CN119452305A - Curable composition, light shielding film, solid-state imaging element, image display device, infrared sensor, and method for producing cured film - Google Patents
Curable composition, light shielding film, solid-state imaging element, image display device, infrared sensor, and method for producing cured film Download PDFInfo
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- CN119452305A CN119452305A CN202380049274.7A CN202380049274A CN119452305A CN 119452305 A CN119452305 A CN 119452305A CN 202380049274 A CN202380049274 A CN 202380049274A CN 119452305 A CN119452305 A CN 119452305A
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
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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
- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/02—Details
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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
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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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
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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- 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
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- 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
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Abstract
The 1 st object of the present invention is to provide a curable composition which exhibits excellent adhesion to a cured film obtained by curing and also exhibits excellent low reflectivity to infrared light. Further, the 2 nd object of the present invention is to provide a light shielding film, a solid-state imaging device, an image display device, and an infrared sensor. The curable composition of the present invention comprises a prescribed resin A, a prescribed resin B, a polymerizable compound, a pigment and a photopolymerization initiator, wherein the ratio of the content of the resin A to the total content of the resin A and the resin B is 0.30 to 0.50, and the ratio of the content of the polymerizable compound to the total content of the resin A, the resin B and the polymerizable compound is 0.30 to 0.50.
Description
Technical Field
The invention relates to a curable composition, a light shielding film, a solid-state imaging element, an image display device, an infrared sensor, and a method for manufacturing a cured film.
Background
Image display devices such as liquid crystal display devices, and solid-state imaging devices such as CCD (Charge Coupled Device: charge coupled device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor: complementary metal oxide semiconductor) image sensors often have color filters or light shielding films disposed at predetermined positions. For example, in a liquid crystal display device, a light shielding film called a black matrix may be disposed between colored pixels on a color filter in order to shield light between the colored pixels and to improve contrast. In addition, a light shielding film may be applied to the solid-state imaging device for the purpose of preventing noise generation, improving image quality, and the like.
The color filter or the light-shielding film is typically produced by curing a curable composition containing a colorant, an alkali-soluble resin, a monomer, and the like.
For example, patent document 1 discloses a coloring composition containing a predetermined component for use in a color filter or the like.
Technical literature of the prior art
Patent literature
Patent document 1 Japanese patent laid-open No. 2022-029341
Disclosure of Invention
Technical problem to be solved by the invention
The light shielding film is required to have not only light shielding properties but also low reflectivity, and in recent years, low reflectivity to infrared light is also desired.
The present invention has been made in consideration of the properties of a cured film of the curable composition described in patent document 1, and has a room for further reducing the reflectivity to infrared light. In the step of forming a cured film using the curable composition, when the film after exposure was subjected to a development treatment with an aqueous alkali solution, the film in the exposed portion was found to be easily peeled off from the support. That is, it was found that there is room for further improvement in the adhesion of the cured film.
Accordingly, an object of the present invention is to provide a curable composition which exhibits excellent adhesion to a cured film obtained by curing and also exhibits excellent low reflectivity to infrared light.
The present invention also provides a light shielding film, a solid-state imaging device, an image display device, an infrared sensor, and a method for manufacturing a cured film.
Means for solving the technical problems
As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configuration.
[ 1 ] A curable composition comprising a resin A, a resin B, a polymerizable compound, a pigment and a photopolymerization initiator,
The resin A contains a repeating unit having an acid group and a repeating unit having a group selected from the group consisting of a polyoxyalkylene group having an average addition number of 3 or more and a polyoxyalkylene carbonyl group having an average addition number of 3 or more,
The content of the repeating unit having a group selected from the group consisting of polyoxyalkylene groups having an average addition number of 3 or more and polyoxyalkylene carbonyl groups having an average addition number of 3 or more is 35% by mass or more relative to all the repeating units of the resin A,
The acid value of the resin A is 50mgKOH/g or more,
The resin B contains a repeating unit derived from a monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, a repeating unit having a hydroxyl group, and a repeating unit having a carboxylic acid group,
The content of the repeating unit derived from the monomer selected from the group consisting of alkyl acrylate and alkyl methacrylate is 60 mass% or more with respect to all the repeating units of the resin B,
The ratio of the content of the resin A to the total content of the resin A and the resin B is 0.30 to 0.50,
The ratio of the content of the polymerizable compound to the total content of the resin A, the resin B and the polymerizable compound is 0.30 to 0.50.
The curable composition according to [ 2], wherein,
The repeating unit having an acid group includes 1 or more selected from the group consisting of a repeating unit represented by the formula (a 11) described below, a repeating unit represented by the formula (a 12) described below, and a repeating unit represented by the formula (a 13) described below.
