Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
• • 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
  • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • 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
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
  • F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
  • F21S41/10—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by the light source
  • F21S41/14—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by the light source characterised by the type of light source
  • F21S41/141—Light emitting diodes [LED]
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
  • F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
  • F21S41/10—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by the light source
  • F21S41/14—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by the light source characterised by the type of light source
  • F21S41/141—Light emitting diodes [LED]
  • F21S41/155—Surface emitters, e.g. organic light emitting diodes [OLED]
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
  • F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
  • F21S41/40—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by screens, non-reflecting members, light-shielding members or fixed shades
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • 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
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
• • 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
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • 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
• • 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
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21W—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO USES OR APPLICATIONS OF LIGHTING DEVICES OR SYSTEMS
  • F21W2102/00—Exterior vehicle lighting devices for illuminating purposes
  • F21W2102/10—Arrangement or contour of the emitted light
  • F21W2102/13—Arrangement or contour of the emitted light for high-beam region or low-beam region
  • F21W2102/135—Arrangement or contour of the emitted light for high-beam region or low-beam region the light having cut-off lines, i.e. clear borderlines between emitted regions and dark regions
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
  • F21Y2115/00—Light-generating elements of semiconductor light sources
  • F21Y2115/10—Light-emitting diodes [LED]
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
  • F21Y2115/00—Light-generating elements of semiconductor light sources
  • F21Y2115/10—Light-emitting diodes [LED]
  • F21Y2115/15—Organic light-emitting diodes [OLED]

Definitions

• the present invention relates to a photosensitive composition, a cured film, a light shielding film, a color filter, an optical element, a solid-state image sensor, and a headlight unit.
• Color filters used in liquid crystal display devices include colored layers and/or light-shielding layers formed by a photolithography method in which a cured film is formed using a photosensitive colored composition and then patterned by development treatment. It is equipped with a colored coating.
• small and thin imaging units are currently installed in portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants).
• Solid-state imaging devices such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors are provided with light-shielding films for the purpose of preventing noise generation, improving image quality, and the like.
• Patent Document 1 discloses that a photosensitive coloring composition used for manufacturing a color filter contains a resin, a dye, a photopolymerization initiator, a polymerizable monomer, and a solvent.
• a photosensitive coloring composition which is a vinyl polymer composed of a specific structural unit (a), a structural unit having a carboxyl group (b), and another structural unit having no hydroxyl group (c).
• the present inventors investigated the characteristics of the photosensitive coloring composition described in Patent Document 1, and found that a coating film was formed using the photosensitive coloring composition, and the coating film was exposed to light and developed.
• a cured film was formed on a substrate, it was found that both the adhesion between the cured film and the substrate and the suppression of development residue were not sufficiently compatible, and there was room for further improvement.
• the term "development residue” refers to the residue that remains in the non-pattern areas removed by the development process when a coating film obtained using a photosensitive composition is exposed and developed. .
• an object of the present invention is to provide a photosensitive composition that can form a cured film with excellent adhesion to a substrate and suppresses the generation of development residues.
• Another object of the present invention is to provide a photosensitive composition, a cured film, a light-shielding film, a color filter, an optical element, a solid-state image sensor, and a headlight unit.
• a photosensitive composition comprising a polymerizable compound, A first resin in which the resin includes a repeating unit having a polyoxyalkylene chain represented by formula (1) and does not substantially contain fluorine atoms; a second resin that does not contain a repeating unit having a polyoxyalkylene chain represented by the above formula (1), A photosensitive composition in which the content of the first resin is 1 to 50% by mass based on the total mass of the resin.
• R 1 each independently represents an alkylene group having 2 or 3 carbon atoms, and n represents 3 to 200.
• the present invention it is possible to provide a photosensitive composition that can form a cured film with excellent adhesion to a substrate and suppresses the generation of development residues. Further, according to the present invention, it is possible to provide a cured film and a light-shielding film formed using the photosensitive composition, as well as a color filter, an optical element, a solid-state image sensor, and a headlight unit having the cured film.
• solid content of the composition in this specification means the components that form a cured film, and when the composition contains a solvent (organic solvent, water, etc.), it means all the components excluding the solvent.
• solvent organic solvent, water, etc.
• liquid components are also considered solid components as long as they form a cured film.
• alkyl group includes not only an alkyl group containing no substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
• an organic group is a group containing at least one carbon atom.
• actinic light or “radiation” in this specification means, for example, far ultraviolet rays, extreme ultraviolet lithography (EUV), X-rays, and electron beams.
• light in this specification means actinic rays and radiation.
• exposure in this specification includes not only exposure with deep ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams.
• (meth)acrylate in this specification means acrylate and methacrylate.
• (Meth)acrylic as used herein means acrylic and methacrylic.
• (Meth)acryloyl as used herein means acryloyl and methacryloyl.
• “Monomer” and “monomer” in this specification have the same meaning.
• ppm means “parts-per-million ( 10-6 )
• ppb means “parts-per-billion (10-9)
• ppt means “parts-per-billion ( 10-9 )”. parts-per-trillion (10 ⁇ 12 )”.
• the "weight average molecular weight (Mw)" in this specification is a polystyrene equivalent value determined by GPC (Gel Permeation Chromatography) method.
• the "GPC method” in this specification uses HLC-8020GPC (manufactured by Tosoh) as a measuring instrument, TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh, 4.6 mm ID x 15 cm) as a column, and THF as an eluent. (tetrahydrofuran).
• the bonding direction of the divalent group (for example, -COO-) described herein is not limited unless otherwise specified.
• Y in a compound represented by the formula "X-Y-Z" is -COO-
• the above compound may be "X-O-CO-Z", and "X-CO -O-Z”.
• examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the photosensitive composition of the present invention (hereinafter also simply referred to as "the present composition”) is a photosensitive compound containing a resin, a coloring material, a photopolymerization initiator, and a polymerizable compound,
• the resin includes a repeating unit having a polyoxyalkylene chain represented by the formula (1) described below and contains a first resin that does not substantially contain a fluorine atom, and a polyoxyalkylene chain represented by the above formula (1). and a second resin that does not contain any repeating units, and the content of the first resin is 1 to 50% by mass based on the total mass of the resin.
• the photosensitive coloring composition described in Patent Document 1 is a composition containing a resin having a repeating unit having a polyoxyalkylene chain (hereinafter also referred to as "first resin").
• the first resin has a polyoxyalkylene chain and thus contributes to suppressing development residues.
• the content of the first resin with respect to the total mass of the resin in Patent Document 1 is compared with the content of the first resin with respect to the total mass of the resin in the present composition. It has become excessive.
• the first resin since the first resin has a polyoxyalkylene chain, it has a high affinity with polar functional groups (silanol groups, etc.) on the silicon wafer (hereinafter also simply referred to as "wafer"), and is unevenly distributed at the wafer interface.
• polar functional groups siliconol groups, etc.
• the content of the first resin was excessive, the amount of constituent components other than the first resin at the wafer interface would be extremely small, and it is assumed that the adhesion was insufficient. Ru.
• this composition by optimizing the content of the first resin in the resin and including the second resin, development residue can be suppressed without reducing the adhesiveness between the cured film and the substrate. The inventors believe that this is the case.
• the first resin is likely to be unevenly distributed at the wafer interface, and even if the content is small as described above, it can contribute to suppressing development residue more effectively, so the present invention The effect will be even better.
• the effect of the present invention is also referred to as being more excellent if at least one or more of the following effects are obtained: better adhesion between the cured film and the substrate and less development residue.
• the composition includes a resin, and the resin includes a first resin and a second resin.
• the first resin is a resin that includes a repeating unit having a polyoxyalkylene chain represented by formula (1) (hereinafter also referred to as "repeat unit X”) and is substantially free of fluorine atoms.
• the repeating unit X has a polyoxyalkylene chain represented by formula (1). -(R 1 -O) n - ...Formula (1)
• R 1 represents an alkylene group having 2 or 3 carbon atoms.
• R 1 is preferably an ethylene group or a branched propylene group, and more preferably an ethylene group, since the effects of the present invention are more excellent.
• Three or more R 1 's may be the same or different.
• all R 1 may be ethylene groups, or R 1 may be selected from the group consisting of ethylene groups and propylene groups.
• the polyoxyalkylene chain represented by formula (1) may consist of only oxyethylene groups, or may include oxyethylene groups and oxypropylene groups. When the polyoxyalkylene chain represented by formula (1) contains an oxyethylene group and an oxypropylene group, both may be arranged in a block shape or randomly arranged.
• n represents 3 to 200.
• n is preferably from 4 to 90, more preferably from 4 to 50, and even more preferably from 6 to 25, in that the effects of the present invention are more excellent.
• the above repeating unit X is preferably a repeating unit represented by the following formula (1a) in that the effects of the present invention are more excellent.
• R 1a each independently represents an alkylene group having 2 or 3 carbon atoms. Preferred embodiments of R 1a are the same as the preferred embodiments of R 1 in the above formula (1). Three or more R 1a may be the same or different. For example, all R 1a may be ethylene groups, or R 1a may be selected from the group consisting of ethylene groups and propylene groups. That is, the polyoxyalkylene chain in formula (1a) may consist of only oxyethylene groups, or may include oxyethylene groups and oxypropylene groups. When the polyoxyalkylene chain in formula (1a) contains an oxyethylene group and an oxypropylene group, both may be arranged in a block shape or randomly arranged.
• R 2a represents a hydrogen atom or a monovalent organic group.
• the monovalent organic group is not particularly limited and includes, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group. Each of the above groups may further have a substituent.
• Substituents are not particularly limited, and include, for example, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylsulfanyl group, an arylsulfanyl group, an alkyl group, an aryl group, a heteroaryl group, a hydroxyl group, a carboxy group, a formyl group, Examples include sulfo group, cyano group, alkylaminocarbonyl group, arylaminocarbonyl group, sulfonamide group, silyl group, amino group, monoalkylamino group, dialkylamino group, arylamino group, polymerizable group, and combinations thereof. It will be done.
• the monovalent organic group may have an oxygen atom, a nitrogen atom, or a sulfur atom.
• Examples of the polymerizable group include a radically polymerizable group and a cationic polymerizable group, and preferably a polymerizable group having an ethylenically unsaturated bond.
• Examples of the polymerizable group include an acryloyl group, a methacryloyl group, a vinyl group, an epoxy group, and an oxetanyl group.
• R 2a is preferably a monovalent organic group not containing an aromatic ring or a hydrogen atom, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, since the effects of the present invention are more excellent.
• the monovalent organic group not containing an aromatic ring include monovalent aliphatic hydrocarbon groups which may have a substituent, and preferably an alkyl group which may have a substituent. .
• the number of carbon atoms in the alkyl group is not particularly limited, and is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 4.
• the monovalent aliphatic hydrocarbon group and alkyl group may be linear, branched, or cyclic.
• R 3a represents a hydrogen atom or a methyl group.
• n 3 to 200.
• a preferred embodiment of n is the same as the preferred embodiment of n in the above formula (1).
• the content of repeating unit X is preferably 30 to 100% by mass, more preferably 55 to 90% by mass, and even more preferably 55 to 80% by mass, based on all repeating units in the first resin.
• the first resin may contain only one type of repeating unit X, or may contain two or more types. When two or more types are included, it is preferable that their total amount falls within the above range.
• the first resin may contain other repeating units other than the above-mentioned repeating unit X.
• the first resin may include a repeating unit (hereinafter also simply referred to as "repeat unit Y") having a polymerizable group.
• Repeating unit Y is a repeating unit different from repeating unit X. Note that the repeating unit having both a polyoxyalkylene chain and a polymerizable group represented by formula (1) is interpreted as a repeating unit X.
