention relates to a photosensitive composition containing a coloring material.
• the present invention also relates to a film, an optical filter, a solid-state image sensor, and an image display device using the photosensitive composition.
• optical filters such as color filters are manufactured using a photosensitive composition containing a coloring material, a photopolymerization initiator, and a polymerizable compound.
• an object of the present invention is to provide a photosensitive composition that can form a film with excellent adhesion to a support. Further, an object of the present invention is to provide a film, an optical filter, a solid-state image sensor, and an image display device.
• the present invention provides the following.
• a photosensitive composition comprising a coloring material, a polymerizable compound, and a photopolymerization initiator,
• the content of the coloring material in the total solid content of the photosensitive composition is 40% by mass or more
• the polymerizable compound includes a polymerizable compound B1 having a weight average molecular weight of 3000 or more, and the content of the polymerizable compound B1 in the total mass of the polymerizable compound is 50% by mass or more
• the photopolymerization initiator is a photosensitive composition containing a compound represented by formula (1);
• X 1 represents a divalent linking group containing at least one member selected from the group consisting of an aromatic ring and a heterocycle
• R 1 represents a hydrogen atom or an acyl group
• R 2 represents an alkyl group or an aryl group
• R 3 and R 4 each independently represent a hydrogen atom or an alkyl group
• Alk 1 and Alk 2 each independently represent an alkyl group
• R 3 and R 4 may
• X 1 in formula (1) is a group represented by any of formulas (X-1) to (X-13):
• R X1 to R X9 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
• X 1 in formula (1) is a group represented by the above formula (X-2) or formula (X-6).
• X-2> The photosensitive composition according to ⁇ 1> or ⁇ 2>, wherein the polymerizable compound B1 includes a repeating unit having a graft chain.
• the polymerizable compound B1 includes a repeating unit having an ethylenically unsaturated bond-containing group in a side chain and a repeating unit having a graft chain, according to any one of ⁇ 1> to ⁇ 4>.
• Photosensitive composition. ⁇ 6> The photosensitivity according to ⁇ 4> or ⁇ 5>, wherein the graft chain contains a repeating unit having at least one type of structure selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylic structure.
• Composition. ⁇ 7> The photosensitive composition according to any one of ⁇ 1> to ⁇ 6>, wherein the content of the coloring material in the total solid content of the photosensitive composition is 50% by mass or more.
• ⁇ 8> The photosensitive composition according to any one of ⁇ 1> to ⁇ 7>, wherein the coloring material includes Color Index Pigment Red 272.
• ⁇ 9> The photosensitive composition according to any one of ⁇ 1> to ⁇ 8>, further comprising a polymerization inhibitor.
• ⁇ 10> The photosensitive composition according to any one of ⁇ 1> to ⁇ 9>, further comprising a silicone surfactant.
• ⁇ 11> A film obtained using the photosensitive composition according to any one of ⁇ 1> to ⁇ 10>.
• ⁇ 12> An optical filter having the film according to ⁇ 11>.
• ⁇ 13> An image display device having the film according to ⁇ 11>.
• ⁇ 14> A solid-state imaging device having the film according to ⁇ 11>.
• the present invention it is possible to provide a photosensitive composition that can form a film with excellent adhesion to a support. Further, according to the present invention, it is possible to provide a film, an optical filter, a solid-state image sensor, and an image display device using the photosensitive composition.
• ⁇ is used to include the numerical values described before and after it as a lower limit and an upper limit.
• the description that does not indicate substituted or unsubstituted includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
• the term "alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
• the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
• EUV light extreme ultraviolet rays
• (meth)acrylate” represents acrylate and/or methacrylate
• (meth)acrylic represents both acrylic and/or methacrylic
• (meth)acrylate” represents acrylic and/or methacrylate.
• Acryloyl refers to either or both of acryloyl and methacryloyl.
• Me in the structural formula represents a methyl group
• Et represents an ethyl group
• Bu represents a butyl group
• Ph represents a phenyl group.
• the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
• the total solid content refers to the total mass of all components of the composition excluding the solvent.
• pigment means a coloring material that is difficult to dissolve in a solvent.
• the term "process” is used not only to refer to an independent process, but also to include a process in which the intended effect of the process is achieved even if the process cannot be clearly distinguished from other processes. .
• the photosensitive composition of the present invention is A photosensitive composition comprising a coloring material, a polymerizable compound, and a photopolymerization initiator,
• the content of the coloring material in the total solid content of the photosensitive composition is 40% by mass or more
• the polymerizable compound includes a polymerizable compound B1 having a weight average molecular weight of 3000 or more, and the content of the polymerizable compound B1 in the total mass of the polymerizable compound is 50% by mass or more
• the photopolymerization initiator is characterized by containing a compound represented by formula (1).
• the photosensitive composition of the present invention forms a film with excellent adhesion to the support, even though the content of the coloring material in the total solid content of the photosensitive composition is 40% by mass or more. can do. Although the reason is unknown, it is presumed that by increasing the amount of generated radicals, the curing reaction can proceed sufficiently even in the deep part of the film.
• a polymerizable compound containing a polymerizable compound B1 having a weight average molecular weight of 3000 or more is used, and the content of the polymerizable compound B1 in the total mass of the polymerizable compound is Since it is 50% by mass or more, it is presumed that the increase in the molecular weight of the polymerizable compound due to the radical reaction during exposure is large, the permeability of the developer can be suppressed, and the adhesion is improved. Therefore, it is presumed that the photosensitive composition of the present invention can form a film with excellent adhesion to the support.
• the film obtained using the photosensitive composition of the present invention also has excellent moisture resistance. This is presumed to be due to a large increase in the molecular weight of the polymerizable compound due to radical reaction during exposure. Furthermore, the photosensitive composition of the present invention has excellent exposure sensitivity. Furthermore, the photosensitive composition of the present invention has excellent developability and can form pixels with excellent linearity when patterned by photolithography to form pixels. , it is also possible to suppress the generation of residue between pixels.
• the photosensitive composition of the present invention is preferably used as a photosensitive composition for optical filters.
• the optical filter include color filters, near-infrared transmission filters, near-infrared cut filters, etc., and color filters are preferred.
• the photosensitive composition of the present invention is preferably used for solid-state imaging devices. More specifically, it is preferably used as a photosensitive composition for optical filters used in solid-state imaging devices, and more preferably used as a photosensitive composition for forming colored pixels in color filters used in solid-state imaging devices.
• color filters include filters that have colored pixels that transmit light of a specific wavelength.
• colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
• the colored pixels of the color filter can be formed using a photosensitive composition containing a chromatic coloring material.
• the maximum absorption wavelength of the near-infrared cut filter preferably exists in a wavelength range of 700 to 1800 nm, more preferably exists in a wavelength range of 700 to 1300 nm, and even more preferably exists in a wavelength range of 700 to 1000 nm.
• the transmittance of the near-infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
• the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.
• the ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at a wavelength of 550 nm is preferably 20 to 500, more preferably 50 to 500. , more preferably from 70 to 450, particularly preferably from 100 to 400.
• the near-infrared cut filter can be formed using a photosensitive composition containing a near-infrared absorbing coloring material.
• a near-infrared transmission filter is a filter that transmits at least a portion of near-infrared rays.
• the near-infrared transmitting filter is preferably a filter that blocks at least a portion of visible light and transmits at least a portion of near-infrared rays.
• the near-infrared transmission filter has a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm, and a transmittance in the wavelength range of 1100 to 1300 nm.
• Preferred examples include filters that satisfy spectral characteristics with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more).
• the near-infrared transmission filter is preferably a filter that satisfies any of the following spectral characteristics (1) to (5).
• the maximum value of transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 800 to 1500 nm is 20% or less (preferably 15% or less, more preferably 10% or less).
• 70% or more preferably 75% or more, more preferably 80% or more).
• the maximum value of transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 900 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
• the maximum value of transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1000 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
• the maximum value of transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1100 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
• the maximum value of transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1200 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
• the solid content concentration of the photosensitive composition of the present invention is preferably 5 to 30% by mass.
• the lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more.
• the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
• the photosensitive composition of the present invention contains a coloring material.
• coloring materials include white coloring materials, black coloring materials, chromatic coloring materials, and near-infrared absorbing coloring materials.
• the white coloring material includes not only pure white but also light gray coloring materials close to white (for example, grayish white, light gray, etc.).
• the coloring material preferably contains at least one selected from the group consisting of a chromatic coloring material, a black coloring material, and a near-infrared absorbing coloring material, and more preferably a chromatic coloring material.
• the coloring material is substantially only a chromatic coloring material.
• the case where the coloring material is substantially only a chromatic coloring material means that the content of the chromatic coloring material in the coloring material is 99% by mass or more, and 99.9% by mass or more. It is preferable that the amount is % by mass or more, and it is more preferable that the coloring material is only a chromatic coloring material.
• the coloring material may be either a pigment or a dye, but preferably contains a pigment.
• the pigment may be either an inorganic pigment or an organic pigment, but organic pigments are preferable from the viewpoints of large color variations, ease of dispersion, safety, and the like. Further, the pigment preferably contains at least one selected from chromatic pigments and near-infrared absorbing pigments, and more preferably contains chromatic pigments.
• the average primary particle diameter 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 average primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment using a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circular equivalent diameter is calculated as the primary particle diameter of the pigment.
• the average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 pigment primary particles.
• the primary particles of pigment refer to independent particles without agglomeration.
• the crystallite size determined from the half-value width of the peak derived from any crystal plane in the X-ray diffraction spectrum when the CuK ⁇ ray of the pigment is used as the X-ray source is preferably 0.1 to 100 nm, and preferably 0.1 to 100 nm. It is more preferably from 5 to 50 nm, even more preferably from 1 to 30 nm, and particularly preferably from 5 to 25 nm.
• the specific surface area of the pigment is preferably 1 to 300 m 2 /g.
• the lower limit is preferably 10 m 2 /g or more, more preferably 30 m 2 /g or more.
• the upper limit is preferably 250 m 2 /g or less, more preferably 200 m 2 /g or less.
• the value of the specific surface area is determined according to DIN 66131: determination of the specific surface area of solids by gas adsorption according to the BET (Brunauer, Emmett and Teller) method. (Measurement of specific surface area of solids).
• the coloring material preferably contains Color Index Pigment Red 272.
• chromatic coloring materials include coloring materials having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. Examples include yellow coloring material, orange coloring material, red coloring material, green coloring material, purple coloring material, blue coloring material, and the like.
• the chromatic color material is preferably a pigment (chromatic pigment), more preferably a red pigment, a yellow pigment, and a blue pigment, and still more preferably a red pigment and a blue pigment. Specific examples of chromatic pigments include those shown below.
• red colorants examples include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, etc. It is preferably a compound, and more preferably a diketopyrrolopyrrole compound. Moreover, it is preferable that the red coloring material is a pigment.
• red coloring materials include C. 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, Examples include red pigments such as 279, 291, 294, 295, 296, 297, and the like.
• red coloring material a compound described in paragraph number 0034 of International Publication No. 2022/085485 and a brominated diketopyrrolopyrrole compound described in JP-A No. 2020-085947 can also be used.
• C. I. Pigment Red 122, 177, 254, 255, 264, 269, 272 are preferred, and C.I. I. Pigment Red 254, 264, and 272 are more preferred, and C.I. I. Pigment Red 254 and 272 are more preferred, and C.I. I. Pigment Red 272 is particularly preferred.