The curable composition according to [1 ] or [ 2 ], wherein,
The resin a further contains a repeating unit having a benzyl group.
The curable composition according to any one of [1] to [ 3 ], wherein,
In the repeating unit derived from the monomer selected from the group consisting of alkyl acrylate and alkyl methacrylate, the number of carbon atoms of the alkyl group bonded to the ester bond in the alkyl acrylate and alkyl methacrylate is 4 or more.
The curable composition according to any one of [1] to [4 ], wherein,
The content of the repeating unit derived from the monomer selected from the alkyl acrylate and the alkyl methacrylate is 80 mass% or more with respect to all the repeating units of the resin B.
The curable composition according to any one of [1] to [ 5], wherein,
The acid value of the resin B is 55mgKOH/g or more.
The curable composition according to any one of [1] to [ 6 ], wherein,
The above-mentioned repeating unit having a hydroxyl group contains a repeating unit derived from a monomer selected from the group consisting of 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
The curable composition according to any one of [1] to [7], wherein,
The pigment contains titanium oxynitride.
The curable composition according to any one of [ 1 ] to [ 8 ], which is a composition for forming a light shielding film.
[ 10 ] A light-shielding film comprising a cured film formed from the curable composition of any one of [ 1] to [ 9 ].
[ 11 ] A solid-state imaging device comprising a cured film formed from the curable composition of any one of [ 1 ] to [ 9 ].
[ 12 ] An image display device comprising a cured film formed from the curable composition of any one of [ 1 ] to [ 9 ].
An infrared sensor comprising a cured film formed from the curable composition of any one of [ 1 ] to [ 9 ].
The optical filter of [ 14 ] comprising a cured film formed from the curable composition of any one of [ 1] to [ 9 ].
[ 15 ] A cover glass comprising a cured film formed from the curable composition of any one of [ 1] to [ 9 ].
[ 16 ] A method for producing a cured film, comprising:
A composition layer forming step of forming a composition layer on a support by using the curable composition described in any one of [1] to [ 9 ];
an exposure step of exposing the composition layer by irradiation of actinic rays or radiation, and
And a developing step of developing the composition layer after exposure.
Effects of the invention
According to the present invention, a curable composition that exhibits excellent adhesion of a cured film obtained by curing and also exhibits excellent low reflectivity to infrared light can be provided.
Further, according to the present invention, a light shielding film, a solid-state imaging device, an image display device, an infrared sensor, and a method for manufacturing a cured film can be provided.
Detailed Description
The present invention will be described in detail below.
The constituent elements described below are described in terms of representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range indicated by "-" means a range including numerical values before and after "-" as a lower limit value and an upper limit value.
In the expression of the group (atomic group) in the present specification, the expression of substituted and unsubstituted includes a group containing no substituent and a group containing a substituent. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent but also an alkyl group (substituted alkyl group) having a substituent.
In the present specification, "actinic rays" or "radiation" means, for example, extreme ultraviolet rays (EUV: extreme ultraviolet lithography), X-rays, electron beams, and the like. In the present specification, light means actinic rays and radiation. The term "exposure" in the present specification includes exposure using extreme ultraviolet rays, X-rays, EUV light, and the like, and drawing using a particle beam such as an electron beam or an ion beam, unless otherwise specified.
In the present specification, "(meth) acrylate" means acrylate and methacrylate. In the present specification, "(meth) acrylic acid" means acrylic acid and methacrylic acid. In the present specification, "(meth) acryl" means acryl and methacryl. In the present specification, "(meth) acrylamide" means acrylamide and methacrylamide. In the present specification, the meaning of "monomer" is the same as that of "monomer".
In the present specification, the weight average molecular weight (Mw) is a polystyrene equivalent based on GPC (Gel Permeation Chromatography: gel permeation chromatography).
In the present specification, the GPC method is based on the method using HLC-8020GPC (manufactured by TOSOH Corporation), TSKgel SuperHZM-H as a column, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH Corporation, 4.6 mmID. Times.15 cm), and THF (tetrahydrofuran) as an eluent.
In the present specification, the "acid value" can be calculated from, for example, the average content of acid groups in the compound.
In the present specification, the solid component in the composition means a composition layer formed using the composition, and when the composition contains a solvent, it means all components except the solvent. In addition, if the composition layer is formed of a component, the liquid component is also regarded as a solid component.
