WO2022168743A1 - 樹脂組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 - Google Patents
樹脂組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 Download PDFInfo
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- WO2022168743A1 WO2022168743A1 PCT/JP2022/003238 JP2022003238W WO2022168743A1 WO 2022168743 A1 WO2022168743 A1 WO 2022168743A1 JP 2022003238 W JP2022003238 W JP 2022003238W WO 2022168743 A1 WO2022168743 A1 WO 2022168743A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
-
- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
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- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- 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
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- 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
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- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- 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
Definitions
- the present invention relates to a resin composition containing a coloring material.
- the present invention also relates to a film, an optical filter, a solid-state imaging device, and an image display device using the resin composition.
- Optical filters such as color filters are manufactured using resin compositions containing colorants.
- the number average particle size of the primary particles is 50 nm or less, and the ratio of the number average particle size to the volume average particle size ([volume average particle size]/[number average particle size]) is 1. .0 to 2.0, a graft polymer having a repeating unit containing at least an organic dye residue in the backbone chain, a polymerizable compound, and a photopolymerization initiator. It is described that a color filter is produced by
- an object of the present invention is to provide a resin composition capable of forming a film with suppressed color unevenness.
- Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, and an image display device.
- the present invention provides the following.
- a resin composition containing a coloring material A and a resin B The coloring material A contains a pigment
- the resin B is a repeating unit b1-1 having an acid group, and a repeating unit b1-2 having a functional group b selected from a group containing two or more aromatic rings, a group containing a heterocyclic group, and a group containing a condensed ring. and a resin b1 containing the repeating unit b1-1 and the repeating unit b1-3 other than the repeating unit b1-2,
- the functional group b has a naphthalimide structure, an acridone structure, a thioxanthone structure, a xanthone structure, an anthrone structure, a benzimidazole structure, a benzothiazole structure, a benzoxazole structure, a benzotriazole structure, a benzoxadiazole structure, and a benzothiadiazole structure.
- benzothiazine structure benzoxazine structure, benzoleinurea structure, isothiazolinone structure, phenoxazine structure, phenothiazine structure, dihydroacridine structure, phenoxathiine structure, dibenzopyran structure, fluorene structure, carbazole structure, carboline structure, dibenzothiophene structure, dibenzofuran structure, pyrimidine structure, pyrazine structure, quinazoline structure, quinoxaline structure, quinoline structure, imidazole structure, thiazole structure, indole structure, benzothiophene structure, benzopyran structure, quinolinone structure, thiochromanone structure, chroman structure, benzimidazolone structure, phthalimide structure, naphthalene-2,3-dicarboximide structure, pyrazole structure, pyrazolone structure, isoindoline structure, isoindolinone structure, anthr
- the functional group b has a naphthalimide structure, an acridone structure, a xanthone structure, a benzimidazole structure, a benzothiazole structure, a benzoxazole structure, a benzotriazole structure, a benzoxadiazole structure, a benzothiadiazole structure, a phenoxazine structure, and a phenothiazine.
- the resin composition according to any one of ⁇ 1> to ⁇ 3> which is a group containing a structure, a phenoxathiin structure, a phthalimide structure, a pyrazolone structure, a tetrazole structure, a benzothiazolone structure, or a benzoxazolinone structure.
- ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the content of the unit b1-2 in the resin b1 is 10 to 35% by mass.
- the repeating unit b1-3 includes a repeating unit having a graft chain of a polyester structure or a polyether structure.
- the resin b2 contains at least one selected from a graft polymer, a star polymer, a block copolymer, and a resin in which at least one end of a polymer chain is blocked with an acid group, ⁇ 8> to ⁇ 10>
- ⁇ 12> The resin composition according to any one of ⁇ 1> to ⁇ 11>, further comprising a polymerizable compound and a photopolymerization initiator.
- ⁇ 13> A film obtained from the resin composition according to any one of ⁇ 1> to ⁇ 12>.
- An optical filter comprising the film according to ⁇ 13>.
- An image display device comprising the film according to ⁇ 13>.
- the present invention it is possible to provide a resin composition capable of forming a film with suppressed color unevenness. Also, films, optical filters, solid-state imaging devices, and image display devices can be provided.
- ⁇ is used to include the numerical values before and after it as lower and upper limits.
- a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent.
- an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
- Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
- (meth)acrylate represents both or either acrylate and methacrylate
- (meth)acryl represents both or either acrylic and methacrylic
- (meth) ) acryloyl refers to acryloyl and/or methacryloyl.
- Me in the structural formulas represents a methyl group
- Et represents an ethyl group
- Bu represents a butyl group
- Ph represents a phenyl group.
- the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
- total solid content refers to the total mass of all components of the composition excluding the solvent.
- pigment means a coloring material that is difficult to dissolve in a solvent.
- the term "process” includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .
- the resin composition of the present invention is a resin composition containing a coloring material A and a resin B,
- the coloring material A contains a pigment
- the resin B is a repeating unit b1-1 having an acid group, and a repeating unit b1-2 having a functional group b selected from a group containing two or more aromatic rings, a group containing a heterocyclic group, and a group containing a condensed ring. and a resin b1 containing repeating units b1-1 and repeating units b1-3 other than repeating units b1-2,
- the content of the coloring material A in the total solid content of the resin composition is 55% by mass or more.
- the resin composition of the present invention by including the resin b1 described above, even though the content of the coloring material A in the total solid content of the resin composition is 55% by mass or more, color unevenness is suppressed. It is possible to form a thin film.
- the resin composition of the present invention is preferably used as a resin composition for optical filters.
- the optical filter include a color filter, a near-infrared transmission filter, a near-infrared cut filter, and the like, and a color filter is preferable.
- the resin composition of the present invention is preferably used for a solid-state imaging device. More specifically, it is preferably used as a resin composition for optical filters used in solid-state imaging devices, and more preferably used as a resin composition for forming colored pixels of color filters used in solid-state imaging devices.
- color filters include filters having colored pixels that transmit light of a specific wavelength.
- colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. Green pixels, blue pixels, or cyan pixels are preferred, and green pixels are preferred. more preferred.
- the colored pixels of the color filter can be formed using a resin composition containing a chromatic coloring material.
- the maximum absorption wavelength of the near-infrared cut filter preferably exists in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm.
- the transmittance of the near-infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Also, the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.
- the ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at a wavelength of 550 nm is preferably 20 to 500, more preferably 50 to 500. , more preferably 70-450, and particularly preferably 100-400.
- a near-infrared cut filter can be formed using a resin composition containing a near-infrared absorbing colorant.
- a near-infrared transmission filter is a filter that transmits at least part of near-infrared rays.
- the near-infrared transmission filter is preferably a filter that blocks at least part of visible light and transmits at least part of near-infrared light.
- the near-infrared transmission filter has a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm, and has a transmittance in the wavelength range of 1100 to 1300 nm. Filters satisfying spectral characteristics with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) are preferred.
- the near-infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (5).
- the maximum transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 800 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 900 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1000 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1100 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1200 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
- the resin composition of the present invention can also be used as a light shielding film.
- the solid content concentration of the resin composition of the present invention is preferably 5 to 30% by mass.
- the lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more.
- the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
- the resin composition of the present invention contains coloring material A (hereinafter referred to as coloring material).
- coloring material A examples include white colorants, black colorants, chromatic colorants, and near-infrared absorption colorants.
- a pigment derivative can also be used as the coloring material.
- the white colorant includes not only a pure white colorant but also a light gray colorant close to white (for example, grayish white, light gray, etc.).
- the coloring material contained in the resin composition of the present invention contains a pigment.
- the pigment may be either an inorganic pigment or an organic pigment, but an organic pigment is preferred from the viewpoints of color variation, ease of dispersibility, safety, and the like.
- the pigment preferably contains at least one selected from chromatic pigments and near-infrared absorbing pigments, and more preferably contains a chromatic pigment.
- the coloring material is at least one selected from phthalocyanine pigments, dioxazine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, azo pigments, azomethine pigments, diketopyrrolopyrrole pigments, pyrrolopyrrole pigments, isoindoline pigments and quinophthalone pigments. It preferably contains a phthalocyanine pigment, more preferably contains at least one selected from a phthalocyanine pigment, a diketopyrrolopyrrole pigment and a pyrrolopyrrole pigment.
- the phthalocyanine pigment is preferably a phthalocyanine pigment having no central metal, or a phthalocyanine pigment having copper or zinc as the central metal, more preferably a phthalocyanine pigment having copper or zinc as the central metal. Further, the phthalocyanine pigment is preferably a halogenated phthalocyanine pigment.
- the average primary particle size of the pigment is preferably 1 to 200 nm.
- the lower limit is preferably 5 nm or more, more preferably 10 nm or more.
- the upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less.
- the primary particle size of the pigment can be determined from the photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment.
- the average primary particle size in the present invention is the arithmetic mean value of the primary particle sizes of 400 primary particles of the pigment. Further, the primary particles of the pigment refer to independent particles without agglomeration.
- the crystallite size of the organic pigment and pigment derivative is preferably 0.1 to 50 nm, more preferably 0.5 to 30 nm, and even more preferably 1 to 15 nm.
- the crystallite size can be obtained from the half width of the diffraction angle peak using an X-ray diffractometer, and is calculated using Scherrer's formula.
- the crystallite size of the organic pigment and pigment derivative can be adjusted by known methods such as adjustment of production conditions and pulverization after production.
- the coloring material contained in the resin composition of the present invention preferably contains a pigment and a pigment derivative.
- Pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton. Details of the pigment derivative will be described later.
- the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
- the coloring material contained in the resin composition of the present invention may further contain a dye.
- a dye When a dye is included, the content of the dye is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the pigment.
- the upper limit is preferably 80 parts by mass or less, more preferably 70 parts by mass or less.
- the lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more. Only one dye may be used, or two or more dyes may be used in combination.
- the coloring material contained in the resin composition of the present invention substantially does not contain a dye. According to this aspect, a film having excellent light resistance and heat resistance can be formed. “Substantially free of dye” means that the content of dye in the coloring material is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably no dye. .
- chromatic coloring materials include coloring materials having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. Examples thereof include yellow colorant, orange colorant, red colorant, green colorant, purple colorant, and blue colorant.
- the chromatic colorant is preferably a pigment (chromatic pigment), more preferably a red pigment, a yellow pigment, and a blue pigment, and still more preferably a red pigment and a blue pigment. Specific examples of chromatic pigments include those shown below.
- red colorants examples include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, and diketopyrrolopyrrole compounds, anthraquinone compounds, azo It is preferably a compound, more preferably a diketopyrrolopyrrole compound. Also, the red colorant is preferably a pigment.
- red colorant examples include C.I. I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, 297 and other red pigments.
- a red colorant a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, a diketopyrrolopyrrole described in paragraph numbers 0016 to 0022 of Japanese Patent No.
- 10-2019-0140741 anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140744, JP 2020 A perylene compound described in JP-A-079396, a diketopyrrolopyrrole compound described in paragraphs 0025 to 0041 of JP-A-2020-066702, and the like can also be used.
- a red colorant a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton is used.
- C.I. I. Pigment Red 122, 177, 254, 255, 264, 269 and 272 are preferred, C.I. I. Pigment Red 254, 264, 272 are more preferred, and C.I. I. Pigment Red 254, 264 are more preferred.
- green colorants examples include phthalocyanine compounds, squarylium compounds, etc., preferably phthalocyanine compounds, and more preferably phthalocyanine pigments. Also, the green colorant is preferably a pigment.
- green colorants include C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, 66 are included. Further, as a green colorant, a halogenated zinc phthalocyanine having an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 Pigments can also be used. Specific examples include compounds described in International Publication No. 2015/118720. In addition, as a green colorant, the compound described in Chinese Patent Application No.
- 106909027 the phthalocyanine compound having a phosphoric acid ester as a ligand described in WO 2012/102395, described in JP 2019-008014.
- the core-shell type dyes described in can also be used.
- C.I. I. Pigment Green 7, 36, 58, 62 and 63 are preferred, C.I. I. Pigment Greens 36 and 58 are more preferred. Used.
- orange colorants include C.I. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. of orange pigments.
- yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds and perylene compounds.
- Specific examples of the yellow coloring material include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166,
- a nickel azobarbiturate complex having the following structure can also be used.
- X 1 to X 16 each independently represent a hydrogen atom or a halogen atom
- Z 1 represents an alkylene group having 1 to 3 carbon atoms.
- Specific examples of the compound represented by formula (QP1) include compounds described in paragraph 0016 of Japanese Patent No. 6443711.
- Y 1 to Y 3 each independently represent a halogen atom.
- n and m are integers of 0 to 6; p is an integer of 0 to 5; (n+m) is 1 or more.
- Specific examples of the compound represented by formula (QP2) include compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.
- purple coloring materials include C.I. I. Purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61 are included.
- blue colorants include C.I. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc. pigments.
- An aluminum phthalocyanine compound having a phosphorus atom can also be used as the blue colorant.
- Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A-2012-247591 and paragraph number 0047 of JP-A-2011-157478.
- a diarylmethane compound described in JP-T-2020-504758 can also be used as a green colorant or blue colorant.
- the pyrrolopyrrole pigment has a crystallite size of 140 ⁇ or less in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes ( ⁇ 1 ⁇ 1 ⁇ 1) of the crystal lattice planes. is also preferred. Further, the physical properties of the pyrrolopyrrole pigment are preferably set as described in paragraphs 0028 to 0073 of JP-A-2020-097744.
- the pigment it is also preferable to use a halogenated zinc phthalocyanine pigment having a Raman spectrum described in Japanese Patent No. 6744002 from the viewpoint of enhancing spectral characteristics.
- a dioxazine pigment with a controlled contact angle described in WO 2019/107166 from the viewpoint of viscosity adjustment.
- Dyes can also be used for chromatic colorants.
- the dye is not particularly limited, and known dyes can be used.
- a pigment multimer can also be used as a chromatic colorant.
- the dye multimer is preferably a dye that is used by dissolving it in a solvent. Further, the dye multimer may form particles. When the dye multimer is particles, it is usually used in a state of being dispersed in a solvent.
- the particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in JP-A-2015-214682.
- a dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less.
- a plurality of dye structures in one molecule may be the same dye structure or different dye structures.
- the weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000.
- the lower limit is more preferably 3000 or more, and even more preferably 6000 or more.
- the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
- Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016/031442, etc. Compounds can also be used.
- chromatic colorants triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP-A-2020-117638, and International Publication No. 2020/174991.
- the halogenated zinc phthalocyanine pigment described in Patent No. 6809649, JP 2020- Isoindoline compounds described in JP-A-180176 can be used.
- the chromatic colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, may be used in the rod-like structure, or may be used in both structures.
- Two or more chromatic colorants may be used in combination.
- the combination of two or more chromatic colorants may form a black color. Examples of such combinations include the following aspects (1) to (7).
- the resin composition of the present invention forms a near-infrared transmission filter. It can be preferably used as a resin composition for (1) A mode containing a red colorant and a blue colorant. (2) A mode containing a red colorant, a blue colorant, and a yellow colorant.
- a mode containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant is a mode containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.
- a mode containing a red colorant, a blue colorant, a yellow colorant, and a green colorant is a mode containing a red colorant, a blue colorant, and a green colorant.
- a mode containing a red colorant, a blue colorant, and a green colorant is containing a yellow colorant and a purple colorant.
- White colorants include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, Examples include hollow resin particles and inorganic pigments (white pigments) such as zinc sulfide.
- the white pigment is preferably particles containing titanium atoms, more preferably titanium oxide.
- the white pigment is preferably particles having a refractive index of 2.10 or more for light with a wavelength of 589 nm. The aforementioned refractive index is preferably 2.10 to 3.00, more preferably 2.50 to 2.75.
- the white pigment can also use the titanium oxide described in "Titanium Oxide Physical Properties and Application Techniques Manabu Seino, Pages 13-45, June 25, 1991, published by Gihodo Publishing".
- the white pigment is not only made of a single inorganic substance, but also particles combined with other materials may be used. For example, particles having voids or other materials inside, particles having a core particle to which a large number of inorganic particles are attached, and core-shell composite particles consisting of a core particle made of polymer particles and a shell layer made of inorganic nanoparticles are used. is preferred.
- the core and shell composite particles composed of the core particles composed of polymer particles and the shell layer composed of inorganic nanoparticles for example, the description of paragraphs 0012 to 0042 of JP-A-2015-047520 can be referred to, The contents of which are incorporated herein.
- Hollow inorganic particles can also be used as the white pigment.
- a hollow inorganic particle is an inorganic particle having a structure having a cavity inside, and refers to an inorganic particle having a cavity surrounded by an outer shell.
- Examples of hollow inorganic particles include hollow inorganic particles described in JP 2011-075786, WO 2013/061621, JP 2015-164881, etc., the contents of which are incorporated herein. be
- the black colorant is not particularly limited, and known ones can be used.
- inorganic black colorants include inorganic pigments (black pigments) such as carbon black, titanium black, and graphite. Carbon black and titanium black are preferred, and titanium black is more preferred.
- Titanium black is black particles containing titanium atoms, preferably low order titanium oxide or titanium oxynitride. Titanium black can be surface-modified as necessary for the purpose of improving dispersibility, suppressing cohesion, and the like. For example, it is possible to coat the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, treatment with a water-repellent substance as disclosed in Japanese Patent Laid-Open No.
- Titanium black preferably has a small primary particle size and an average primary particle size of individual particles. Specifically, the average primary particle size is preferably 10 to 45 nm. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms and Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50. Regarding the dispersion, the description in paragraphs 0020 to 0105 of JP-A-2012-169556 can be referred to, and the contents thereof are incorporated herein.
- titanium black Commercially available examples include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilac D ( Trade name: manufactured by Ako Kasei Co., Ltd.) and the like.
- organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds.
- bisbenzofuranone compounds include compounds described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, Japanese Patent Application Publication No. 2012-515234, etc.
- "Irgaphor Black” manufactured by BASF Corporation. Available examples of perylene compounds include compounds described in paragraphs 0016 to 0020 of JP-A-2017-226821, C.I. I. Pigment Black 31, 32 and the like.
- the azomethine compound include compounds described in JP-A-01-170601, JP-A-02-034664, and the like.
- the coloring material used in the resin composition of the present invention may be the above-described black coloring material only, or may further contain a chromatic coloring material. According to this aspect, it is easy to obtain a resin composition capable of forming a film having excellent light-shielding properties in the visible region.