• the green coloring material examples include phthalocyanine compounds and squarylium compounds, preferably phthalocyanine compounds, and more preferably phthalocyanine pigments. Moreover, it is preferable that the green coloring material is a pigment.
• a specific example of the green coloring material is C. I.
• examples include green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66.
• halogenated zinc phthalocyanine has an average number of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule.
• Pigments can also be used.
• Specific examples include compounds described in International Publication No. 2015/118720.
• the compound described in paragraph number 0029 of International Publication No. 2022/085485, the aluminum phthalocyanine compound described in JP 2020-070426, etc. can also be used.
• C. I. Pigment Green 7, 36, 58, 62, 63 are preferred; I. Pigment Green 36 and 58 are more preferred. used.
• a specific example of the orange coloring material is C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. orange pigments.
• yellow colorants examples include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds.
• Specific examples of yellow colorants 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
• an azobarbituric acid nickel complex having the following structure can also be used.
• a specific example of the purple coloring material is C. I.
• Examples include purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.
• C. I. Pigment Blue 1 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc.
• examples include pigments.
• an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue coloring material. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A No. 2012-247591 and paragraph number 0047 of JP-A No. 2011-157478.
• Diarylmethane compounds described in Japanese Patent Publication No. 2020-504758 can also be used as the green coloring material or the blue coloring material.
• Pyrrolopyrrole pigments include those whose crystallite size in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight ( ⁇ 1 ⁇ 1 ⁇ 1) crystal lattice planes is 140 ⁇ or less. It is also preferable to use Further, the physical properties of the pyrrolopyrrole pigment are also preferably set as described in paragraph numbers 0028 to 0073 of JP-A-2020-097744.
• the pigment it is also preferable to use a halogenated zinc phthalocyanine pigment having a Raman spectrum described in Japanese Patent No. 6744002 from the viewpoint of improving spectral characteristics. Further, as the pigment, it is also preferable to use a dioxazine pigment with a controlled contact angle described in International Publication No. 2019/107166 from the viewpoint of viscosity adjustment.
• Dyes can also be used as chromatic coloring materials. There are no particular restrictions on the dye, and known dyes can be used. For example, pyrazole azo series, anilinoazo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, xanthene series, Examples include phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes.
• a pigment multimer can also be used as a chromatic coloring material.
• the dye multimer is preferably a dye that is dissolved in a solvent. Further, the dye multimer may form particles. When the dye multimer is in the form of particles, it is usually used in a state of being dispersed in a solvent.
• the dye multimer in a particle state can be obtained, for example, by emulsion polymerization, and specific examples include the compound and manufacturing method described in JP-A No. 2015-214682.
• the dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less.
• the plurality of dye structures contained in one molecule may be the same dye structure or may be different dye structures.
• the weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000.
• the lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more.
• the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
• Dye multimers are described in JP 2011-213925, JP 2013-041097, JP 2015-028144, JP 2015-030742, WO 2016/031442, etc. Compounds can also be used.
• triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP 2020-117638, and International Publication No. 2020/174991 are used.
• a halogenated zinc phthalocyanine pigment described in Patent No. 6809649, JP 2020-180176 Isoindoline compounds described in the publication, phenothiazine compounds described in JP2021-187913A, halogenated zinc phthalocyanine described in International Publication No. 2022/004261, zinc halide described in International Publication No. 2021/250883 Phthalocyanines can be used.
• the chromatic coloring material may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, the rod-like structure, or both structures.
• a chromatic coloring agent As a chromatic coloring agent, a quinophthalone compound represented by formula 1 of Korean Patent Publication No. 10-2020-0030759, a polymer dye described in Korean Publication Patent No. 10-2020-0061793, and Japanese Patent Application Publication No. 2022-029701. You may use the coloring agent described in WO 2022/014635, the isoindoline compound described in WO 2022/024926, and the aluminum phthalocyanine compound described in WO 2022/024926.
• Two or more chromatic color materials may be used in combination. Furthermore, when two or more chromatic coloring materials are used in combination, black may be formed by a combination of two or more chromatic coloring materials. Examples of such combinations include the following embodiments (1) to (7).
• the photosensitive composition of the present invention has near-infrared transmittance. It can be preferably used as a photosensitive composition for forming a filter.
• Embodiment containing a red coloring material and a blue coloring material (2) An embodiment containing a red coloring material, a blue coloring material, and a yellow coloring material.
• An embodiment containing a red coloring material, a blue coloring material, a yellow coloring material, and a purple coloring material An embodiment containing a red coloring material, a blue coloring material, a yellow coloring material, a purple coloring material, and a green coloring material.
• An embodiment containing a red coloring material, a blue coloring material, a yellow coloring material, and a green coloring material An embodiment containing a red coloring material, a blue coloring material, and a green coloring material.
• An embodiment containing a yellow coloring material and a purple coloring material An embodiment containing a yellow coloring material and a purple coloring material.
• White coloring materials include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, Examples include hollow resin particles and inorganic pigments (white pigments) such as zinc sulfide.
• the white pigment is preferably particles containing titanium atoms, and more preferably titanium oxide.
• the white pigment is preferably a particle having a refractive index of 2.10 or more with respect to light with a wavelength of 589 nm. The above-mentioned refractive index is preferably 2.10 to 3.00, more preferably 2.50 to 2.75.
• titanium oxide described in "Titanium oxide physical properties and applied technology, Manabu Seino, pages 13-45, published June 25, 1991, published by Gihodo Publishing" can also be used.
• the white pigment is not only made of a single inorganic substance, but also particles made of a composite with other materials may be used. For example, particles with pores or other materials inside, particles with a core particle attached to a large number of inorganic particles, and core/shell composite particles with a core particle made of polymer particles and a shell layer made of inorganic nanoparticles are used. It is preferable.
• the core and shell composite particles consisting of a core particle consisting of a polymer particle and a shell layer consisting of an inorganic nanoparticle for example, the description in paragraphs 0012 to 0042 of JP 2015-047520A can be referred to, This content is incorporated herein.
• Hollow inorganic particles can also be used as the white pigment.
• a hollow inorganic particle is an inorganic particle having a structure that has a cavity inside, and is an inorganic particle having a cavity surrounded by an outer shell.
• Examples of hollow inorganic particles include hollow inorganic particles described in JP2011-075786A, WO2013/061621A, JP2015-164881A, etc., the contents of which are not incorporated herein. It will be done.
• the black coloring material is not particularly limited, and any known material can be used.
• examples of the inorganic black coloring material include inorganic pigments (black pigments) such as carbon black, titanium black, and graphite, with carbon black and titanium black being preferred, and titanium black being more preferred.
• Titanium black is black particles containing titanium atoms, and lower titanium oxide and titanium oxynitride are preferable.
• the surface of titanium black can be modified as necessary for the purpose of improving dispersibility, suppressing agglomeration, 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. Furthermore, treatment with a water-repellent substance as disclosed in JP-A No.
• 2007-302836 is also possible.
• a black pigment C. I. Pigment Black 1, 7, etc.
• the titanium black has a small primary particle size and an average primary particle size of each particle. Specifically, it is preferable that the average primary particle diameter is 10 to 45 nm.
• Titanium black can also be used as a dispersion. For example, there may be mentioned a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms to Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50.
• titanium blacks examples include Titanium Black 10S, 12S, 13R, 13M, 13MC, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilac D ( Product name: Ako Kasei Co., Ltd.).
• organic black coloring materials include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds.
• bisbenzofuranone compounds include compounds described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, and Japanese Patent Application Publication No. 2012-515234, and for example, as "Irgaphor Black” manufactured by BASF. available.
• perylene compounds include compounds described in paragraph numbers 0016 to 0020 of JP-A No. 2017-226821, C.I. I. Pigment Black 31, 32 and the like.
• Examples of the azomethine compound include compounds described in JP-A-01-170601 and JP-A-02-034664, and are available as "Chromofine Black A1103" manufactured by Dainichiseika Kaisha, Ltd., for example. Further, as a black coloring material, a black organic pigment described in Japanese Patent No. 6985715, Lumogen Black FK4280, Paliogen Black S0084 (manufactured by BASF) may be used.
• the coloring material used in the photosensitive composition of the present invention may be only the above-mentioned black coloring material, or may further include a chromatic coloring material. According to this aspect, it is easy to obtain a photosensitive composition that can form a film with excellent light-shielding properties in the visible region.
• Examples of preferable combinations of black coloring materials and chromatic coloring materials include the following.
• the ratio is preferably 100:15 to 85:15 to 80, even more preferably 100:20 to 80:20 to 70.
• the near-infrared absorbing coloring material is preferably a compound having a maximum absorption wavelength on the longer wavelength side than the wavelength of 700 nm.
• the near-infrared absorbing coloring material is preferably a compound having a maximum absorption wavelength in a range of more than 700 nm and 1800 nm, more preferably a compound having a maximum absorption wavelength in a range of more than 700 nm and 1400 nm.
• a compound having a maximum absorption wavelength in a range of more than 700 nm and 1200 nm or less is more preferable, and a compound having a maximum absorption wavelength in a range of more than 700 nm and 1000 nm or less is particularly preferable.
• the ratio A 1 /A 2 between the absorbance A 1 at a wavelength of 500 nm and the absorbance A 2 at the maximum absorption wavelength of the near-infrared absorbing coloring material is preferably 0.08 or less, and more preferably 0.04 or less. preferable.
• the near-infrared absorbing coloring material is preferably a pigment, and more preferably an organic pigment.
• Near-infrared absorbing coloring materials include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, and pyrromethene compounds. , azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, and the like. Specific examples of these include compounds described in paragraph number 0114 of International Publication No. 2022/065215.
• the compound described in paragraph number 0121 of International Publication No. 2022/065215 the compound described in paragraph number 0121 of International Publication No. 2022/065215, the squarylium compound described in JP 2020-075959, Korean Published Patent No. 10-2019-0135217 Copper complexes described in the publication, croconic acid compounds described in JP 2021-195515, and near-infrared absorbing dyes described in JP 2022-022070 can also be used.
• the content of the coloring material in the total solid content of the photosensitive composition is 40% by mass or more, preferably 50% by mass or more, and more preferably 55% by mass or more.
• the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.
• the content of pigment in the total solid content of the photosensitive composition is preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more.
• the upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and even more preferably 75% by mass or less.
• the content of pigment in the coloring material is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass.
• the photosensitive composition of the present invention contains a polymerizable compound.
• the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group.
• the ethylenically unsaturated bond-containing group include a vinyl group, (meth)allyl group, (meth)acryloyl group, and (meth)acryloyloxy group.
• the polymerizable compound is preferably a radically polymerizable compound.
• the polymerizable compound used includes a polymerizable compound B1 having a weight average molecular weight of 3000 or more.
• the content of polymerizable compound B1 in the total mass of polymerizable compounds contained in the photosensitive composition is 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more. .
• the upper limit can be 100% by mass or less, 95% by mass or less, and 90% by mass or less.
• the weight average molecular weight of the polymerizable compound B1 is 3,000 or more, preferably 3,000 to 300,000.
• the upper limit is preferably 200,000 or less, more preferably 100,000 or less.
• the lower limit is preferably 5,000 or more, more preferably 10,000 or more.
• the ethylenically unsaturated bond-containing group value (hereinafter referred to as C ⁇ C value) of the polymerizable compound B1 is preferably 0.1 to 5.0 mmol/g.
• the upper limit is preferably 4.0 mmol/g or less, more preferably 3.0 mmol/g or less.
• the lower limit is preferably 0.2 mmol/g or more, more preferably 0.2 mmol/g or more.