• the type of polymerizable group is not particularly limited, and examples of the polymerizable group include a radically polymerizable group and a cationic polymerizable group, and a polymerizable group having an ethylenically unsaturated bond is preferred.
• the polymerizable group includes an acryloyl group, a methacryloyl group, a vinyl group, a styrene group, an epoxy group, and an oxetanyl group.
• examples of the styrene group include a group represented by the following formula (S-1). In formula (S-1), * represents the bonding position.
• the above repeating unit Y is preferably a repeating unit represented by the following formula (1b) in that the effects of the present invention are more excellent.
• R 1b represents a hydrogen atom or a methyl group.
• L 1b represents a single bond or a divalent linking group.
• the divalent linking group include an alkylene group (preferably an alkylene group having 1 to 20 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 - , -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these groups.
• the alkylene group is preferably a linear or branched alkylene group.
• the alkylene group and arylene group may have a substituent, and examples of the substituent include a hydroxy group and an alkoxy group.
• L 1b a group represented by -CO-L 2b -L 3b - is preferable.
• L 2b represents -O- or -NH-.
• L 2b is preferably -O-.
• L 3b represents an alkylene group which may have a substituent and may include -O-, -OCONH-, -CO-, or a phenylene group. Examples of substituents include hydroxy groups and alkoxy groups.
• the number of carbon atoms in the alkylene group is not particularly limited, but is preferably from 1 to 20, more preferably from 1 to 10, even more preferably from 1 to 5.
• the alkylene group may be linear or may have a cyclic structure.
• L 3b is -alkylene group optionally having a substituent -O-, -alkylene group optionally having a substituent -L 4b -alkylene group optionally having a substituent -O -, or -(alkylene group which may have a substituent -L 5b ) r1 -(alkylene group which may have a substituent -O) r2 - is preferred.
• L 4b represents -O- or -O-phenylene group -CO-O-.
• L 5b represents -CO-O-.
• r1 and r2 each independently represent 1 or 2.
• Examples of the group represented by -CO-L 2b -L 3b - include -CO-O-CH 2 -CH(OH)-CH 2 -O-, -CO-O-CH 2 CH 2 -OCONH- Examples include CH 2 CH 2 -O-, -CO-O-CH 2 -CH(OH)-CH 2 -O-(CH 2 ) 4 -O-.
• the divalent linking group represented by L 1b may have an onium salt structure. It is preferable that the divalent linking group represented by L 1b has an onium salt structure, since the adhesion is not deteriorated while generation of development residue can be suppressed. As the onium salt structure, a quaternary ammonium salt structure is preferable.
• the divalent linking group represented by L 1b having an onium salt structure is preferably a group represented by formula (O). In formula (O), * on the left side of the paper represents the bonding position with the carbon atom to which R 1b is bonded, and * on the right side of the paper represents the bonding position with R 2b .
• L 6b and L 7b are each independently a single bond or an alkylene group which may have a substituent, -O-, -CO-, or a phenylene group. represents.
• substituents include hydroxy groups and alkoxy groups.
• the number of carbon atoms in the alkylene group is not particularly limited, but is preferably from 1 to 20, more preferably from 1 to 10, even more preferably from 1 to 5.
• L 6b includes -alkylene group optionally having a substituent -O-CO-alkylene group -CO-, and alkylene group optionally having a -substituent -O-phenylene group -CO- can be mentioned.
• L 7b examples include an optionally substituted alkylene group --O- and an optionally substituted alkylene group --O-.
• R 3b each independently represents an alkyl group having 1 to 20 carbon atoms or a group represented by *-L 8b -R 4b .
• L 8b represents an alkylene group which may have a substituent and may include -O-, -CO- or -phenylene group. Examples of substituents include hydroxy groups and alkoxy groups.
• R 4b represents a polymerizable group. Examples of the polymerizable group include the groups exemplified above.
• R 2b represents a polymerizable group.
• the polymerizable group include the groups exemplified above.
• the content of the repeating unit Y is preferably 5 to 70% by mass, more preferably 10 to 45% by mass, and even more preferably 10 to 40% by mass, based on all repeating units in the first resin.
• the first resin may contain only one type of repeating unit Y, or may contain two or more types of repeating units Y. When two or more types are included, it is preferable that their total amount falls within the above range.
• the first resin may include a repeating unit having an acid group (hereinafter also simply referred to as "repeat unit Z").
• Repeating unit Z is a repeating unit different from repeating units X and Y.
• the acid group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
• the above repeating unit Z is preferably a repeating unit represented by the following formula (1c) in that the effects of the present invention are more excellent.
• R 1c represents a hydrogen atom or a methyl group.
• L c represents a single bond or a divalent linking group.
• the divalent linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 - , -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these groups.
• the alkylene group is preferably a linear or branched alkylene group.
• the alkylene group and arylene group may have a substituent, and examples of the substituent include a hydroxy group and an alkoxy group.
• R 2c represents an acid group.
• the acid group include the groups exemplified above.
• the content of repeating unit Z is preferably 1 to 15% by mass, more preferably 1 to 5% by mass, and even more preferably 0.1 to 2% by mass, based on all repeating units in the first resin.
• the first resin may contain only one type of repeating unit Z, or may contain two or more types. When two or more types are included, it is preferable that their total amount falls within the above range.
• the first resin may have a repeating unit (other repeating unit) different from any of the repeating unit X, the repeating unit Y, and the repeating unit Z.
• other repeating units include repeating units represented by the following structural formula and repeating units derived from known (meth)acrylate monomers.
• known (meth)acrylate monomers include butyl methacrylate monomers. , and 2-hydroxyethyl methacrylate.
• the first resin does not substantially contain fluorine atoms.
• the above expression "the first resin does not substantially contain fluorine atoms” means that the content of fluorine atoms in the total mass of the first resin is 2.0% by mass or less. If the first resin contains fluorine atoms, the affinity between the base material and the first resin decreases when forming a cured film, and the amount of the first resin unevenly distributed at the base material interface decreases, resulting in an increase in development residue. This is a contributing factor.
• the content of fluorine atoms in the first resin can be measured by a known method, for example, by an energy dispersive X-ray fluorescence spectrometer (EDX).
• the content of fluorine atoms in the resin can be calculated using the following procedure. After adding lithium fluoride (LiF) powder to cellulose powder and mixing thoroughly, a standard sample was prepared by making briquettes by pressure molding, and the fluorine atoms in the resin were measured by EDX measurement of the standard sample. Create a calibration curve to calculate the content of Subsequently, after producing briquettes of resin powder in the same manner as described above, the content of fluorine atoms in the resin can be determined by performing EDX measurement.
• LiF lithium fluoride
• the polymerizable group value of the first resin is preferably 0.2 mmol/g or more, more preferably 0.4 mmol/g or more, even more preferably 0.5 mmol/g or more, and particularly preferably 0.6 mmol/g or more.
• the upper limit is preferably 5.0 mmol/g or less, more preferably 3.0 mmol/g or less, and even more preferably 2.0 mmol/g or less.
• the above polymerizable group value means the ethylenically unsaturated bond equivalent.
• the ethylenically unsaturated bond equivalent of the first resin is 0.5 mmol/g or more, since the effect of the present invention is more excellent. It is preferable.
• the polymerizable group value of the first resin is a numerical value representing the molar amount of polymerizable groups per gram of solid content of the first resin.
• the polymerizable group value of the first resin is determined by extracting the low molecular weight component (a) in the polymerizable group part from the first resin by alkali treatment, and measuring its content by high performance liquid chromatography (HPLC). ) can be calculated from Moreover, in the case where the polymerizable group site cannot be extracted from the first resin by alkali treatment, a value measured by NMR (nuclear magnetic resonance) method is used.
• Formula (X): Polymerizable group value of first resin [mmol/g] (content of low molecular component (a) [ppm]/molecular weight of low molecular component (a) [g/mol])/(first resin Weighing value of 1 resin [g] x (concentration of 1st resin in sample [mass%]/100) x 10)
• the acid value of the first resin is preferably 60 mgKOH/g or less, more preferably 15 mgKOH/g or less, even more preferably 5 mgKOH/g or less, and particularly preferably 0 mgKOH/g, in terms of the effect of the present invention being more excellent.
• the weight average molecular weight of the first resin is not particularly limited, but is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, even more preferably from 10,000 to 40,000.
• the content of the first resin is 1 to 50% by mass based on the total mass of resins in the composition. Among these, 2 to 30% by mass is preferred, more preferably 3 to 20% by mass, and even more preferably 3 to 15% by mass, in terms of the effects of the present invention being more excellent.
• the content of the first resin is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, based on the total solid content of the present composition. More preferably, it is 2.0% by mass or less.
• the lower limit is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and even more preferably 1.0% by mass or more.
• the composition includes a resin, and the resin includes a second resin.
• the second resin is a resin that does not contain a repeating unit having a polyoxyalkylene chain represented by the above formula (1). It is preferable that the second resin can function as a dispersant for the coloring material described below and as a binder in the cured film. Therefore, the second resin is preferably a resin having a graft chain or a resin having a block structure. Moreover, it is also preferable that the second resin has a polyester structure. When the second resin has a polyester structure, the compatibility with the first resin decreases, so the first resin can be more effectively unevenly distributed at the interface of the substrate, without reducing the adhesion of the cured film to the substrate. Generation of development residue can be suppressed.
• the second resin may include a polyester structure in any of the graft chain, the main chain in the second resin, and the block structure.
• the graft chain is a polymer chain that branches and extends from the main chain, and the polymer chain has a plurality of repeating units.
• the length of the graft chain is not particularly limited, but the number of atoms excluding hydrogen atoms is 40 to 10,000, since the longer the graft chain is, the higher the steric repulsion effect is, and the dispersibility of the coloring material can be improved. It is preferable that the number of atoms excluding hydrogen atoms is 50 to 2,000, and even more preferably that the number of atoms excluding hydrogen atoms is 60 to 500.
• the graft chain may be a polymer chain containing at least one 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. More preferably, it is a polymer chain containing at least one type of structure selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylic structure.
• the polyester structure include a polycaprolactone structure and a polyvalerolactone structure.
• polycaprolactone structure refers to a structure containing a ring-opened structure of ⁇ -caprolactone as a repeating unit
• polyvalerolactone structure refers to a structure containing a ring-opened structure of ⁇ -valerolactone as a repeating unit
• the resin having a graft chain contains at least one of resin P and resin Q.
• the resin P is a resin containing repeating units having a graft chain, which is a polymer chain containing a polyester structure.
• Examples of the repeating unit having the graft chain include repeating units represented by formula (1-1) or formula (1-2).
• Q 1 is a group represented by any one of formula (QX1), formula (QNA), and formula (QNB)
• Q 2 is It is a group represented by any one of formula (QX2), formula (QNA), and formula (QNB).
• *a represents the bonding position on the main chain side
• *b represents the bonding position on the side chain side.
• W 1 and W 2 each independently represent a single bond, an oxygen atom, or NH.
• X 1 and X 2 each independently represent a hydrogen atom or a monovalent organic group, and X 1 and X 2 represent a hydrogen atom or a hydrogen atom having 1 to 12 carbon atoms.
• An alkyl group is preferred, and a hydrogen atom or a methyl group is more preferred.
• Y 1 and Y 2 each independently represent a single bond or a divalent linking group, and examples of the divalent linking group include formula (Y- 1) to linking groups represented by formulas (Y-23).
• A represents the bonding position with W 1 or W 2 in formula (1-1) or formula (1-2).
• B represents the bonding position with the group opposite to W 1 or W 2 to which A is bonded.
• Z 1 and Z 2 each independently represent a hydrogen atom or a monovalent organic group.