- Preferred combinations of black colorants and chromatic colorants include, for example, the following.
- A-1 An embodiment containing an organic black colorant and a blue colorant.
- A-2) An embodiment containing an organic black colorant, a blue colorant and a yellow colorant.
- A-3) An embodiment containing an organic black colorant, a blue colorant, a yellow colorant and a red colorant.
- A-4) An embodiment containing an organic black colorant, a blue colorant, a yellow colorant and a purple colorant.
- the near-infrared absorbing colorant is preferably a compound having a maximum absorption wavelength on the longer wavelength side than the wavelength of 700 nm.
- the infrared absorbing agent is preferably a compound having a maximum absorption wavelength in the range of 700 nm and 1800 nm or less, more preferably a compound having a maximum absorption wavelength in the range of 700 nm and 1400 nm or less.
- a compound having a maximum absorption wavelength in the range of more than 1200 nm or less is more preferable, and a compound having a maximum absorption wavelength in the range of more than 700 nm and 1000 nm or less is particularly preferable.
- the ratio A 1 /A 2 between the absorbance A 1 at a wavelength of 500 nm and the absorbance A 2 at the maximum absorption wavelength of the near-infrared absorbing colorant is preferably 0.08 or less, more preferably 0.04 or less.
- the near-infrared absorbing colorant is preferably a pigment, more preferably an organic pigment.
- Near-infrared absorbing colorants include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, and pyrromethene compounds. , azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, and the like.
- pyrrolopyrrole compound compounds described in paragraph numbers 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph numbers 0037-0052 of JP-A-2011-068731, WO 2015/166873 Compounds described in Paragraph Nos. 0010 to 0033 and the like.
- examples of the squarylium compound include compounds described in paragraph numbers 0044 to 0049 of JP-A-2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese Patent No. 6065169, and paragraph number 0040 of WO 2016/181987.
- cyanine compound compounds described in paragraph numbers 0044 to 0045 of JP-A-2009-108267, compounds described in paragraph numbers 0026-0030 of JP-A-2002-194040, described in JP-A-2015-172004
- Examples of croconium compounds include compounds described in JP-A-2017-082029.
- the iminium compound for example, compounds described in JP-A-2008-528706, compounds described in JP-A-2012-012399, compounds described in JP-A-2007-092060, International Publication No. 2018/043564 and the compounds described in paragraphs 0048 to 0063 of.
- the phthalocyanine compound include compounds described in paragraph number 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraph numbers 0013 to 0029 of JP-A-2013-195480.
- naphthalocyanine compounds include compounds described in paragraph number 0093 of JP-A-2012-077153.
- Dithiolene metal complexes include compounds described in Japanese Patent No. 5733804.
- metal oxides include indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide.
- metal borides include lanthanum boride.
- lanthanum boride products include LaB 6 -F (manufactured by Nippon New Metal Co., Ltd.). Moreover, as a metal boride, the compound as described in international publication 2017/119394 can also be used.
- commercial products of indium tin oxide include F-ITO (manufactured by DOWA Hi-Tech Co., Ltd.).
- the near-infrared absorbing colorant the squarylium compound described in JP-A-2017-197437, the squarylium compound described in JP-A-2017-025311, the squarylium compound described in International Publication No. 2016/154782, the patent Squarylium compounds described in Japanese Patent No. 5884953, squarylium compounds described in Japanese Patent No. 6036689, squarylium compounds described in Japanese Patent No. 5810604, squarylium compounds described in paragraph numbers 0090 to 0107 of International Publication No.
- amide-linked squarylium compounds compounds having a pyrrole bis-type squarylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazole bis-type squarylium compounds described in JP-A-2017-082029, JP-A-2017 -Asymmetric compounds described in paragraphs 0027 to 0114 of JP-A-068120, pyrrole ring-containing compounds (carbazole type) described in JP-A-2017-067963, phthalocyanine compounds described in Japanese Patent No. 6251530, A squarylium compound described in JP-A-2020-075959, a copper complex described in Korean Patent Publication No. 10-2019-0135217, and the like can also be used.
- pigment derivative in the present invention, a pigment derivative can also be used as the coloring material. In the present invention, it is preferable to use a pigment and a pigment derivative together.
- Pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.
- Dye skeletons constituting pigment derivatives include quinoline dye skeletons, benzimidazolone dye skeletons, benzoisoindole dye skeletons, benzothiazole dye skeletons, iminium dye skeletons, squarylium dye skeletons, croconium dye skeletons, oxonol dye skeletons, and pyrrolopyrrole dye skeletons.
- diketopyrrolopyrrole dye skeleton azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, quinacridone dye skeleton, dioxazine dye skeleton, perinone dye skeleton, perylene dye skeleton, thioindigo dye skeleton, Isoindoline dye skeletons, isoindolinone dye skeletons, quinophthalone dye skeletons, iminium dye skeletons, dithiol dye skeletons, triarylmethane dye skeletons, pyrromethene dye skeletons, and the like can be mentioned.
- the acid group includes a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imidic acid group and salts thereof.
- Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ion and the like.
- the carboxylic acid amide group a group represented by —NHCOR X1 is preferable.
- sulfonic acid amide group a group represented by —NHSO 2 R X2 is preferable.
- the imidic acid group is preferably a group represented by —SO 2 NHSO 2 R X3 , —CONHSO 2 R X4 , —CONHCOR X5 or —SO 2 NHCOR X6 , more preferably —SO 2 NHSO 2 R X3 .
- R X1 to R X6 each independently represent an alkyl group or an aryl group.
- the alkyl groups and aryl groups represented by R X1 to R X6 may have substituents.
- the substituent is preferably a halogen atom, more preferably a fluorine atom.
- Basic groups include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups.
- Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
- the pigment derivative include the compounds described in Examples below, the compounds described in JP-A-56-118462, the compounds described in JP-A-63-264674, and JP-A-01-217077.
- Compounds described in, compounds described in JP-A-03-009961, compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, described in JP-A-03-045662 The compound, the compound described in JP-A-04-285669, the compound described in JP-A-06-145546, the compound described in JP-A-06-212088, the compound described in JP-A-06-240158 , the compound described in JP-A-10-030063, the compound described in JP-A-10-195326, the compound described in paragraph numbers 0086 to 0098 of WO 2011/024896, WO 2012/102399
- the content of the coloring material in the total solid content of the resin composition is 55% by mass or more, preferably 57.5% by mass or more, more preferably 60% by mass or more, and 62.5% by mass. It is more preferable that it is above.
- the upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and even more preferably 75% by mass or less.
- the pigment content in the total solid content of the resin composition is preferably 30% by mass or more, more preferably 45% by mass or more, and even more preferably 55% by mass or more.
- the upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and even more preferably 75% by mass or less. According to the resin composition of the present invention, even when the pigment content is high, it is possible to form a film in which color unevenness is suppressed. played.
- the content of the pigment in the colorant is preferably 20-100% by mass, more preferably 50-100% by mass, and even more preferably 70-100% by mass. Further, the total content of the pigment and the pigment derivative in the colorant is preferably 25 to 100% by mass, more preferably 55 to 100% by mass, and further preferably 75 to 100% by mass. preferable.
- the resin composition of the present invention contains a resin (hereinafter referred to as resin).
- resin a resin
- the resin is blended, for example, for dispersing a pigment or the like in a resin composition or for a binder.
- a resin mainly used for dispersing a pigment or the like in a resin composition is also called a dispersant.
- such uses of the resin are only examples, and the resin can be used for purposes other than such uses.
- the resin contained in the resin composition of the present invention is a repeating unit b1-1 having an acid group, a group containing two or more aromatic rings, a group containing a heterocyclic group, and a group containing a condensed ring. and a repeating unit b1-3 other than the repeating unit b1-1 and the repeating unit b1-2 (hereinafter also referred to as a specific resin).
- the specific resin contains a repeating unit b1-1 having an acid group (hereinafter also referred to as repeating unit b1-1).
- the acid group includes a carboxy group, a phosphoric acid group, a sulfo group and a phenolic hydroxy group, preferably a carboxy group.
- the number of acid groups contained in the repeating unit b1-1 may be one, or two or more.
- the number of acid groups contained in the repeating unit b1-1 is preferably 1 to 4, more preferably 1 or 2.
- repeating unit b1-1 examples include repeating units represented by the following formula (bb-1).
- R b1 to R b3 in formula (bb-1) each independently represent a hydrogen atom or an alkyl group.
- the number of carbon atoms in the alkyl group represented by R b1 to R b3 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.
- L b1 in formula (bb-1) represents a single bond or an n1+1-valent linking group. However, when n1 is 2 or more, L b1 is an n1+1-valent linking group.
- the n1+1-valent linking group represented by L b1 includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, —NH—, —SO—, —SO 2 —, —CO—, —O—, —COO—, OCO -, -S-, and groups formed by combining two or more of these.
- the aliphatic hydrocarbon group and aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.
- a b1 in formula (bb-1) represents an acid group.
- the acid group represented by A b1 includes a carboxy group, a phosphoric acid group, a sulfo group and a phenolic hydroxy group, preferably a carboxy group.
- n1 in formula (bb-1) represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2.
- repeating unit b1-1 include repeating units having the structures shown below.
- the content of the repeating unit b1-1 in the specific resin is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, even more preferably 10 to 35% by mass.
- the lower limit is preferably 12% by mass or more, more preferably 14% by mass or more.
- the specific resin is a repeating unit b1-2 (hereinafter also referred to as repeating unit b1-2) having a functional group b selected from a group containing two or more aromatic rings, a group containing a heterocyclic group, and a group containing a condensed ring. include.
- the functional group b of the repeating unit b1-2 is preferably a group containing a ketone structure.
- the functional group b is a group containing a ketone structure, it is possible to form a film with more suppressed color unevenness when a phthalocyanine pigment is used as the colorant.
- the functional group b is preferably a group having 2 to 4 ring structures.
- the number of ring structures contained in the functional group b is preferably 2-3.
- the functional group b is preferably a group containing 2 to 5 heteroatoms.
- the number of heteroatoms contained in the functional group b is preferably 2-4.
- the functional group b is preferably a group having 2 to 4 ring structures and containing 2 to 5 hetero atoms, having 2 to 3 ring structures and hetero Groups containing 2 to 4 atoms are more preferred.
- the functional group b is a group containing a ketone structure, has 2 to 4 ring structures (preferably 2 to 3 ring structures), and has 2 to 5 heteroatoms (preferably 2 to 4) are preferred.
- Functional group b has a naphthalimide structure, an acridone structure, a thioxanthone structure, a xanthone structure, anthrone structure, a benzimidazole structure, a benzothiazole structure, a benzoxazole structure, a benzotriazole structure, a benzoxadiazole structure, a benzothiadiazole structure, a benzothiazine structure, Benzoxazine structure, benzolein urea structure, isothiazolinone structure, phenoxazine structure, phenothiazine structure, dihydroacridine structure, phenoxathiin structure, dibenzopyran structure, fluorene structure, carbazole structure, carboline structure, dibenzothiophene structure, dibenzofuran structure, pyrimidine structure , pyrazine structure, quinazoline structure, quinoxaline structure, quinoline structure, imidazole structure
- naphthalimide structure acridone structure, xanthone structure, anthrone structure, benzimidazole structure, benzothiazole structure, benzoxazole structure, benzotriazole structure, benzoxodiazole structure, benzothiadiazole structure, phenoxazine structure, phenothiazine structure, dihydroacridine structure, phenoxathiin structure, dibenzopyran structure, carbazole structure, carboline structure, dibenzothiophene structure, dibenzofuran structure, pyrimidine structure, pyrazine structure, quinazoline structure, quinoxaline structure, imidazole structure, thiazole structure, indole structure, benzothiophene structure, benzopyran structure, quinolinone structure, thiochromanone structure, chroman structure, phthalimide structure, naphthalene-2,3-dicarboximide structure, pyrazole structure, pyrazolone structure, is
- the functional group b include groups having the structures shown below and groups having a structure in which a substituent is bonded to these groups.
- substituents include the groups exemplified for the substituent T described later.
- * represents a linking hand
- R represents a hydrogen atom or a substituent.
- substituent include the groups exemplified for the substituent T described later.
- Halogen atom e.g., fluorine atom, chlorine atom, bromine atom, iodine atom
- alkyl group preferably alkyl group having 1 to 30 carbon atoms
- alkenyl group preferably alkenyl group having 2 to 30 carbon atoms
- alkynyl group preferably an alkynyl group having 2 to 30 carbon atoms
- an aryl group preferably an aryl group having 6 to 30 carbon atoms
- a heterocyclic group preferably a heterocyclic group having 1 to 30 carbon atoms
- an amino group preferably amino group having 0 to 30 carbon atoms
- alkoxy group preferably alkoxy group having 1 to 30 carbon atoms
- aryloxy group preferably aryloxy group having 6 to 30 carbon atoms
- heterocyclic oxy group preferably carbon 1 to 30 heterocyclic oxy groups
- acyl groups preferably acyl groups having 2 to 30 carbon atoms
- alkoxy group preferably al
- repeating unit b1-2 examples include repeating units represented by the following formula (bb-2).
- R b11 to R b13 in formula (bb-2) each independently represent a hydrogen atom or an alkyl group.
- the number of carbon atoms in the alkyl group represented by R b11 to R b13 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.
- L b11 in formula (bb-2) represents a single bond or a divalent linking group.
- the divalent linking group represented by L b11 includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, —NH—, —SO—, —SO 2 —, —CO—, —O—, —COO—, and OCO -, -S- and groups formed by combinations of two or more thereof.
- the aliphatic hydrocarbon group and aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.
- a b11 in formula (bb-2) represents the above functional group b.
- repeating unit b1-2 include repeating units A-1 to A-57 described later in Examples.
- the content of the repeating unit b1-2 in the specific resin is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, even more preferably 10 to 35% by mass.
- the lower limit is preferably 12% by mass or more, more preferably 14% by mass or more.
- the specific resin contains a repeating unit b1-3 other than the repeating unit b1-1 and the repeating unit b1-2.
- repeating unit b1-3 a repeating unit having a crosslinkable group (hereinafter also referred to as repeating unit b1-3a), a repeating unit having a graft chain (hereinafter also referred to as repeating unit b1-3b), an acid group, crosslinkable and a repeating unit (hereinafter also referred to as repeating unit b1-3c) having a functional group other than the functional group b described above (hereinafter also referred to as other functional group).
- Repeating units b1-3 are also preferably repeating units having a urea structure.
- Examples of the crosslinkable group possessed by the repeating unit b1-3a include an ethylenically unsaturated bond-containing group and a cyclic ether group.
- Examples of ethylenically unsaturated bond-containing groups include vinyl groups, styrene groups, (meth)allyl groups, and (meth)acryloyl groups.
- Examples of the cyclic ether group include an epoxy group and an oxetanyl group, and the epoxy group is preferred.
- the epoxy group may be a cycloaliphatic epoxy group.
- the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
- repeating unit b1-3a examples include repeating units represented by the following formula (bb-3a).
- R b21 to R b23 in formula (bb-3a) each independently represent a hydrogen atom or an alkyl group.
- the number of carbon atoms in the alkyl group represented by R b21 to R b23 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.
- L b21 in formula (bb-3a) represents a single bond or a divalent linking group.
- the divalent linking group represented by L b21 includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, OCO -, -S- and groups formed by combinations of two or more thereof.
- the aliphatic hydrocarbon group and aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.
- a b21 in formula (bb-3a) represents a crosslinkable group.
- repeating unit b1-3a include repeating units having the structures shown below.
- Examples of the graft chain possessed by the repeating unit b1-3b include a graft chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure and a poly(meth)acrylic structure, which further suppresses color unevenness.
- a graft chain having a polyester structure or a polyether structure is preferable, and a graft chain having a polyester structure is more preferable, because a thick film can be formed and the generation of coarse particles can be more effectively suppressed.
- the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
- substituents include alkyl groups, alkoxy groups, alkylthioether groups, and the like. Among them, from the viewpoint of improving the dispersibility of the pigment, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 30 carbon atoms is preferable.
- the alkyl group and alkoxy group may be linear, branched or cyclic, preferably linear or branched.
- a graft chain means a molecular chain branched from the main chain. Moreover, the main chain means a molecular chain having the largest number of branch points.
- the weight average molecular weight of the graft chain is preferably 500 to 30,000, more preferably 1,000 to 20,000, even more preferably 2,000 to 10,000.
- repeating unit b1-3b examples include repeating units represented by the following formula (bb-3b).
- R b31 to R b33 in formula (bb-3b) each independently represent a hydrogen atom or an alkyl group.
- the number of carbon atoms in the alkyl group represented by R b31 to R b33 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1.
- L b31 in formula (bb-3b) represents a single bond or a divalent linking group.
- the divalent linking group represented by L b31 includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, —NH—, —SO—, —SO 2 —, —CO—, —O—, —COO—, and OCO. -, -S- and groups formed by combinations of two or more thereof.
- the aliphatic hydrocarbon group and aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.
- a b31 in formula (bb-3b) represents a graft chain.
- the graft chain represented by A b31 is preferably a graft chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure and a poly(meth)acrylic structure, and is a graft chain of a polyester structure or a polyether structure. is more preferable.
- the preferred range of the graft chain is the same as described above.
- repeating unit b1-3b include repeating units having the structures shown below.
- Examples of other functional groups possessed by the repeating unit b1-3c include an alkyl group, a phenyl group, an amino group, a hydroxy group, and a cyano group.
- repeating unit b1-3c examples include repeating units represented by the following formula (bb-3c).
- R b41 to R b43 in formula (bb-3c) each independently represent a hydrogen atom or an alkyl group.
- the number of carbon atoms in the alkyl group represented by R b41 to R b43 is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1.
- L b41 in formula (bb-3c) represents a single bond or a divalent linking group.
- the divalent linking group represented by L b41 includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, OCO -, -S- and groups formed by combinations of two or more thereof.
- the aliphatic hydrocarbon group and aromatic hydrocarbon group may have a substituent. A hydroxy group, a halogen atom, etc. are mentioned as a substituent.
- a b41 in formula (bb-3c) represents another functional group.
- Other functional groups include alkyl groups, phenyl groups, amino groups, hydroxy groups, cyano groups and the like.
- repeating unit b1-3c include repeating units having the structures shown below.
- repeating unit b1-3 include repeating units F-1 to F-7 described in Examples described later.
- the specific resin may contain only one type of repeating unit b1-3, or may contain two or more types.