• the C ⁇ C value of the polymerizable compound B1 is a numerical value representing the molar amount of the ethylenically unsaturated bond-containing group value per 1 g of solid content of the polymerizable compound B1.
• the value calculated from the structural formula of polymerizable compound B1 is used. Further, in cases where the value cannot be calculated from the structural formula and can be calculated from the raw materials used in the synthesis of the polymerizable compound B1, the value calculated from the raw materials used is used. Further, regarding the ethylenically unsaturated bond-containing group value of the polymerizable compound B1, if it cannot be calculated from the raw materials used for the synthesis of the polymerizable compound B1, a value measured using a hydrolysis method is used.
• component (a) of the ethylenically unsaturated bond-containing group site is extracted from the polymerizable compound B1 by alkali treatment, and its content is measured by high performance liquid chromatography (HPLC) and calculated from the following formula. Moreover, in the case where the component (a) cannot be extracted from the polymerizable compound B1 by alkali treatment, a value measured by NMR method (nuclear magnetic resonance) is used.
• Ethylenically unsaturated bond-containing group value of polymerizable compound B1 [mmol/g] (content of component (a) [ppm]/molecular weight of component (a) [g/mol])/(of polymerizable compound B1 Weighing value [g] x (solid concentration of polymerizable compound B1 [mass%]/100) x 10)
• the polymerizable compound B1 is a compound containing an acid group.
• the acid group include a carboxy group, a sulfo group, and a phosphoric acid group, with a carboxy group being preferred.
• the acid value of the polymerizable compound B1 is preferably 20 to 200 mgKOH/g.
• the upper limit is preferably 150 mgKOH/g or less, more preferably 100 mgKOH/g or less.
• the lower limit is preferably 30 mgKOH/g or more, more preferably 35 mgKOH/g or more.
• the polymerizable compound B1 is preferably a compound containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain.
• Examples of the repeating unit having an ethylenically unsaturated bond-containing group in its side chain include a repeating unit represented by formula (b1-1).
• a b11 represents a trivalent linking group
• L b11 represents a single bond or an n+1-valent linking group
• Y b11 represents an ethylenically unsaturated bond-containing group
• n represents 1 or 2.
• the trivalent linking group represented by A b11 includes a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, and a polyether linking group.
• Examples include a poly(meth)acrylic coupling group and a polystyrene coupling group, preferably a poly(meth)acrylic coupling group or a polyalkyleneimine coupling group, and more preferably a poly(meth)acrylic coupling group.
• the n+1-valent linking group represented by L b11 is an aliphatic hydrocarbon group (preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms), an aromatic hydrocarbon group (preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms), (hydrogen group), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, OCO-, -S-, and a combination of two or more of these groups.
• Examples of the ethylenically unsaturated bond-containing group represented by Y b11 include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group, with a (meth)acryloyloxy group being preferred. .
• the content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 1 mol% or more, and 1 to 80 mol% of the total repeating units of the polymerizable compound B1. It is more preferable that there be.
• the upper limit is preferably 70 mol% or less, more preferably 60 mol% or less.
• the lower limit is preferably 2 mol% or more, more preferably 5 mol% or more.
• the polymerizable compound B1 further includes a repeating unit having a graft chain in addition to the repeating unit having an ethylenically unsaturated bond-containing group in its side chain. That is, the polymerizable compound B1 is preferably a compound containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain and a repeating unit having a graft chain.
• a graft chain refers to a polymer chain that branches and extends from the main chain of a repeating unit.
• the graft chain preferably has a number of atoms excluding hydrogen atoms of 40 to 10,000, more preferably has a number of atoms excluding hydrogen atoms of 50 to 2,000, and has a number of atoms excluding hydrogen atoms of 60 to 10,000. More preferably, it is 500.
• the graft chain preferably contains a repeating unit of at least one type of structure selected from the group consisting of a polyester structure, a polyether structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure. structure, a polyether structure, a poly(meth)acrylic structure, and a polystyrene structure. It is more preferable to contain a repeating unit having at least one type of structure selected from the group consisting of: even more preferably to contain a repeating unit having a polyester structure or a polyether structure, and particularly preferably to contain a repeating unit having a polyester structure.
• repeating units having a polyester structure include repeating units having a structure represented by the following formula (G-1), formula (G-4) or formula (G-5).
• Examples of repeating units having a polyether structure include repeating units having a structure represented by the following formula (G-2).
• Examples of the repeating unit of the poly(meth)acrylic structure include a repeating unit of the structure represented by the following formula (G-3).
• Examples of the repeating unit of the polystyrene structure include a repeating unit of the structure represented by the following formula (G-6).
• R G1 and R G2 each independently represent an alkylene group.
• the alkylene groups represented by R G1 and R G2 are not particularly limited, but are preferably linear or branched alkylene groups having 1 to 20 carbon atoms, and linear or branched alkylene groups having 2 to 16 carbon atoms. More preferred are linear or branched alkylene groups having 3 to 12 carbon atoms.
• R G3 represents a hydrogen atom or a methyl group
• Q G1 represents -O- or -NH-
• L G1 represents a single bond or a divalent linking group
• R G4 represents hydrogen Represents an atom or substituent.
• the divalent linking group represented by L G1 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), and an oxyalkylenecarbonyl group (preferably an alkylene group having 1 to 12 carbon atoms).
• R G4 is an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, - Examples include COO-, OCO-, -S-, and a combination of two or more of these groups.
• Substituents represented by R G4 include hydroxy group, carboxy group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthioether group, arylthioether group, heterocyclic thioether group, etc. can be mentioned.
• R G5 represents a hydrogen atom or a methyl group
• R G6 represents an aryl group.
• the number of carbon atoms in the aryl group represented by R G6 is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
• the aryl group represented by R G6 may have a substituent. Examples of the substituent include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, a heterocyclic thioether group, and the like.
• the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
• substituents include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, a heterocyclic thioether group, and the like.
• groups having a steric repulsion effect are preferred, and alkyl groups or alkoxy groups having 5 to 24 carbon atoms are preferred.
• the alkyl group and the alkoxy group may be linear, branched, or cyclic, and preferably linear or branched.
• the graft chain is represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a), formula (G-5a) or formula (G-6a). It is preferable to have a structure represented by formula (G-1a), formula (G-4a) or formula (G-5a).
• R G1 and R G2 each represent an alkylene group
• R G3 represents a hydrogen atom or a methyl group
• Q G1 represents -O- or -NH-
• L G1 represents a single bond or Represents a divalent linking group
• R G4 represents a hydrogen atom or a substituent
• R G5 represents a hydrogen atom or a methyl group
• R G6 represents an aryl group
• W 100 represents a hydrogen atom or a substituent.
• n1 to n6 each independently represent an integer of 2 or more.
• R G1 to R G6 , Q G1 , and L G1 have the same meanings as R G1 to R G6 , Q G1 , and L G1 explained in formulas (G-1) to (G-6 ) , and the preferred ranges are also the same. be.
• W 100 is preferably a substituent.
• the substituent include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, a heterocyclic thioether group, and the like.
• groups having a steric repulsion effect are preferred, and alkyl groups or alkoxy groups having 5 to 24 carbon atoms are preferred.
• the alkyl group and the alkoxy group may be linear, branched, or cyclic, and preferably linear or branched.
• n1 to n6 are each preferably an integer of 2 to 100, more preferably an integer of 2 to 80, and even more preferably an integer of 8 to 60.
• R G1 in each repeating unit may be the same or different.
• R G1 contains two or more types of different repeating units
• the arrangement of each repeating unit is not particularly limited and may be random, alternating, or block. The same applies to formulas (G-2a) to (G-6a).
• the graft chain has a structure represented by formula (G-1a), formula (G-4a), or formula (G-5a), and has a structure containing two or more types of repeating units in which R G1 is different. is also preferable.
• repeating unit having a graft chain examples include a repeating unit represented by formula (b1-2).
• a b12 represents a trivalent linking group
• L b12 represents a single bond or a divalent linking group
• Y b12 represents a graft chain.
• the trivalent linking group represented by A b12 includes a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, and a polyether linking group.
• Examples include a poly(meth)acrylic coupling group and a polystyrene coupling group, preferably a poly(meth)acrylic coupling group or a polyalkyleneimine coupling group, and more preferably a poly(meth)acrylic coupling group.
• the divalent linking group represented by L b12 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-, Examples thereof include -SO 2 -, -CO-, -O-, -COO-, OCO-, -S-, and a combination of two or more of these groups.
• Examples of the graft chain represented by Y b12 include the above-mentioned graft chains.
• the weight average molecular weight of the repeating unit having a graft chain is preferably 1000 or more, more preferably 1000 to 10000, and even more preferably 1000 to 7500.
• the weight average molecular weight of a repeating unit having a graft chain is a value calculated from the weight average molecular weight of a raw material monomer used for polymerization of the same repeating unit.
• a repeating unit having a graft chain can be formed by polymerizing a macromonomer.
• the macromonomer refers to a polymer compound having a polymerizable group introduced at the end of the polymer.
• the weight average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.
• the content of the repeating unit having a graft chain is preferably 1 to 60 mol% of the total repeating units of the polymerizable compound B1.
• the upper limit is preferably 50 mol% or less, more preferably 40 mol% or less.
• the lower limit is preferably 2 mol% or more, more preferably 5 mol% or more.
• the polymerizable compound B1 further includes a repeating unit having an acid group in addition to the repeating unit having an ethylenically unsaturated bond-containing group in its side chain.
• the acid group include a carboxy group, a sulfo group, and a phosphoric acid group.
• repeating unit having an acid group examples include a repeating unit represented by formula (b1-3).
• a b13 represents a trivalent linking group
• L b13 represents a single bond or an n+1-valent linking group
• Y b13 represents an acid group
• n represents 1 or 2.
• the trivalent linking group represented by A b13 includes a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, and a polyether linking group.
• Examples include a poly(meth)acrylic coupling group and a polystyrene coupling group, preferably a poly(meth)acrylic coupling group or a polyalkyleneimine coupling group, and more preferably a poly(meth)acrylic coupling group.
• the n+1-valent linking group represented by L b13 includes an aliphatic hydrocarbon group (preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms), an aromatic hydrocarbon group (preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms) (hydrogen group), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, OCO-, -S-, and a combination of two or more of these groups.
• the acid group represented by Y b13 includes a carboxy group, a sulfo group, and a phosphoric acid group.
• the content of the repeating unit having an acid group is preferably 1 to 80 mol%, and 5 to 80% by mole based on the total repeating units of the polymerizable compound B1. It is more preferably mol%, and even more preferably 10 to 80 mol%.
• Polymerizable compound B1 is derived from a monomer component containing a compound represented by formula (ED1) and/or a compound represented by formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer”). It may contain repeating units.
• 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.
• Polymerizable compound B1 may contain a repeating unit derived from the compound represented by formula (X).
• R 1 represents a hydrogen atom or a methyl group
• R 21 and R 22 each independently represent an alkylene group
• n represents an integer of 0 to 15.
• the alkylene group represented by R 21 and R 22 preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly 2 or 3 carbon atoms.
• n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 3.
• the polymerizable compound B1 is a resin containing a repeating unit represented by formula (Ac-2).
• Ar 10 represents a group containing an aromatic carboxy group
• L 11 represents -COO- or -CONH-
• L 12 represents a trivalent linking group
• P 10 is Represents a polymer chain containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain.