[ Curable composition ]
The curable composition of the present invention comprises a resin A, a resin B, a polymerizable compound, a pigment, and a photopolymerization initiator,
The resin a contains a repeating unit having an acid group (hereinafter also referred to as "repeating unit A1") and a repeating unit having a group selected from the group consisting of a polyoxyalkylene group having an average addition number of 3 or more and a polyoxyalkylene carbonyl group having an average addition number of 3 or more (hereinafter also referred to as "repeating unit A2"),
The content of the repeating unit (repeating unit A2) having a group selected from the polyoxyalkylene group and the polyoxyalkylene carbonyl group is 35% by mass or more with respect to all the repeating units of the resin A,
The acid value of the resin A is 50mgKOH/g or more,
The resin B contains a repeating unit derived from a monomer selected from the group consisting of alkyl acrylate and alkyl methacrylate (hereinafter also referred to as "repeating unit B1"), a repeating unit having a hydroxyl group (hereinafter also referred to as "repeating unit B2"), a repeating unit having a carboxylic acid group (hereinafter also referred to as "repeating unit B3"),
The content of the repeating unit (repeating unit B1) derived from the monomer selected from the alkyl acrylate and the alkyl methacrylate is 60 mass% or more with respect to all the repeating units of the resin B,
The ratio of the content of the resin A to the total content of the resin A and the resin B (hereinafter also referred to as "content ratio T1") is 0.30 to 0.50,
The ratio of the content of the polymerizable compound to the total content of the resin a, the resin B, and the polymerizable compound (hereinafter also referred to as "content ratio T2") is 0.30 to 0.50.
In the curable composition having the above-described structure, even when the film is formed into a cured film, the film in the exposed portion is not easily peeled from the support by performing a development treatment with an aqueous alkali solution on the film after exposure. That is, the cured film obtained by curing the curable composition having the above structure is excellent in adhesion. The cured film obtained by curing the curable composition is excellent in low reflectivity to infrared light.
The mechanism by which the constitution and effect of the present invention are estimated will be described below.
The cured film obtained by curing the curable composition having the above structure has a phase separation structure (for example, an island structure, a co-continuous structure, and a structure in which the island structure and the co-continuous structure coexist) due to the difference in compatibility of the resin a and the resin B, and can have a fine uneven structure on the surface of the film. The cured film was presumed to have excellent light scattering properties particularly for infrared light due to the concave-convex structure, and as a result, it exhibited excellent low reflectivity for infrared light.
The resin B contained in the curable composition has a high hydrophobicity because the content of the repeating unit (repeating unit B1) derived from the alkyl (meth) acrylate is 60 mass% or more with respect to all the repeating units of the resin B. Therefore, it is presumed that, when a cured film is produced by using the curable composition, the film after exposure is subjected to a development treatment with an aqueous alkali solution, and permeation of the aqueous alkali solution into the film after exposure is not easily generated, and as a result, the film in the exposed portion is not easily peeled from the support.
Further, it is considered that even when the content ratio T1 and the content ratio T2 are within a predetermined numerical range, both excellent adhesion of the cured film and excellent low reflectivity of infrared light to the cured film are greatly facilitated.
In addition, specific examples of the phase separation structure of the cured film include a sea-island structure or a co-continuous structure in which a domain portion composed of a pigment, a resin a, and a resin derived from the resin a (for example, a resin obtained by polymerizing a resin a having a polymerizable group) and a matrix portion composed of a resin B and a resin derived from the resin B (for example, a resin obtained by polymerizing a resin B having a polymerizable group).
Hereinafter, the effect of the present invention is also referred to as "more excellent" when the reflectivity of infrared light of a cured film obtained by curing the curable composition is more excellent, the adhesion of the cured film is more excellent, and/or development residues (unexposed portion residues) are less.
Hereinafter, the components of the curable composition of the present invention will be described.
[ Resin A ]
The curable composition contains a resin a.
The resin A contains a repeating unit (repeating unit A1) having an acid group and a repeating unit (repeating unit A2) selected from the group consisting of a polyoxyalkylene group having an average addition number of 3 or more and a polyoxyalkylene carbonyl group having an average addition number of 3 or more, and has an acid value of 50mgKOH/g or more. The content of the repeating unit A2 is 35 mass% or more with respect to all the repeating units of the resin a.