- the repeating unit b1-3 includes a repeating unit having a graft chain (repeating unit b1-3b). According to this aspect, it is possible to form a film in which color unevenness is further suppressed. Furthermore, generation of coarse particles can be suppressed, and the stability of the resin composition over time can be improved.
- the repeating unit b1-3b is preferably a repeating unit having a graft chain of a polyester structure or a polyether structure, more preferably a repeating unit having a graft chain of a polyester structure.
- the specific resin is an embodiment in which the repeating unit b1-3 does not contain a repeating unit having a graft chain (repeating unit b1-3b).
- This aspect also makes it possible to form a film in which color unevenness is further suppressed. Furthermore, generation of coarse particles can be suppressed, and the stability of the resin composition over time can be improved.
- the content of the repeating unit b1-3 in the specific resin is preferably 10-85% by mass.
- the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.
- the lower limit is preferably 15% by mass or more, more preferably 20% by mass or more.
- the content of the repeating unit b1-3a in the specific resin is 1 to 30% by mass. is preferred.
- the upper limit is preferably 25% by mass or less, more preferably 15% by mass or less.
- the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.
- the content of the repeating unit b1-3b in the specific resin is 1 to 80% by mass. is preferred.
- the upper limit is preferably 70% by mass or less, more preferably 60% by mass or less.
- the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.
- the content of the repeating unit b1-3c in the specific resin is 1 to 80% by mass. is preferred.
- the upper limit is preferably 70% by mass or less, more preferably 60% by mass or less.
- the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.
- Specific examples of specific resins include resins P1 to P188, PP1, PP2, and PP101 to PP136 shown in Examples described later.
- the acid value of the specific resin is preferably 10-250 mgKOH/g.
- the upper limit is preferably 220 mgKOH/g or less, more preferably 200 mgKOH/g or less.
- the lower limit is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more.
- the weight average molecular weight of the specific resin is preferably 1,000 to 100,000.
- the lower limit is preferably 2000 or more, more preferably 4000 or more.
- the upper limit is preferably 60,000 or less, more preferably 40,000 or less. If the weight average molecular weight of the specific resin is within the above range, it is possible to form a film with more suppressed color unevenness. Furthermore, the stability over time of the resin composition can be further improved. Furthermore, when the pattern is formed by photolithography, the generation of development residue can be more effectively suppressed.
- the specific absorbance represented by the following formula (A ⁇ ) of the specific resin is preferably 3 or less, more preferably 2 or less, and even more preferably 1 or less.
- E A/(c ⁇ l ) (A ⁇ )
- A represents the absorbance of the specific resin at the maximum absorption wavelength at a wavelength of 400 to 800 nm
- l represents the cell length in cm
- c represents the concentration of the particular resin in solution, expressed in units of mg/ml.
- the amount of crosslinkable groups in the specific resin is preferably 0.01 to 2.5 mmol/g.
- the lower limit is preferably 0.2 mmol/g or more, more preferably 0.5 mmol/g or more.
- the upper limit is preferably 2 mmol/g or less, more preferably 1.5 mmol/g or less.
- the crosslinkable group amount of the specific resin is a numerical value representing the molar amount of the crosslinkable group per 1 g of the solid content of the specific resin.
- the resin composition of the present invention can contain a resin different from the specific resin described above (hereinafter also referred to as other resin).
- Examples of other resins include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, Examples include polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins. Further, as the resin, the resin described in the examples of International Publication No.
- the weight average molecular weight (Mw) of other resins is preferably 3,000 to 2,000,000.
- the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
- the lower limit is preferably 4000 or more, more preferably 5000 or more.
- the other resin it is preferable to use a resin having an acid group.
- acid groups include carboxy groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups.
- the type of acid group possessed by the other resin may be the same as the acid group possessed by the specific resin described above, or may be different.
- the other resin should contain a resin having an acid group with a pKa lower than that of the specific resin (hereinafter also referred to as resin X). is preferred.
- the difference between the pKa of the acid group of the specific resin and the pKa of the acid group of the resin X is preferably 1.0 or more, and preferably 1.5. It is more preferably 2.0 or more, and even more preferably 2.0 or more.
- the acid group of the specific resin is a carboxy group
- the acid group of the resin X is a sulfo group or a phosphoric acid group (preferably phosphoric acid group). acid group).
- the acid value of the resin having acid groups is preferably 30-500 mgKOH/g.
- the lower limit is more preferably 40 mgKOH/g or more, particularly preferably 50 mgKOH/g or more.
- the upper limit is more preferably 400 mgKOH/g or less, still more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less.
- the weight average molecular weight (Mw) of the acid group-containing resin is preferably 5,000 to 100,000, more preferably 5,000 to 50,000.
- the number average molecular weight (Mn) of the resin having an acid group is preferably 1,000 to 20,000.
- the resin having an acid group preferably contains a repeating unit having an acid group on its side chain, and more preferably contains 5 to 70 mol % of repeating units having an acid group on its side chain in all repeating units of the resin.
- the upper limit of the content of repeating units having an acid group in a side chain is preferably 50 mol % or less, more preferably 30 mol % or less.
- the lower limit of the content of repeating units having an acid group in the side chain is preferably 10 mol % or more, more preferably 20 mol % or more.
- resins having basic groups can also be used.
- the resin having a basic group is preferably a resin containing a repeating unit having a basic group in its side chain. It is more preferably a polymer, and more preferably a block copolymer having a repeating unit having a basic group on its side chain and a repeating unit containing no basic group. Resins having basic groups can also be used as dispersants.
- the amine value of the resin having basic groups is preferably 5-300 mgKOH/g.
- the lower limit is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more.
- the upper limit is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less.
- resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (manufactured by BYK-Chemie), Solsperse 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 3309, 50500, 390500, 390500 56000, 7100 (manufactured by Nippon Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (manufactured by BASF) and the like.
- the resin having a basic group is a block copolymer (B) described in paragraph numbers 0063 to 0112 of JP-A-2014-219665, and described in paragraph numbers 0046-0076 of JP-A-2018-156021. It is also possible to use the block copolymer A1 described above and vinyl resins having basic groups described in paragraphs 0150 to 0153 of JP-A-2019-184763, the contents of which are incorporated herein.
- the other resins it is also preferable to use a resin having an acid group and a resin having a basic group. According to this aspect, the stability over time of the resin composition can be further improved.
- the content of the resin having a basic group is 20 to 500 parts by mass with respect to 100 parts by mass of the resin having an acid group. It is preferably from 30 to 300 parts by mass, and even more preferably from 50 to 200 parts by mass.
- resins include a monomer component containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimers"). It is also preferable to use a resin containing a repeating unit derived from.
- R 1 and R 2 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
- R 1 represents a hydrogen atom or a methyl group
- R 21 and R 22 each independently represent an alkylene group
- n represents an integer of 0-15.
- the number of carbon atoms in the alkylene group represented by R 21 and R 22 is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly 2 or 3.
- n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.
- Examples of the compound represented by formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of paracumylphenol.
- Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
- Crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.
- ethylenically unsaturated bond-containing groups include vinyl groups, styrene groups, (meth)allyl groups, and (meth)acryloyl groups.
- the cyclic ether group include an epoxy group and an oxetanyl group, and the epoxy group is preferred.
- the epoxy group may be a cycloaliphatic epoxy group.
- the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
- resin Ac a resin having an aromatic carboxy group
- the aromatic carboxy group may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit.
- the aromatic carboxy group is preferably contained in the main chain of the repeating unit.
- an aromatic carboxy group is a group having a structure in which one or more carboxy groups are bonded to an aromatic ring.
- the number of carboxy groups bonded to the aromatic ring is preferably 1-4, more preferably 1-2.
- Resin Ac is preferably a resin containing at least one repeating unit selected from repeating units represented by formula (Ac-1) and repeating units represented by formula (Ac-2).
- Ar 1 represents a group containing an aromatic carboxyl group
- L 1 represents -COO- or -CONH-
- L 2 represents a divalent linking group
- Ar 10 represents a group containing an aromatic carboxyl group
- L 11 represents -COO- or -CONH-
- L 12 represents a trivalent linking group
- P 10 represents a polymer represents a chain.
- aromatic carboxy group-containing group represented by Ar 1 in formula (Ac-1) examples include structures derived from aromatic tricarboxylic acid anhydrides, structures derived from aromatic tetracarboxylic acid anhydrides, and the like.
- Aromatic tricarboxylic anhydrides and aromatic tetracarboxylic anhydrides include compounds having the following structures.
- Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, represented by the following formula (Q-1) or a group represented by the following formula (Q-2).
- the group containing an aromatic carboxyl group represented by Ar 1 may have a crosslinkable group.
- the crosslinkable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, more preferably an ethylenically unsaturated bond-containing group.
- Specific examples of the group containing an aromatic carboxyl group represented by Ar 1 include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13). and the like.
- n1 represents an integer of 1 to 4, preferably 1 or 2, more preferably 2.
- n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 2.
- n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, preferably 1 More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
- Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, the above formula (Q- 1) or a group represented by the above formula (Q-2).
- * 1 represents the bonding position with L1.
- L 1 represents -COO- or -CONH-, preferably -COO-.
- the divalent linking group represented by L 2 in formula (Ac-1) includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and these A group obtained by combining two or more of
- the number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, and even more preferably 1-15.
- the alkylene group may be linear, branched or cyclic.
- the arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- An alkylene group and an arylene group may have a substituent. A hydroxy group etc.
- the divalent linking group represented by L 2 is preferably a group represented by -L 2a -O-.
- L 2a is an alkylene group; an arylene group; a group in which an alkylene group and an arylene group are combined; at least one selected from an alkylene group and an arylene group; Examples include groups in which at least one selected from —NH— and —S— are combined, and alkylene groups are preferred.
- the number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, and even more preferably 1-15.
- the alkylene group may be linear, branched or cyclic. An alkylene group and an arylene group may have a substituent. A hydroxy group etc. are mentioned as a substituent.
- the group containing an aromatic carboxyl group represented by Ar 10 in formula (Ac-2) has the same meaning as Ar 1 in formula (Ac-1), and the preferred range is also the same.
- L 11 represents -COO- or -CONH-, preferably -COO-.
- the trivalent linking group represented by L 12 in formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and 2 of these Groups in which more than one species are combined are included.
- Hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-15.
- the aliphatic hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, even more preferably 6-10.
- the hydrocarbon group may have a substituent. A hydroxy group etc. are mentioned as a substituent.
- the trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), more preferably a group represented by formula (L12-2).
- L 12b represents a trivalent linking group
- X 1 represents S
- *1 represents the bonding position with L 11 of formula (Ac-2)
- *2 represents formula ( The binding position of Ac- 2 ) with P10 is shown.
- the trivalent linking group represented by L 12b includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- is preferably a hydrocarbon group or a group of a combination of a hydrocarbon group and —O—.
- L 12c represents a trivalent linking group
- X 1 represents S
- *1 represents the bonding position with L 11 of formula (Ac-2)
- *2 represents formula ( The binding position of Ac- 2 ) with P10 is shown.
- the trivalent linking group represented by L 12c includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- and the like, preferably a hydrocarbon group.
- P 10 in formula (Ac-2) represents a polymer chain.
- the polymer chain represented by P10 preferably has at least one structure selected from polyester structure, polyether structure, polystyrene structure and poly(meth)acrylic structure.
- the weight average molecular weight of the polymer chain P10 is preferably 500-20,000 .
- the lower limit is preferably 1000 or more.
- the upper limit is preferably 10,000 or less, more preferably 5,000 or less, even more preferably 3,000 or less. If the weight average molecular weight of P10 is within the above range, the dispersibility of the pigment in the composition is good.
- the resin having an aromatic carboxyl group is a resin having repeating units represented by formula (Ac-2), this resin is preferably used as a dispersant.
- the polymer chain represented by P10 may contain crosslinkable groups.
- Crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.
- the other resin it is preferable to use at least one selected from graft polymers, star polymers, block copolymers, and resins in which at least one end of the polymer chain is blocked with an acid group.
- Such resins are preferably used as dispersants.
- Examples of the graft polymer include a resin having a repeating unit having a graft chain and a resin having a repeating unit represented by the above formula (Ac-2).
- Examples of graft chains include graft chains containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure and a poly(meth)acrylic structure.
- the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of substituents include alkyl groups, alkoxy groups, alkylthioether groups, and the like.
- a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 30 carbon atoms is preferable.
- the alkyl group and alkoxy group may be linear, branched or cyclic, preferably linear or branched.
- graft polymer examples include paragraph numbers 0025 to 0094 of JP-A-2012-255128, paragraph numbers 0022-0097 of JP-A-2009-203462, and paragraph numbers 0102-0166 of JP-A-2012-255128. Mention may be made of the resins mentioned.
- Star-shaped polymers include resins with a structure in which multiple polymer chains are bonded to the core.
- Specific examples of the star polymer include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.
- Block copolymers include a polymer block having a repeating unit containing an acid group or a basic group (hereinafter also referred to as block A) and a polymer block having a repeating unit containing no acid group or basic group. (hereinafter also referred to as block B).
- Block copolymers include block copolymers (B) described in paragraph numbers 0063 to 0112 of JP-A-2014-219665, and blocks described in paragraph numbers 0046-0076 of JP-A-2018-156021. Copolymer A1 can also be used, the contents of which are incorporated herein.
- At least one end of the polymer chain containing at least one structure selected from a polyester structure, a polyether structure and a poly(meth)acrylic structure is A resin having a structure sealed with an acid group can be mentioned.
- a carboxy group, a sulfo group, and a phosphoric acid group are examples of the acid group that seals the end of the polymer chain.
- Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins).
- the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups.
- the acidic dispersant (acidic resin) a resin having an acid group content of 70 mol % or more is preferable when the total amount of the acid group and the basic group is 100 mol %.
- the acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group.
- the acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g.
- a basic dispersant represents a resin in which the amount of basic groups is greater than the amount of acid groups.
- a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and basic groups is 100 mol %.
- the basic group possessed by the basic dispersant is preferably an amino group.
- Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine Techno Co., Ltd. Ajisper series, A208F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), H-3606 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Sandet ET (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
- the product described in paragraph number 0129 of JP-A-2012-137564 and the product described in paragraph number 0235 of JP-A-2017-194662 can also be used as a dispersant.
- the resin content in the total solid content of the resin composition is preferably 1 to 50% by mass.
- the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
- the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
- the content of the specific resin in the total solid content of the resin composition is preferably 1 to 50% by mass.
- the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
- the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
- the content of the specific resin in the resin contained in the resin composition is preferably 10-100% by mass, more preferably 25-100% by mass, and even more preferably 45-100% by mass.
- the resin composition of the present invention may contain only one type of resin, or may contain two or more types. When two or more resins are included, the total amount thereof is preferably within the above range.
- the resin composition of the present invention preferably contains a polymerizable compound.
- the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group.
- ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.
- the polymerizable compound used in the present invention is preferably a radically polymerizable compound.
- the polymerizable compound may be in any chemical form such as monomer, prepolymer, oligomer, etc., but monomer is preferred.
- the molecular weight of the polymerizable compound is preferably 100-2500.
- the upper limit is preferably 2000 or less, more preferably 1500 or less.
- the lower limit is preferably 150 or more, more preferably 250 or more.
- the lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and even more preferably 5 mmol/g or more.
- the upper limit is preferably 12 mmol/g or less, more preferably 10 mmol/g or less, and even more preferably 8 mmol/g or less.
- the polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 4 or more ethylenically unsaturated bond-containing groups.
- the upper limit of the ethylenically unsaturated bond-containing groups is preferably 15 or less, more preferably 10 or less, even more preferably 6 or less, from the viewpoint of the stability of the resin composition over time.
- the polymerizable compound is preferably a tri- or more functional (meth) acrylate compound, more preferably a 3- to 15-functional (meth) acrylate compound, and a 3- to 10-functional (meth) acrylate compound.
- the polymerizable compound include paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph numbers 0254-0257 of JP-A-2008-292970, and JP-A-2008-292970. 2013-253224, paragraphs 0034 to 0038, JP 2012-208494, paragraph 0477, JP 2017-048367, JP 6057891, the compound described in JP 6031807 , the contents of which are incorporated herein.
- polymerizable compounds examples include dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and modified products of these compounds. mentioned.
- Modified compounds include compounds having a structure in which the (meth)acryloyl groups of the above compounds are bonded via an alkyleneoxy group, such as ethoxylated dipentaerythritol hexa(meth)acrylate. Specific examples include compounds represented by formula (Z-4) and compounds represented by formula (Z-5).
- E is each independently -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)- , each y independently represents an integer of 0 to 10, and each X independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxy group.
- the total number of (meth)acryloyl groups is 3 or 4
- each m independently represents an integer of 0 to 10
- the sum of m is an integer of 0 to 40.
- the total number of (meth)acryloyl groups is 5 or 6
- each n independently represents an integer of 0-10, and the sum of each n is an integer of 0-60.
- m is preferably an integer of 0-6, more preferably an integer of 0-4.
- the sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
- n is preferably an integer of 0-6, more preferably an integer of 0-4.
- the sum of n is preferably an integer of 3-60, more preferably an integer of 3-24, and particularly preferably an integer of 6-12.
- E in formula (Z-4) or formula (Z-5), that is, -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)- is A form in which the end on the oxygen atom side is bonded to X is preferred.
- Polypentaerythritol poly(meth)acrylate represented by the following formula (Z-6) can also be used as the polymerizable compound.
- X 1 to X 6 each independently represent a hydrogen atom or a (meth)acryloyl group, and n represents an integer of 1-10. However, at least one of X 1 to X 6 is a (meth)acryloyl group.
- the polymerizable compound used in the present invention is at least one selected from the group consisting of dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol poly(meth)acrylate and modified products thereof. Seeds are preferred.
- Commercially available products include KAYARAD D-310, DPHA, DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.), NK Ester A-DPH-12E, TPOA-50 (manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. mentioned.
- diglycerin EO ethylene oxide modified (meth) acrylate
- pentaerythritol tetra (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-TMMT
- 1,6-hexanediol diacrylate manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA
- RP-1040 manufactured by Nippon Kayaku Co., Ltd.
- Aronix TO-2349 Toagosei Co., Ltd.
- NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), Light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL80 (manufactured by Daicel Allnex, amine-containing tetrafunctional acrylate) and the like can also be used.