• Examples of the group containing an aromatic carboxy group represented by Ar 10 in formula (Ac-2) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like.
• Examples of the aromatic tricarboxylic anhydride and aromatic tetracarboxylic anhydride include compounds having the following structures.
• Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, represented by the following formula (Q-1). or a group represented by the following formula (Q-2).
• the aromatic carboxy group-containing group represented by Ar 10 may have an ethylenically unsaturated bond-containing group.
• Specific examples of the group containing an aromatic carboxy group represented by Ar 10 include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13). Examples include groups such as
• n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
• n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2.
• n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and preferably 1. More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
• Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, the above formula (Q- Represents a group represented by 1) or a group represented by the above formula (Q-2).
• *1 represents the bonding position with L 10 .
• L 11 in formula (Ac-2) represents -COO- or -CONH-, and preferably -COO-.
• the trivalent linking group represented by L 12 in formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these two groups. Examples include groups that combine more than one species.
• Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15.
• the aliphatic hydrocarbon group may be linear, branched, or cyclic.
• the aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
• the hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group.
• the trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), more preferably a group represented by formula
• L 12b represents a trivalent linking group
• X 1 represents S
• *1 represents the bonding position with L 11 of formula (Ac-2)
• *2 represents the bonding position of formula (Ac-2). It represents the bonding position of Ac-2) with P10 .
• the trivalent linking group represented by L 12b is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-.
• a hydrocarbon group or a group consisting of a hydrocarbon group and -O- is preferable.
• L 12c represents a trivalent linking group
• X 1 represents S
• *1 represents the bonding position with L 11 of formula (Ac-2)
• *2 represents the bonding position of formula (Ac-2). It represents the bonding position of Ac-2) with P10 .
• the trivalent linking group represented by L 12c is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-.
• a hydrocarbon group is preferable.
• P 10 in formula (Ac-2) represents a polymer chain containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain.
• the polymer chain represented by P10 includes a repeating unit of at least one type of structure selected from the group consisting of a polyester structure, a polyether structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure.
• Examples include polymer chains.
• Examples of repeating units having a polyester structure include repeating units having a structure represented by the above formula (G-1), formula (G-4) or formula (G-5).
• Examples of the repeating unit of the polyether structure include a repeating unit of the structure represented by the above formula (G-2).
• Examples of the repeating unit of the poly(meth)acrylic structure include a repeating unit of the structure represented by the above formula (G-3).
• Examples of the repeating unit of the polystyrene structure include a repeating unit of the structure represented by the above formula (G-6).
• Examples of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain of the polymer chain represented by P 10 include the repeating unit represented by the above-mentioned formula (b1-1).
• the proportion of repeating units having an ethylenically unsaturated bond-containing group in the side chain in all repeating units constituting P 10 is preferably 1 mol% or more, and more preferably 1 to 80 mol%.
• the upper limit is preferably 70 mol% or less, more preferably 60 mol% or less.
• the lower limit is preferably 2 mol% or more, more preferably 5 mol% or more.
• the polymer chain represented by P 10 has a repeating unit containing an acid group.
• the acid group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
• the repeating unit having an acid group include the repeating unit represented by the above-mentioned formula (b1-3).
• the proportion of the repeating unit having an acid group in all the repeating units constituting P 10 is preferably 1 to 80 mol%, and 5 It is more preferably from 10 to 80 mol%, and even more preferably from 10 to 80 mol%.
• the weight average molecular weight of the polymer chain represented by P 10 is preferably 500 to 20,000.
• the lower limit is preferably 1000 or more.
• the upper limit is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.
• the photosensitive composition of the present invention may further contain a polymerizable compound B2 having a molecular weight of less than 3,000.
• the polymerizable compound B2 may be in any chemical form such as a monomer, prepolymer, or oligomer, but a monomer is preferable.
• the molecular weight of the polymerizable compound B2 is preferably 100 to 2,500.
• the upper limit is preferably 2000 or less, more preferably 1500 or less.
• the lower limit is preferably 150 or more, more preferably 250 or more.
• the lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and even more preferably 5 mmol/g or more.
• the upper limit is preferably 12 mmol/g or less, more preferably 10 mmol/g or less, and even more preferably 8 mmol/g or less.
• the C ⁇ C value of the polymerizable compound B2 is a value calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the polymerizable compound by the molecular weight of the polymerizable compound.
• the polymerizable compound B2 is preferably a compound containing three or more ethylenically unsaturated bond-containing groups, and more preferably a compound containing four or more ethylenically unsaturated bond-containing groups.
• the upper limit of the ethylenically unsaturated bond-containing group is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less from the viewpoint of storage stability of the photosensitive composition.
• the polymerizable compound B2 is preferably a trifunctional or more functional (meth)acrylate compound, more preferably a trifunctional to 15 functional (meth)acrylate compound, and a trifunctional to 10 functional (meth)acrylate compound.
• the polymerizable compound B2 includes paragraph numbers 0095 to 0108 of JP 2009-288705, paragraph 0227 of JP 2013-029760, paragraph 0254 to 0257 of JP 2008-292970, and Compounds described in paragraph numbers 0034 to 0038 of JP 2013-253224, paragraph 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, JP 6031807 , the contents of which are incorporated herein.
• Examples of the polymerizable compound B2 include dipentaerythritol tri(meth)acrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (as a commercial product, KAYARAD D- 320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercial product) is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industries, Ltd.), and these (meth)acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues
• Polymerizable compound B2 includes trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, penta Trifunctional (meth)acrylate compounds such as erythritol tri(meth)acrylate can also be used.
• Trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, 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.) Examples include.
• a compound having an acid group can also be used as the polymerizable compound B2.
• the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a carboxy group is preferred.
• Commercially available polymerizable compounds having acid groups include Aronix M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), and the like.
• the preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, more preferably 5 to 30 mgKOH/g.
• a compound having a caprolactone structure can also be used as the polymerizable compound B2.
• Commercially available polymerizable compounds having a caprolactone structure include KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.).
• a polymerizable compound having an alkyleneoxy group can also be used as the polymerizable compound B2.
• the polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and/or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and a polymerizable compound having 4 to 20 ethyleneoxy groups. More preferred are hexafunctional (meth)acrylate compounds.
• Commercially available polymerizable compounds having an alkyleneoxy group include, for example, SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer Co., Ltd., and isobutyleneoxy group manufactured by Nippon Kayaku Co., Ltd. Examples include KAYARAD TPA-330, which is a trifunctional (meth)acrylate having three.
• a polymerizable compound having a fluorene skeleton can also be used as the polymerizable compound B2.
• the polymerizable compound having a fluorene skeleton is preferably a bifunctional polymerizable compound.
• Examples of the polymerizable compound having a fluorene skeleton include a compound having a partial structure represented by the following formula (Fr).
• the wavy line represents a bond
• R f1 and R f2 each independently represent a substituent
• m and n each independently represent an integer from 0 to 5.
• m 2 or more
• the m R f1s may be the same or different, and two R f1s out of the m R f1s combine to form a ring.
• n 2 or more
• the n R f2s may be the same or different, and two R f2s out of the n R f2s combine to form a ring. Good too.
• R f1 and R f2 include a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, -OR f11 , -COR f12 , -COOR f13 , -OCOR f14 , -NR f15 R f16 , -NHCOR f17 , -CONR f18 R f19 , -NHCONR f20 R f21 , -NHCOOR f22 , -SR f23 , -SO 2 R f24 , -SO 2 OR f25 , -NHSO 2 R f26 or -SO 2 NR f27 R f28 is mentioned.
• R f11 to R f28 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
• polymerizable compounds having a fluorene skeleton include compounds having the following structure.
• Commercially available polymerizable compounds having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).
• the polymerizable compound B2 it is also preferable to use a compound that does not substantially contain environmentally controlled substances such as toluene.
• environmentally controlled substances such as toluene.
• Commercially available products of such compounds include KAYARAD DPHA LT, KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.), and the like.
• the content of the polymerizable compound in the total solid content of the photosensitive composition is preferably 5 to 50% by mass.
• the upper limit is preferably 45% by mass or less, more preferably 40% by mass or less.
• the lower limit is preferably 10% by mass or more, more preferably 15% by mass or more.
• the content of the above-mentioned polymerizable compound B1 in the total solid content of the photosensitive composition is preferably 5 to 50% by mass.
• the upper limit is preferably 45% by mass or less, more preferably 40% by mass or less.
• the lower limit is preferably 10% by mass or more, more preferably 15% by mass or more.
• the content of the polymerizable compound B1 is preferably 100 to 5000 parts by mass based on 100 parts by mass of the specific oxime compound described below.
• the upper limit is preferably 3000 parts by mass or less, more preferably 2000 parts by mass or less.
• the lower limit is preferably 200 parts by mass or more, more preferably 300 parts by mass or more.
• the content of the above-mentioned polymerizable compound B2 in the total solid content of the photosensitive composition is preferably 1 to 30% by mass.
• the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
• the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more.
• the content of the polymerizable compound B2 is preferably 50 to 1000 parts by mass based on 100 parts by mass of the specific oxime compound described below.
• the upper limit is preferably 700 parts by mass or less, more preferably 500 parts by mass or less.
• the lower limit is preferably 75 parts by mass or more, more preferably 100 parts by mass or more.
• the photosensitive composition of the present invention may contain only one kind of polymerizable compound, or may contain two or more kinds of polymerizable compounds. When two or more types of polymerizable compounds are included, it is preferable that the total amount thereof falls within the above range.
• the photosensitive composition of the present invention contains a photopolymerization initiator.
• the photosensitive composition of the present invention contains a compound represented by formula (1) as a photopolymerization initiator.
• the compound represented by formula (1) is also referred to as a specific oxime compound.
• X 1 represents a divalent linking group containing at least one member selected from the group consisting of an aromatic ring and a heterocycle
• R 1 represents a hydrogen atom or an acyl group
• R 2 represents an alkyl group or an aryl group
• R 3 and R 4 each independently represent a hydrogen atom or an alkyl group
• Alk 1 and Alk 2 each independently represent an alkyl group
• R 3 and R 4 may be combined to form a ring
• Alk 1 and Alk 2 may be combined to form a ring
• n represents 0 or 1.
• X 1 in formula (1) represents a divalent linking group containing at least one member selected from the group consisting of an aromatic ring and a heterocycle.
• X 1 is a divalent aromatic ring group, a divalent heterocyclic group, a divalent group in which two or more aromatic rings are bonded via a single bond or a linking group, or a divalent group in which two or more aromatic rings are bonded via a single bond or a linking group.
• examples include a divalent group bonded via a linking group, and a divalent group bonding an aromatic ring and a heterocycle via a single bond or a linking group.
• linking group examples include -CH 2 -, -O-, -CO-, -S-, -NR x -, and groups combining these.
• R x represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
• X 1 in formula (1) is preferably a group represented by any of formulas (X-1) to (X-13) because it can form a film with better adhesion.
• a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6) or formula (X-8) is more preferable; 2) or a group represented by formula (X-6) is more preferable, and a group represented by formula (X-6) is particularly preferable.
• R X1 to R X9 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
• the number of carbon atoms in the alkyl group represented by R X1 to R X9 is preferably 1 to 15, more preferably 1 to 10.
• the alkyl group may be linear, branched, or cyclic.
• the alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heterocyclic group.
• the alkenyl group represented by R X1 to R X9 preferably has 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms.
• the alkenyl group may be linear, branched, or cyclic.
• the alkenyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heterocyclic group.
• the alkynyl group represented by R X1 to R X9 preferably has 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms.