The resin A contains a repeating unit (repeating unit A1 and a repeating unit B3 described later) having a carboxylic acid group, a repeating unit (repeating unit A2) having a group selected from the group consisting of a polyoxyalkylene group having an average addition number of 3 or more and a polyoxyalkylene carbonyl group having an average addition number of 3 or more, a repeating unit (repeating unit B1 described later) derived from a monomer selected from the group consisting of an alkyl acrylate and an alkyl methacrylate, and a repeating unit (repeating unit B2 described later) having a hydroxyl group, and the resin A contains a repeating unit (repeating unit A2) having a group selected from the group consisting of a polyoxyalkylene group having an average addition number of 3 or more and a polyoxyalkylene carbonyl group having an average addition number of 3 or more in terms of an acid value of 60 mass% or more relative to all repeating units of the resin.
In addition, the structures are different from those of the repeating unit A1 and the repeating unit A2.
The repeating unit A1 may have a group selected from the group consisting of an oxyalkylene group and an oxyalkylene carbonyl group. When the repeating unit A1 contains a group selected from the group consisting of an oxyalkylene group and an oxyalkylene carbonyl group, the average addition number of the oxyalkylene group and the average addition number of the oxyalkylene carbonyl group are preferably 1 to 2.
The repeating unit A2 preferably contains no acid groups.
It is assumed that the resin a is adsorbed on the surface of the dispersion such as pigment by the above structure and also functions as a resin capable of preventing the re-aggregation of the dispersion. Specifically, the repeating unit A1 included in the resin a serves as an anchor (anchor) site to the pigment surface, and the space-repellent effect of the repeating unit A2 prevents the dispersion from re-agglomerating.
Further, from the viewpoint of further excellent steric exclusion effect due to the repeating unit A2 and further excellent effect of the present invention, the resin a is preferably a graft polymer having a graft chain containing a group selected from the group consisting of a polyoxyalkylene group having an average addition number of 3 or more and a polyoxyalkylene carbonyl group having an average addition number of 3 or more.
When the resin a is a graft polymer, the resin a has affinity with a solvent through a graft chain, and therefore dispersibility of a pigment or the like and dispersion stability over time are excellent. In addition, the compatibility difference between the resin A and the resin B is more likely to occur due to the existence of the graft chain, and the effect of the present invention is more likely to be excellent. Further, if the graft chain is a predetermined length, the adsorption force to the dispersion of pigment or the like is increased, and the dispersibility tends to be improved. Therefore, the number of atoms other than hydrogen atoms in the graft chain is preferably 40 to 10000, more preferably 50 to 2000, and still more preferably 60 to 500. Here, the graft chain represents the root of the main chain of the copolymer (the atom bonded to the main chain from the main chain branched group) to the end of the group branched from the main chain.
The macromonomer containing such a graft chain (a monomer having a polymer structure and constituting a graft chain by bonding to the main chain of the copolymer) is not particularly limited, and a macromonomer containing a reactive double bond group can be preferably used.
The repeating units contained in the resin a will be described below.
< Repeat Unit A1>
The resin a contains a repeating unit (repeating unit A1) having an acid group. In the resin a, the repeating unit A1 functions as the pigment adsorbing group, and further improves the developability of the resin a with an alkali developer.
Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and among these, a carboxylic acid group is preferable.
The number of the acid groups in the repeating unit A1 may be 1 or more, and for example, 1 to 6 may be mentioned.
The specific structure of the repeating unit A1 is not particularly limited, and a repeating unit represented by the following formula (AX 1) is preferable from the viewpoint of easy and more excellent effects of the present invention.
[ Chemical formula 1]
Wherein R A1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
The number of carbon atoms of the alkyl group represented by R A1 is preferably 1 to 3, more preferably 1.
L A1 represents a single bond, -COO-or-CONR A2-.RA2 has the same meaning as R A1, and the preferable mode is the same.
L A2 represents a single bond or a 2-valent linking group.
The type of the 2-valent linking group is not particularly limited, and examples thereof include a 2-valent aliphatic hydrocarbon group, a 2-valent aromatic hydrocarbon group, -O-, -S-, -SO 2-、-NRA3 -, -CO-, and a combination of 2 or more of these groups.
The aliphatic hydrocarbon group having a valence of 2 may be any of a linear, branched, and cyclic one. The number of carbon atoms is preferably 1 to 20, more preferably 1 to 10.
Examples of the aliphatic hydrocarbon group having a valence of 2 include an alkylene group, an alkenylene group, and an alkynylene group, and among these, an alkylene group is preferable.
The 2-valent aromatic hydrocarbon group is preferably a C6-10 hydrocarbon group, and examples thereof include phenylene groups.
The aliphatic hydrocarbon group having 2 valences and the aromatic hydrocarbon group having 2 valences may further have a substituent. The substituent is not particularly limited, and may be, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, or the like.
The meaning of R A3 is the same as that of R A1, and the preferable mode is the same.