- trimethylolpropane tri(meth)acrylate trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, isocyanuric acid ethylene oxide-modified tri(meth)acrylate
- trifunctional (meth)acrylate compounds such as pentaerythritol tri(meth)acrylate.
- Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305.
- M-303, M-452, M-450 manufactured by Toagosei Co., Ltd.
- a compound having an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group can be used as the polymerizable compound.
- Commercially available products of such compounds include Aronix M-305, M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
- a compound having a caprolactone structure can also be used as the polymerizable compound.
- the descriptions in paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, the contents of which are incorporated herein.
- Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd.
- a polymerizable compound having a fluorene skeleton can also be used.
- Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).
- the polymerizable compound it is also preferable to use a compound such as toluene that does not substantially contain environmentally regulated substances.
- a compound such as toluene that does not substantially contain environmentally regulated substances.
- Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
- urethane acrylates such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765
- urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418.
- the polymerizable compound includes UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, Commercially available products such as T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.
- the content of the polymerizable compound in the total solid content of the resin composition is preferably 1 to 35% by mass.
- the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
- the lower limit is preferably 2% by mass or more, more preferably 5% by mass or more.
- the resin composition of the present invention may contain only one polymerizable compound, or may contain two or more polymerizable compounds. When two or more polymerizable compounds are included, the total amount thereof is preferably within the above range.
- the resin composition of the present invention can contain a photopolymerization initiator.
- the resin composition of the present invention preferably further contains a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet region to the visible region are preferred.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
- halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
- acylphosphine compounds e.g., acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
- photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbi imidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl-substituted coumarin compounds, oxime compounds, ⁇ -hydroxyketones compounds, ⁇ -aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds.
- hexaarylbiimidazole compounds include 2,2′,4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1′-biimidazole, etc. are mentioned.
- ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above company) and the like.
- ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by Irgacure 369E, Irgacure 379EG). made), etc.
- acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).
- Examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No.
- oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O
- Photopolymerization initiator 2 described in JP-A-2012-014052 manufactured by ADEKA.
- the oxime compound it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration.
- Commercially available products include ADEKA Arkles NCI-730, NCI-831 and NCI-930 (manufactured by ADEKA Corporation).
- An oxime compound having a fluorene ring can also be used as the photopolymerization initiator.
- Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466, compounds described in Japanese Patent No. 6636081, and compounds described in Korean Patent Publication No. 10-2016-0109444. mentioned.
- an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
- Specific examples of such oxime compounds include compounds described in WO2013/083505.
- An oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
- Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of.
- An oxime compound having a nitro group can be used as the photopolymerization initiator.
- the oxime compound having a nitro group is also preferably a dimer.
- Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.
- An oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator.
- Specific examples include OE-01 to OE-75 described in WO 2015/036910.
- an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton can also be used.
- Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
- an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used.
- the electron-withdrawing group possessed by the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
- An acyl group and a nitro group are preferred, an acyl group is more preferred, and a benzoyl group is even more preferred.
- a benzoyl group may have a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclicoxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group. A sulfanyl group or an amino group is more preferred.
- the oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
- R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group
- R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group
- the electron-withdrawing group includes an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group, preferably an acyl group and a nitro group. is more preferably a group, more preferably a benzoyl group.
- R X12 is an electron-withdrawing group
- R X10 , R X11 , R X13 and R X14 are preferably hydrogen atoms.
- oxime compound OX examples include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.
- oxime compounds preferably used in the present invention are shown below, but the present invention is not limited to these.
- the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
- the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300000, even more preferably 2000 to 300000, even more preferably 5000 to 200000, from the viewpoint of sensitivity. It is particularly preferred to have
- the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
- the photopolymerization initiator it is also preferable to use a combination of Irgacure OXE01 (manufactured by BASF) and/or Irgacure OXE02 (manufactured by BASF) and Omnirad 2959 (manufactured by IGM Resins B.V.).
- a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photopolymerization initiator.
- a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained.
- the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the stability over time of the resin composition can be improved.
- Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
- the content of the photopolymerization initiator in the total solid content of the resin composition is preferably 0.1 to 30% by mass.
- the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
- the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
- only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
- the resin composition of the present invention preferably contains a solvent.
- An organic solvent is mentioned as a solvent.
- the type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition.
- organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.
- Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used.
- organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N
- aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be better reduced for environmental reasons (for example, 50 mass ppm (parts per million), 10 mass ppm or less, or 1 mass ppm or less).
- an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content.
- the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015). .
- Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
- the filter pore size of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
- the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
- the organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers may be contained.
- the content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.
- the content of the solvent in the resin composition is preferably 10-95% by mass, more preferably 20-90% by mass, and even more preferably 30-90% by mass.
- the resin composition of the present invention does not substantially contain environmentally regulated substances from the viewpoint of environmental regulations.
- substantially free of environmental regulation substances means that the content of environmental regulation substances in the resin composition is 50 mass ppm or less, preferably 30 mass ppm or less. , is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less.
- Environmental control substances include, for example, benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
- distillation methods are at the stage of raw materials, the stage of products obtained by reacting raw materials (for example, resin solution or polyfunctional monomer solution after polymerization), or the stage of resin compositions prepared by mixing these compounds. It is possible at any stage such as
- the resin composition of the present invention can contain a thermosetting agent as a component other than the resin and polymerizable compound described above.
- a heat curing agent includes a compound having a cyclic ether group. Cyclic ether groups include epoxy groups and oxetanyl groups.
- the epoxy group may be a cycloaliphatic epoxy group.
- the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
- the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound).
- Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred.
- the epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule.
- the upper limit of the number of epoxy groups contained in the epoxy compound may be, for example, 10 or less, or 5 or less.
- the lower limit of the number of epoxy groups contained in the epoxy compound is preferably two or more.
- As the epoxy compound paragraph numbers 0034 to 0036 of JP-A-2013-011869, paragraph numbers 0147-0156 of JP-A-2014-043556, paragraph numbers 0085-0092 of JP-A-2014-089408.
- Compounds, compounds described in JP-A-2017-179172 can also be used. The contents of these are incorporated herein.
- the compound having a cyclic ether group may be a low-molecular compound (e.g., molecular weight less than 2000, further molecular weight less than 1000), or a macromolecular compound (e.g., molecular weight 1000 or more, weight-average molecular weight in the case of polymer is 1000 or more).
- the weight average molecular weight of the compound having a cyclic ether group is preferably 200-100,000, more preferably 500-50,000.
- the upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5,000 or less, and even more preferably 3,000 or less.
- Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (these are epoxy group-containing polymers manufactured by NOF Corporation) and the like. Further, as the compound having a cyclic ether group, the compounds described in Examples described later can also be used.
- the content of the thermosetting agent in the total solid content of the resin composition is preferably 0.1 to 20% by mass.
- the lower limit is, for example, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
- the upper limit is, for example, more preferably 15% by mass or less, and even more preferably 10% by mass or less. Only one type of thermosetting agent may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
- the resin composition of the present invention can also contain a polyalkyleneimine.
- Polyalkyleneimines are used, for example, as dispersing aids for pigments.
- a dispersing aid is a material for enhancing the dispersibility of a coloring material such as a pigment in a resin composition.
- Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine.
- the polyalkyleneimine is preferably a polymer having a branched structure each containing a primary amino group, a secondary amino group and a tertiary amino group.
- the number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2.
- the molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more.
- the upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less.
- the molecular weight of the polyalkyleneimine when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula.
- the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used.
- the value of the number average molecular weight measured by the viscosity method is used.
- the value of the number average molecular weight in terms of polystyrene measured by the GPC (gel permeation chromatography) method is used.
- the amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
- alkyleneimine examples include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine and the like, preferably ethyleneimine or propyleneimine, more preferably ethyleneimine. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. In addition, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more, of the primary amino group with respect to the total of the primary amino group, the secondary amino group and the tertiary amino group. , more preferably 30 mol % or more.
- Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, P-1000 (manufactured by Nippon Shokubai Co., Ltd.).
- the content of polyalkyleneimine in the total solid content of the resin composition is preferably 0.1 to 5% by mass.
- the lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
- the upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
- the content of the polyalkyleneimine is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the pigment.
- the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more.
- the upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. Only one kind of polyalkyleneimine may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
- the resin composition of the present invention may contain a curing accelerator.
- Curing accelerators include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds and the like.
- the curing accelerator include compounds described in paragraph numbers 0094 to 0097 of WO 2018/056189, compounds described in paragraph numbers 0246 to 0253 of JP 2015-034963, JP 2013-041165 Compounds described in paragraphs 0186 to 0251 of the publication, ionic compounds described in JP 2014-055114, compounds described in paragraphs 0071 to 0080 of JP 2012-150180, JP 2011-253054 Alkoxysilane compounds having an epoxy group described in JP-A-2005-200557, compounds described in paragraphs 0085 to 0092 of Japanese Patent No. 5765059, and carboxy group-containing epoxy curing agents described in JP-A-2017-036379.
- the content of the curing accelerator in the total solid content of the resin composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
- the resin composition of the present invention can contain an ultraviolet absorber.
- ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, and paragraph numbers 0317-0317 of JP-A-2013-068814.
- UV absorber examples include compounds having the following structures.
- examples of commercially available UV absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.), Tinuvin series and Uvinul series manufactured by BASF, and Sumisorb series manufactured by Sumika Chemtex Co., Ltd. .
- Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016).
- the ultraviolet absorber is a compound described in paragraph numbers 0049 to 0059 of Japanese Patent No.
- the content of the ultraviolet absorber in the total solid content of the resin composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass.
- only one ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used.
- the total amount is preferably within the above range.
- the resin composition of the present invention can contain a polymerization inhibitor.
- Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred.
- the content of the polymerization inhibitor in the total solid content of the resin composition is preferably 0.0001 to 5% by mass. Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.
- the resin composition of the present invention can contain a silane coupling agent.
- a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
- the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
- Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
- Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group and isocyanate group. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferred.
- silane coupling agent examples include N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N- ⁇ -aminoethyl- ⁇ -amino propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), ⁇ -aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM
- silane coupling agent examples include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. , the contents of which are incorporated herein.
- the content of the silane coupling agent in the total solid content of the resin composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass. Only one kind of silane coupling agent may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount is preferably within the above range.
- the resin composition of the present invention can contain a surfactant.
- a surfactant various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants can be used.
- the surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant.
- surfactants reference can be made to surfactants described in paragraphs 0238-0245 of WO2015/166779, the contents of which are incorporated herein.
- the fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass.
- a fluorosurfactant having a fluorine content within this range is effective in uniformity of the thickness of the coating film and liquid saving, and has good solubility in the resin composition.
- JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-132503 and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein.
- Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 and F-144.
- the fluorosurfactant has a molecular structure with a functional group containing a fluorine atom, and an acrylic compound in which the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied is also suitable.
- fluorine-based surfactants include MegaFac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Mega Fac DS-21.
- fluorosurfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant.
- fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.
- a block polymer can also be used as the fluorosurfactant.
- the fluorosurfactant has 2 or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) (meta).
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
- the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
- the weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol%.
- a fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used as the fluorosurfactant.
- Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, MEGAFACE RS-101, RS-102 and RS-718K manufactured by DIC Corporation, and RS-72-K.
- compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
- a fluorine-containing imide salt compound represented by formula (fi-1) is also preferable to use as a surfactant.
- m represents 1 or 2
- n represents an integer of 1 to 4
- a represents 1 or 2
- X a+ is a valent metal ion, primary ammonium ion, Represents secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH 4 + .
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fuji
- Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) , BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by BYK-Chemie) and the like.
- a compound having the following structure can also be used as the silicone-based surfactant.
- the content of the surfactant in the total solid content of the resin composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.
- the resin composition of the present invention can contain an antioxidant.
- Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred.
- the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
- Phosphorus-based antioxidants can also be suitably used as antioxidants.
- a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
- antioxidants examples include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like.
- antioxidants are compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, compounds described in WO 2017/164024, Compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used.
- the content of the antioxidant in the total solid content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, the total amount is preferably within the above range.
- the resin composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are described, for example, from paragraph number 0183 of JP-A-2012-003225 (paragraph number 0237 of corresponding US Patent Application Publication No. 2013/0034812), paragraph of JP-A-2008-250074 The descriptions of numbers 0101 to 0104, 0107 to 0109, etc.
- auxiliaries e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.
- the resin composition of the present invention may contain a latent antioxidant, if necessary.
- the latent antioxidant is a compound in which the site functioning as an antioxidant is protected by a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst.
- a compound that functions as an antioxidant by removing the protecting group by the reaction is exemplified.
- Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
- Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
- the resin composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film.
- metal oxides include TiO 2 , ZrO 2 , Al 2 O 3 and SiO 2 .
- the primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, even more preferably 5 to 50 nm.
- Metal oxides may have a core-shell structure. Moreover, in this case, the core portion may be hollow.
- the resin composition of the present invention may contain a light resistance improver.
- a light resistance improver compounds described in paragraph numbers 0036 to 0037 of JP-A-2017-198787, compounds described in paragraph numbers 0029-0034 of JP-A-2017-146350, JP-A-2017-129774 Compounds described in paragraph numbers 0036 to 0037, 0049 to 0052 of JP 2017-129674 JP 2017-129674 paragraph numbers 0031 to 0034, 0058 to 0059 compounds described in JP 2017-122803 paragraph numbers 0036 to 0037 , compounds described in 0051 to 0054, compounds described in paragraph numbers 0025 to 0039 of WO 2017/164127, compounds described in paragraph numbers 0034 to 0047 of JP 2017-186546, JP 2015-025116 Compounds described in paragraph numbers 0019 to 0041 of JP-A-2012-145604, compounds described in paragraph numbers 0101-0125 of JP-A-2012-103475, compounds
- the resin composition of the present invention preferably does not substantially contain terephthalic acid ester.
- substantially free means that the content of the terephthalic acid ester is 1000 mass ppb or less, more preferably 100 mass ppb or less, in the total amount of the resin composition. Zero is particularly preferred.
- perfluoroalkylsulfonic acid and its salts may be regulated.
- perfluoroalkylsulfonic acid especially perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
- perfluoroalkylsulfonic acid especially perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
- the content of fluoroalkylcarboxylic acid (especially perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is 0.01ppb to 1,000ppb with respect to the total solid content of the resin composition.
- the resin composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts.
- a compound that can substitute for perfluoroalkylsulfonic acid and its salt and a compound that can substitute for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and salts thereof may be selected.
- Examples of compounds that can substitute for regulated compounds include compounds that are excluded from the scope of regulation due to differences in the number of carbon atoms in perfluoroalkyl groups. However, the above content does not prevent the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts.
- the resin composition of the present invention may contain perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts within the maximum permissible range.
- the water content of the resin composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, more preferably 0.1 to 1.0% by mass.
- the water content can be measured by the Karl Fischer method.
- the resin composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (flatness, etc.) and adjusting the film thickness.
- the viscosity value can be appropriately selected as necessary, and is preferably, for example, 0.3 mPa ⁇ s to 50 mPa ⁇ s, more preferably 0.5 mPa ⁇ s to 20 mPa ⁇ s at 25°C.
- a method for measuring the viscosity for example, a cone-plate type viscometer can be used, and the viscosity can be measured in a state where the temperature is adjusted to 25°C.
- the storage container for the resin composition is not particularly limited, and known storage containers can be used.
- a storage container for the purpose of suppressing the contamination of raw materials and resin compositions, a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resin, and a bottle with a 7-layer structure of 6 types of resin It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351.
- the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the stability of the resin composition over time, and suppressing deterioration of components.
- the resin composition of the present invention can be prepared by mixing the aforementioned components. In preparing the resin composition, all components may be dissolved and/or dispersed in a solvent at the same time to prepare the resin composition, or if necessary, each component may be appropriately prepared as two or more solutions or dispersions. , these may be mixed at the time of use (at the time of coating) to prepare a resin composition.
- a process of dispersing the pigment when preparing the resin composition.
- mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like.
- Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like.
- 2015-157893 can be suitably used.
- the particles may be made finer in the salt milling process.
- Materials, equipment, processing conditions, etc. used in the salt milling step can be referred to, for example, Japanese Patent Application Laid-Open Nos. 2015-194521 and 2012-046629.
- any filter that has been conventionally used for filtration or the like can be used without particular limitation.
- fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF)
- polyamide resins such as nylon (eg nylon-6, nylon-6,6)
- polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high-molecular-weight polyolefin resin) and other materials.
- PP polypropylene
- nylon including high density polypropylene
- nylon including high density polypropylene
- the pore size of the filter is preferably 0.01-7.0 ⁇ m, more preferably 0.01-3.0 ⁇ m, and even more preferably 0.05-0.5 ⁇ m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably.
- the pore size value of the filter reference can be made to the filter manufacturer's nominal value.
- Various filters provided by Nippon Pall Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used as filters. .
- fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers.
- Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.
- filters When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Alternatively, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed. In addition, the filter can be appropriately selected according to the hydrophilicity/hydrophobicity of the composition.
- the film of the present invention is a film obtained from the resin composition of the present invention described above.
- the film of the present invention can be used for optical filters such as color filters, near-infrared transmission filters and near-infrared cut filters.
- the film thickness of the film of the present invention can be appropriately adjusted according to the purpose.
- the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
- the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more.
- the film of the present invention when used as a color filter, preferably has a hue of green, red, blue, cyan, magenta or yellow, and may have a hue of green, blue or cyan. More preferably, it has a green hue.
- the film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. Green pixels, blue pixels, or cyan pixels are preferred, and green pixels are preferred. more preferred.
- the film of the present invention can be produced through the step of applying the resin composition of the present invention.
- the film manufacturing method further includes a step of forming a pattern (pixels).
- a method for forming the pattern (pixels) includes a photolithography method and a dry etching method, and the photolithography method is preferable.
- Pattern formation by photolithography includes the steps of forming a resin composition layer on a support using the resin composition of the present invention, exposing the resin composition layer in a pattern, and exposing the resin composition layer to light. forming a pattern (pixels) by developing and removing the exposed portion. If necessary, a step of baking the resin composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.
- the resin composition of the present invention is used to form a resin composition layer on a support.
- the support is not particularly limited and can be appropriately selected depending on the application. Examples thereof include glass substrates and silicon substrates, and silicon substrates are preferred. Also, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate.
- CCD charge-coupled device
- CMOS complementary metal oxide semiconductor
- the silicon substrate is formed with a black matrix that isolates each pixel.
- the silicon substrate may be provided with an underlying layer for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.