• the alkynyl group may be linear, branched, or cyclic.
• the alkynyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heterocyclic group.
• the number of carbon atoms in the aryl group represented by R X1 to R X9 is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6.
• the aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group.
• the heterocyclic group represented by R X1 to R X9 is preferably a 5-membered ring or a 6-membered ring.
• the heteroatom contained in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
• the number of heteroatoms that the heterocyclic group has is preferably 1 to 3.
• the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and the like.
• R 1 in formula (1) represents a hydrogen atom or an acyl group, and is preferably an acyl group.
• the acyl group represented by R 1 is preferably a group represented by -C(O)-R 101 .
• R 101 represents an aryl group or a heterocyclic group, and is preferably an aryl group.
• the number of carbon atoms in the aryl group represented by R 101 is preferably 6 to 20, more preferably 6 to 12.
• the aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group.
• the aryl group represented by R 101 is preferably a phenyl group, a methylphenyl group or a naphthyl group, more preferably a methylphenyl group or a naphthyl group.
• the heterocyclic group represented by R 101 is preferably a 5-membered ring or a 6-membered ring.
• the heteroatom contained in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
• the number of heteroatoms that the heterocyclic group has is preferably 1 to 3.
• the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and the like.
• R 2 in formula (1) represents an alkyl group or an aryl group, and is preferably an alkyl group because the generated radical has high reactivity.
• the number of carbon atoms in the alkyl group represented by R 2 is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. .
• the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
• the alkyl group may have a substituent, but is preferably an unsubstituted alkyl group.
• the alkyl group represented by R 2 is preferably an unsubstituted straight-chain or branched alkyl group, and more preferably an unsubstituted straight-chain alkyl group.
• the number of carbon atoms in the aryl group represented by R 2 is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6.
• the aryl group may have a substituent, but is preferably an unsubstituted aryl group.
• R 3 and R 4 in formula (1) each independently represent a hydrogen atom or an alkyl group, and preferably a hydrogen atom.
• the number of carbon atoms in the alkyl group represented by R 3 and R 4 is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and preferably 1 to 3. Even more preferred.
• the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. Although the alkyl group may have a substituent, it is preferably an unsubstituted alkyl group.
• R 3 and R 4 may be combined to form a ring.
• the ring formed is preferably a 5- or 6-membered ring, more preferably a 5- or 6-membered aliphatic hydrocarbon ring.
• Alk 1 and Alk 2 in formula (1) each independently represent an alkyl group.
• the number of carbon atoms in the alkyl group represented by R 3 and R 4 is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and preferably 1 to 3. Even more preferred.
• the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
• the alkyl group may have a substituent, but is preferably an unsubstituted alkyl group.
• Alk 1 and Alk 2 may be combined to form a ring, and preferably form a ring.
• the ring formed is preferably a 5-membered or 6-membered ring, more preferably a 5- or 6-membered aliphatic hydrocarbon ring, and is a cyclopentane ring or a cyclohexane ring. is more preferable.
• n 0 or 1, and is preferably 0.
• specific examples of specific oxime compounds include compounds I-1 to I-21 described in the Examples described below, compounds described in paragraph numbers 0092 to 0096 of JP2012-113104A, and JP2012-189997A. Examples include the compounds described in paragraph number 0041 of .
• the content of the specific oxime compound in the total mass of the photopolymerization initiator contained in the photosensitive composition is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. It is even more preferable that there be.
• the upper limit can be 100% by mass or less.
• the photopolymerization initiator contained in the photosensitive composition of the present invention may be substantially only the above-mentioned specific oxime compound, or may be a photopolymerization initiator other than the above-mentioned specific oxime compound (hereinafter, other photopolymerization initiators). (also referred to as an agent) may further be included.
• the photopolymerization initiator is substantially only a specific oxime compound because the exposure sensitivity is high.
• the case where the photopolymerization initiator is substantially only a specific oxime compound means that the specific oxime compound in the photopolymerization initiator is 99% by mass or more, and 99.9% by mass % or more, and more preferably only the specific oxime compound.
• the exposure sensitivity can be adjusted.
• the photopolymerization initiator further contains other photopolymerization initiators in addition to the specific oxime compound, the content of the other photopolymerization initiators is 5 to 50 parts by mass based on 100 parts by mass of the specific oxime compound. It is preferable that there be.
• the lower limit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more.
• the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.
• photopolymerization initiators include halogenated hydrocarbon derivatives (for example, compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, and organic peroxides. , thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, and the like.
• halogenated hydrocarbon derivatives for example, compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.
• acylphosphine compounds for example, compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.
• acylphosphine compounds for example, compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.
• acylphosphine compounds for
• photopolymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and hexaarylbylene compounds.
• imidazole compounds onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds, oxime compounds, ⁇ -hydroxyketones
• the compound is more preferably a compound selected from a compound, an ⁇ -aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound.
• photopolymerization initiators compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No.
• hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole, etc. can be mentioned.
• ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, and Irgacure 117. 3, Irgacure 2959, Irgacure 127 (all BASF (manufactured by a company).
• Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, and Irgacure 36.
• Irgacure 369E Irgacure 379EG (all manufactured by BASF) (manufactured by).
• Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.
• Examples of oxime compounds include the compounds described in JP-A No. 2001-233842, the compounds described in JP-A No. 2000-080068, the compounds described in JP-A No. 2006-342166, and the compounds described in J. C. S. 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), JP-A-2000-0 Compounds described in Publication No. 66385, Compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2006-342166, compounds described in Japanese Patent Application Publication No.
• oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like.
• oxime compounds having a fluorene ring can also be used.
• Specific examples of oxime compounds having a fluorene ring include compounds described in JP-A No. 2014-137466, compounds described in Japanese Patent No. 6636081, compounds described in Korean Patent Publication No. 10-2016-0109444, Examples include fluorenylaminoketone photoinitiators described in Japanese Patent Publication No. 2020-507664 and oxime ester compounds described in International Publication No. 2021/023144.
• oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring.
• Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.
• oxime compounds having a fluorine atom can also be used.
• Specific examples of oxime compounds having a fluorine atom include compounds described in JP-A No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Application Publication No. 2014-500852, and compounds described in JP-A No. 2013-164471. Examples include compound (C-3).
• oxime compounds having a nitro group can be used as other photopolymerization initiators. It is also preferable that the oxime compound having a nitro group is in the form of a dimer.
• Specific examples of oxime compounds having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP 2013-114249, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466, Examples include compounds described in paragraph numbers 0007 to 0025 of Japanese Patent No. 4223071, and Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).
• oxime compounds having a benzofuran skeleton can also be used.
• Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
• photopolymerization initiators it is also possible to use oxime compounds in which a substituent having a hydroxy group is bonded to the carbazole skeleton.
• photopolymerization initiators include compounds described in International Publication No. 2019/088055.
• an oxime compound having an aromatic ring group Ar OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX).
• 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.
• the 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, and 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. More preferably, it is a sulfanyl group or an amino group.
• oxime compound OX examples include compounds described in paragraph numbers 0083 to 0105 of Japanese Patent No. 4,600,600.
• difunctional or trifunctional or more functional photoradical polymerization initiators may be used as other photopolymerization initiators.
• a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained.
• the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time and improving the storage stability of the photosensitive composition.
• Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include those listed in 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 photosensitive composition is preferably 0.5 to 20% by mass.
• the lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and even more preferably 3.5% by mass or more.
• the upper limit is preferably 15% by mass or less, more preferably 10% by mass or less.
• the content of the specific oxime compound in the total solid content of the photosensitive composition is preferably 0.5 to 20% by mass.
• the lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and even more preferably 3.5% by mass or more.
• the upper limit is preferably 15% by mass or less, more preferably 10% by mass or less.
• only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
• the photosensitive composition of the present invention can contain a pigment derivative.
• the coloring material used in the photosensitive composition of the present invention contains a pigment
• Pigment derivatives are used, for example, as dispersion aids.
• the pigment derivative include compounds having at least one structure selected from the group consisting of a pigment structure and a triazine structure, and an acid group or a basic group.
• the above dye structures include quinoline dye structure, benzimidazolone dye structure, benzisoindole dye structure, benzothiazole dye structure, iminium dye structure, squarylium dye structure, croconium dye structure, oxonol dye structure, pyrrolopyrrole dye structure, diketo Pyrrolopyrrole dye structure, azo dye structure, azomethine dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, anthraquinone dye structure, quinacridone dye structure, dioxazine dye structure, perinone dye structure, perylene dye structure, thiazine indigo dye structure, thioindigo dye structure, isoindoline dye structure, isoindolinone dye structure, quinophthalone dye structure, dithiol dye structure, triarylmethane dye structure, pyrromethene dye structure, etc.
• Examples of acid groups possessed by pigment derivatives include carboxy groups, sulfo groups, phosphoric acid groups, phosphonic acids, and phenolic hydroxy groups.
• Examples of the basic group that the pigment derivative has include an amino group, a pyridinyl group and its salts, an ammonium group salt, and a phthalimidomethyl group.
• Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
• a pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative) can be used.
• the maximum molar extinction coefficient ( ⁇ max) of the transparent pigment derivative in the wavelength range of 400 to 700 nm is preferably 3000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less, and preferably 1000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less. is more preferable, and even more preferably 100 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less.
• the lower limit of ⁇ max is, for example, 1 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more, and may be 10 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more.
• pigment derivatives include compounds described in paragraph 0124 of International Publication No. 2022/085485, benzimidazolone compounds or salts thereof described in JP 2018-168244, and the like.
• a compound having an isoindoline skeleton described in the general formula (1) of Japanese Patent No. 6996282 may be used.
• the content of the pigment derivative is preferably 1 to 30 parts by weight per 100 parts by weight of the pigment.
• the lower limit is preferably 2 parts by mass or more, more preferably 4 parts by mass or more.
• the upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less. Only one type of pigment derivative may be used, or two or more types may be used in combination. When two or more types are used in combination, it is preferable that the total amount is within the above range.
• the photosensitive composition of the present invention can also contain polyalkyleneimine.
• Polyalkyleneimines are used, for example, as dispersion aids for pigments.
• Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine, and is a polymer having at least a secondary amino group.
• the polyalkyleneimine may contain a primary amino group or a tertiary amino group in addition to the secondary amino group.
• the polyalkylene imine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group, respectively.
• the alkyleneimine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
• Specific examples of alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, etc. Ethyleneimine or propyleneimine is preferable, and ethyleneimine is more preferable. preferable.
• the molecular weight of the polyalkylene imine is preferably 200 or more, more preferably 250 or more.
• the upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less.
• the molecular weight of the polyalkylene imine if the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkylene imine is the value calculated from the structural formula.
• the molecular weight of a specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used.
• the value of the number average molecular weight measured by the viscosity method is used. If the viscosity method cannot be used or it is difficult to measure, the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) is used.
• the amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
• the polyalkyleneimine is polyethyleneimine.
• the polyethyleneimine preferably contains a primary amino group of 10 mol% or more, more preferably 20 mol% or more, based on the total of the primary amino group, secondary amino group, and tertiary amino group. It is more preferable that the content is mol % or more.
• Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).
• the content of polyalkyleneimine in the total solid content of the photosensitive composition is preferably 0.1 to 5% by mass.
• the lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
• the upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
• the content of polyalkyleneimine is preferably 0.5 to 20 parts by weight per 100 parts by weight of the pigment.
• the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more.
• the upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. Only one type of polyalkylene imine may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
• the photosensitive composition of the present invention can further contain resins other than the above-mentioned polymerizable compound B1.