• the above-mentioned acyloxy group, alkyl group, and alkoxy group may be linear, branched, or cyclic, and may further have a substituent. Examples of the above-mentioned substituents include hydroxy groups.
• the monovalent organic group preferably has 5 to 24 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
• the monovalent organic group represented by Z 1 and Z 2 is preferably an acryloyl group, a hydroxy group, an acyloxy group, or an alkoxy group.
• the monovalent organic group includes a polymerizable group.
• the monovalent organic group containing a polymerizable group is preferably an acyloxy group having a polymerizable group at its end or an alkoxy group having a polymerizable group at its end.
• Examples of the polymerizable group include an acryloyl group, a methacryloyl group, a vinyl group, an epoxy group, and an oxetanyl group.
• a group represented by formula (W1) or a group represented by formula (W2) is also preferable.
• L W1 in formula (W1) and L W2 in formula (W2) each independently represent a single bond or a divalent linking group.
• divalent linking groups include ether group (-O-), carbonyl group (-CO-), ester group (-COO-), thioether group (-S-), -SO 2 -, -NR N -( R N represents a hydrogen atom or an alkyl group), a divalent hydrocarbon group that may have a substituent (an alkylene group, an alkenylene group (e.g.
• the number of carbon atoms in the divalent hydrocarbon group is not particularly limited, and is preferably from 1 to 10, more preferably from 1 to 5.
• Examples of the substituents that the divalent hydrocarbon group may have include a hydroxy group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, and an amino group. Examples include groups.
• n1 -O- a divalent hydrocarbon group which may have a substituent - (even if it has an O- substituent) (Good divalent hydrocarbon group)
• n1 -O- a divalent hydrocarbon group which may have a substituent - (even if it has an O- substituent) (Good divalent hydrocarbon group)
• n1 -O- a divalent hydrocarbon group which may have a substituent - (even if it has an O- substituent) (Good divalent hydrocarbon group)
• n1 -O- a divalent hydrocarbon group which may have a substituent - (even if it has an O- substituent)
• n1 -O- a divalent hydrocarbon group which may have a substituent - (even if it has an O- substituent)
• n1 -O- a divalent hydrocarbon group which may have a substituent - (even if it has an O- substituent) (Good divalent hydrocarbon group)
• Formula (W2) is a group having an onium salt structure, and an ionic bond is formed between O ⁇ (oxygen anion) and N + (quaternized nitrogen cation).
• R W each independently represents an alkyl group.
• the number of carbon atoms in the alkyl group is not particularly limited, and is preferably 1 to 20, more preferably 1 to 15. Note that among the three R Ws , the number of carbon atoms in the alkyl group represented by one R W is preferably 1 to 15, more preferably 10 to 15, and the number of carbon atoms in the alkyl group represented by the remaining two R Ws is preferably 1 to 15, more preferably 10 to 15. The number is preferably 1 to 5, more preferably 1 to 3.
• Z 5 represents a (meth)acryloyl group, a vinyl group, or a styrene group.
• n and m are each independently an integer of 2 to 500. Among these, an integer of 6 to 200 is more preferable. Furthermore, in formula (1-1) and formula (1-2), j and k each independently represent an integer of 2 to 8, and in that the effect of the present invention is better, an integer of 4 to 6 is preferred. Preferably, 5 is more preferable.
• the resin having a graft chain may contain repeating units represented by formula (1-1) or formula (1-2) with mutually different structures, and may also contain repeating units in which j and k have different structures in the side chains. May contain.
• Resin Q is a resin containing a repeating unit represented by formula (b-10).
• Ar 10 represents a group containing an aromatic carboxy group
• L 11 represents a carbonyl group
• L 12 represents a trivalent linking group
• P 10 represents a polymer chain.
• an aromatic carboxy group refers to a group having a structure in which one or more carboxyl 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.
• group containing an aromatic carboxy group represented by Ar 10 include a group represented by the formula (Ar-1), a group represented by the formula (Ar-2), and a group represented by the formula (Ar- Examples include groups represented by 3).
• n1 represents an integer of 1 to 4, preferably an integer of 1 to 2, and more preferably 2.
• n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 to 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 to 2, and even more preferably 1. 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 following formula (Q- Represents a group represented by 1) or a group represented by the following formula (Q-2).
• the trivalent linking group represented by L 12 includes hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these groups. Examples include groups in which two or more types are combined.
• the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
• the hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group.
• the aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 15 carbon atoms.
• 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.
• L 12 As the trivalent linking group represented by L 12 , a group represented by the following formula (L12-1) is particularly preferred, and a group represented by the formula (L12-2) is more preferred.
• L 12a and L 12b each represent a trivalent linking group
• X 1 represents S (sulfur atom)
• * represents the bonding position with L 11 of formula (b-10)
• ** represents the bonding position with L 11 of formula (b-10).
• -10) represents the bonding position with P10 .
• the trivalent linking groups represented by L 12a and L 12b include trivalent hydrocarbon groups, and hydrocarbon groups and -O-, -CO-, -COO-, -OCO-, -NH-, and - Examples include a group in combination with at least one selected from S-. Among these, a trivalent aliphatic hydrocarbon group is preferable as the trivalent hydrocarbon group. Further, the number of carbon atoms in the trivalent hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.
• P 10 represents a polymer chain.
• the polymer chain preferably has at least one structure selected from a polyester structure, a polyether structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure.
• the weight average molecular weight of the polymer chain is preferably 500 to 20,000.
• the lower limit is preferably 500 or more, more 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 resin containing the repeating unit represented by the above formula (b-10) can be synthesized by the synthesis method described in paragraphs [0059] to [0061] of International Publication No. 2020/044720.
• the weight average molecular weight of the resin Q is preferably 2,000 to 35,000.
• the upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
• the lower limit is preferably 4000 or more, more preferably 6000 or more, and even more preferably 7000 or more.
• the acid value of resin Q is preferably 5 to 200 mgKOH/g.
• the upper limit is preferably 150 mgKOH/g or less, more preferably 100 mgKOH/g or less, and even more preferably 80 mgKOH/g or less.
• the lower limit is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, and even more preferably 20 mgKOH/g or more.
• the resin having a block structure is a resin having a block structure formed by a series of single repeating units.
• the resin having a block structure may include two types of block structures, or may include three or more types of block structures.
• a resin including a block structure R1 consisting of a repeating unit A having a basic group and a block structure R2 consisting of a repeating unit B not containing a basic group but containing an alkyl group is preferable.
• the basic group is a group that can interact with the above-mentioned coloring material. Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium base.
• Examples of the repeating unit A include a repeating unit represented by formula (2-1), and examples of the repeating unit B include a repeating unit represented by formula (2-2).
• R b-1 and R b-2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• L b-1 and L b-2 each independently represent a single bond or a divalent linking group.
• B represents a basic group.
• A represents an alkyl group.
• the alkyl group having 1 to 4 carbon atoms represented by R b-1 or R b-2 is preferably a linear alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
• the divalent linking group represented by L b-1 or L b-2 includes an ether group (-O-), a carbonyl group (-CO-), an ester group (-COO-), a thioether group (-S -), -SO 2 -, -NR N - (R N represents a hydrogen atom or an alkyl group), a divalent hydrocarbon group that may have a substituent (for example, an alkylene group, Examples include alkenylene groups (eg -CH ⁇ CH-, etc.), alkynylene groups (eg -C ⁇ C-, etc.), and arylene groups), and groups combining these.
• the number of carbon atoms in the divalent hydrocarbon group is not particularly limited, and is preferably from 1 to 10, more preferably from 1 to 5.
• the basic group represented by B is as described above, and is preferably a tertiary amino group.
• Examples of the above-mentioned tertiary amino group include dimethylamino group.
• the alkyl group represented by A may be linear, branched, or cyclic. Among these, straight-chain alkyl groups are preferred, straight-chain alkyl groups having 1 to 10 carbon atoms are preferred, and straight-chain alkyl groups having 1 to 6 carbon atoms are more preferred.
• the above-mentioned resins include block copolymers (B) described in paragraphs [0063] to [0112] of JP-A No. 2014-219665, and paragraphs [0046] to [0076] of JP-A-2018-156021. It is also possible to use block copolymers A1, the contents of which are incorporated herein.
• polyimide resins are also preferable.
• the polyimide resin is an alkali-soluble resin, and by including the polyimide resin as the second resin, it is preferable to obtain a photosensitive composition in which the generation of development residues is further suppressed.
• the polyimide resin for example, the polyimide resin described in International Publication No. 2008/123097 and the polyimide precursor described in paragraphs [0186] to [0193] of International Publication No. 2020/203080 can be considered, and the contents thereof is incorporated herein.
• the acid value of the second resin is preferably 70 mgKOH/g or less, more preferably 50 mgKOH/g or less, and even more preferably 40 mgKOH/g or less, in terms of the effect of the present invention being more excellent.
• the lower limit is not particularly limited, but is preferably 0 mgKOH/g or more.
• the content of the second resin is preferably 50 to 98% by mass, more preferably 70 to 98% by mass, even more preferably 80 to 97% by mass, and even more preferably 85 to 97% by mass, based on the total mass of the resins in the present composition. % by weight is particularly preferred. Further, the content of the second resin is preferably 15.0 to 30.0% by mass, more preferably 17.0 to 25.0% by mass, based on the total solid content of the present composition.
• the composition includes a resin, and the resin may include a third resin.
• the third resin is a resin containing a repeating unit having a polyoxyalkylene chain represented by formula (1) and containing a fluorine atom.
• the content of the third resin is preferably 0 to 5% by mass, more preferably 0 to 2% by mass, and 0 to 2% by mass, based on the total mass of the resin in the present composition, in order to improve the effects of the present invention. More preferably 0.5% by mass.
• the content of the resin in the present composition is preferably 5 to 30% by mass, preferably 10 to 25% by mass, and more preferably 10 to 20% by mass, based on the total solid content of the composition.
• the composition may contain only one type of resin, or may contain two or more types of resin. When two or more types are included, it is preferable that their total amount falls within the above range.
• the composition includes a coloring material.
• colorants include chromatic colorants, achromatic colorants, and infrared absorbers.
• a chromatic colorant means a colorant other than a white colorant and a black colorant.
• the chromatic colorant is preferably a colorant having absorption in a wavelength range of 400 nm or more and less than 650 nm.
• the coloring material preferably contains a pigment, and more preferably contains an inorganic pigment.
• the coloring material at least one selected from the group consisting of chromatic coloring agents and achromatic coloring agents is preferable, and at least one type selected from the group consisting of chromatic coloring agents and black coloring agents is more preferable.
• at least one selected from the group consisting of chromatic colorants of organic pigments and black colorants of inorganic pigments is more preferable, and black colorants of inorganic pigments other than carbon black are particularly preferable.
• Chromatic colorants include red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants.
• Examples of the chromatic colorant include pigments and dyes, with pigments being preferred and organic pigments being more preferred.
• the content of pigment in the chromatic colorant is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
• the upper limit is preferably 100% by mass or less.
• an inorganic pigment or an organic-inorganic pigment partially substituted with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be facilitated.
• the average primary particle diameter of the pigment is preferably 1 to 200 nm.
• the lower limit is more preferably 5 nm or more, and even more preferably 10 nm or more.
• the upper limit is more preferably 180 nm or less, further preferably 150 nm or less, and particularly preferably 100 nm or less.
• the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment in the composition is good.
• paragraph [0133] of JP-A-2021-007037 can be referred to, the contents of which are incorporated herein.
• pigments used as chromatic colorants include the following. Color Index (C.I.) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32 , 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83 , 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127 , 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173 , 174, 175, 176, 177
• Dyes can also be used as chromatic colorants.