- the underlayer may be formed using a composition obtained by removing the coloring agent from the resin composition described herein, or a composition containing the resin described herein, a polymerizable compound, a surfactant, or the like. good.
- the surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferably 30 to 80° when measured with water.
- a known method can be used as a method for applying the resin composition.
- dropping method drop cast
- slit coating method spray method
- roll coating method spin coating
- methods described in publications inkjet
- ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc.
- Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like.
- the application method for inkjet is not particularly limited.
- the resin composition layer formed on the support may be dried (pre-baked). Pre-baking may not be performed when the film is manufactured by a low-temperature process.
- the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower.
- the lower limit can be, for example, 50° C. or higher, and can also be 80° C. or higher.
- the pre-bake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.
- the resin composition layer is exposed in a pattern (exposure step).
- the resin composition layer can be exposed in a pattern by exposing through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.
- Radiation (light) that can be used for exposure includes g-line, i-line, and the like.
- Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used.
- Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferred.
- a long-wave light source of 300 nm or more can also be used.
- the light when exposing, the light may be continuously irradiated and exposed, or may be irradiated and exposed in pulses (pulse exposure).
- pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and rest in short-time (for example, millisecond level or less) cycles.
- the dose is, for example, preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2 .
- the oxygen concentration at the time of exposure can be selected as appropriate.
- the exposure may be in an oxygen-free atmosphere, or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume).
- the exposure illuminance can be set as appropriate, and is usually selected from a range of 1000 W/m 2 to 100000 W/m 2 (eg, 5000 W/m 2 , 15000 W/m 2 or 35000 W/m 2 ). can be done.
- the oxygen concentration and exposure illuminance may be appropriately combined.
- the illuminance may be 10000 W/m 2 at an oxygen concentration of 10% by volume and 20000 W/m 2 at an oxygen concentration of 35% by volume.
- the unexposed portions of the resin composition layer are removed by development to form a pattern (pixels).
- the development and removal of the unexposed portion of the resin composition layer can be performed using a developer.
- the unexposed portion of the resin composition layer in the exposure step is eluted into the developer, leaving only the photocured portion.
- the temperature of the developer is preferably 20 to 30° C., for example.
- the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the step of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.
- the developer includes an organic solvent, an alkaline developer, etc., and an alkaline developer is preferably used.
- an alkaline developer an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable.
- alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
- ethyltrimethylammonium hydroxide ethyltrimethylammonium hydroxide
- benzyltrimethylammonium hydroxide dimethylbis(2-hydroxyethyl)ammonium hydroxide
- choline pyrrole
- piperidine 1,8-diazabicyclo-[5.4.0]-7-undecene
- examples include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate and sodium metasilicate.
- a compound having a large molecular weight is preferable for the alkaline agent from the standpoint of environment and safety.
- the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
- the developer may further contain a surfactant. From the viewpoint of transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse liquid to the resin composition layer after development while rotating the support on which the resin composition layer after development is formed.
- the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support.
- the moving speed of the nozzle may be gradually decreased.
- Additional exposure processing and post-baking are post-development curing treatments for complete curing.
- the heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree.
- Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. .
- the light used for exposure preferably has a wavelength of 400 nm or less.
- the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
- Pattern formation by a dry etching method includes the steps of forming a resin composition layer on a support using the resin composition of the present invention, and curing the entire resin composition layer to form a cured product layer; a step of forming a photoresist layer on the cured layer; a step of patternwise exposing the photoresist layer and then developing it to form a resist pattern; and etching the cured layer using the resist pattern as a mask. and dry etching using a gas.
- a mode in which heat treatment after exposure and heat treatment (post-baking treatment) after development are performed is desirable.
- pattern formation by a dry etching method descriptions in paragraphs 0010 to 0067 of JP-A-2013-064993 can be referred to, and the contents thereof are incorporated herein.
- the optical filter of the present invention has the film of the present invention as described above.
- Types of optical filters include color filters, near-infrared cut filters, and near-infrared transmission filters, and color filters are preferred.
- the color filter preferably has the film of the present invention as its pixels, more preferably has the film of the present invention as its color pixels, and still more preferably has the film of the present invention as its green pixels.
- the optical filter may have a protective layer on the surface of the film of the present invention.
- a protective layer By providing the protective layer, it is possible to impart various functions such as blocking oxygen, reducing reflection, making the film hydrophilic and hydrophobic, and blocking light of a specific wavelength (ultraviolet rays, near-infrared rays, etc.).
- the thickness of the protective layer is preferably 0.01-10 ⁇ m, more preferably 0.1-5 ⁇ m.
- Examples of the method of forming the protective layer include a method of applying a resin composition for forming the protective layer, a chemical vapor deposition method, and a method of adhering a molded resin with an adhesive.
- Components constituting the protective layer include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, and polyimides.
- the protective layer preferably contains a polyol resin, SiO 2 and Si 2 N 4 .
- the protective layer preferably contains a (meth)acrylic resin and a fluororesin.
- a resin composition When a resin composition is applied to form a protective layer, known methods such as spin coating, casting, screen printing, and ink-jetting can be used as methods for applying the resin composition.
- Known organic solvents eg, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.
- the protective layer is formed by a chemical vapor deposition method
- the chemical vapor deposition method includes known chemical vapor deposition methods (thermal chemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method). can be used.
- the protective layer contains organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index modifiers, antioxidants, adhesion agents, additives such as surfactants. may contain.
- organic/inorganic fine particles include polymeric fine particles (eg, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like.
- a known absorber can be used as the absorber for light of a specific wavelength.
- the content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the protective layer.
- the protective layer the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.
- the optical filter may have a structure in which each pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.
- the solid-state imaging device of the present invention has the film of the present invention described above.
- the configuration of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device.
- a plurality of photodiodes and transfer electrodes made of polysilicon or the like are provided on the substrate, forming the light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal-oxide semiconductor) image sensor, etc.). and a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. and a color filter on the device protective film.
- CCD charge-coupled device
- CMOS complementary metal-oxide semiconductor
- the color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.
- the partition wall preferably has a lower refractive index than each color pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478, JP-A-2014-179577, and International Publication No. 2018/043654.
- an ultraviolet absorption layer may be provided in the structure of the solid-state imaging device to improve light resistance.
- An imaging device equipped with the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having an imaging function (mobile phones, etc.), but also for vehicle-mounted cameras and monitoring cameras.
- the image display device of the present invention has the film of the present invention described above.
- image display devices include liquid crystal display devices and organic electroluminescence display devices.
- electroluminescence display devices For a definition of an image display device and details of each image display device, see, for example, “Electronic Display Device (by Akio Sasaki, Industrial Research Institute, 1990)", “Display Device (by Junsho Ibuki, Sangyo Tosho ( Co., Ltd.) issued in 1989).
- Liquid crystal display devices are described, for example, in “Next Generation Liquid Crystal Display Technology” (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994). There is no particular limitation on the liquid crystal display device to which the present invention can be applied.
- Resins P1 to P188, PP1 to PP23, PP101 to PP136, CP1 to CP3 are resins containing repeating units shown in the table below. The acid value and weight average molecular weight (Mw) of the resin are also shown. Resins P1 to P188, PP1, PP2, PP101 to PP136 are the specific resins described above.
- A-1 a repeating unit having the following structure (a repeating unit having a naphthalimide structure)
- A-2 A repeating unit having the following structure (a repeating unit having a naphthalimide structure)
- A-3 Repeating unit having the following structure (repeating unit having an acridone structure)
- A-4 a repeating unit having the following structure (a repeating unit having a benzothiazole structure)
- A-5 Repeating unit having the following structure (repeating unit having a benzimidazole structure)
- A-6 Repeating unit having the following structure (repeating unit having a benzoxazole structure)
- A-7 a repeating unit having the following structure (a repeating unit having a benzotriazole structure)
- A-8 a repeating unit having the following structure (a repeating unit having a tetrazole structure)
- A-9 Repeating unit having the following structure (repeating unit having a phthalimide structure)
- A-10 Repeating unit having the following structure
- the average particle size of the pigment was measured by a dynamic light scattering method using nanoSAQLA (manufactured by Otsuka Electronics Co., Ltd.).
- the viscosity of the pigment dispersion was measured by adjusting the temperature of the pigment dispersion to 25°C.
- Pigment Blue 15:6 phthalocyanine compound, blue pigment
- PV23 C.I. I. Pigment Violet 23 (dioxazine compound, purple pigment)
- PBk32 C.I. I. Pigment Black 32 (perylene compound, organic black pigment)
- IR colorant 1 compound having the following structure (near-infrared absorbing pigment)
- Derivatives 1 to 3 compounds having the following structures (pigment derivatives)
- Pigment dispersion described in the table below 520 parts by mass Polymerizable compound 1: 6.6 parts by mass Polymerizable compound 2: 12.6 parts by mass Resin solution 1: 3 parts by mass Photopolymerization initiation Agent 1...5 parts by mass Surfactant 1...0.1 parts by mass Heat curing agent 1...2 parts by mass Solvent 1...200 parts by mass Solvent 2...100 parts by mass Solvent 3... ⁇ 21.96 parts by mass
- Polymerizable compound 1 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
- Polymerizable compound 2 KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.)
- Resin solution 1 A 30% by mass propylene glycol monomethyl ether acetate solution of a resin having the following structure (weight average molecular weight: 9000, the numerical value attached to the repeating unit is the mass ratio)
- Photoinitiator 1 Irgacure OXE01 (manufactured by BASF, oxime compound)
- Surfactant 1 KF6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant)
- Thermosetting agent 1 compound T-1 having the following structure
- Solvent 1 Propylene glycol monomethyl ether acetate
- ⁇ Performance evaluation> (Color unevenness)
- a composition for forming an underlayer (CT-4000, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied by a spin coating method so that the film thickness was 0.1 ⁇ m, and 220 degrees using a hot plate. C. for 1 hour to form an underlayer.
- Each resin composition was applied onto the glass substrate with the underlayer by spin coating, and then heated at 100° C. for 2 minutes using a hot plate to obtain a composition layer with a film thickness of 0.5 ⁇ m.
- This composition layer was exposed to light with a wavelength of 365 nm at an exposure amount of 500 mJ/cm 2 using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.).
- the exposed composition layer was subjected to puddle development at 23° C. for 60 seconds using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide. After that, it was rinsed with water in a spin shower, and then washed with pure water. Thereafter, water droplets were blown off with high-pressure air, and the glass substrate was air-dried, followed by post-baking at 220° C. for 300 seconds using a hot plate to form a film.
- the luminance distribution was analyzed by the following method, and color unevenness was evaluated based on the number of pixels with a deviation from the average of ⁇ 10% or more.
- a method for measuring the luminance distribution will be described.
- the substrate for evaluation is installed between the observation lens of an optical microscope and a light source, and light is irradiated toward the observation lens, and the state of transmitted light is observed using an optical microscope MX-50 (manufactured by Olympus Corporation) equipped with a digital camera. observed using Imaging of the membrane surface was performed on five arbitrarily selected regions.
- the brightness of the photographed image was quantified as a density distribution of 256 gradations from 0 to 255 and stored.
- the luminance distribution was analyzed from this image, and color unevenness was evaluated based on the number of pixels with a deviation of more than ⁇ 10% from the average. Evaluation criteria are as follows. If the evaluation is A to C, it is judged that there is no practical problem. A: The number of pixels exceeding ⁇ 10% deviation from the average is 1000 or less. B: The number of pixels with a deviation of more than ⁇ 10% from the average is more than 1000 and 3000 or less. C: The number of pixels exceeding ⁇ 10% from the average is more than 3000 and 5000 or less. D: The number of pixels exceeding ⁇ 10% from the average exceeds 5,000.
- a composition for forming an underlayer (CT-4000, manufactured by Fuji Film Electronic Materials Co., Ltd.) was applied using a spin coater so that the thickness was 0.1 ⁇ m after post-baking, and a hot plate was applied. was used to form an underlayer by heating at 220° C. for 300 seconds to obtain an underlayer-attached glass substrate (support).
- Each resin composition was applied onto the glass substrate with the underlayer by spin coating, and then heated at 100° C. for 2 minutes using a hot plate to form a film having a thickness of 0.5 ⁇ m.
- Foreign matter contained in this film is detected by a foreign matter evaluation device Compplus III (manufactured by Applied Materials, Inc.), and foreign matter (coarse particles) with a maximum width of 1.0 ⁇ m or more is visually classified from all detected foreign matter. Then, the number of classified coarse particles having a maximum width of 1.0 ⁇ m or more (the number of coarse particles per 1 cm 2 ) was counted.
- B The number of coarse particles per 1 cm 2 of the film is 10 or more and less than 30
- C The number of coarse particles per 1 cm 2 of the film is 30
- the number of coarse particles per 1 cm 2 of the film is 100 or more
- the resin compositions of Examples were able to form films with suppressed color unevenness.
- the films obtained from the resin compositions described in Examples can be suitably used for optical filters, solid-state imaging devices, and image display devices.
- Example 43 similar effects were obtained even when polymerizable compound 2 was changed to compound M-2 or M-3 having the structure shown below.
- Example 43 similar effects were obtained even when the photopolymerization initiator 1 was changed to compounds I-2 to I-5 having the structures shown below.
- Example 43 even when the heat curing agent 1 was changed to a compound T-2 or T-3 having the structure shown below, similar effects were obtained.
- surfactant 1 was a compound having the structure shown below (weight-average molecular weight of 14,000, percent of repeating units is mol%, fluorosurfactant) or PolyFox PF6320 ( A similar effect was obtained even when the surfactant was changed to a fluorosurfactant manufactured by OMNOVA.
- P1 A solution of silica particles (beaded silica) in which a plurality of spherical silica particles having an average particle diameter of 10 nm are connected in a beaded manner by a metal oxide-containing silica (connecting material).
- P2 Sururia 4110: manufactured by Nikki Shokubai Kasei Co., Ltd., a solution of silica particles having an average particle diameter of 60 nm (silica particles having a hollow structure). Solid content concentration of 20 mass% in terms of SiO2
- F2 Silwet L-7220 (manufactured by Momentive Performance Materials)
- F3 Pionin B-111 (manufactured by Takemoto Oil, lauryltrimethylammonium chloride)
- Partition walls 40 to 43 of FIG. 1 of JP-A-2017-028241 were prepared on a silicon wafer using the composition for partition walls produced above.
- a green pixel-forming composition, a red pixel-forming composition, and a blue pixel-forming composition are patterned by photolithography in regions partitioned by partition walls on a silicon wafer to form green pixels and red pixels.
- a pixel and a blue pixel were formed respectively to manufacture an image sensor.
- the obtained image sensor was excellent in sensitivity.
- the resin composition of Example 1 was used as the green pixel-forming composition.
- the resin composition of Example 70 was used as the red pixel-forming composition.
- the resin composition of Example 76 was used as the blue pixel-forming composition.