• the resin is blended, for example, for dispersing pigments and the like in a photosensitive composition or for use as a binder.
• a resin used mainly for dispersing pigments and the like in a photosensitive composition is also referred to as a dispersant.
• this use of the resin is just an example, and the resin can also be used for purposes other than this use.
• the resin examples include (meth)acrylic resin, epoxy resin, (meth)acrylamide resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene.
• examples include ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin.
• Polyisocyanate resin resin described in JP 2020-122052, resin described in JP 2020-111656, resin described in JP 2020-139021, JP 2017-138503 Resin containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain described in JP 2020-186373, paragraphs 0199 to 0233, JP 2020-186325 Alkali-soluble resins described in the publication, resins represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339, copolymers containing epoxy groups and acid groups described in International Publication No. 2022/030445 You can also use
• the weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000.
• the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
• the lower limit is preferably 4000 or more, more preferably 5000 or more.
• the resin it is preferable to use a resin having acid groups.
• the acid group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
• a 1 in formula (1) is a group containing a basic group as the specific compound described later, it is preferable to use a resin having an acid group as the resin. According to this aspect, the storage stability of the photosensitive composition can be further improved.
• the acid value of the resin having acid groups is preferably 30 to 500 mgKOH/g.
• the lower limit is more preferably 40 mgKOH/g or more, particularly preferably 50 mgKOH/g or more.
• the upper limit is more preferably 400 mgKOH/g or less, even more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less.
• the weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, more preferably 5,000 to 50,000. Further, the number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.
• the resin having an acid group preferably contains a repeating unit having an acid group in its side chain, and more preferably contains 5 to 70 mol% of repeating units having an acid group in its side chain based on the total repeating units of the resin.
• the upper limit of the content of repeating units having acid groups in their side chains is preferably 50 mol% or less, more preferably 30 mol% or less.
• the lower limit of the content of repeating units having acid groups in their side chains is preferably 10 mol% or more, more preferably 20 mol% or more.
• a resin having a basic group can also be used.
• a 1 in formula (1) is a group containing an acid group as the specific compound described later, it is preferable to use a resin having a basic group as the resin. According to this aspect, the storage stability of the photosensitive composition can be further improved.
• the resin having a basic group is preferably a resin containing a repeating unit having a basic group in its side chain, and a resin having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group.
• a polymer is more preferable, and a block copolymer having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group is even more preferable.
• a resin having a basic group can also be used as a dispersant.
• the amine value of the resin having a basic group is preferably 5 to 300 mgKOH/g.
• the lower limit is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more.
• the upper limit is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less.
• resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (manufactured by BYK Chemie), Solsperse 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 385 00, 39000, 53095, 56000, 7100 (all manufactured by Japan Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like.
• the resin having a basic group is the block copolymer (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and the block copolymer (B) described in paragraphs 0046 to 0076 of JP2018-156021A. It is also possible to use a vinyl resin having a basic group described in paragraph numbers 0150 to 0153 of JP-A No. 2019-184763, the contents of which are incorporated herein.
• the storage stability of the photosensitive composition can be further improved.
• the content of the resin having a basic group is preferably 20 to 500 parts by mass per 100 parts by mass of the resin having an acid group.
• the amount is preferably 30 to 300 parts by weight, more preferably 50 to 200 parts by weight.
• the resin it is also preferable to use a resin having an aromatic carboxy group (hereinafter also referred to as resin Ac).
• the aromatic carboxy group may be included in the main chain of the repeating unit, or may be included in the side chain of the repeating unit.
• the aromatic carboxy group is preferably contained in the main chain of the repeating unit.
• an aromatic carboxy group refers to a group having a structure in which one or more carboxy groups are bonded to an aromatic ring.
• the number of carboxy groups bonded to the aromatic ring is preferably 1 to 4, more preferably 1 to 2.
• At least one type of resin selected from graft polymers, star polymers, block copolymers, and resins in which at least one end of a polymer chain is capped with an acid group.
• Such resins are preferably used as dispersants.
• Examples of the graft polymer include resins having repeating units with graft chains.
• Examples of the graft chain include a graft chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure.
• the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
• Examples of the substituent include an alkyl group, an alkoxy group, an alkylthioether group, and the like. Among these, from the viewpoint of improving the dispersibility of the pigment, groups having a steric repulsion effect are preferred, and alkyl groups or alkoxy groups having 5 to 30 carbon atoms are preferred.
• the alkyl group and the alkoxy group may be linear, branched, or cyclic, and preferably linear or branched.
• graft polymers include paragraph numbers 0025 to 0094 of JP2012-255128A, paragraphs 0022 to 0097 of JP2009-203462A, and paragraphs 0102 to 0166 of JP2012-255128A. Mention may be made of the resins mentioned.
• star-shaped polymers include resins with a structure in which a plurality of polymer chains are bonded to a core portion.
• Specific examples of star-shaped polymers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A No. 2013-043962.
• the block copolymers include a polymer block having a repeating unit containing an acid group or a basic group (hereinafter also referred to as block A), and a polymer block having a repeating unit not containing an acid group or a basic group. (hereinafter also referred to as block B) is preferably a block copolymer.
• the block copolymers include block copolymers (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and blocks described in paragraph numbers 0046 to 0076 of JP2018-156021A. Copolymers A1 can also be used, the contents of which are incorporated herein.
• the resin in which at least one end of the polymer chain is capped with an acid group is a resin in which at least one end of the polymer chain contains at least one type of structure selected from a polyester structure, a polyether structure, and a poly(meth)acrylic structure.
• examples include resins with a structure sealed with acid groups.
• acid groups that block the ends of polymer chains include carboxy groups, sulfo groups, and phosphoric acid groups.
• a resin as a dispersant can also be used.
• the dispersant include acidic dispersants (acidic resins) and basic dispersants (basic resins).
• the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups.
• the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %.
• the acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group.
• the acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g.
• the basic dispersant refers to a resin in which the amount of basic groups is greater than the amount of acid groups.
• the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%.
• the basic group that the basic dispersant has is preferably an amino group.
• Dispersants are also available as commercial products, and specific examples include the Disperbyk series manufactured by Byk Chemie (for example, Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajisper series manufactured by Ajinomoto Fine Techno Co., Ltd., A208F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), H-3606 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Sandet Examples include ET (manufactured by Sanyo Chemical Industries, Ltd.). Further, the product described in paragraph number 0129 of JP 2012-137564A and the product described in paragraph number 0235 of JP 2017-194662A can also be used as a dispersant.
• Disperbyk series manufactured by Byk Chemie for example, Disperbyk-111, 161, 2001, etc.
• the content of the resin in the total solid content of the photosensitive composition is preferably 1 to 50% by mass.
• the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
• the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
• the photosensitive composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more types of resin are included, the total amount thereof is preferably within the above range.
• the photosensitive composition of the present invention preferably contains a solvent.
• the solvent include 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.
• the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
• paragraph number 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein.
• Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used.
• organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N
• aromatic hydrocarbons benzene, toluene, xylene, ethylbenzene, etc.
• organic solvents for environmental reasons (for example, 50 mass ppm (parts) based on the total amount of organic solvents). per million), 10 mass ppm or less, and 1 mass ppm or less).
• an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content. It is preferable that the metal content of the organic solvent is, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by Toyo Gosei Co., Ltd. (Kagaku Kogyo Nippo, November 13, 2015). .
• Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
• the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
• the material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.
• the organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one type of isomer may be included, or multiple types may be included.
• the content of peroxide in the organic solvent is 0.8 mmol/L or less, and it is more preferable that the organic solvent contains substantially no peroxide.
• the content of the solvent in the photosensitive composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.
• the photosensitive composition of the present invention preferably does not substantially contain environmentally regulated substances from the viewpoint of environmental regulations.
• "not substantially containing environmentally controlled substances” means that the content of environmentally controlled substances in the photosensitive composition is 50 mass ppm or less, and 30 mass ppm or less is preferable. It is preferably 10 mass ppm or less, more preferably 1 mass ppm or less, and particularly preferably 1 mass ppm or less.
• environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
• REACH Registration Evaluation Authorization and Restriction of CHemicals
• PRTR Policy Release and It is registered as an environmentally regulated substance under the Transfer Register Act
• VOC Volatile Organic Compounds
• VOC Volatile Organic Compounds
• the method is strictly regulated.
• These compounds may be used as a solvent when producing each component used in the photosensitive composition, and may be mixed into the photosensitive composition as a residual solvent. From the viewpoint of human safety and environmental considerations, it is preferable to reduce the amount of these substances as much as possible.
• methods for reducing environmentally controlled substances include a method of heating or reducing pressure in the system to raise the temperature above the boiling point of the environmentally controlled substance to distill off the environmentally controlled substances from the system.
• distillation methods can be used at the stage of raw materials, at the stage of products obtained by reacting raw materials (for example, resin solution or polyfunctional monomer solution after polymerization), or at the stage of photosensitive compositions prepared by mixing these compounds. It is possible at any stage, such as a stage.
• the photosensitive composition of the present invention can further contain a compound having a cyclic ether group.
• the cyclic ether group include an epoxy group and an oxetanyl group.
• the epoxy group may be a cycloaliphatic epoxy group. Note that the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
• the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound).
• the epoxy compound include compounds having one or more epoxy groups in one molecule, and preferably compounds having two or more epoxy groups.
• the epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule.
• the upper limit of the epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less.
• the lower limit of the epoxy groups contained in the epoxy compound is preferably two or more.
• Examples of epoxy compounds include those described in paragraph numbers 0034 to 0036 of JP2013-011869, paragraphs 0147 to 0156 of JP2014-043556, and paragraphs 0085 to 0092 of JP2014-089408.
• Compounds, compounds described in JP 2017-179172, xanthene type epoxy resins described in JP 2021-195421, and xanthene epoxy resins described in JP 2021-195422 can also be used.
• the compound having a cyclic ether group may be a low-molecular compound (e.g., molecular weight less than 2,000, further, molecular weight less than 1,000), or a macromolecule (e.g., molecular weight 1,000 or more, in the case of a polymer, a weight average molecular weight may be 1000 or more).
• the weight average molecular weight of the compound having a cyclic ether group is preferably 200 to 100,000, more preferably 500 to 50,000.
• the upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5,000 or less, and even more preferably 3,000 or less.
• cyclic ether group Commercially available compounds having a cyclic ether group include, for example, EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, and G-0130SP. -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all of which are epoxy group-containing polymers manufactured by NOF Corporation). Further, as a compound having a cyclic ether group, compounds described in Examples described later can also be used.
• the content of the compound having a cyclic ether group in the total solid content of the photosensitive composition is preferably 0.1 to 20% by mass.
• the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
• the upper limit is preferably 15% by mass or less, more preferably 10% by mass or less. Only one kind of compound having a cyclic ether group may be used, or two or more kinds thereof may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
• the photosensitive composition of the present invention may also contain a curing accelerator.
• the curing accelerator 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 the compound described in paragraph 0164 of International Publication No. 2022/085485, the compound described in JP 2021-181406, and the like.
• the content of the curing accelerator in the total solid content of the photosensitive composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
• the photosensitive composition of the present invention can contain an ultraviolet absorber.
• the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. Specific examples of such compounds include the compound described in paragraph number 0179 of International Publication No. 2022/085485, the reactive triazine ultraviolet absorber described in JP 2021-178918, and JP 2022-007884. It is also possible to use the ultraviolet absorbers described in .