• dyes There are no particular restrictions on the dye, and known dyes can be used.
• 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.
• paragraph [0142] of JP-A-2021-007037 can be referred to, the contents of which are incorporated herein.
• achromatic colorant examples include black colorants and white colorants, with black colorants being preferred.
• black colorant examples include one or more selected from the group consisting of black pigments and black dyes.
• a black colorant may be obtained by combining a plurality of colorants that cannot be used alone as a black colorant and adjusting the color as a whole to be black.
• a combination of a plurality of pigments having a color other than black when used alone may be used as a black pigment.
• a combination of multiple dyes that have a color other than black when used alone may be used as a black dye
• a combination of a pigment that has a color other than black when used alone and a dye that has a color other than black when used alone may be used as a black dye. May be used as
• black colorant means a colorant that absorbs over the entire wavelength range of 400 to 700 nm. More specifically, for example, a black colorant that meets evaluation criteria Z described below is preferable.
• a composition is prepared that includes a coloring material, a transparent resin matrix (such as acrylic resin), and a solvent, and the content of the coloring material is 60% by mass based on the total solid content.
• the obtained composition is applied onto a glass substrate so that the thickness of the cured film after drying is 1 ⁇ m to form a cured film.
• the light-shielding property of the cured film after drying is evaluated using a spectrophotometer (UV-3600, manufactured by Hitachi, Ltd., etc.).
• the maximum transmittance of the cured film after drying at a wavelength of 400 to 700 nm is less than 10%, it can be determined that the colorant is a black colorant that meets evaluation criteria Z.
• the maximum transmittance of the cured film after drying at a wavelength of 400 to 700 nm is more preferably less than 8%, and even more preferably less than 5%.
• the black pigment may be an inorganic pigment or an organic pigment.
• the black coloring agent is preferably a black pigment, and more preferably an inorganic pigment, since the light resistance of the light-shielding film is more excellent.
• the black pigment a pigment that independently expresses black color is preferable, and a pigment that independently expresses black color and absorbs infrared rays is more preferable.
• the black pigment that absorbs infrared rays has absorption in the infrared region (preferably a wavelength of 650 to 1300 nm), for example.
• a black pigment having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is also preferred.
• the particle size of the black pigment is not particularly limited, but is preferably 5 to 100 nm, more preferably 5 to 50 nm, from the viewpoint of a better balance between handleability and stability of the composition over time (the black pigment does not settle). More preferably 5 to 30 nm.
• the particle size of the black pigment means the average primary particle size of particles measured by the method described in paragraph [0149] of JP 2021-007037A.
• the inorganic pigment used as a black coloring agent is not particularly limited as long as it has light blocking properties and contains an inorganic compound, but any known inorganic pigment can be used. Inorganic pigments are preferable as the black colorant because the light-shielding film has better low reflectivity and light-shielding properties.
• Inorganic pigments include metal elements of group 4 such as titanium (Ti) and zirconium (Zr), metal elements of group 5 such as vanadium (V) and niobium (Nb), yttrium (Y), and aluminum (Al). , cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and silver (Ag).
• metal elements selected from the group consisting of titanium (Ti), zirconium (Zr), vanadium (V), yttrium (Y), aluminum (Al), and iron (Fe).
• Metal oxides, metal nitrides and metal oxynitrides are preferred. That is, the inorganic pigment may contain two or more types of metal atoms.
• the metal oxide, metal nitride, and metal oxynitride particles containing other metal atoms may also be used.
• metal nitride-containing particles further containing an atom (preferably an oxygen atom and/or a sulfur atom) selected from elements of groups 13 to 17 of the periodic table can be used.
• the metal oxide, metal nitride, and metal oxynitride may be coated with an inorganic substance and/or an organic substance.
• the inorganic substance include metal atoms contained in the inorganic pigment.
• the above-mentioned organic substance include the above-mentioned organic substances having a hydrophobic group, and silane compounds are preferable.
• the method for producing the above metal nitride, metal oxide or metal oxynitride is not particularly limited as long as a black pigment having desired physical properties can be obtained, but known production methods such as a gas phase reaction method can be used. method can be used.
• gas phase reaction method include an electric furnace method and a thermal plasma method, but the thermal plasma method is preferable because it is less likely to contain impurities, the particle size can be easily made uniform, and productivity is high.
• the above metal nitride, metal oxide or metal oxynitride may be subjected to a surface modification treatment.
• the surface may be modified with a surface treatment agent having both a silicone group and an alkyl group.
• examples of such inorganic particles include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.).
• nitrides or oxynitrides of one or more metals selected from the group consisting of titanium, vanadium, zirconium, niobium, and iron are preferred because they can suppress the occurrence of undercuts when forming a cured film.
• oxynitrides of one or more metals selected from the group consisting of titanium, vanadium, zirconium, and iron are more preferable, and zirconium oxynitride or titanium oxynitride (titanium black) is more preferable. ) is particularly preferred.
• Titanium black is black particles containing titanium oxynitride.
• the surface of titanium black can be modified as necessary for the purpose of improving dispersibility, suppressing agglomeration, and the like.
• Titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and can also be coated with a water-repellent substance as described in JP-A No. 2007-302836. It is also possible to process
• the particle size of titanium black is not particularly limited, but is preferably 10 to 45 nm, more preferably 12 to 20 nm.
• the specific surface area of titanium black is not particularly limited, but in order for the water repellency after surface treatment with a water repellent agent to achieve a predetermined performance, the value measured by the BET (Brunauer, Emmett, Teller) method should be 5 to 5. 150 m 2 /g is preferred, and 20 to 100 m 2 /g is more preferred.
• titanium black examples include Titanium Black 10S, 12S, 13R, 13M, 13MC, 13R, 13R-N, 13M-T (product name, manufactured by Mitsubishi Materials Corporation), Tilac D (product name). , manufactured by Ako Kasei Co., Ltd.), and MT-150A (trade name, manufactured by Teika Co., Ltd.).
• the composition contains titanium black as a dispersed element containing titanium black and Si atoms.
• titanium black is included as a dispersant in the composition.
• the content ratio of Si atoms to Ti atoms (Si/Ti) in the dispersed body is preferably 0.05 to 0.5, more preferably 0.07 to 0.4, in terms of mass.
• the above-mentioned object to be dispersed includes both titanium black in the state of primary particles and titanium black in the state of aggregates (secondary particles).
• the Si/Ti ratio of the dispersed elements is greater than a predetermined value, when a composition layer using the dispersed elements is patterned by photolithography or the like, residues are less likely to remain in the removed areas, and the Si/Ti of the dispersed elements is less likely to remain. /Ti is less than a predetermined value, the light shielding function tends to be good.
• paragraph [0166] of JP-A-2021-007037 can be referred to, and the contents thereof are incorporated herein.
• the titanium black described above can be used.
• this dispersed material also contains composite oxides of multiple metals selected from Cu, Fe, Mn, V, Ni, etc., cobalt oxide, Black pigments such as iron oxide, carbon black, and aniline black may be used alone or in combination as a dispersion object.
• the dispersible material made of titanium black accounts for 50% by mass or more of the total dispersible material.
• inorganic pigments examples include zirconium nitride containing aluminum.
• zirconium nitride coated with alumina is preferable.
• Zirconium nitride is coated with alumina to improve moisture resistance.
• inorganic pigments examples include zirconium nitride containing yttrium. When the composition contains zirconium nitride containing yttrium, visible light shielding properties can be improved while maintaining i-line transmittance.
• examples of inorganic pigments include zirconium disclosed in JP 2017-222559, WO 2019/130772, WO 2019/059359, and JP 2009-091205. The contents are incorporated herein.
• Carbon black can also be mentioned as an inorganic pigment.
• examples of carbon black include furnace black, channel black, thermal black, acetylene black, and lamp black.
• carbon black carbon black manufactured by a known method such as an oil furnace method may be used, or a commercially available product may be used.
• Specific examples of commercially available carbon blacks include C. I. Pigment Black 1 and other organic pigments, and C.I. I. Examples include inorganic pigments such as Pigment Black 7.
• surface-treated carbon black is preferable.
• Surface treatment can modify the surface condition of carbon black particles and improve the dispersion stability in the composition.
• examples of the surface treatment include coating treatment with a resin, surface treatment to introduce an acidic group, and surface treatment with a silane coupling agent, and among these, coating treatment with a resin is preferred.
• paragraph [0170] of JP-A No. 2021-007037 can be referred to, the contents of which are incorporated herein.
• organic pigment used as a black coloring agent is not particularly limited as long as it has light blocking properties and contains an organic compound, but any known organic pigment can be used.
• examples of the organic pigment include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds or perylene compounds being preferred.
• Examples of the bisbenzofuranone compound include compounds described in Japanese Translated Patent Publication No. 2010-534726, Japanese Translated Patent Publication No. 2012-515233, and Japanese Translated Transparent Publication No. 2012-515234.
• the bisbenzofuranone compound is available as "Irgaphor Black” (trade name) manufactured by BASF.
• Examples of perylene compounds include compounds described in JP-A-62-001753 and JP-B-63-026784.
• the perylene compound is C. I. Pigment Black 21, 30, 31, 32, 33, and 34.
• Black dye dyes that express black color by themselves can be used, such as pyrazole azo compounds, pyrromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds. , pyridone azo compounds, cyanine compounds, phenothiazine compounds, and pyrrolopyrazole azomethine compounds can be used. Further, as the black dye, reference can be made to the compounds described in paragraph [0177] of JP-A-2021-007037, the contents of which are incorporated herein.
• black dyes include dyes defined by Color Index (C.I.) of Solvent Black 27 to 47; I. Dyes defined by are preferred.
• Commercial products of these black dyes include Spiron Black MH, Black BH (manufactured by Hodogaya Chemical Industry Co., Ltd.), VALIFAST Black 3804, 3810, 3820, 3830 (manufactured by Orient Chemical Industry Co., Ltd.), Examples include dyes such as Savinyl Black RLSN (manufactured by Clariant), KAYASET Black K-R, K-BL (manufactured by Nippon Kayaku Co., Ltd.).
• a pigment multimer may be used as the black dye.
• the dye multimer include compounds described in JP-A No. 2011-213925 and JP-A No. 2013-041097.
• a polymerizable dye having polymerizability in the molecule may be used, and examples of commercially available dyes include the RDW series manufactured by Wako Pure Chemical Industries, Ltd.
• a combination of a plurality of dyes having a color other than black when used alone may be used as the black dye.
• Examples of such colored dyes include chromatic dyes (chromatic dyes) such as R (red), G (green), and B (blue), as well as paragraph [0027 ] to [0200] can also be used.
• white colorant examples include one or more selected from the group consisting of white pigments and white dyes, and white pigments are preferred from the viewpoint of weather resistance and the like.
• white pigments include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, and aluminum silicate. , hollow resin particles, and zinc sulfide.
• the white pigment is preferably particles containing titanium atoms, and more preferably titanium oxide.
• titanium oxide described in "Titanium oxide, physical properties and applied technology, written by Manabu Seino, published June 25, 1991, published by Gihodo Publishing" can also be suitably used.
• a white pigment C.I. I. Pigment White 1, 3, 6, 16, 18, and 21 can be used.
• the infrared absorber refers to a compound having absorption in the infrared wavelength region (preferably wavelength of 650 to 1300 nm).
• a compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferable.
• colorants having such spectral properties include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, and quatarylene. compounds, dithiol metal complex compounds, and croconium compounds.
• phthalocyanine compound naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound
• compounds disclosed in paragraphs [0010] to [0081] of JP-A No. 2010-111750 may be used; The contents are incorporated herein.