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Abstract
Description
上記色材Aは、顔料を含み、
上記樹脂Bは、酸基を有する繰り返し単位b1-1と、芳香族環を2以上含む基、複素環基を含む基および縮合環を含む基から選ばれる官能基bを有する繰り返し単位b1-2と、上記繰り返し単位b1-1および上記繰り返し単位b1-2以外の繰り返し単位b1-3とを含む樹脂b1を含有し、
上記樹脂組成物の全固形分中における上記色材Aの含有量が55質量%以上である、樹脂組成物。
<2> 上記色材Aはフタロシアニン顔料を含む、<1>に記載の樹脂組成物。
<3> 上記色材Aは、更に染料を含む、<1>または<2>に記載の樹脂組成物。
<4> 上記官能基bは、ナフタルイミド構造、アクリドン構造、チオキサントン構造、キサントン構造、アントロン構造、ベンゾイミダゾール構造、ベンゾチアゾール構造、ベンゾオキサゾール構造、ベンゾトリアゾール構造、ベンゾオキサジアゾール構造、ベンゾチアジアゾール構造、ベンゾチアジン構造、ベンゾオキサジン構造、ベンゾレインウレア構造、イソチアゾリノン構造、フェノキサジン構造、フェノチアジン構造、ジヒドロアクリジン構造、フェノキサチイン構造、ジベンゾピラン構造、フルオレン構造、カルバゾール構造、カルボリン構造、ジベンゾチオフェン構造、ジベンゾフラン構造、ピリミジン構造、ピラジン構造、キナゾリン構造、キノキサリン構造、キノリン構造、イミダゾール構造、チアゾール構造、インドール構造、ベンゾチオフェン構造、ベンゾピラン構造、キノリノン構造、チオクロマノン構造、クロマン構造、ベンゾイミダゾロン構造、フタルイミド構造、ナフタレン-2,3-ジカルボキシイミド構造、ピラゾール構造、ピラゾロン構造、イソインドリン構造、イソインドリノン構造、アントラキノン構造、テトラゾール構造、ベンゾフェノン構造、トリアジン構造、アゾベンゼン構造、ベンザルアニリン構造、フェナジン構造、バルビツル酸構造、ペリレン構造、ペリノン構造、キノフタロン構造、カプロラクタム構造、サッカリン構造、ビフェニル構造、トリアリールベンゼン構造、トリアリールアミン構造、ベンゾチアゾロン構造またはベンゾオキサゾリノン構造を含む基である、<1>~<3>のいずれか1つに記載の樹脂組成物。
<5> 上記官能基bは、ナフタルイミド構造、アクリドン構造、キサントン構造、ベンゾイミダゾール構造、ベンゾチアゾール構造、ベンゾオキサゾール構造、ベンゾトリアゾール構造、ベンゾオキサジアゾール構造、ベンゾチアジアゾール構造、フェノキサジン構造、フェノチアジン構造、フェノキサチイン構造、フタルイミド構造、ピラゾロン構造、テトラゾール構造、ベンゾチアゾロン構造またはベンゾオキサゾリノン構造を含む基である、<1>~<3>のいずれか1つに記載の樹脂組成物。
<6> 上記樹脂b1中における上記単位b1-2の含有量が10~35質量%である、<1>~<5>のいずれか1つに記載の樹脂組成物。
<7> 上記繰り返し単位b1-3は、ポリエステル構造またはポリエーテル構造のグラフト鎖を有する繰り返し単位を含む、<1>~<6>のいずれか1つに記載の樹脂組成物。
<8> 上記樹脂Bは、更に、上記樹脂b1とは異なる樹脂b2を含む、<1>~<7>のいずれか1つに記載の樹脂組成物。
<9> 上記樹脂b2は、上記樹脂b1とは異なる酸基を有する樹脂を含む、<8>に記載の樹脂組成物。
<10> 上記樹脂b2は、上記樹脂b1が有する酸基よりも小さいpKaの酸基を有する、<9>に記載の樹脂組成物。
<11> 上記樹脂b2は、グラフトポリマー、星形ポリマー、ブロック共重合体およびポリマー鎖の少なくとも一方の末端が酸基で封止された樹脂から選ばれる少なくとも1種を含む、<8>~<10>のいずれか1つに記載の樹脂組成物。
<12> 更に、重合性化合物と光重合開始剤とを含む、<1>~<11>のいずれか1つに記載の樹脂組成物。
<13> <1>~<12>のいずれか1つに記載の樹脂組成物から得られる膜。
<14> <13>に記載の膜を有する光学フィルタ。
<15> <13>に記載の膜を有する固体撮像素子。
<16> <13>に記載の膜を有する画像表示装置。
本明細書において、「~」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さない基(原子団)と共に置換基を有する基(原子団)をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。
本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線または放射線が挙げられる。
本明細書において、「(メタ)アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「(メタ)アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「(メタ)アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
本明細書において、構造式中のMeはメチル基を表し、Etはエチル基を表し、Buはブチル基を表し、Phはフェニル基を表す。
本明細書において、重量平均分子量および数平均分子量は、GPC(ゲルパーミエーションクロマトグラフィ)法により測定したポリスチレン換算値である。
本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。
本明細書において、顔料とは、溶剤に対して溶解しにくい色材を意味する。
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
本発明の樹脂組成物は、色材Aと樹脂Bとを含む樹脂組成物であって、
上記色材Aは、顔料を含み、
上記樹脂Bは、酸基を有する繰り返し単位b1-1と、芳香族環を2以上含む基、複素環基を含む基および縮合環を含む基から選ばれる官能基bを有する繰り返し単位b1-2と、繰り返し単位b1-1および繰り返し単位b1-2以外の繰り返し単位b1-3とを含む樹脂b1を含有し、
樹脂組成物の全固形分中における色材Aの含有量が55質量%以上であることを特徴とする。
(1):波長400~640nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長800~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ。
(2):波長400~750nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長900~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ。
(3):波長400~830nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1000~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ。
(4):波長400~950nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1100~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ。
(5):波長400~1050nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1200~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ。
本発明の樹脂組成物は、色材A(以下、色材と記す)を含有する。色材としては白色色材、黒色色材、有彩色色材、近赤外線吸収色材が挙げられる。また、色材には顔料誘導体を用いることもできる。なお、本発明において、白色色材には純白色のみならず、白に近い明るい灰色(例えば灰白色、薄灰色など)の色材も含まれる。
また、本発明の樹脂組成物に含まれる色材は、染料を実質的に含まないものであることも好ましい。この態様によれば、耐光性や耐熱性に優れた膜を形成することができる。染料を実質的に含まないとは、色材中における染料の含有量が0.1質量%以下であることを意味し、0.01質量%以下であることが好ましく、含有しないことが更に好ましい。
有彩色色材としては、波長400~700nmの範囲に極大吸収波長を有する色材が挙げられる。例えば、黄色色材、オレンジ色色材、赤色色材、緑色色材、紫色色材、青色色材などが挙げられる。耐熱性の観点から有彩色色材は、顔料(有彩色顔料)であることが好ましく、赤色顔料、黄色顔料、及び青色顔料がより好ましく、赤色顔料及び青色顔料が更に好ましい。有彩色顔料の具体例としては、例えば、以下に示すものが挙げられる。
用いられる。
(1)赤色色材と青色色材とを含有する態様。
(2)赤色色材と青色色材と黄色色材とを含有する態様。
(3)赤色色材と青色色材と黄色色材と紫色色材とを含有する態様。
(4)赤色色材と青色色材と黄色色材と紫色色材と緑色色材とを含有する態様。
(5)赤色色材と青色色材と黄色色材と緑色色材とを含有する態様。
(6)赤色色材と青色色材と緑色色材とを含有する態様。
(7)黄色色材と紫色色材とを含有する態様。
白色色材としては、酸化チタン、チタン酸ストロンチウム、チタン酸バリウム、酸化亜鉛、酸化マグネシウム、酸化ジルコニウム、酸化アルミニウム、硫酸バリウム、シリカ、タルク、マイカ、水酸化アルミニウム、ケイ酸カルシウム、ケイ酸アルミニウム、中空樹脂粒子、硫化亜鉛などの無機顔料(白色顔料)が挙げられる。白色顔料は、チタン原子を有する粒子が好ましく、酸化チタンがより好ましい。また、白色顔料は、波長589nmの光に対する屈折率が2.10以上の粒子であることが好ましい。前述の屈折率は、2.10~3.00であることが好ましく、2.50~2.75であることがより好ましい。
黒色色材としては特に限定されず、公知のものを用いることができる。例えば、無機黒色色材としては、カーボンブラック、チタンブラック、グラファイト等の無機顔料(黒色顔料)が挙げられ、カーボンブラック、チタンブラックが好ましく、チタンブラックがより好ましい。チタンブラックとは、チタン原子を含有する黒色粒子であり、低次酸化チタンや酸窒化チタンが好ましい。チタンブラックは、分散性向上、凝集性抑制などの目的で必要に応じ、表面を修飾することが可能である。例えば、酸化珪素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化マグネシウム、又は、酸化ジルコニウムでチタンブラックの表面を被覆することが可能である。また、特開2007-302836号公報に表されるような撥水性物質での処理も可能である。黒色顔料として、C.I.ピグメントブラック1,7等が挙げられる。チタンブラックは、個々の粒子の一次粒子径及び平均一次粒子径のいずれもが小さいことが好ましい。具体的には、平均一次粒子径が10~45nmであることが好ましい。チタンブラックは、分散物として用いることもできる。例えば、チタンブラック粒子とシリカ粒子とを含み、分散物中のSi原子とTi原子との含有比が0.20~0.50の範囲に調整された分散物などが挙げられる。上記分散物については、特開2012-169556号公報の段落0020~0105の記載を参酌でき、この内容は本明細書に組み込まれる。チタンブラックの市販品の例としては、チタンブラック10S、12S、13R、13M、13M-C、13R-N、13M-T(商品名:三菱マテリアル(株)製)、ティラック(Tilack)D(商品名:赤穂化成(株)製)などが挙げられる。
(A-1)有機黒色色材と青色色材とを含有する態様。
(A-2)有機黒色色材と青色色材と黄色色材とを含有する態様。
(A-3)有機黒色色材と青色色材と黄色色材と赤色色材とを含有する態様。
(A-4)有機黒色色材と青色色材と黄色色材と紫色色材とを含有する態様。
上記(A-2)の態様において、有機黒色色材と青色色材と黄色色材の質量比は、有機黒色色材:青色色材:黄色色材=100:10~90:10~90であることが好ましく、100:15~85:15~80であることがより好ましく、100:20~80:20~70であることが更に好ましい。
上記(A-3)の態様において、有機黒色色材と青色色材と黄色色材と赤色色材との質量比は、有機黒色色材:青色色材:黄色色材:赤色色材=100:20~150:1~60:10~100であることが好ましく、100:30~130:5~50:20~90であることがより好ましく、100:40~120:10~40:30~80であることが更に好ましい。
上記(A-4)の態様において、有機黒色色材と青色色材と黄色色材と紫色色材との質量比は、有機黒色色材:青色色材:黄色色材:紫色色材=100:20~150:1~60:10~100であることが好ましく、100:30~130:5~50:20~90であることがより好ましく、100:40~120:10~40:30~80であることが更に好ましい。
近赤外線吸収色材は、極大吸収波長を波長700nmよりも長波長側に有する化合物であることが好ましい。赤外線吸収剤は波長700nmを超え1800nm以下の範囲に極大吸収波長を有する化合物であることが好ましく、波長700nmを超え1400nm以下の範囲に極大吸収波長を有する化合物であることがより好ましく、波長700nmを超え1200nm以下の範囲に極大吸収波長を有する化合物であることが更に好ましく、波長700nmを超え1000nm以下の範囲に極大吸収波長を有する化合物であることが特に好ましい。また、近赤外線吸収色材の波長500nmにおける吸光度A1と極大吸収波長における吸光度A2との比率A1/A2が0.08以下であることが好ましく、0.04以下であることがより好ましい。また、近赤外線吸収色材は、顔料であることが好ましく、有機顔料であることがより好ましい。
本発明において、色材には顔料誘導体を用いることもできる。本発明では、顔料と顔料誘導体を併用することが好ましい。顔料誘導体としては、色素骨格に酸基または塩基性基が結合した構造を有する化合物が挙げられる。
本発明の樹脂組成物は樹脂(以下、樹脂と記す)を含む。樹脂は、例えば、顔料などを樹脂組成物中で分散させる用途や、バインダーの用途で配合される。なお、主に顔料などを樹脂組成物中で分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外を目的として樹脂を使用することもできる。
本発明の樹脂組成物に含まれる樹脂は、酸基を有する繰り返し単位b1-1と、芳香族環を2以上含む基、複素環基を含む基および縮合環を含む基から選ばれる官能基bを有する繰り返し単位b1-2と、繰り返し単位b1-1および繰り返し単位b1-2以外の繰り返し単位b1-3とを含む樹脂b1(以下、特定樹脂ともいう)を含む。
特定樹脂は、酸基を有する繰り返し単位b1-1(以下、繰り返し単位b1-1ともいう)を含む。酸基としては、カルボキシ基、リン酸基、スルホ基およびフェノール性ヒドロキシ基が挙げられ、カルボキシ基であることが好ましい。
Lb1が表すn1+1価の連結基としては、脂肪族炭化水素基、芳香族炭化水素基、-NH-、-SO-、-SO2-、-CO-、-O-、-COO-、OCO-、-S-およびこれらの2以上を組み合わせてなる基が挙げられる。脂肪族炭化水素基、芳香族炭化水素基は、置換基を有していてもよい。置換基としてはヒドロキシ基、ハロゲン原子などが挙げられる。
特定樹脂は、芳香族環を2以上含む基、複素環基を含む基および縮合環を含む基から選ばれる官能基bを有する繰り返し単位b1-2(以下、繰り返し単位b1-2ともいう)を含む。
ナフタルイミド構造、アクリドン構造、キサントン構造、アントロン構造、ベンゾイミダゾール構造、ベンゾチアゾール構造、ベンゾオキサゾール構造、ベンゾトリアゾール構造、ベンゾオキソジアゾール構造、ベンゾチアジアゾール構造、フェノキサジン構造、フェノチアジン構造、ジヒドロアクリジン構造、フェノキサチイン構造、ジベンゾピラン構造、カルバゾール構造、カルボリン構造、ジベンゾチオフェン構造、ジベンゾフラン構造、ピリミジン構造、ピラジン構造、キナゾリン構造、キノキサリン構造、イミダゾール構造、チアゾール構造、インドール構造、ベンゾチオフェン構造、ベンゾピラン構造、キノリノン構造、チオクロマノン構造、クロマン構造、フタルイミド構造、ナフタレン-2,3-ジカルボキシイミド構造、ピラゾール構造、ピラゾロン構造、イソインドリン構造、イソインドリノン構造、アントラキノン構造、テトラゾール構造、ベンゾフェノン構造、トリアジン構造、アゾベンゼン構造、ベンザルアニリン構造、フェナジン構造、バルビツル酸構造、ペリレン構造、ペリノン構造、サッカリン構造、ビフェニル構造、トリアリールベンゼン構造、トリアリールアミン構造、ベンゾチアゾロン構造またはベンゾオキサゾリノン構造を含む基であることがより好ましく、
ナフタルイミド構造、アクリドン構造、キサントン構造、アントロン構造、ベンゾイミダゾール構造、ベンゾチアゾール構造、ベンゾオキサゾール構造、ベンゾトリアゾール構造、ベンゾオキソジアゾール構造、ベンゾチアジアゾール構造、フェノキサジン構造、フェノチアジン構造、ジヒドロアクリジン構造、フェノキサチイン構造、ジベンゾピラン構造、カルボリン構造、ジベンゾチオフェン構造、ジベンゾフラン構造、ピリミジン構造、ピラジン構造、キナゾリン構造、キノキサリン構造、チオクロマノン構造、クロマン構造、フタルイミド構造、ピラゾロン構造、イソインドリノン構造、テトラゾール構造、ベンザルアニリン構造、ベンゾチアゾロン構造またはベンゾオキサゾリノン構造を含む基であることがより好ましく、
ナフタルイミド構造、アクリドン構造、キサントン構造、ベンゾイミダゾール構造、ベンゾチアゾール構造、ベンゾオキサゾール構造、ベンゾトリアゾール構造、ベンゾオキサジアゾール構造、ベンゾチアジアゾール構造、フェノキサジン構造、フェノチアジン構造、フェノキサチイン構造、フタルイミド構造、ピラゾロン構造、テトラゾール構造、ベンゾチアゾロン構造またはベンゾオキサゾリノン構造を含む基であることが更に好ましく、
ナフタルイミド構造、アクリドン構造、ベンゾイミダゾール構造、ベンゾチアゾール構造、ベンゾオキサゾール構造、フェノキサジン構造、フェノチアジン構造、フェノキサチイン構造、フタルイミド構造、ピラゾロン構造またはテトラゾール構造を含む基であることがより一層に好ましく、
色ムラのより抑制された膜を形成しやすいという理由からナフタルイミド構造またはアクリドン構造を含む基であることが特に好ましい。
特定樹脂は、繰り返し単位b1-1および繰り返し単位b1-2以外の繰り返し単位b1-3を含む。
特定樹脂の具体例としては、後述する実施例に示す樹脂P1~P188、PP1、PP2、PP101~PP136が挙げられる。
特定樹脂の酸価は、10~250mgKOH/gであることが好ましい。上限は、220mgKOH/g以下であることが好ましく、200mgKOH/g以下であることがより好ましい。下限は、30mgKOH/g以上であることが好ましく、50mgKOH/g以上であることがより好ましい。特定樹脂の酸価が上記範囲であれば、樹脂組成物中における顔料の分散性が良好であり、より色ムラの抑制された膜を形成することができる。更には、樹脂組成物中での粗大粒子の発生などもより効果的に抑制することができる。更にまた、フォトリソグラフィ法でパターン形成した際において、現像残渣の発生もより効果的に抑制できる。
E=A/(c×l) ・・・(Aλ)
式(Aλ)中、Eは、波長400~800nmでの最大吸収波長における特定樹脂の比吸光度を表し、
Aは、波長400~800nmでの最大吸収波長における特定樹脂の吸光度を表し、
lは、単位がcmで表されるセル長を表し、
cは、単位がmg/mlで表される、溶液中の特定樹脂の濃度を表す。
本発明の樹脂組成物は、上述した特定樹脂とは異なる樹脂(以下、他の樹脂ともいう)を含有することができる。
式(Ac-2)中、Ar10は芳香族カルボキシ基を含む基を表し、L11は、-COO-または-CONH-を表し、L12は3価の連結基を表し、P10はポリマー鎖を表す。
式(Ar-12)中、n2は1~8の整数を表し、1~4の整数であることが好ましく、1または2であることがより好ましく、2であることが更に好ましい。
式(Ar-13)中、n3およびn4はそれぞれ独立して0~4の整数を表し、0~2の整数であることが好ましく、1または2であることがより好ましく、1であることが更に好ましい。ただし、n3およびn4の少なくとも一方は1以上の整数である。
式(Ar-13)中、Q1は、単結合、-O-、-CO-、-COOCH2CH2OCO-、-SO2-、-C(CF3)2-、上記式(Q-1)で表される基または上記式(Q-2)で表される基を表す。