• the content of the ultraviolet absorber in the total solid content of the photosensitive composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass.
• only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.
• the photosensitive composition of the present invention can contain a polymerization inhibitor.
• Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred.
• the content of the polymerization inhibitor in the total solid content of the photosensitive composition is preferably 0.0001 to 5% by mass.
• the number of polymerization inhibitors may be one, or two or more. In the case of two or more types, it is preferable that the total amount falls within the above range.
• the photosensitive composition of the present invention can contain a silane coupling agent.
• the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
• the term "hydrolyzable group" refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkoxy group is preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
• Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, and isocyanate groups. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferable.
• silane coupling agents 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 No. 2009-288703 and compounds described in paragraph numbers 0056 to 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 photosensitive composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass. Only one type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, it is preferable that the total amount falls within the above range.
• the photosensitive composition of the present invention can contain a surfactant.
• a surfactant various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.
• the surfactant is preferably a silicone surfactant or a fluorine surfactant.
• the fluorine content in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
• a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving, and has good solubility in the photosensitive composition.
• fluorine-based surfactant compounds described in paragraph numbers 0167 to 0169 of International Publication No. 2022/085485 can be used.
• a block polymer can also be used as the fluorosurfactant.
• the fluorine-based surfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) (meth).
• 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 paragraph numbers 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-containing surfactant used in the present invention.
• the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example 14,000. In the above compounds, % indicating the proportion of repeating units is mol%.
• a fluorine-based surfactant a fluorine-containing copolymer having an ethylenically unsaturated bond-containing group in its side chain can also be used. Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A No. 2010-164965, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation, Examples include RS-72-K. Further, as the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 and fluorine-containing copolymers described in JP-A No. 2022-000494 can also be used.
• a fluorine-containing imide salt compound represented by formula (fi-1) is also preferable to use as a surfactant.
• m represents 1 or 2
• n represents an integer of 1 to 4
• a represents 1 or 2
• X a+ represents an a-valent metal ion, a primary ammonium ion
• a Re represents a secondary ammonium ion, a tertiary ammonium ion, a quaternary ammonium ion, or NH 4 + .
• nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm Wa
• silicone surfactants examples include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), and TSF- 4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) , BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by BYK Chemie), and the like.
• a compound having the following structure can also be used as the silicone surfactant.
• the content of the surfactant in the total solid content of the photosensitive composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% to 3.0% by mass.
• the number of surfactants may be one, or two or more. In the case of two or more types, it is preferable that the total amount falls within the above range.
• the photosensitive composition of the present invention can contain an antioxidant.
• antioxidants include phenol compounds, phosphite compounds, thioether compounds, and the like.
• the phenol compound any phenol compound known as a phenolic antioxidant can be used.
• Preferred phenol compounds include hindered phenol compounds.
• a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred.
• the above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms.
• the antioxidant a compound having a phenol group and a phosphorous acid ester group in the same molecule is also preferable.
• phosphorus-based antioxidants can also be suitably used.
• a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl )oxy]ethyl]amine, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
• antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Co., Ltd.).
• antioxidants include compounds described in paragraph numbers 0023 to 0048 of Patent No. 6268967, compounds described in International Publication No. 2017/006600, compounds described in International Publication No. 2017/164024, Compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used.
• the content of the antioxidant in the total solid content of the photosensitive composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.
• the photosensitive composition of the present invention may contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents (e.g., conductive particles, antifoaming agents, flame retardants), as necessary. , a leveling agent, a peeling accelerator, a fragrance, a surface tension regulator, a chain transfer agent, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. As these components, the compounds described in paragraph 0182 of International Publication No. 2022/085485 can be used.
• the photosensitive composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film.
• metal oxides include TiO 2 , ZrO 2 , Al 2 O 3 , and SiO 2 .
• the primary particle diameter of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, even more preferably 5 to 50 nm.
• the metal oxide may have a core-shell structure. Further, in this case, the core portion may be hollow.
• the photosensitive composition of the present invention may also contain a lightfastness improver.
• Examples of the light resistance improver include compounds described in paragraph number 0183 of International Publication No. 2022/085485.
• the photosensitive composition of the present invention is substantially free of terephthalic acid ester.
• “substantially not containing” means that the content of terephthalic acid ester is 1000 mass ppb or less in the total amount of the photosensitive composition, and more preferably 100 mass ppb or less. , is particularly preferably zero.
• the photosensitive composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less. Further, the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Examples of methods for reducing free metals and halogens in the photosensitive composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification using ion-exchange resins.
• perfluoroalkyl sulfonic acids and their salts may be regulated.
• perfluoroalkylsulfonic acids particularly perfluoroalkylsulfonic acids whose perfluoroalkyl group has 6 to 8 carbon atoms
• the content of perfluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid whose perfluoroalkyl group has 6 to 8 carbon atoms) and its salts is 0.01 ppb to 1 ppb based on the total solid content of the photosensitive composition.
• the photosensitive composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt.
• perfluoroalkylsulfonic acid and its salt and perfluoroalkylcarboxylic acid and its salt.
• Compounds that can be substituted for regulated compounds include, for example, compounds that are excluded from regulated targets due to differences in the number of carbon atoms in perfluoroalkyl groups.
• the above content does not preclude the use of perfluoroalkylsulfonic acids and salts thereof, and perfluoroalkylcarboxylic acids and salts thereof.
• the photosensitive compositions of the present invention may include perfluoroalkyl sulfonic acids and salts thereof, and perfluoroalkyl carboxylic acids and salts thereof, to the maximum extent permitted.
• the water content of the photosensitive composition of the present invention is usually 3% by mass or less, preferably from 0.01 to 1.5% by mass, and more preferably from 0.1 to 1.0% by mass.
• the water content can be measured by the Karl Fischer method.
• the photosensitive composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface condition (flatness, etc.), adjusting the film thickness, etc.
• the value of viscosity can be appropriately selected as required, but for example, at 25° C., 0.3 mPa ⁇ s to 50 mPa ⁇ s is preferable, and 0.5 mPa ⁇ s to 20 mPa ⁇ s is more preferable.
• the viscosity can be measured using, for example, a cone plate type viscometer with the temperature adjusted to 25°C.
• the container for storing the photosensitive composition is not particularly limited, and any known container can be used.
• a multilayer bottle with the inner wall of the container made of six types and six layers of resin, and a seven-layer structure made of six types of resin. It is also preferable to use bottles. Examples of such a container include the container described in JP-A No. 2015-123351.
• the inner wall of the container is preferably made of glass, stainless steel, etc. for the purpose of preventing metal elution from the inner wall of the container, increasing the storage stability of the photosensitive composition, and suppressing component deterioration.
• the photosensitive composition of the present invention can be prepared by mixing the above-mentioned components.
• the photosensitive composition may be prepared by dissolving and/or dispersing all components in a solvent at the same time, or, if necessary, each component may be suitably dissolved or dispersed in two or more solutions.
• a photosensitive composition may be prepared by preparing a liquid and mixing these at the time of use (at the time of application).
• a process of dispersing pigments when preparing the photosensitive 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 a salt milling step.
• Bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass.
• an inorganic compound having a Mohs hardness of 2 or more can also be used for the beads.
• the photosensitive composition may contain 1 to 10,000 ppm of the beads.
• the photosensitive composition In preparing the photosensitive composition, it is preferable to filter the photosensitive composition with a filter for the purpose of removing foreign substances and reducing defects.
• a filter for the purpose of removing foreign substances and reducing defects.
• Examples of the type of filter and filtration method used for filtration include the filters and filtration methods described in paragraph numbers 0196 to 0199 of International Publication No. 2022/085485.
• the film of the present invention is a film obtained from the photosensitive composition of the present invention described above.
• the film of the present invention can be used for optical filters such as color filters, near-infrared transmission filters, and near-infrared cut filters.
• the film thickness of the film of the present invention can be adjusted as appropriate depending on the purpose.
• the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
• the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more.
• the film of the present invention When the film of the present invention is used as a color filter, the film of the present invention preferably has a hue of green, red, blue, cyan, magenta, or yellow. Further, 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 is preferably in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, More preferably, the wavelength is in the range of 700 to 1000 nm.
• the transmittance of the film over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Further, the transmittance of the film 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 to absorbance A550 at a wavelength of 550 nm, is preferably 20 to 500, more preferably 50 to 500, and 70 to 450. It is more preferably 100 to 400, particularly preferably 100 to 400.
• the film of the present invention preferably has, for example, any of the following spectral characteristics (i1) to (i5).
• a film having such spectral characteristics can block light in a wavelength range of 400 to 640 nm and transmit light with a wavelength exceeding 750 nm.
• the maximum value of transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 900 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
• a film having such spectral characteristics can block light in a wavelength range of 400 to 750 nm and transmit light with a wavelength exceeding 850 nm.
• the maximum value of transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1000 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
• a film having such spectral characteristics can block light in a wavelength range of 400 to 830 nm and transmit light with a wavelength exceeding 950 nm.
• the maximum value of transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1100 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
• a film having such spectral characteristics can block light in the wavelength range of 400 to 950 nm and transmit light with a wavelength exceeding 1050 nm.
• the maximum value of transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1200 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
• a film having such spectral characteristics can block light in the wavelength range of 400 to 1050 nm and transmit light with a wavelength exceeding 1150 nm.
• the optical filter of the present invention has the film of the present invention described above.
• Types of optical filters include color filters, near-infrared cut filters, near-infrared transmission filters, etc., and color filters are preferred.
• the color filter preferably has the film of the present invention as its pixels, and more preferably has the film of the present invention as its colored pixels.
• the film thickness of the film of the present invention can be adjusted as appropriate depending on 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 the pixels included in the optical filter is preferably 0.4 to 10.0 ⁇ m.
• the lower limit is preferably 0.4 ⁇ m or more, more preferably 0.5 ⁇ m or more, and even more preferably 0.6 ⁇ m or more.
• the upper limit is preferably 5.0 ⁇ m or less, more preferably 2.0 ⁇ m or less, even more preferably 1.0 ⁇ m or less, and even more preferably 0.8 ⁇ m or less.
• the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
• a protective layer may be provided on the surface of the film of the present invention.
• various functions such as oxygen blocking, low reflection, hydrophilic and hydrophobic properties, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted.
• the thickness of the protective layer is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
• Examples of the method for forming the protective layer include a method of applying a resin composition for forming the protective layer, a chemical vapor deposition method, and a method of pasting a molded resin with an adhesive.
• Components constituting the protective layer include (meth)acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, and polyimide.
• Resin polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Examples include resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al 2 O 3 , Mo, SiO 2 , Si 2 N 4 and the like, and two or more of these components may be contained.
• the protective layer preferably contains a polyol resin, SiO 2 and Si 2 N 4 .
• the protective layer preferably contains a (meth)acrylic resin and a fluororesin.
• a protective layer by applying a resin composition known methods such as a spin coating method, a casting method, a screen printing method, an inkjet method, etc. can be used as a method for applying the photosensitive composition.
• organic solvent contained in the photosensitive composition known organic solvents (eg, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used.
• chemical vapor deposition methods thermal chemical vapor deposition, plasma enhanced chemical vapor deposition, photochemical vapor deposition
• photochemical vapor deposition can be used as the chemical vapor deposition method.
• the protective layer may contain organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants, and other additives, as necessary. It may contain.
• organic/inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like.
• the absorber for light of a specific wavelength a known absorber can be used.
• the content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, based on the total weight of the protective layer.