• the cyanine compound for example, "Functional Pigment, Written by Makoto Okawara/Ken Matsuoka/Teijiro Kitao/Tsunesuke Hirashima, Kodansha Scientific" can be referred to, the contents of which are incorporated herein.
• the compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.
• the infrared absorber is preferably a compound that dissolves in water at 25°C in an amount of 1% by mass or more, and more preferably a compound that dissolves in water at 25°C in an amount of 10% by mass or more. By using such a compound, solvent resistance is improved.
• the cyanine compound, pyrrolopyrrole compound, and squarylium compound paragraph [0183] of JP-A-2021-007037 can be referred to, the contents of which are incorporated herein.
• the coloring materials may be used alone or in combination of two or more.
• the content of the coloring material is preferably 30 to 80% by mass based on the total solid content of the composition.
• the lower limit is more preferably 40% by mass or more, further preferably 44% by mass or more, and particularly preferably 48% by mass or more.
• the upper limit is more preferably 70% by mass or less, and even more preferably 65% by mass or less, from the viewpoint of further improving the accuracy of pattern shape. When two or more types of colorants are included, the total amount thereof is preferably within the above range.
• the composition includes a photoinitiator.
• a photopolymerization initiator for example, a known photopolymerization initiator can be used.
• a radical photopolymerization initiator is preferable.
• photopolymerization initiators include halogenated hydrocarbon derivatives (for example, compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, and thio compounds. , ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, and ⁇ -aminoketone compounds.
• photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triaryls.
• Imidazole dimer onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound or 3-aryl substituted coumarin compound are preferred, and oxime compound, ⁇ -hydroxyketone compound, ⁇ - Compounds selected from aminoketone compounds and acylphosphine compounds are more preferred, and oxime compounds are even more preferred.
• the photopolymerization initiator include compounds described in paragraphs [0065] to [0111] of JP-A No. 2014-130173 and Japanese Patent No. 6301489, the contents of which are incorporated herein.
• JP-A-2021-007037 As for commercially available ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, and acylphosphine compounds, paragraph [0220] of JP-A-2021-007037 can be referred to, the contents of which are incorporated herein.
• 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 JP-A No. 2006-342166.
• compounds described in JP-A No. 2000-066385 things Compounds described in JP-A No. 2000-080068, compounds described in Japanese Patent Application Publication No. 2004-534797, compounds described in JP-A 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 and 2-ethoxycarbonyloxyimino- 1-phenylpropan-1-one is mentioned.
• an oxime compound having a fluorene ring can also be used as a photopolymerization initiator.
• examples of the oxime compound having a fluorene ring include compounds described in JP-A No. 2014-137466.
• oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring.
• oxime compounds include the compounds described in International Publication No. 2013/083505.
• an oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
• 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.
• Compound (C-3) is mentioned.
• an oxime compound having a nitro group can be used as a photopolymerization initiator. 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 paragraphs [0031] to [0047] of JP2013-114249A, and paragraphs [0008] to [0012], and [0070] to JP2014-137466A. Examples include the compound described in [0079], the compound described in paragraphs [0007] to [0025] of Japanese Patent No. 4223071, and Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).
• an oxime compound having a benzofuran skeleton can also be used.
• Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
• oxime compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.
• the oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm.
• the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high from the viewpoint of sensitivity, preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and even more preferably from 5,000 to 200,000.
• the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
• a difunctional, trifunctional or more functional photoradical polymerization initiator may be used as the photopolymerization initiator.
• a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained.
• the crystallinity is reduced and the solubility in solvents etc. is improved, making it difficult to precipitate over time, and the stability of the composition over time can be improved.
• Examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include the paragraphs of Japanese Translated Patent Publication No. 2010-527339, Japanese Translated Patent Publication No. 2011-524436, International Publication No.
• the photopolymerization initiator contains an oxime compound and an ⁇ -aminoketone compound.
• an oxime compound and an ⁇ -aminoketone compound are used together, the ⁇ -aminoketone compound is preferably 50 to 600 parts by weight, more preferably 150 to 400 parts by weight, per 100 parts by weight of the oxime compound.
• the content of the polymerization initiator is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, and even more preferably 1.5 to 8% by mass, based on the total solid content of the composition.
• the composition may contain only one kind of polymerization initiator, or may contain two or more kinds of polymerization initiators. When two or more types are included, it is preferable that their total amount falls within the above range.
• the composition includes a polymerizable compound.
• the term "polymerizable compound” refers to an organic compound (for example, an organic compound containing an ethylenically unsaturated group) that can be polymerized under the action of the above-mentioned photopolymerization initiator, and includes the above-mentioned resin. It is a different compound from When the composition of the present invention contains a solvent, the polymerizable compound is preferably present dissolved in the solvent.
• the molecular weight of the polymerizable compound (or weight average molecular weight if it has a molecular weight distribution) is not particularly limited, but is preferably 2500 or less.
• the lower limit is preferably 100 or more.
• the polymerizable compound is preferably a compound containing an ethylenically unsaturated group (a group containing an ethylenically unsaturated bond). That is, the composition of the present invention preferably contains a low molecular weight compound containing an ethylenically unsaturated group as a polymerizable compound.
• the number of ethylenically unsaturated bond groups contained in the polymerizable compound is preferably one or more, more preferably two or more, even more preferably three or more, and particularly preferably four or more.
• the upper limit of the number of ethylenically unsaturated bond groups that the polymerizable compound has is, for example, 15 or less.
• Examples of the ethylenically unsaturated group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group.
• the polymerizable compound for example, compounds described in paragraph [0050] of JP-A No. 2008-260927 and paragraph [0040] of JP-A No. 2015-068893 can be cited, and the contents of these are incorporated herein. be incorporated into.
• the polymerizable compound may be in any chemical form such as a monomer, a prepolymer, an oligomer, a mixture thereof, or a multimer thereof.
• the polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.
• the polymerizable compound is also preferably a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100° C. or higher under normal pressure.
• a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100° C. or higher under normal pressure.
• the polymerizable compounds include dipentaerythritol triacrylate (as a commercially available product, for example, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (as a commercially available product, for example, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.).
• oligomeric types can also be used.
• NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin Nakamura Chemical Co., Ltd.
• KAYARAD RP-1040 penentaerythritol tetraacrylate, manufactured by Shin Nakamura Chemical Co., Ltd.
• KAYARAD DPEA-12LT KAYARAD DPHA LT
• KAYARAD RP-3060 KAYARAD DPEA-12
• KAYARAD DPEA-12 all product names, (manufactured by Nippon Kayaku Co., Ltd.) may also be used.
• a urethane (meth)acrylate compound having both a (meth)acryloyl group and a urethane bond in the compound may be used.
• KAYARAD DPHA-40H trade name, Nippon Kayaku Co., Ltd.
• Preferred embodiments of the polymerizable compound are shown below.
• the polymerizable compound may have acid groups such as carboxy groups, sulfonic acid groups, and phosphoric acid groups.
• the polymerizable compound containing an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group.
• a polymerizable compound having the following is more preferable, and a compound in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol is even more preferable.
• Commercially available products include, for example, Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei.
• the acid value of the polymerizable compound is preferably 0 to 40 mgKOH/g, more preferably 0 to 30 mgKOH/g, and even more preferably 0 to 5 mgKOH.
• the acid value of the polymerizable compound is 0 mgKOH/g or more, development and dissolution characteristics are good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and/or handling. Furthermore, it has good photopolymerization performance and excellent curability.
• a preferred embodiment of the polymerizable compound is a compound containing a caprolactone structure.
• Compounds containing a caprolactone structure are not particularly limited as long as they contain a caprolactone structure in the molecule, but examples include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.
• Examples include ⁇ -caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying polyhydric alcohols such as erythritol, glycerin, diglycerol, and trimethylolmelamine with (meth)acrylic acid and ⁇ -caprolactone.
• a compound containing a caprolactone structure represented by the following formula (Z-1) is preferred.
• R 1 represents a hydrogen atom or a methyl group
• m represents 1 or 2
• * represents a bonding position
• R 1 represents a hydrogen atom or a methyl group
• "*" represents a bonding position
• M-350 trade name (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd. may be mentioned.
• E represents -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)-, and y represents an integer from 0 to 10, and X represents a (meth)acryloyl group, a hydrogen atom, or a carboxy group.
• the total number of (meth)acryloyl groups is 3 or 4
• m represents an integer of 0 to 10
• the sum of each m is an integer of 0 to 40.
• the total number of (meth)acryloyl groups is 5 or 6
• n represents an integer of 0 to 10
• the total of each n is an integer of 0 to 60.
• m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8.
• n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12.
• -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)- in formula (Z-4) or formula (Z-5) is on the oxygen atom side. A form in which the terminal of is bonded to X is preferable.
• the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
• all six X are acryloyl groups
• all six X are acryloyl groups
• a preferred embodiment is a mixture with a compound having at least one hydrogen atom. With such a configuration, the developability can be further improved.
• the total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, more preferably 50% by mass or more.
• pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferred.
• the polymerizable compound may contain a cardo skeleton.
• the polymerizable compound containing a cardo skeleton is preferably a polymerizable compound containing a 9,9-bisarylfluorene skeleton.
• Examples of the polymerizable compound containing a cardo skeleton include Oncoat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogusol (manufactured by Osaka Gas Chemical Co., Ltd.).
• the polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core.
• a polymerizable compound is NK Ester A-9300 (manufactured by Shin Nakamura Chemical Co., Ltd.).
• the content of ethylenically unsaturated groups in the polymerizable compound (meaning the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g/mol) of the polymerizable compound) is 5.0 mmol/ g or more is preferable.
• the upper limit is preferably 20.0 mmol/g or less.
• the content of the polymerizable compound in the composition is preferably 5 to 60% by mass, preferably 7 to 30% by mass, and more preferably 10 to 20% by mass, based on the total solid content of the composition.
• the composition may contain only one kind of polymerizable compound, or may contain two or more kinds of polymerizable compounds. When two or more types are included, it is preferable that their total amount falls within the above range.
• the present composition may contain other components other than the above-mentioned resin, coloring material, photopolymerization initiator, and polymerizable compound.
• the composition may also include a surfactant.
• the surfactant include fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants. Among these, it is preferable that the present composition contains a silicone surfactant.
• the content of the surfactant is preferably 0.001 to 2.0% by mass, and 0.003 to 0.5% by mass based on the total solid content of the composition. is more preferable, and even more preferably 0.005 to 0.1% by mass.
• the composition may contain only one kind of surfactant, or may contain two or more kinds of surfactants. When two or more types are included, it is preferable that their total amount falls within the above range.
• the composition may also include a polymerization inhibitor.
• a polymerization inhibitor for example, known polymerization inhibitors can be used.
• the polymerization inhibitor include phenolic polymerization inhibitors (for example, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4-methoxynaphthol, etc.); hydroquinone polymerization inhibitors (e.g.
• hydroquinone, 2,6-di-tert-butylhydroquinone, etc. Quinone polymerization inhibitors (e.g., benzoquinone, etc.); Free radical polymerization inhibitors (e.g., 2,2,6,6-tetramethylpiperidine) 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, etc.); nitrobenzene-based polymerization inhibitors (e.g., nitrobenzene, 4-nitrotoluene, etc.); and phenothiazine-based polymerization inhibitors agents (eg, phenothiazine, 2-methoxyphenothiazine, etc.); Among these, phenolic polymerization inhibitors and free radical polymerization inhibitors are preferred from the viewpoint of providing better effects of the present invention.
• Free radical polymerization inhibitors e.g., 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6
• the content of the polymerization inhibitor is preferably 0.0001 to 0.5% by mass, more preferably 0.001 to 0.2% by mass, and 0.002 to 0.05% by mass based on the total solid content of the composition. Mass % is more preferred.