式(Ar-11)~(Ar-13)中、*1はL1との結合位置を表す。
本発明の樹脂組成物は、重合性化合物を含有することが好ましい。重合性化合物としては、エチレン性不飽和結合含有基を有する化合物などが挙げられる。エチレン性不飽和結合含有基としては、ビニル基、(メタ)アリル基、(メタ)アクリロイル基などが挙げられる。本発明で用いられる重合性化合物は、ラジカル重合性化合物であることが好ましい。
式(Z-5)中、nは、0~6の整数が好ましく、0~4の整数がより好ましい。また、各nの合計は、3~60の整数が好ましく、3~24の整数がより好ましく、6~12の整数が特に好ましい。
また、式(Z-4)又は式(Z-5)中のE、すなわち-((CH2)yCH2O)-又は-((CH2)yCH(CH3)O)-は、酸素原子側の末端がXに結合する形態が好ましい。
本発明の樹脂組成物は光重合開始剤を含有することができる。本発明の樹脂組成物が重合性化合物を含む場合、本発明の樹脂組成物は更に光重合開始剤を含有することが好ましい。光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する化合物が好ましい。光重合開始剤は、光ラジカル重合開始剤であることが好ましい。
RX2は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、ヘテロ環基、ヘテロ環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシルオキシ基またはアミノ基を表し、
RX3~RX14は、それぞれ独立して水素原子または置換基を表す;
ただし、RX10~RX14のうち少なくとも一つは、電子求引性基である。
本発明の樹脂組成物は、溶剤を含有することが好ましい。溶剤としては、有機溶剤が挙げられる。溶剤の種類は、各成分の溶解性や組成物の塗布性を満足すれば基本的には特に制限はない。有機溶剤としては、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤などが挙げられる。これらの詳細については、国際公開第2015/166779号の段落番号0223を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤も好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、ジクロロメタン、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、3-メトキシプロピオン酸メチル、2-ヘプタノン、2-ペンタノン、3-ペンタノン、4-ヘプタノン、シクロヘキサノン、2-メチルシクロヘキサノン、3-メチルシクロヘキサノン、4-メチルシクロヘキサノン、シクロヘプタノン、シクロオクタノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、3-メトキシ-N,N-ジメチルプロパンアミド、3-ブトキシ-N,N-ジメチルプロパンアミド、プロピレングリコールジアセテート、3-メトキシブタノール、メチルエチルケトン、ガンマブチロラクトン、スルホラン、アニソール、1,4-ジアセトキシブタン、ジエチレングリコールモノエチルエーテルアセタート、二酢酸ブタン-1,3-ジイル、ジプロピレングリコールメチルエーテルアセタート、ジアセトンアルコール(別名としてダイアセトンアルコール、4-ヒドロキシ-4-メチル-2-ペンタノン)、2-メトキシプロピルアセテート、2-メトキシ-1-プロパノール、イソプロピルアルコールなどが挙げられる。ただし有機溶剤としての芳香族炭化水素類(ベンゼン、トルエン、キシレン、エチルベンゼン等)は、環境面等の理由により低減したほうがよい場合がある(例えば、有機溶剤全量に対して、50質量ppm(parts per million)以下とすることもでき、10質量ppm以下とすることもでき、1質量ppm以下とすることもできる)。
本発明の樹脂組成物は、上述した樹脂及び重合性化合物以外の成分として熱硬化剤を含有することができる。熱硬化剤としては、環状エーテル基を有する化合物が挙げられる。環状エーテル基としては、エポキシ基、オキセタニル基などが挙げられる。エポキシ基は、脂環式エポキシ基であってもよい。なお、脂環式エポキシ基とは、エポキシ環と飽和炭化水素環とが縮合した環状構造を有する1価の官能基のことを意味する。環状エーテル基を有する化合物は、エポキシ基を有する化合物(以下、エポキシ化合物ともいう)であることが好ましい。エポキシ化合物としては、1分子内にエポキシ基を1つ以上有する化合物が挙げられ、エポキシ基を2つ以上有する化合物が好ましい。エポキシ化合物はエポキシ基を1分子内に1~100個有する化合物であることが好ましい。エポキシ化合物に含まれるエポキシ基の上限は、例えば、10個以下とすることもでき、5個以下とすることもできる。エポキシ化合物に含まれるエポキシ基の下限は、2個以上が好ましい。エポキシ化合物としては、特開2013-011869号公報の段落番号0034~0036、特開2014-043556号公報の段落番号0147~0156、特開2014-089408号公報の段落番号0085~0092に記載された化合物、特開2017-179172号公報に記載された化合物を用いることもできる。これらの内容は、本明細書に組み込まれる。
本発明の樹脂組成物は、ポリアルキレンイミンを含有することもできる。ポリアルキレンイミンは例えば顔料の分散助剤として用いられる。分散助剤とは、樹脂組成物中において顔料などの色材の分散性を高めるための素材のことである。ポリアルキレンイミンとは、アルキレンイミンを開環重合したポリマーのことである。ポリアルキレンイミンは1級アミノ基と、2級アミノ基と、3級アミノ基とをそれぞれ含む分岐構造を有するポリマーであることが好ましい。アルキレンイミンの炭素数は2~6が好ましく、2~4がより好ましく、2または3であることが更に好ましく、2であることが特に好ましい。
本発明の樹脂組成物は、硬化促進剤を含んでもよい。硬化促進剤としては、チオール化合物、メチロール化合物、アミン化合物、ホスホニウム塩化合物、アミジン塩化合物、アミド化合物、塩基発生剤、イソシアネート化合物、アルコキシシラン化合物、オニウム塩化合物などが挙げられる。硬化促進剤の具体例としては、国際公開第2018/056189号の段落番号0094~0097に記載の化合物、特開2015-034963号公報の段落番号0246~0253に記載の化合物、特開2013-041165号公報の段落番号0186~0251に記載の化合物、特開2014-055114号公報に記載のイオン性化合物、特開2012-150180号公報の段落番号0071~0080に記載の化合物、特開2011-253054号公報に記載のエポキシ基を有するアルコキシシラン化合物、特許第5765059号公報の段落番号0085~0092に記載の化合物、特開2017-036379号公報に記載のカルボキシ基含有エポキシ硬化剤などが挙げられる。樹脂組成物の全固形分中における硬化促進剤の含有量は0.3~8.9質量%が好ましく、0.8~6.4質量%がより好ましい。
本発明の樹脂組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤としては、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物などが挙げられる。このような化合物の具体例としては、特開2009-217221号公報の段落番号0038~0052、特開2012-208374号公報の段落番号0052~0072、特開2013-068814号公報の段落番号0317~0334、特開2016-162946号公報の段落番号0061~0080に記載された化合物が挙げられ、これらの内容は本明細書に組み込まれる。紫外線吸収剤の具体例としては、下記構造の化合物などが挙げられる。紫外線吸収剤の市販品としては、例えば、UV-503(大東化学(株)製)、BASF社製のTinuvinシリーズ、Uvinul(ユビナール)シリーズ、住化ケムテックス(株)製のSumisorbシリーズなどが挙げられる。また、ベンゾトリアゾール化合物としては、ミヨシ油脂製のMYUAシリーズ(化学工業日報、2016年2月1日)が挙げられる。また、紫外線吸収剤は、特許第6268967号公報の段落番号0049~0059に記載された化合物、国際公開第2016/181987号の段落番号0059~0076に記載された化合物、国際公開第2020/137819号に記載されたチオアリール基置換ベンゾトリアゾール型紫外線吸収剤を用いることもできる。
本発明の樹脂組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、p-メトキシフェノール、ジ-tert-ブチル-p-クレゾール、ピロガロール、tert-ブチルカテコール、ベンゾキノン、4,4’-チオビス(3-メチル-6-tert-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、N-ニトロソフェニルヒドロキシアミン塩(アンモニウム塩、第一セリウム塩等)が挙げられる。中でも、p-メトキシフェノールが好ましい。樹脂組成物の全固形分中における重合禁止剤の含有量は、0.0001~5質量%が好ましい。重合禁止剤は、1種類のみでもよく、2種類以上でもよい。2種類以上の場合は、合計量が上記範囲となることが好ましい。
本発明の樹脂組成物は、シランカップリング剤を含有することができる。本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、ケイ素原子に直結し、加水分解反応及び縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基としては、例えば、ビニル基、(メタ)アリル基、(メタ)アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基、フェニル基などが挙げられ、アミノ基、(メタ)アクリロイル基およびエポキシ基が好ましい。シランカップリング剤の具体例としては、N-β-アミノエチル-γ-アミノプロピルメチルジメトキシシラン(信越化学工業(株)製、商品名 KBM-602)、N-β-アミノエチル-γ-アミノプロピルトリメトキシシラン(信越化学工業(株)製、商品名 KBM-603)、N-β-アミノエチル-γ-アミノプロピルトリエトキシシラン(信越化学工業(株)製、商品名 KBE-602)、γ-アミノプロピルトリメトキシシラン(信越化学工業(株)製、商品名 KBM-903)、γ-アミノプロピルトリエトキシシラン(信越化学工業(株)製、商品名 KBE-903)、3-メタクリロキシプロピルメチルジメトキシシラン(信越化学工業(株)製、商品名 KBM-502)、3-メタクリロキシプロピルトリメトキシシラン(信越化学工業(株)製、商品名 KBM-503)等がある。また、シランカップリング剤の具体例については、特開2009-288703号公報の段落番号0018~0036に記載の化合物、特開2009-242604号公報の段落番号0056~0066に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。樹脂組成物の全固形分中におけるシランカップリング剤の含有量は、0.01~15.0質量%が好ましく、0.05~10.0質量%がより好ましい。シランカップリング剤は、1種類のみでもよく、2種類以上でもよい。2種類以上の場合は、合計量が上記範囲となることが好ましい。
本発明の樹脂組成物は、界面活性剤を含有することができる。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用することができる。界面活性剤はシリコーン系界面活性剤またはフッ素系界面活性剤であることが好ましい。界面活性剤については、国際公開第2015/166779号の段落番号0238~0245に記載された界面活性剤を参照することができ、この内容は本明細書に組み込まれる。
本発明の樹脂組成物は、酸化防止剤を含有することができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位(オルト位)に置換基を有する化合物が好ましい。前述の置換基としては炭素数1~22の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン、トリス[2-[(4,6,9,11-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-2-イル)オキシ]エチル]アミン、亜リン酸エチルビス(2,4-ジ-tert-ブチル-6-メチルフェニル)などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ AO-20、アデカスタブ AO-30、アデカスタブ AO-40、アデカスタブ AO-50、アデカスタブ AO-50F、アデカスタブ AO-60、アデカスタブ AO-60G、アデカスタブ AO-80、アデカスタブ AO-330(以上、(株)ADEKA製)などが挙げられる。また、酸化防止剤は、特許第6268967号公報の段落番号0023~0048に記載された化合物、国際公開第2017/006600号に記載された化合物、国際公開第2017/164024号に記載された化合物、韓国公開特許第10-2019-0059371号公報に記載された化合物を使用することもできる。樹脂組成物の全固形分中における酸化防止剤の含有量は、0.01~20質量%であることが好ましく、0.3~15質量%であることがより好ましい。酸化防止剤は1種のみを用いてもよく、2種以上を用いてもよい。2種以上を用いる場合は、合計量が上記範囲となることが好ましい。
本発明の樹脂組成物は、必要に応じて、増感剤、硬化促進剤、フィラー、熱硬化促進剤、可塑剤及びその他の助剤類(例えば、導電性粒子、消泡剤、難燃剤、レベリング剤、剥離促進剤、香料、表面張力調整剤、連鎖移動剤など)を含有してもよい。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開2012-003225号公報の段落番号0183以降(対応する米国特許出願公開第2013/0034812号明細書の段落番号0237)の記載、特開2008-250074号公報の段落番号0101~0104、0107~0109等の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、本発明の樹脂組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第2014/021023号、国際公開第2017/030005号、特開2017-008219号公報に記載された化合物が挙げられる。潜在酸化防止剤の市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。
樹脂組成物の収容容器としては、特に限定はなく、公知の収容容器を用いることができる。また、収容容器として、原材料や樹脂組成物中への不純物混入を抑制することを目的に、容器内壁を6種6層の樹脂で構成する多層ボトルや6種の樹脂を7層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開2015-123351号公報に記載の容器が挙げられる。また、容器内壁は、容器内壁からの金属溶出を防ぎ、樹脂組成物の経時安定性を高めたり、成分変質を抑制するなど目的で、ガラス製やステンレス製などにすることも好ましい。
本発明の樹脂組成物は、前述の成分を混合して調製できる。樹脂組成物の調製に際しては、全成分を同時に溶剤に溶解および/または分散して樹脂組成物を調製してもよいし、必要に応じて、各成分を適宜2つ以上の溶液または分散液としておいて、使用時(塗布時)にこれらを混合して樹脂組成物を調製してもよい。
本発明の膜は、上述した本発明の樹脂組成物から得られる膜である。本発明の膜は、カラーフィルタ、近赤外線透過フィルタおよび近赤外線カットフィルタなどの光学フィルタに用いることができる。
次に、本発明の膜の製造方法について説明する。本発明の膜は、本発明の樹脂組成物を塗布する工程を経て製造できる。膜の製造方法においては、更にパターン(画素)を形成する工程を含むことが好ましい。パターン(画素)の形成方法としては、フォトリソグラフィ法、ドライエッチング法が挙げられ、フォトリソグラフィ法が好ましい。
本発明の光学フィルタは、上述した本発明の膜を有する。光学フィルタの種類としては、カラーフィルタ、近赤外線カットフィルタおよび近赤外線透過フィルタなどが挙げられ、カラーフィルタであることが好ましい。カラーフィルタは、その画素として本発明の膜を有することが好ましく、着色画素として本発明の膜を有することがより好ましく、緑色画素として本発明の膜を有することが更に好ましい。
本発明の固体撮像素子は、上述した本発明の膜を有する。固体撮像素子の構成としては、本発明の膜を備え、固体撮像素子として機能する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。
本発明の画像表示装置は、上述した本発明の膜を有する。画像表示装置としては、液晶表示装置や有機エレクトロルミネッセンス表示装置などが挙げられる。画像表示装置の定義や各画像表示装置の詳細については、例えば「電子ディスプレイデバイス(佐々木昭夫著、(株)工業調査会、1990年発行)」、「ディスプレイデバイス(伊吹順章著、産業図書(株)平成元年発行)」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術(内田龍男編集、(株)工業調査会、1994年発行)」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。
樹脂P1~P188、PP1~PP23、PP101~PP136、CP1~CP3は、それぞれ下記表に示す繰り返し単位を含む樹脂である。樹脂の酸価および重量平均分子量(Mw)を合わせて記す。樹脂P1~P188、PP1、PP2、PP101~PP136は、上述した特定樹脂である。
A-1:下記構造の繰り返し単位(ナフタルイミド構造を有する繰り返し単位)
A-2:下記構造の繰り返し単位(ナフタルイミド構造を有する繰り返し単位)
A-3:下記構造の繰り返し単位(アクリドン構造を有する繰り返し単位)
A-4:下記構造の繰り返し単位(ベンゾチアゾール構造を有する繰り返し単位)
A-5:下記構造の繰り返し単位(ベンゾイミダゾール構造を有する繰り返し単位)
A-6:下記構造の繰り返し単位(ベンゾオキサゾール構造を有する繰り返し単位)
A-7:下記構造の繰り返し単位(ベンゾトリアゾール構造を有する繰り返し単位)
A-8:下記構造の繰り返し単位(テトラゾール構造を有する繰り返し単位)
A-9:下記構造の繰り返し単位(フタルイミド構造を有する繰り返し単位)
A-10:下記構造の繰り返し単位(フタルイミド構造を有する繰り返し単位)
A-11:下記構造の繰り返し単位(カルバゾール構造を有する繰り返し単位)
A-12:下記構造の繰り返し単位(フルオレン構造を有する繰り返し単位)
A-13:下記構造の繰り返し単位(ベンゾイミダゾロン構造を有する繰り返し単位)
A-14:下記構造の繰り返し単位(アントラキノン構造を有する繰り返し単位)
A-15:下記構造の繰り返し単位(ベンゾチアジン構造を有する繰り返し単位)
A-16:下記構造の繰り返し単位(ベンゾオキサジン構造を有する繰り返し単位)
A-17:下記構造の繰り返し単位(ベンゾレインウレア構造を有する繰り返し単位)
A-18:下記構造の繰り返し単位(イソインドリン構造を有する繰り返し単位)
A-19:下記構造の繰り返し単位(イソインドリノン構造を有する繰り返し単位)
A-20:下記構造の繰り返し単位(フェノキサジン構造を有する繰り返し単位)
A-21:下記構造の繰り返し単位(フェノチアジン構造を有する繰り返し単位)
A-22:下記構造の繰り返し単位(ジヒドロアクリジン構造を有する繰り返し単位)
A-23:下記構造の繰り返し単位(ベンゾチアゾロン構造を有する繰り返し単位)
A-24:下記構造の繰り返し単位(ベンゾオキサゾリノン構造を有する繰り返し単位)
A-25:下記構造の繰り返し単位(イミダゾール構造を有する繰り返し単位)
A-26:下記構造の繰り返し単位(チアゾール構造を有する繰り返し単位)
A-27:下記構造の繰り返し単位(ピリミジン構造を有する繰り返し単位)
A-28:下記構造の繰り返し単位(キナゾリン構造を有する繰り返し単位)
A-29:下記構造の繰り返し単位(ピラジン構造を有する繰り返し単位)
A-30:下記構造の繰り返し単位(キノキサリン構造を有する繰り返し単位)