• the protective layer the protective layers described in paragraph numbers 0073 to 0092 of JP-A No. 2017-151176 can also be used.
• the optical filter may have a structure in which each pixel is embedded in a space partitioned into a lattice shape by partition walls, for example.
• optical filter of the present invention can be used in optical sensors such as solid-state image sensors, image display devices, and the like.
• the method for producing an optical filter includes a step of forming a photosensitive composition layer on a support using the photosensitive composition of the present invention, a step of exposing the photosensitive composition layer to light in a pattern, and a step of exposing the photosensitive composition layer to light in a pattern. It is preferable to include a step of developing and removing unexposed portions of the layer to form a pattern (pixel). If necessary, a step of baking the photosensitive composition layer (pre-bake step) and a step of baking the developed pattern (pixel) (post-bake step) may be provided.
• a photosensitive composition layer is formed on a support using the photosensitive composition of the present invention.
• the support is not particularly limited and can be appropriately selected depending on the application.
• a glass substrate, a silicon substrate, etc. may be mentioned, and a silicon substrate is preferable.
• a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the silicon substrate.
• CMOS complementary metal oxide semiconductor
• a black matrix that isolates each pixel may be formed on the silicon substrate.
• the silicon substrate may be provided with a base layer for improving adhesion with the upper layer, preventing substance diffusion, or flattening the substrate surface.
• the surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferable that the angle is 30 to 80° when measured with water.
• a known method can be used to apply the photosensitive composition.
• the coating method described in paragraph number 0207 of International Publication No. 2022/085485 can be used.
• the photosensitive composition layer formed on the support may be dried (prebaked). If the film is manufactured by a low-temperature process, prebaking may not be performed.
• the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower.
• the lower limit can be, for example, 50°C or higher, or 80°C or higher.
• the prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Prebaking can be performed on a hot plate, oven, or the like.
• the photosensitive composition layer formed on the support is exposed in a pattern.
• the photosensitive composition layer can be exposed in a pattern by exposing it to light through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. This allows the exposed portion to be cured.
• Radiation (light) that can be used during exposure includes g-line, i-line, etc. Furthermore, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm). Furthermore, a long-wave light source of 300 nm or more can also be used. As a light source, an electrodeless ultraviolet lamp system, a hybrid ultraviolet and infrared curing can be used.
• pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the millisecond level or less).
• the irradiation amount is, for example, preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2 .
• the oxygen concentration during exposure can be appropriately selected, and in addition to being carried out in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially
• the exposure may be performed in an oxygen-free atmosphere (without oxygen), or in a high oxygen atmosphere where the oxygen concentration exceeds 21 volume % (for example, 22 volume %, 30 volume %, or 50 volume %).
• the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000W/m 2 to 100000W/m 2 (for example, 5000W/m 2 , 15000W/m 2 , or 35000W/m 2 ). Can be done.
• the oxygen concentration and the exposure illuminance may be appropriately combined.
• the illuminance may be 10,000 W/m 2 when the oxygen concentration is 10% by volume, and 20,000 W/m 2 when the oxygen concentration is 35% by volume.
• the unexposed areas of the photosensitive composition layer are developed and removed to form a pattern (pixel).
• the unexposed areas of the photosensitive composition layer can be removed by development using a developer.
• the unexposed portions of the photosensitive composition layer in the exposure step are eluted into the developer, leaving only the photocured portions.
• the temperature of the developer is preferably, for example, 20 to 30°C.
• the development time is preferably 20 to 180 seconds.
• the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
• Examples of the developer include organic solvents, alkaline developers, and alkaline developers are preferably used.
• the developer and cleaning method after development the developer and cleaning method described in paragraph number 0214 of International Publication No. 2022/085485 can be used.
• Additional exposure processing and post-bake are post-development curing processing to complete curing.
• the heating temperature in post-baking is, for example, preferably 100 to 240°C, more preferably 200 to 240°C.
• Post-baking can be carried out in a continuous or batch manner using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to maintain the developed film under the above conditions.
• the light used for exposure is preferably light with a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
• the solid-state imaging device of the present invention has the film of the present invention described above.
• the structure of the solid-state image sensor is not particularly limited as long as it includes the film of the present invention and functions as a solid-state image sensor, but examples include the following structure.
• the substrate has a plurality of photodiodes that constitute the light receiving area of a solid-state image sensor (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon or the like.
• a device protective film made of silicon nitride or the like is formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a configuration in which a color filter is provided on the device protective film.
• the color filter may have a structure in which each colored pixel is embedded in a space partitioned into, for example, a lattice shape by partition walls.
• the partition wall preferably has a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include devices described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, and International Publication No.
• an ultraviolet absorbing layer may be provided within the structure of the solid-state image sensor to improve light resistance.
• An imaging device equipped with the solid-state imaging device of the present invention can be used not only as a digital camera or an electronic device having an imaging function (such as a mobile phone), but also as a vehicle-mounted camera or a surveillance camera.
• the image display device of the present invention has the film of the present invention described above.
• Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device.
• Examples of image display devices and details of each image display device see, for example, “Electronic Display Devices (written by Akio Sasaki, Kogyo Chosenkai Co., Ltd., published in 1990)” and “Display Devices (written by Junaki Ibuki, published by Sangyo Tosho)”. Co., Ltd., issued in 1989).
• liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosenkai Co., Ltd., published in 1994)".
• Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosenkai Co., Ltd., published in 1994)
• the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology.”
• a mixed solution was obtained by mixing the materials listed in the table below.
• the obtained mixed liquid was subjected to a dispersion treatment using an Ultra Apex Mill manufactured by Kotobuki Kogyo Co., Ltd. as a circulating dispersion device (bead mill) to produce a dispersion liquid.
• the units of numerical values for the amounts added in the table are parts by mass.
• resins B-1 to B-4 are materials corresponding to polymerizable compounds having a weight average molecular weight of 3000 or more.
• (resin) B-1 Resin with the following structure (a polymerizable compound with a weight average molecular weight of 3000 or more. The numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units.
• B-2 Resin with the following structure (a polymerizable compound with a weight average molecular weight of 3000 or more. The numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units.
• Weight average molecular weight 23000, acid value 59.6mgKOH/g) B-3 Resin with the following structure (a polymerizable compound with a weight average molecular weight of 3000 or more. The numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units.
• B-4 Resin with the following structure (a polymerizable compound with a weight average molecular weight of 3000 or more.
• the resins C-1 and C-2 are materials corresponding to polymerizable compounds having a weight average molecular weight of 3000 or more.
• M-2 Compound with the following structure
• M-3 Compound with the following structure
• M-4 Compound with the following structure
• M-5 Aronix M-521 (polybasic acid-modified acrylic oligomer, manufactured by Toagosei Co., Ltd.)
• (resin) C-1 Resin with the following structure (a polymerizable compound with a weight average molecular weight of 3000 or more. The numbers appended to the main chain are molar ratios. Weight average molecular weight 11000, acid value 69.2 mgKOH/g)
• C-2 Resin with the following structure (a polymerizable compound with a weight average molecular weight of 3000 or more. The numbers appended to the main chain are molar ratios. Weight average molecular weight 21000, acid value 80 mgKOH/g)
• S-1 Karenz MTBD1 (manufactured by Showa Denko K.K., polyfunctional thiol compound)
• S-2 Karenz MTPE1 (manufactured by Showa Denko K.K., polyfunctional thiol compound)
• S-3 Karenz MTNR1 (manufactured by Showa Denko K.K., polyfunctional thiol compound)
• S-4 Karenz MTTPMB (manufactured by Showa Denko K.K., polyfunctional thiol compound)
• E-1 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol
• E-2 Pionin D-6112-W (Takemoto Yushi Co., Ltd.) (Nonionic surfactant)
• the exposed composition layer was subjected to shower development at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer. Thereafter, rinsing was performed using a spin shower using pure water to form pixels. The obtained pixels were observed using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Tech Corporation) at a magnification of 20,000 times. Based on the observed images, adhesion and residue were evaluated according to the following criteria.
• TMAH tetramethylammonium hydroxide
• the exposure amount required for the pattern line width to reach 0.7 ⁇ m was calculated, and the exposure sensitivity was evaluated based on the following criteria. 5: The exposure amount is 60 mJ/cm 2 or less 4: The exposure amount is more than 60 mJ/cm 2 and 100 mJ/cm 2 or less 3: The exposure amount is more than 100 mJ/cm 2 and 150 mJ/cm 2 or less 2: Exposure amount exceeds 150 mJ/cm 2 and is 200 mJ/cm 2 or less 1: Exposure amount exceeds 200 mJ/cm 2
• Adhesion evaluation Among the areas of the obtained pixels exposed at an exposure dose of 100 mJ/cm 2 , 1071 x 1071 areas were observed with an optical microscope, and the number of peeled pixels was counted. Adhesion was determined based on the number of peeled pixels based on the following criteria. 5: The number of peeled pixels is 10 or less. 4: The number of peeled pixels is more than 10 and 20 or less. 3: The number of peeled pixels is more than 20 and 50 or less. 2: The number of peeled pixels is 50 or less. more than 200 or less 1: The number of peeled pixels exceeds 200
• Each of the photosensitive compositions obtained above was applied onto a silicon wafer having a grid structure with a pitch of 0.7 ⁇ m, a grid width of 120 nm, and a grid height of 0.4 ⁇ m so that the film thickness after coating was 0.4 ⁇ m.
• the composition layer was applied by spin coating, and then heated using a hot plate at 100° C. for 2 minutes to form a composition layer.
• light with a wavelength of 248 nm was applied to the obtained composition layer through a mask having a 0.5 ⁇ m square pattern at an illuminance of 35000 W/m 2 and an exposure amount of 100 mJ/m.
• Exposure was performed by irradiating at cm 2 .
• the exposed composition layer was subjected to shower development at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer.
• TMAH tetramethylammonium hydroxide
• rinsing was performed using a spin shower using pure water to create an evaluation substrate with a pattern embedded in the grid.
• This evaluation board was held at 110° C. and 85% humidity for 168 hours using a highly accelerated life expectancy (HAST) tester (HAST CHAMBER EHS221, manufactured by Espec).
• HAST highly accelerated life expectancy
• the substrate was cut into pieces, and the cross-sectional shape was observed using a scanning electron microscope (SEM) S-4800 (manufactured by Hitachi High-Tech Corporation), and the moisture resistance was evaluated according to the following criteria.
• SEM scanning electron microscope
• the pattern is embedded within the grid and no voids are visible.
• 4 The pattern is embedded in the grid, but some voids occur.
• 3 The pattern is embedded in the grid, but voids occur.
• 2 The pattern is embedded within the grid, but has peeled off from the grid. 1: The pattern is completely peeled off and does not exist within the grid.
• the colored compositions of Examples were able to form pixels with excellent moisture resistance and adhesion.
• W-2 FZ-2122 (manufactured by Dow Toray Industries, Inc., silicone surfactant)
• W-3 BYK-322 (manufactured by BYK Chemie, silicone surfactant)
• W-4 BYK-323 (manufactured by BYK Chemie, silicone surfactant)
• W-6 BYK-3760 (manufactured by BYK Chemie, silicone surfactant)
• W-7 BYK-UV3510 (manufactured by BYK Chemie, silicone surfactant)
• W-8 KF-6001 (Shin-Etsu Chemical, silicone surfactant)
• W-10 Megafac F-554 (DIC Corporation, fluorine-based surfactant)
• W-11 Megafac F-555-A (DIC Corporation, fluorine-based surfactant

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