• the composition may contain only one kind of polymerization inhibitor, or may contain two or more kinds of polymerization inhibitors. When two or more types are included, it is preferable that their total amount falls within the above range.
• compositions of the invention may include inorganic particles or modified inorganic particles.
• Inorganic particles are particles different from the pigments mentioned above.
• a modified inorganic particle is an inorganic particle having a coating layer covering at least a portion of its surface.
• the particle diameter of the inorganic particles is preferably 200 nm or less, more preferably less than 100 nm, even more preferably 10 to 90 nm, particularly preferably 20 to 80 nm, and particularly preferably 30 to 70 nm, from the viewpoint of an excellent balance between each performance and handling property of the cured film. is most preferred.
• particle diameter means the average primary particle diameter of particles measured by the following method. For the method of measuring the average primary particle diameter, paragraph [0133] of JP-A-2021-007037 can be referred to, the contents of which are incorporated herein.
• the shape of the inorganic particles examples include fibrous, needle, plate, spherical, tetrapod, and balloon shapes, with spherical being preferred.
• the form of the inorganic particles may be monodispersed particles or aggregated particles.
• the inorganic particles may be hollow particles or solid particles.
• a hollow particle is a particle in which a cavity exists inside the particle.
• the hollow particle may have a structure in which the particle consists of an internal cavity and an outer shell surrounding the cavity.
• the hollow particle may have a structure in which a plurality of cavities exist inside the particle.
• the porosity of the hollow particles is preferably 3% or more.
• the upper limit is not particularly limited, but is preferably less than 100%, more preferably 90% or less.
• Examples of the hollow particles include hollow silica particles described in JP-A No. 2001-233611 and Japanese Patent No. 3272111, and Thrulia 4110 (trade name, manufactured by JGC Catalysts & Chemicals).
• a solid particle refers to a particle in which there are substantially no cavities inside the particle. Specifically, the porosity of the solid particles is preferably less than 3%. Examples of solid particles include IPA-ST-L (trade name, manufactured by Nissan Chemical Co., Ltd.).
• the form of the inorganic particles may be a particle aggregate (hereinafter also referred to as beaded inorganic particles) in which a plurality of inorganic particles are connected in a chain.
• the beaded inorganic particles are preferably those in which a plurality of spherical colloidal inorganic particles having a particle diameter of 5 to 50 nm are joined by metal oxide-containing inorganic particles.
• Examples of the bead-like inorganic particles include silica sols described in Japanese Patent No. 4328935 and JP-A-2013-253145, and bead-like colloidal inorganic particles are preferred.
• Examples of materials constituting the inorganic particles include inorganic oxides, inorganic nitrides, inorganic carbides, carbonates, sulfates, silicates, phosphates, and composites of two or more of these. , an inorganic oxide, an inorganic nitride, or a carbonate are preferable, and an inorganic oxide is more preferable. Note that the inorganic particles preferably contain at least silicon.
• Examples of materials constituting the inorganic particles include silica (silicon dioxide), titania (titanium dioxide), alumina (aluminum oxide), mica compounds, zinc oxide, zirconium oxide, tin oxide, potassium titanate, strontium titanate, and boric acid.
• silica silicon dioxide
• titania titanium dioxide
• alumina aluminum oxide
• mica compounds zinc oxide, zirconium oxide, tin oxide, potassium titanate, strontium titanate, and boric acid.
• the inorganic particles may be used alone or in combination of two or more.
• the content of silica (silicon dioxide) is preferably 75 to 100% by mass, more preferably 90 to 100% by mass, and 99 to 100% by mass, based on the total mass of the inorganic particles. 100% by mass is more preferred.
• the modified inorganic particles have a coating layer that covers at least a portion of the inorganic particles.
• the coating layer is a layer that covers some or all of the inorganic particles. That is, the inorganic particles may be covered with the coating layer over the entire surface of the inorganic particles, or only a portion of the inorganic particles may be covered.
• the coverage of the inorganic particles by the coating layer is preferably 10% or more, more preferably 30% or more, even more preferably 50% or more, based on the total surface area of the inorganic particles.
• the upper limit is preferably 100% or less, more preferably 80% or less, based on the total surface area of the inorganic particles.
• the coating layer may be disposed directly on the surface of the inorganic particles, or may be disposed with another layer interposed between the inorganic particles and the inorganic particles.
• the coating layer may have a substituent, and examples of the substituent include hydrophobic groups and substituents other than hydrophobic groups.
• the content of the coating layer is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass, based on the total mass of the modified inorganic particles, in order to obtain better effects of the present invention.
• the above is more preferable.
• the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the total mass of the modified inorganic particles.
• the modified inorganic particles may be used alone or in combination of two or more. When using two or more types of modified inorganic particles, the total content is preferably within the following range.
• the total content of the inorganic particles and modified inorganic particles is preferably 0.1 to 30.0% by mass, more preferably 0.5 to 20.0% by mass, based on the total solid content of the composition.
• the composition may also contain a solvent.
• a solvent an organic solvent is preferable.
• the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
• 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, 3-methoxybutyl acetate, 3- Mention may be made of methyl methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
• the organic solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only one type of isomer may be included, or multiple types may be included. However, it may be better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, 50 mass ppm (based on the total amount of organic solvents). parts per million), 10 mass ppm or less, and 1 mass ppm or less). Further, the content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.
• isomers compounds having the same number of atoms but different structures. Moreover, only one type of isomer may be included, or multiple types may be included. However, it may be better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.
• an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably 10 mass ppb (parts per billion) or less, for example. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by Toyo Gosei Co., Ltd. (Kagaku Kogyo Nippo, November 13, 2015).
• a method for removing impurities such as metals from an organic solvent for example, paragraph [0238] of JP-A-2021-007037 can be referred to, the contents of which are incorporated herein.
• the content of the solvent is preferably 10 to 97% by mass based on the total amount of the composition.
• the lower limit is more preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 50% by mass or more, even more preferably 60% by mass or more, and most preferably 65% by mass or more.
• the upper limit is more preferably 95% by mass or less, and even more preferably 80% by mass or less.
• the composition may contain only one type of solvent, or may contain two or more types. When two or more types are included, it is preferable that their total amount falls within the above range.
• the composition may also include a dispersion aid.
• the dispersion aid is a component other than the above-mentioned resin, and is a component that can suppress aggregation and/or sedimentation of components that are present in a solid state in the composition, such as a coloring material.
• Examples of the dispersion aid include pigment derivatives.
• the content of the dispersion aid is preferably 0.01 to 10% by mass, more preferably 0.1 to 8% by mass, and even more preferably 0.3 to 4% by mass, based on the total solid content of the composition.
• the composition may further contain other optional ingredients other than those mentioned above.
• acid anhydrides e.g. succinic anhydride
• ultraviolet absorbers e.g., ultraviolet absorbers
• adhesives silane coupling agents, etc.
• sensitizers e.g
• the method for producing the present composition is not particularly limited, and any known method can be employed.
• the method for producing the present composition includes producing a dispersion containing a coloring material (coloring material dispersion), and further mixing the obtained coloring material dispersion with other components to obtain a composition.
• a coloring material coloring material dispersion
• Step 1 A step of mixing a pre-mixture containing a coloring material and a resin (for example, at least one of a first resin and a second resin) in a bead mill to obtain a mixture (coloring material dispersion, etc.)
• Step 2 The above mixture , a resin (for example, at least one of a first resin and a second resin), a photopolymerization initiator, and a polymerizable compound to obtain the present composition.
• the above-mentioned pre-mixture may contain components other than those mentioned above, and such components include, for example, a dispersion aid (such as a pigment derivative) and a solvent.
• a dispersion aid such as a pigment derivative
• the components included in the pre-mixture may be blended all at once, or may be blended sequentially after each component is dissolved or dispersed in a solvent. good.
• the order of addition and working conditions during blending are not particularly limited.
• the premix is mixed in a bead mill to form a mixture. If the premix contains a solvent and the mixture contains a solvent, such a mixture is also especially referred to as a colorant dispersion. It is also preferable that the pre-mixture be roughly mixed before being mixed using a bead mill.
• the rough mixing method is not particularly limited, and known means can be used.
• the beads in the bead mill inorganic beads such as glass beads and zirconia beads, resin beads, etc. can be used.
• the bead diameter is preferably 0.01 to 1.0 mm, more preferably 0.03 to 0.65 mm.
• the bead filling rate is preferably 50 to 90% by volume, more preferably 60 to 80% by volume.
• the rotational speed (peripheral speed) is preferably 1 to 20 m/sec, more preferably 5 to 14 m/sec.
• the temperature of the object to be treated is preferably 5 to 80°C, more preferably 15 to 60°C.
• the bead mill may be, for example, a batch type device, a circulation type device, or a continuous type device, and a plurality of devices may be used in combination.
• the processing time is preferably 0.5 to 6 hours, more preferably 2 to 4 hours.
• the number of passes is preferably 10 to 1000, more preferably 60 to 200.
• Step 2 the mixture obtained in Step 1, a resin, a photopolymerization initiator, and a polymerizable compound are mixed to obtain the present composition.
• at least a photopolymerization initiator and a polymerizable compound may be mixed into the above mixture, and other components (adhesive agent (silane coupling agent, etc.), polymerization inhibitor, surfactant, inorganic particles, modification Inorganic particles and/or additional solvents, etc.) may be further mixed.
• Each component to be mixed in Step 2 (including the mixture obtained in Step 1) may be blended all at once, or may be blended sequentially after each component is dissolved or dispersed in a solvent. .
• a composition can be prepared by mixing the above-mentioned components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, etc.).
• a mixing method for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, etc.
• step 2 at least a part of the coloring material contained in the present composition only needs to be derived from the mixture obtained in step 1, and a coloring material different from the components blended in step 1, and A resin or the like may be further mixed in step 2.
• the composition is preferably filtered for the purpose of removing foreign substances and reducing defects.
• any filter that has been conventionally used for filtration purposes can be used without particular restriction.
• filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP).
• PTFE polytetrafluoroethylene
• nylon polyamide resins
• polyolefin resins including high density and ultra-high molecular weight
• polyethylene and polypropylene (PP). polypropylene
• polypropylene including high-density polypropylene
• nylon is preferred.
• the pore diameter of the filter is preferably 0.1 to 7.0 ⁇ m, more preferably 0.2 to 2.5 ⁇ m, even more preferably 0.2 to 1.5 ⁇ m, and particularly preferably 0.3 to 0.7 ⁇ m. Within this range, fine foreign matter such as impurities and aggregates contained in the coloring material can be reliably removed while suppressing the coloring material from clogging the filtration.
• the composition preferably does not contain impurities such as metals, metal salts containing halogens, acids, and alkalis.
• the type of metal is not particularly limited, but includes alkali metals, alkaline earth metals, transition metals, Al, Sn, Pb, and Bi.
• the content of impurities contained in these materials is preferably 1 ppm by mass or less, more preferably 1 ppb by mass or less, even more preferably 100 ppt by mass or less, particularly preferably 10 ppt by mass or less, and substantially not contained (measured). most preferably below the detection limit of the device).
• the above impurities can be measured using an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
• a "cured film” is a film formed by subjecting a composition layer formed using the present composition to a curing treatment such as an exposure treatment.
• the cured film formed using the present composition has excellent light-shielding properties, and has a high optical density per 1.5 ⁇ m film thickness in the wavelength region of 400 to 1100 nm.
• OD Optical Density
• the cured film can be preferably used as a light-shielding film or a colored pixel in a color filter to be described later.