A-31:下記構造の繰り返し単位(ナフタレン-2,3-ジカルボキシイミド構造を有する繰り返し単位)
A-32:下記構造の繰り返し単位(キノリン構造を有する繰り返し単位)
A-33:下記構造の繰り返し単位(ベンゾフェノン構造を有する繰り返し単位)
A-34:下記構造の繰り返し単位(トリアジン構造を有する繰り返し単位)
A-35:下記構造の繰り返し単位(チオキサントン構造を有する繰り返し単位)
A-36:下記構造の繰り返し単位(クロマン構造を有する繰り返し単位)
A-37:下記構造の繰り返し単位(チオクロマノン構造を有する繰り返し単位)
A-38:下記構造の繰り返し単位(アゾベンゼン構造を有する繰り返し単位)
A-39:下記構造の繰り返し単位(ジベンゾピラン構造を有する繰り返し単位)
A-40:下記構造の繰り返し単位(ベンザルアニリン構造を有する繰り返し単位)
A-41:下記構造の繰り返し単位(フェナジン構造を有する繰り返し単位)
A-42:下記構造の繰り返し単位(バルビツル酸構造を有する繰り返し単位)
A-43:下記構造の繰り返し単位(キサントン構造を有する繰り返し単位)
A-44:下記構造の繰り返し単位(サッカリン構造を有する繰り返し単位)
A-45:下記構造の繰り返し単位(フェノキサチイン構造を有する繰り返し単位)
A-46:下記構造の繰り返し単位(ピラゾール構造を有する繰り返し単位)
A-47:下記構造の繰り返し単位(ピラゾロン構造を有する繰り返し単位)
A-48:下記構造の繰り返し単位(カプロラクタム構造を有する繰り返し単位)
A-49:下記構造の繰り返し単位(インドール構造を有する繰り返し単位)
A-50:下記構造の繰り返し単位(ビフェニル構造を有する繰り返し単位)
A-51:下記構造の繰り返し単位(ベンゾチオフェン構造を有する繰り返し単位)
A-52:下記構造の繰り返し単位(カルボリン構造を有する繰り返し単位)
A-53:下記構造の繰り返し単位(ベンゾオキサジアゾール構造を有する繰り返し単位)
A-54:下記構造の繰り返し単位(ベンゾチアジアゾール構造を有する繰り返し単位)
A-55:下記構造の繰り返し単位(トリアリールベンゼン構造を有する繰り返し単位)
A-56:下記構造の繰り返し単位(トリアリールアミン構造を有する繰り返し単位)
A-57:下記構造の繰り返し単位(イソチアゾリノン構造を有する繰り返し単位)
下記表に記載の素材を混合した混合液を、ビーズミル(0.1mm径のジルコニアビーズを使用)を用いて3時間混合及び分散した後さらに減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、2000MPaの圧力下で流量500g/minとして分散処理を行った。この分散処理を10回繰り返して各顔料分散液を得た。下記表に記載の数値は質量部での値である。各顔料分散液中の顔料の平均粒子径(nm)、粘度の値(mPa・s)を合わせて記す。顔料の平均粒子径はnanoSAQLA(大塚電子社製)を用いて動的光散乱法にて測定した。顔料分散液の粘度は、顔料分散液の温度を25℃に調整して測定した。
(色材)
PR254 : C.I.ピグメントレッド254(ジケトピロロピロール化合物、赤色顔料)
PR272 : C.I.ピグメントレッド272(ジケトピロロピロール化合物、赤色顔料)
PY139 : C.I.ピグメントイエロー139(イソインドリン化合物、黄色顔料)
PG36 : C.I.ピグメントグリーン36(フタロシアニン化合物、緑色顔料)
PG58 : C.I.ピグメントグリーン58(フタロシアニン化合物、緑色顔料)
PB15:6 : C.I.ピグメントブルー15:6(フタロシアニン化合物、青色顔料)
PV23 : C.I.ピグメントバイオレット23(ジオキサジン化合物、紫色顔料)
PBk32 : C.I.ピグメントブラック32(ペリレン化合物、有機黒色顔料)
IR色材1:下記構造の化合物(近赤外線吸収顔料)
P1~P188、PP1~PP23、PP101~PP136、CP1、CP2、CP3:上述した樹脂
CP11:プライサーフA208F(第一工業製薬(株)製、リン酸基(pKa=約2)を有する樹脂、末端酸基型)
CP12:プライサーフH-3606(第一工業製薬(株)製、カルボキシ基(pKa=約4.5)を有する樹脂、末端酸基型)
CP13:下記構造の樹脂(スルホ基(pKa=約2)を有する樹脂、末端酸基型)
溶剤1:プロピレングリコールモノメチルエーテルアセテート
溶剤2:シクロペンタノン
溶剤3:1-メトキシ-2-プロパノール
各素材を、以下に示す処方1~7の割合で混合し、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製)でろ過して各樹脂組成物を製造した。下記表において、樹脂組成物の全固形分中における色材の含有量の値を「色材の含有量」の欄に記載する。
下記表に記載の顔料分散液 ・・・520質量部
重合性化合物1 ・・・6.6質量部
重合性化合物2 ・・・12.6質量部
樹脂溶液1 ・・・3質量部
光重合開始剤1 ・・・5質量部
界面活性剤1 ・・・0.1質量部
熱硬化剤1 ・・・2質量部
溶剤1 ・・・200質量部
溶剤2 ・・・100質量部
溶剤3 ・・・21.96質量部
下記表に記載の顔料分散液 ・・・566.4質量部
重合性化合物1 ・・・6.6質量部
重合性化合物2 ・・・6.1質量部
樹脂溶液1 ・・・3質量部
光重合開始剤1 ・・・5質量部
界面活性剤1 ・・・0.1質量部
熱硬化剤1 ・・・2質量部
溶剤1 ・・・200質量部
溶剤2 ・・・100質量部
溶剤3 ・・・21.96質量部
下記表に記載の顔料分散液 ・・・603.6質量部
重合性化合物1 ・・・6.6質量部
重合性化合物2 ・・・1.9質量部
樹脂溶液1 ・・・3質量部
光重合開始剤1 ・・・4質量部
界面活性剤1 ・・・0.1質量部
熱硬化剤1 ・・・2質量部
溶剤1 ・・・200質量部
溶剤2 ・・・100質量部
溶剤3 ・・・21.96質量部
下記表に記載の顔料分散液 ・・・650質量部
重合性化合物1 ・・・6.6質量部
重合性化合物2 ・・・1.4質量部
樹脂溶液1 ・・・3質量部
光重合開始剤1 ・・・5質量部
界面活性剤1 ・・・0.1質量部
熱硬化剤1 ・・・2質量部
溶剤1 ・・・200質量部
溶剤2 ・・・100質量部
溶剤3 ・・・21.96質量部
下記表に記載の顔料分散液 ・・・566.4質量部
重合性化合物1 ・・・3.9質量部
重合性化合物2 ・・・15.9質量部
樹脂溶液1 ・・・3質量部
光重合開始剤1 ・・・5質量部
界面活性剤1 ・・・0.1質量部
熱硬化剤1 ・・・1質量部
溶剤1 ・・・200質量部
溶剤2 ・・・100質量部
溶剤3 ・・・21.96質量部
下記表に記載の顔料分散液 ・・・371.4質量部
染料1 ・・・21質量部
重合性化合物1 ・・・6.6質量部
重合性化合物2 ・・・12.4質量部
樹脂溶液1 ・・・3質量部
光重合開始剤1 ・・・5質量部
界面活性剤1 ・・・0.1質量部
熱硬化剤1 ・・・2質量部
溶剤1 ・・・200質量部
溶剤2 ・・・100質量部
溶剤3 ・・・21.96質量部
下記表に記載の顔料分散液 ・・・566.4質量部
重合性化合物1 ・・・3.9質量部
重合性化合物2 ・・・5.7質量部
樹脂溶液1 ・・・3質量部
光重合開始剤1 ・・・3質量部
界面活性剤1 ・・・0.1質量部
熱硬化剤1 ・・・1質量部
溶剤1 ・・・200質量部
溶剤2 ・・・100質量部
溶剤3 ・・・21.96質量部
下記表に記載の顔料分散液 ・・・696.4質量部
重合性化合物1 ・・・3.9質量部
重合性化合物2 ・・・1.1質量部
樹脂溶液1 ・・・3質量部
光重合開始剤1 ・・・3質量部
界面活性剤1 ・・・0.1質量部
熱硬化剤1 ・・・1質量部
溶剤1 ・・・200質量部
溶剤2 ・・・100質量部
溶剤3 ・・・21.96質量部
下記表に記載の顔料分散液 ・・・464.3質量部
重合性化合物1 ・・・6.6質量部
重合性化合物2 ・・・12.6質量部
樹脂溶液1 ・・・3質量部
光重合開始剤1 ・・・5質量部
界面活性剤1 ・・・0.1質量部
熱硬化剤1 ・・・2質量部
溶剤1 ・・・200質量部
溶剤2 ・・・100質量部
溶剤3 ・・・21.96質量部
重合性化合物2:KAYARAD RP-1040(日本化薬(株)製)
樹脂溶液1:下記構造の樹脂(重量平均分子量9000、繰り返し単位に付記した数値は質量比である)の30質量%プロピレングリコールモノメチルエーテルアセテート溶液
界面活性剤1:KF6001(信越化学工業(株)製、シリコーン系界面活性剤)
熱硬化剤1:下記構造の化合物T-1
溶剤2:シクロペンタノン
溶剤3:1-メトキシ-2-プロパノール
(色ムラ)
ガラス基板上に、下地層形成用組成物(CT-4000、富士フイルムエレクトロニクスマテリアルズ(株)製)を膜厚が0.1μmとなるようにスピンコート法で塗布し、ホットプレートを用いて220℃で1時間加熱して下地層を形成した。この下地層付きのガラス基板上に各樹脂組成物をスピンコート法で塗布し、その後、ホットプレートを用いて100℃で2分間加熱して、膜厚0.5μmの組成物層を得た。この組成物層に対して、i線ステッパー露光装置FPA-3000i5+(キヤノン(株)製)を用いて365nmの波長の光を500mJ/cm2の露光量で照射して露光した。露光後の組成物層に対し、テトラメチルアンモニウムハイドロオキサイドの0.3質量%水溶液を用い、23℃で60秒間パドル現像を行った。その後、スピン・シャワーにて水を用いてリンスを行い、更に純水にて水洗いを行った。その後、水滴を高圧のエアーで飛ばし、ガラス基板を自然乾燥させたのち、ホットプレートを用いて220℃で300秒間ポストベークを行い、膜を形成した。この膜が形成されたガラス基板(評価用基板)をいて輝度分布を下記方法で解析し、平均からのずれが±10%以上である画素数をもとに色ムラの評価を行った。
輝度分布の測定方法について説明する。評価用基板を光学顕微鏡の観測レンズと光源との間に設置して光を観測レンズに向けて照射し、その透過光状態をデジタルカメラが設置された光学顕微鏡MX-50(オリンパス社製)を用いて観察した。膜表面の撮影は、任意に選択した5つの領域に対して行った。撮影画像の輝度を0~255までの256階調の濃度分布として数値化して保存した。この画像から輝度分布を解析し、平均からのズレが±10%を超える画素数にて色ムラを評価した。評価基準は以下の通りである。A~Cの評価であれば実用上問題ないと判断する。
A:平均からのズレが±10%を超える画素数が1000以下である。
B:平均からのズレが±10%を超える画素数が1000を超え3000以下である。
C:平均からのズレが±10%を超える画素数が3000を超え5000以下である。
D:平均からのズレが±10%を超える画素数が5000を超える。
ガラス基板上に、下地層形成用組成物(CT-4000、富士フイルムエレクトロニクスマテリアルズ(株)製)をポストベーク後に厚さが0.1μmになるようにスピンコーターを用いて塗布し、ホットプレートを用いて220℃で300秒間加熱して下地層を形成し、下地層付ガラス基板(支持体)を得た。この下地層付きのガラス基板上に各樹脂組成物をスピンコート法で塗布し、その後、ホットプレートを用いて100℃で2分間加熱して、膜厚0.5μmの膜を形成した。この膜に含まれる異物を、異物評価装置コンプラスIII(アプライドマテリアルズ社製)にて検出し、検出された全ての異物から、最大幅1.0μm以上の異物(粗大粒子)を目視で分類し、分類された最大幅1.0μm以上の粗大粒子の個数(1cm2あたりの粗大粒子の個数)をカウントした。
A:膜1cm2あたりの粗大粒子の個数が10個未満である
B:膜1cm2あたりの粗大粒子の個数が10個以上30個未満である
C:膜1cm2あたりの粗大粒子の個数が30個以上100個未満である
D:膜1cm2あたりの粗大粒子の個数が100個以上である
8インチ(20.32cm)シリコンウエハに、下地層形成用組成物(CT-4000、富士フイルムエレクトロニクスマテリアルズ(株)製)をポストベーク後に厚さが0.1μmになるようにスピンコーターを用いて塗布し、ホットプレートを用いて220℃で300秒間加熱して下地層を形成し、下地層付シリコンウエハ(支持体)を得た。次いで、各樹脂組成物をポストベーク後の膜厚が0.62μmになるようにスピンコート法で塗布した。次いで、ホットプレートを用いて、100℃で2分間加熱した。次いで、i線ステッパー露光装置FPA-3000i5+(キヤノン(株)製)を用い、365nmの波長の光を1000mJ/cm2の露光量で1.0μm四方のドットパターンのマスクを介して露光した。次いで、露光された塗布膜が形成されているシリコンウエハをスピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、CD-2000(富士フイルムエレクトロニクスマテリアルズ(株)製)の60%希釈液を用いて23℃で60秒間パドル現像を行ったのち、シリコンウエハを真空チャック方式で水平回転テーブルに固定し、回転装置によってシリコンウエハを回転数50rpmで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行い、その後スプレー乾燥した。さらに、200℃のホットプレートを用いて300秒間加熱処理(ポストベーク)を行いパターン(画素)を形成した。
画素が形成されたシリコンウエハについて、走査型電子顕微鏡(SEM)(倍率10000倍)で観察し、下記評価基準に従って現像性を評価した。
A:画素の形成領域外(未露光部)には、残渣がまったく確認されなかった
B:画素の形成領域外(未露光部)に、残渣がごくわずかに確認されたが、実用上問題のない程度であった
C:画素の形成領域外(未露光部)に、残渣がわずかに確認されたが、実用上問題のない程度であった
D:画素の形成領域外(未露光部)に、残渣が著しく確認された
実施例及び比較例の樹脂組成物の粘度(mPa・s)を、東機産業(株)製「RE-85L」にて測定した。上記測定後、樹脂組成物を45℃、遮光、5日間の条件にて静置し、再度粘度(mPa・s)を測定した。上記静置前後での粘度差(ΔVis)から下記評価基準に従って経時安定性を評価した。粘度差(ΔVis)の数値が小さいほど、樹脂組成物の経時安定性が良好であるといえる。上記粘度測定は、いずれも、温湿度を22±5℃、60±20%に管理した実験室で、樹脂組成物の温度を25℃に調整した状態で測定した。いずれの測定も3回測定を行い、平均値を用いた。
A:ΔVisが0.2mPa・s以下であった
B:ΔVisが0.2mPa・sを超え、0.3mPa・s以下であった
C:ΔVisが0.3mPa・sを超え、0.5mPa・s以下であった
D:ΔVisが0.5mPa・sを超えた
[隔壁用組成物の製造]
以下の表の組成となるように各成分を混合したのち、ろ過フィルタ(Protego Plus PRL00S1S1、Entegris製)でろ過した後、更にろ過フィルタ(DFA4201J006、Pall製)でろ過し隔壁用組成物を得た。下記表に記載の配合量の数値は質量部である。また、シリカ粒子液の配合量はシリカ粒子液中のSiO2の値である。溶剤の配合量の数値は、シリカ粒子液に含まれている溶剤量を合計した数値である。
(シリカ粒子液)
P1:平均粒子径10nmの球状シリカの複数個が、金属酸化物含有シリカ(連結材)によって数珠状に連結された形状のシリカ粒子(数珠状シリカ)の溶液である。
P2:スルーリア4110:日揮触媒化成(株)製、平均粒子径60nmのシリカ粒子(中空構造のシリカ粒子)の溶液である。SiO2換算の固形分濃度20質量%
F1:下記構造の化合物(重量平均分子量=3000)
F3:パイオニンB-111(竹本油脂製、ラウリルトリメチルアンモニウムクロリド)
S1:1,4-ブタンジオールジアセテート
S2:プロピレングリコールモノメチルエーテルアセテート
S3:プロピレングリコールモノメチルエーテル
S4:エタノール
S5:水
シリコンウエハ上に、上記で製造した隔壁用組成物を用いて上記で製造した隔壁用組成物を用いて特開2017-028241号公報の図1の隔壁40~43を作製した。
次に、シリコンウエハ上の隔壁で区画された領域に、緑色画素形成用組成物、赤色画素形成用組成物および青色画素形成用組成物を用いてフォトリソグラフィ法でパターン形成して緑色画素、赤色画素および青色画素をそれぞれ形成し、イメージセンサを製造した。得られたイメージセンサは感度に優れていた。
なお、緑色画素形成用組成物には実施例1の樹脂組成物を用いた。また、赤色画素形成用組成物には、実施例70の樹脂組成物を用いた。また、青色画素形成用組成物には、実施例76の樹脂組成物を用いた。
Claims (16)
- 色材Aと樹脂Bとを含む樹脂組成物であって、
前記色材Aは、顔料を含み、
前記樹脂Bは、酸基を有する繰り返し単位b1-1と、芳香族環を2以上含む基、複素環基を含む基および縮合環を含む基から選ばれる官能基bを有する繰り返し単位b1-2と、前記繰り返し単位b1-1および前記繰り返し単位b1-2以外の繰り返し単位b1-3とを含む樹脂b1を含有し、
前記樹脂組成物の全固形分中における前記色材Aの含有量が55質量%以上である、樹脂組成物。 - 前記色材Aはフタロシアニン顔料を含む、請求項1に記載の樹脂組成物。
- 前記色材Aは、更に染料を含む、請求項1または2に記載の樹脂組成物。
- 前記官能基bは、ナフタルイミド構造、アクリドン構造、チオキサントン構造、キサントン構造、アントロン構造、ベンゾイミダゾール構造、ベンゾチアゾール構造、ベンゾオキサゾール構造、ベンゾトリアゾール構造、ベンゾオキサジアゾール構造、ベンゾチアジアゾール構造、ベンゾチアジン構造、ベンゾオキサジン構造、ベンゾレインウレア構造、イソチアゾリノン構造、フェノキサジン構造、フェノチアジン構造、ジヒドロアクリジン構造、フェノキサチイン構造、ジベンゾピラン構造、フルオレン構造、カルバゾール構造、カルボリン構造、ジベンゾチオフェン構造、ジベンゾフラン構造、ピリミジン構造、ピラジン構造、キナゾリン構造、キノキサリン構造、キノリン構造、イミダゾール構造、チアゾール構造、インドール構造、ベンゾチオフェン構造、ベンゾピラン構造、キノリノン構造、チオクロマノン構造、クロマン構造、ベンゾイミダゾロン構造、フタルイミド構造、ナフタレン-2,3-ジカルボキシイミド構造、ピラゾール構造、ピラゾロン構造、イソインドリン構造、イソインドリノン構造、アントラキノン構造、テトラゾール構造、ベンゾフェノン構造、トリアジン構造、アゾベンゼン構造、ベンザルアニリン構造、フェナジン構造、バルビツル酸構造、ペリレン構造、ペリノン構造、キノフタロン構造、カプロラクタム構造、サッカリン構造、ビフェニル構造、トリアリールベンゼン構造、トリアリールアミン構造、ベンゾチアゾロン構造またはベンゾオキサゾリノン構造を含む基である、請求項1~3のいずれか1項に記載の樹脂組成物。
- 前記官能基bは、ナフタルイミド構造、アクリドン構造、キサントン構造、ベンゾイミダゾール構造、ベンゾチアゾール構造、ベンゾオキサゾール構造、ベンゾトリアゾール構造、ベンゾオキサジアゾール構造、ベンゾチアジアゾール構造、フェノキサジン構造、フェノチアジン構造、フェノキサチイン構造、フタルイミド構造、ピラゾロン構造、テトラゾール構造、ベンゾチアゾロン構造またはベンゾオキサゾリノン構造を含む基である、請求項1~3のいずれか1項に記載の樹脂組成物。
- 前記樹脂b1中における前記単位b1-2の含有量が10~35質量%である、請求項1~5のいずれか1項に記載の樹脂組成物。
- 前記繰り返し単位b1-3は、ポリエステル構造またはポリエーテル構造のグラフト鎖を有する繰り返し単位を含む、請求項1~6のいずれか1項に記載の樹脂組成物。
- 前記樹脂Bは、更に、前記樹脂b1とは異なる樹脂b2を含む、請求項1~7のいずれか1項に記載の樹脂組成物。
- 前記樹脂b2は、前記樹脂b1とは異なる酸基を有する樹脂を含む、請求項8に記載の樹脂組成物。
- 前記樹脂b2は、前記樹脂b1が有する酸基よりも小さいpKaの酸基を有する、請求項9に記載の樹脂組成物。
- 前記樹脂b2は、グラフトポリマー、星形ポリマー、ブロック共重合体およびポリマー鎖の少なくとも一方の末端が酸基で封止された樹脂から選ばれる少なくとも1種を含む、請求項8~10のいずれか1項に記載の樹脂組成物。
- 更に、重合性化合物と光重合開始剤とを含む、請求項1~11のいずれか1項に記載の樹脂組成物。
- 請求項1~12のいずれか1項に記載の樹脂組成物から得られる膜。
- 請求項13に記載の膜を有する光学フィルタ。
- 請求項13に記載の膜を有する固体撮像素子。
- 請求項13に記載の膜を有する画像表示装置。
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