• the optical density per 1.5 ⁇ m of film thickness in the wavelength region of 400 to 1100 nm is 2.5 or more means the optical density per 1.5 ⁇ m of film thickness in the entire wavelength range of 400 to 1100 nm. is 2.5 or more.
• a method for measuring the optical density of a cured film first, a cured film is formed on a glass substrate, and a spectrophotometer U-4100 (trade name, manufactured by Hitachi High-Technologies, Inc.) of an integrating sphere type is used. The measurement is performed using a light receiving unit, the film thickness at the measurement location is also measured, and the optical density per predetermined film thickness is calculated.
• the thickness of the cured film is, for example, preferably 0.1 to 4.0 ⁇ m, more preferably 1.0 to 2.5 ⁇ m. Further, the cured film may be made thinner or thicker than this range depending on the purpose. Further, when the cured film is used as a light attenuation film, the light-shielding property may be adjusted by making the film thinner than the above range (for example, 0.1 to 0.5 ⁇ m). In this case, the optical density per 1.0 ⁇ m of film thickness in the wavelength range of 400 to 1200 nm is preferably 0.1 to 1.5, more preferably 0.2 to 1.0.
• the reflectance of the cured film is preferably less than 8%, more preferably less than 6%, and even more preferably less than 4%.
• the lower limit is preferably 0% or more.
• the reflectance is determined from the reflectance spectrum obtained by incident light with a wavelength of 400 to 1100 nm at an incident angle of 5° using a VAR unit of a spectrometer V7200 (manufactured by JASCO Corporation). Specifically, the reflectance of the light having the maximum reflectance in the wavelength range of 400 to 1100 nm is defined as the reflectance of the cured film.
• the method for producing a cured film is not particularly limited, but preferably includes the following steps.
• a patterned cured film can be formed through the following steps. Each step will be explained below.
• composition layer formation process In the composition layer forming step, prior to exposure, a composition is applied onto a support or the like to form a composition layer (composition layer).
• the support include a glass substrate, a silicon substrate (which may be subjected to hydrophobization treatment with hexamethyldisilazane, etc.), and a CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide) on a silicon substrate.
• a substrate for a solid-state image sensor provided with an image sensor (light-receiving element) such as manufactured by Semiconductor (Semiconductor) can be used.
• an undercoat layer may be provided on the support, if necessary, for improving adhesion with the upper layer, preventing substance diffusion, flattening the substrate surface, and the like.
• Examples of methods for applying the composition onto the support include various coating methods such as slit coating, inkjet coating, spin coating, cast coating, roll coating, and screen printing.
• the thickness of the composition layer is preferably 0.1 to 10.0 ⁇ m, more preferably 0.2 to 5.0 ⁇ m, and even more preferably 0.2 to 3.0 ⁇ m. Drying (prebaking) of the composition layer coated on the support can be performed at a temperature of 50 to 140° C. for 10 to 300 seconds using a hot plate, oven, or the like.
• the exposure step is a step of irradiating and exposing the composition layer formed in the composition layer forming step with actinic light or radiation, and curing the light irradiated area of the composition layer.
• the method of light irradiation is not particularly limited, it is preferable to irradiate light through a photomask having patterned openings.
• the exposure is preferably carried out by irradiation with radiation, and the radiation that can be used for exposure is particularly preferably ultraviolet rays such as G-line, H-line, and I-line, and a high-pressure mercury lamp is preferable as the light source.
• the irradiation intensity is preferably 5 to 1500 mJ/cm 2 , more preferably 10 to 1000 mJ/cm 2 .
• the developing step is a step of performing a developing treatment on the exposed composition layer. Through this step, the composition layer in the unexposed region in the exposure step is eluted, and only the photocured portion remains. For example, when light irradiation is performed through a photomask having patterned openings in the exposure process, a patterned cured film is obtained.
• the type of developer used in the developing step is not particularly limited, but an alkaline developer is preferred as it does not cause damage to the underlying image sensor, circuits, etc.
• the developing temperature is, for example, 20 to 30°C.
• the developing time is, for example, 20 to 90 seconds.
• the alkaline developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water to a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass).
• alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (TMAH), and tetraethylammonium hydroxide.
• tetrapropylammonium hydroxide tetrabutylammonium hydroxide
• benzyltrimethylammonium hydroxide choline, pyrrole, piperidine and 1,8-diazabicyclo[5.4.0]-7-undecene (among them, organic alkali is preferred).
• rinsing treatment or washing treatment with water is generally performed after development.
• Post-bake is a heat treatment after development to complete curing.
• the heating temperature is preferably 240°C or lower, more preferably 220°C or lower. Although there is no particular lower limit, it is preferably 50°C or higher, more preferably 100°C or higher.
• Post-baking can be performed in a continuous or batch manner using heating means such as a hot plate, a convection oven (hot air circulation dryer), and a high-frequency heater.
• the above post-bake is preferably performed in an atmosphere with a low oxygen concentration.
• the oxygen concentration is preferably 19 vol% or less, more preferably 15 vol% or less, even more preferably 10 vol% or less, particularly preferably 7 vol% or less, and most preferably 3 vol% or less. Although there is no particular lower limit, it is preferably 10 volume ppm or more.
• the above cured film can be applied to portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as printers and scanners; surveillance cameras, barcode readers, and automated teller machines (ATMs).
• Industrial equipment such as automated teller machines), high-speed cameras, and equipment with personal authentication functions using facial image authentication or biometric authentication; Vehicle-mounted camera equipment; Medical equipment such as endoscopes, capsule endoscopes, and catheters. Camera equipment; and space equipment such as biosensors, biosensors, military reconnaissance cameras, three-dimensional mapping cameras, weather and ocean observation cameras, land resource exploration cameras, and exploration cameras for space astronomy and deep space targets; etc. It is suitable for light-shielding members and light-shielding films of optical filters and modules used for, and further for anti-reflection members and anti-reflection films.
• the cured film can also be used for applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes).
• the cured film is suitable for optical filters and optical films used in micro LEDs and micro OLEDs, as well as members that provide light shielding or antireflection functions. Examples of micro LEDs and micro OLEDs include those described in Japanese Translation of PCT Publication No. 2015-500562 and Japanese Translation of PCT Publication No. 2014-533890.
• the above-mentioned cured film is also suitable as optics and optical films used in quantum dot sensors and quantum dot solid-state imaging devices. Further, it is suitable as a member that provides a light shielding function and an antireflection function. Examples of quantum dot sensors and quantum dot solid-state imaging devices include those described in US Patent Application Publication No. 2012/37789 and International Publication No. 2008/131313.
• the cured film of the present invention is also preferably used as a so-called light-shielding film. It is also preferable to use such a light-shielding film in a solid-state image sensing device, which will be described later.
• the cured film formed using the light-shielding composition of the present invention has excellent light-shielding properties and low reflectivity.
• the light-shielding film is one of the preferred uses of the cured film of the present invention, and the light-shielding film of the present invention can be produced in the same manner as described above as the method for producing the cured film.
• a light-shielding film can be manufactured by applying a composition to a substrate to form a composition layer, exposing it to light, and developing it.
• the cured film obtained using the composition of the present invention is included in a color filter.
• the color filter includes a cured film include, but are not particularly limited to, color filters that include a substrate and a black matrix.
• the color filter is equipped with a light-shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.
• One form of the color filter includes, for example, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate.
• a color filter including a black matrix can be manufactured, for example, by the following method. First, a composition layer of a composition containing a coloring material corresponding to each colored pixel of a color filter is formed in the openings of a patterned black matrix formed on a substrate. Note that as the composition for each color, for example, a known composition can be used, but it is preferable to use the present composition containing a coloring material corresponding to each pixel. Next, the composition layer is exposed to light through a photomask having a pattern corresponding to the openings in the black matrix. Next, after removing the unexposed areas through a development process, it is baked to form colored pixels in the openings of the black matrix. By performing a series of operations using, for example, compositions for each color containing red, green, and blue pigments, a color filter having red, green, and blue pixels can be manufactured.
• the present invention also includes the invention of optical elements.
• the optical element of the present invention is an optical element having the above-mentioned cured film (light-shielding film).
• Examples of the optical element include optical elements used in optical instruments such as cameras, binoculars, microscopes, and semiconductor exposure equipment. Among these, the optical element is preferably, for example, a solid-state image sensor mounted on a camera or the like.
• the solid-state image sensor of the present invention is a solid-state image sensor that includes the above-mentioned cured film (light-shielding film) of the present invention.
• the solid-state image sensor of the present invention may include a cured film (light-shielding film), for example, on a substrate, a plurality of photodiodes and a polymer that constitute the light-receiving area of the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.).
• Examples include a form that has a light-receiving element made of silicon or the like, and has a cured film on the side of the support where the light-receiving element is formed (for example, a portion other than the light-receiving part and/or a pixel for color adjustment, etc.) or on the opposite side of the formation surface.
• the solid-state imaging device includes the solid-state imaging device described above.
• the cured film of the present invention is also preferably included as a light-shielding film in a headlight unit of an on-vehicle lamp such as an automobile. More specifically, the headlight unit of the present invention includes a light source and a light shielding portion that blocks at least a portion of the light emitted from the light source, and the cured film of the present invention is applied to the light shielding portion.
• the cured film of the present invention included in the headlight unit is preferably formed in a pattern so as to block at least a portion of the light emitted from the light source.
• Titanium oxide MT-150A (trade name: manufactured by Teika) with an average particle size of 15 nm (100 g), silica particles AEROGIL (registered trademark) 300/30 (manufactured by Evonik) with a BET surface area of 300 m 2 /g (25 g), and a dispersant.
• Disperbyk 190 product name: manufactured by BYK Chemie
• ionized electric exchange water 71 g
• MAZERSTAR KK-400W manufactured by KURABO
• a homogeneous aqueous mixture solution was obtained by processing for a minute.
• This aqueous solution was filled into a quartz container and heated to 920°C in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama), then the atmosphere was replaced with nitrogen and ammonia gas was flowed at 100 mL/min for 5 hours at the same temperature.
• the nitridation reduction treatment was carried out by this.
• the collected powder was crushed in a mortar to obtain titanium black (a-1) [dispersed material containing titanium black particles and Si atoms] containing Si atoms and having a specific surface area of 73 m 2 /g in powder form. .
• Second resin B-1 (7.3 parts by mass) was added to the titanium black (a-1) (24.3 parts by mass), and further cyclopentanone (41.4 parts by mass) and propylene glycol monomethyl Ether acetate (PGMEA, 27.0 parts by mass) was added to obtain a dispersion.
• the obtained dispersion was sufficiently stirred using a stirrer to perform premixing.
• the obtained dispersion was subjected to dispersion treatment using NPM Pilot (bead mill) manufactured by Shinmaru Enterprises under the following conditions to obtain color material dispersion Black-1.
• Second resin B-7 (7.6 parts by mass) and succinic anhydride (0.64 parts by mass) were added to titanium black (a-1) (27.3 parts by mass) prepared above, and Then, propylene glycol monomethyl ether acetate (PGMEA) and cyclopentanone were added at a ratio (mass ratio) of 25.4 to 74.6 so that the total amount of liquid was 100 parts by mass to obtain a dispersion.
• the obtained dispersion was sufficiently stirred using a stirrer to perform premixing.
• the obtained dispersion was subjected to a dispersion treatment using NPM Pilot (bead mill) manufactured by Shinmaru Enterprises under the following conditions to obtain color material dispersion Black-12.
• each component in the colorant dispersion was changed as shown in Table 1 below, and the other procedures were the same as the method shown in ⁇ Manufacture of colorant dispersion Black-1>.
• Each coloring material dispersion liquid was manufactured.
• the coloring material dispersion liquid was manufactured by adding the said pigment derivative before adding the 1st resin or the 2nd resin. Numerical values in the table indicate parts by mass unless otherwise specified.
• details of the components represented by abbreviations or symbols are as follows.
• ⁇ B-2 Resin having the structure shown below (weight average molecular weight 9000, acid value 43 mgKOH/g) Note that the resin B-2 can be synthesized by the method described in paragraph [0196] of International Publication No. 2020/044720.
• ⁇ B-3 Resin with the structure shown below (weight average molecular weight 10,000, acid value 0 mgKOH/g) (corresponds to resin with block structure)
• the numerical value in the repeating unit in the following formula represents the content (mass%) with respect to all repeating units in the resin.
• ⁇ B-4 Resin having the structure shown below (weight average molecular weight 21000, acid value 36 mgKOH/g)
• a to e represent the content (mol %) of each repeating unit with respect to all repeating units contained in the resin.
• x and y represent the number of repeating units.
• ⁇ B-5 Resin obtained by the following procedure (weight average molecular weight 21000, acid value 36 mgKOH/g)
• NMP N-methyl-2-pyrrolidone
• ⁇ B-7 The following resin which is the second resin (weight average molecular weight 21000, acid value 85 mgKOH/g, ethylenically unsaturated bond equivalent (polymerizable group value) 0.7 mmol/g, resin having a graft chain)
• the numbers attached to each repeating unit and r to u indicate mol% of each repeating unit.
• Photosensitive compositions of Examples 2-101 to 2-119 were prepared in the same manner as the photosensitive compositions.
• the "post-added resin” column indicates at least one of the first resin and second resin used in preparing the photosensitive composition, in addition to the resin contained in the coloring material dispersion.
• ⁇ M-1 NK ester A-TMMT (tetrafunctional acrylate, manufactured by Shin Nakamura Chemical Co., Ltd.)
• ⁇ M-2 Aronix TO-2349 (acid-modified polyfunctional acrylate, manufactured by Toagosei Co., Ltd.)
• ⁇ M-3 Ogsol EA-0300 (fluorene-containing acrylate, manufactured by Osaka Gas Chemical Co., Ltd.)
• ⁇ M-4 Aronix M-305 (pentaerythritol tri and tetraacrylate, manufactured by Toagosei Co., Ltd.)
• ⁇ M-5 The following compound ⁇ M-6: KBM-5103 (manufactured by Shin-Etsu Silicone Co., Ltd.)
• nW-1 The following surfactant (weight average molecular weight 3000, in the formula, n represents an integer of 1 or more)
• ⁇ W-2 KF6000 (manufactured by Shin-Etsu Silicone)
• ⁇ W-3 Futergent 710FL (manufactured by Neos)
• Surulia 4110 manufactured by JGC Catalysts & Chemicals, solid content 20% by mass, isopropyl alcohol solvent, hollow silica sol, average primary particle size 60 nm) (100 g), KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropyltrimethoxy) silane) (4 g), a 10% by mass formic acid aqueous solution (0.5 g), and water (1 g) to obtain a mixed solution. The resulting mixture was stirred at 60°C for 3 hours. Furthermore, the solvent in the mixture was replaced with 1-methoxy-2-propanol using a rotary evaporator.
• the inorganic particle dispersion PS-1 (hollow silica surface-modified with methacryloyl groups) with a solid content of 20% by mass is obtained. A dispersion liquid) was obtained. Next, the inorganic particle dispersion PS-1 (30.0 g) obtained above and X-22-2404 (manufactured by Shin-Etsu Chemical Co., Ltd., one end methacrylic modified silicone oil, 1.8 g) were placed in a three-necked flask.
• ⁇ Synthesis Example 1 Production of Silica Dispersion 2> (Coating layer formation process) Surulia 4110 (manufactured by JGC Catalysts & Chemicals Co., Ltd., solid content concentration 20% by mass, isopropyl alcohol solvent, hollow silica sol, average primary particle diameter 60 nm) 150 parts by mass, 100 parts by mass of ethanol, a silane coupling agent containing a hydrophobic group.
• Surulia 4110 manufactured by JGC Catalysts & Chemicals Co., Ltd., solid content concentration 20% by mass, isopropyl alcohol solvent, hollow silica sol, average primary particle diameter 60 nm
• KP983 manufactured by Shin-Etsu Silicone Co., Ltd.
• KBM-5803 manufactured by Shin-Etsu Silicone Co., Ltd.
• silica dispersion liquid 3 was prepared in the same manner as in Synthesis Example 1, except that KP983 was changed to a fluorine-containing silane coupling agent of the following formula, and KBM-5803 was changed to 3-glycidoxypropyltrimethoxysilane.
• the content of the coating layer in the obtained modified inorganic particles was 7 parts by mass based on 100 parts by mass of the modified inorganic particles.
• the content of the uncoated material was 0.1 parts by mass based on 100 parts by mass of the entire modified inorganic particles.
• IPA-ST-L (manufactured by Nissan Chemical Co., Ltd., isopropanol dispersion of solid silica particles, solid content concentration 30% by mass, average primary particle diameter 45 nm) 100 parts by mass, 100 parts by mass of ethanol, silane cup containing a hydrophobic group
• Aqueous ammonia (1% concentration by mass) was added to a solution containing 3 parts by mass of KP983 (manufactured by Shin-Etsu Silicone), which is a ring agent, and 0.5 parts by mass of [3-(trimethoxysilyl)propyl]succinic anhydride. was added in an amount of 1% by mass based on the mass of the mixed liquid, and the mixture was stirred at 25°C for 72 hours.
• the obtained solution was purified using a rotary ceramic membrane filter (Mitsubishi Dynafilter), and 10 times the amount of PGMEA of the obtained solution was used as a cleaning liquid to purify the silica particles (conditions: pore size of the ceramic membrane 5 nm, disk rotation speed 1000 rpm, filtration pressure 0.2 MPa).
• the obtained silica solution was concentrated to a solid content concentration of 30% by mass to obtain a silica dispersion 4.
• the content of the coating layer in the obtained modified inorganic particles was 7 parts by mass based on 100 parts by mass of the modified inorganic particles.
• Silica Dispersion 4 the content of the uncoated material was 0.3 parts by mass based on 100 parts by mass of the entire modified inorganic particles.
• Coloring material dispersion Each coloring material dispersion shown in Table 1 was used.
• the exposed coating film was paddle developed at 23°C for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH), rinsed with a spin shower, and further developed with pure water for 30 seconds. The uncured portion of the coating was removed by washing for seconds. Thereafter, the above coating film was post-baked at 220° C. for 300 seconds to obtain a patterned wafer.
• TMAH tetramethylammonium hydroxide
• the above coating film was post-baked at 220° C. for 300 seconds to obtain a patterned wafer.
• a line pattern with a width of 50 ⁇ m was observed using an optical microscope, and the presence or absence of pattern peeling was evaluated based on the following evaluation criteria. If the evaluation is A to D, it is judged that there is no problem in practical use.
• a pattern without peeling can be formed with an exposure amount of 50 mJ/cm 2 or more.
• a pattern without peeling can be formed at an exposure dose of 1000 mJ/cm 2 (peeling occurs at an exposure dose of 50 to 950 mJ/cm 2 ).
• Adhesion to glass substrate (adhesion 2)
• Each photosensitive composition was applied onto a glass substrate by a spin coating method to produce a coating film having a thickness of 1.5 ⁇ m after drying.
• After pre-baking the obtained coating film at 100°C for 120 seconds, it was coated with UX-1000SM through a mask having an L/S pattern (line width: space width 1:1) with an opening line width of 50 ⁇ m.
• -EH04 manufactured by Ushio Inc.
• the exposed coating film was paddle-developed at 23° C.
• a line pattern with a width of 50 ⁇ m was observed using an optical microscope, and the presence or absence of pattern peeling was evaluated based on the following evaluation criteria. If the evaluation is A to D, it is judged that there is no problem in practical use. The smaller the exposure amount that can form a pattern (image area) that is in close contact with the base material and does not peel off, the better.
• a pattern without peeling can be formed with an exposure amount of 50 mJ/cm 2 or more.
• B A pattern without peeling can be formed at an exposure dose of 250 mJ/cm 2 or more (peeling occurs at an exposure dose of 50 to 200 mJ/cm 2 ).
• C A pattern without peeling can be formed at an exposure dose of 500 mJ/cm2 or more (peeling occurs at an exposure dose of 50 to 450 mJ/ cm2 ).
• D A pattern without peeling can be formed at an exposure dose of 1000 mJ/cm 2 (peeling occurs at an exposure dose of 50 to 950 mJ/cm 2 ).
• E Peeling occurs at an exposure dose of 1000 mJ/cm 2 .
• the tape was peeled off at a speed of 75 mm per second while tilting the end of the tape at an angle of 45°.
• the number of peeled lattice patterns on the glass substrate was counted and evaluated based on the following evaluation criteria. The fewer the number of peeled lattice patterns, the better the pattern adhesion, which is preferable. (Evaluation criteria) A: No peeling occurred at all. B: The number of lattice patterns that peeled off was less than 5% of the total. C: The number of grid patterns in which peeling occurred is 5% or more and less than 15% of the total. D: The number of grid patterns in which peeling occurred is 15% or more and less than 35% of the total. E: The number of lattice patterns that peeled off was 35% or more of the total.
• Tables 5 to 8 below show the evaluation results of the photosensitive compositions of Examples 1-1 to 1-35 and Comparative Examples 1-1 to 1-2, and Tables 9 to 11 show the evaluation results of Examples 2-1 to 2-32 and The evaluation results of the photosensitive compositions of Comparative Examples 2-1 to 2-4 are shown. Further, Table 104 below shows the evaluation results of the photosensitive compositions of Examples 1-101 to 1-105, and Table 201 shows the evaluation results of the photosensitive compositions of Examples 2-101 to 2-119. The numerical values in the table are based on mass unless otherwise specified. Moreover, the usage amount of each component in the table is expressed in parts by mass. For example, the amount of PGMEA used in Example 1-1 is 22.71 parts by mass.
• the "solid content ratio” column indicates the content of the first resin or second resin relative to the total solid content of each photosensitive composition.
• the "Resin ratio” column indicates the content of the first resin or second resin relative to the total mass of resin in each photosensitive composition.
• the numerical value attached to each repeating unit is the content (mass%) of each repeating unit with respect to all repeating units in the first resin. shows.
• the photosensitive compositions of Comparative Example 2-1 or Comparative Example 2-4 which did not contain the first resin, had low evaluation results and could not achieve the above effects.
• A-r4 used in place of A-9 is a resin that does not fall under the first resin because the number n of repeating units is less than 3, although it has a polyoxyalkylene chain.
• the photosensitive compositions of Comparative Example 2-2 or Comparative Example 2-3, in which the first resin contains a fluorine atom had low evaluation results and did not achieve the above effects.
• R 2a in the repeating unit represented by formula (1a) is a monovalent organic group that does not contain an aromatic ring, the generation of development residues on wafers and glass substrates can be further suppressed. It was confirmed (comparison between Example 2-23 and Example 1-3, etc.). Regarding the first resin, it was confirmed that in the repeating unit represented by formula (1a), when R 2a represents an alkyl group having 1 to 4 carbon atoms, the generation of development residues on wafers and glass substrates is further suppressed.
• the adhesion to the wafer and the glass substrate as well as the adhesion to the glass substrate were good (Example 2-4 and Example 2-8). (Comparison with etc.) It was confirmed that when the ethylenically unsaturated bond equivalent of the first resin was 0.6 mmol/g or more, the adhesion to the wafer and glass substrate was good (Example 2-9 and Example 1-3).

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