Among these, 2 or more kinds of groups selected from the group consisting of an alkylene group which may have a substituent, a phenylene group which may have a substituent, -O-and-CO-are preferably combined.
In the above formula (AX 1), the number of atoms other than hydrogen atoms in the moiety represented by-L A1-LA2 -is preferably, for example, less than 40.
W A1 represents an acid group.
As the acid group, the above is mentioned.
The repeating unit A1 preferably contains 1 or more selected from the repeating unit represented by the following formula (a 11), the repeating unit represented by the following formula (a 12), and the repeating unit represented by the following formula (a 13) from the viewpoint of further excellent effects of the present invention.
In the formula (A13), n represents an average addition number of 1 to 2.
[ Chemical formula 2]
The resin a may contain 1 kind of repeating unit A1 alone or 2 or more kinds.
The content of the repeating unit A1 in the resin a is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 40% by mass, based on the total repeating units of the resin a. When 2 or more kinds of repeating units A1 are used simultaneously, the total content is preferably within the above range.
< Repeat unit A2>
The resin a contains a repeating unit (repeating unit A2) having a group selected from a polyoxyalkylene group having an average addition number of 3 or more and a polyoxyalkylene carbonyl group having an average addition number of 3 or more. As described above, it is assumed that the repeating unit A2 in the resin a not only plays a role of preventing the pigment and the like from being re-coagulated by the dispersion, but also contributes to the formation of a phase separation structure when the resin is formed into a cured film.
In addition, oxyalkylene represents a group represented by-O-AL-, the oxyalkylene carbonyl group represents a group represented by-O-AL-CO-. AL represents an alkylene group.
Further, a polyoxyalkylene group represents a group represented by- (O-AL) n1 -and a polyoxyalkylene carbonyl group represents a group represented by- (O-AL-CO) n2 -.
In addition, in the polyoxyalkylene and polyoxyalkylene carbonyl groups, a plurality of oxyalkylene groups (-O-AL-) may be the same or different.
The number of carbon atoms (number of carbon atoms of AL) of the alkylene group in the oxyalkylene group and the oxyalkylene carbonyl group is not particularly limited, but is preferably 2 to 10, more preferably 2 to 9, and further preferably 2 to 7.
The average addition number (n 1) in the polyoxyethylene is 3 or more, preferably 4 or more, more preferably 5 or more, further preferably 6 or more, particularly preferably 10 or more, and most preferably 15 or more. The upper limit value is preferably 100 or less, more preferably 70 or less, and even more preferably 30 or less.
The average addition number (n 2) in the oxyalkylene carbonyl group is 3 or more, preferably 4 or more, more preferably 5 or more, and still more preferably 6 or more. The upper limit value is preferably 100 or less, more preferably 70 or less, and even more preferably 30 or less.
In the polyoxyalkylene group having an average addition number of 3 or more, the number of carbon atoms of the alkylene portion of the plurality of oxyalkylene groups may be the same or different. The case where the alkylene portions of the plurality of oxyalkylene groups have different numbers of carbon atoms means, for example, a structure including oxyethylene groups and oxypropylene groups, and the like. In addition, in the polyoxyalkylene carbonyl group having an average addition number of 3 or more, the number of carbon atoms in the alkylene portion of the plurality of polyoxyalkylene carbonyl groups may be the same or different. The case where the alkylene portions of the plurality of oxyalkylene carbonyl groups have different numbers of carbon atoms means, specifically, a structure including an oxyethylene carbonyl group and an oxypropylene carbonyl group, and the like.
The repeating unit A2 is preferably a repeating unit represented by any one of the following formulas (1) to (3), and more preferably a repeating unit represented by the following formulas (1) or (3).
[ Chemical formula 3]
In the formulas (1) to (3), W 1、W2 and W 3 each independently represent an oxygen atom or NH. The preferable examples of W 1、W2 and W 3 are oxygen atoms.
In the formulas (1) to (3), X 1、X2 and X 3 each independently represent a hydrogen atom or a 1-valent organic group. From the viewpoint of restrictions on synthesis, X 1、X2 and X 3 are preferably each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (the number of carbon atoms), more preferably each independently a hydrogen atom or a methyl group, and still more preferably a methyl group.
In the formulas (1) to (3), Y 1、Y2 and Y 3 each independently represent a 2-valent linking group. The structure of the 2-valent linking group represented by Y 1、Y2 and Y 3 is not particularly limited, and specifically, examples thereof include the following linking groups (Y-1) to (Y-21). In the structures shown below, A, B refers to bonding sites with the left end group and the right end group in the formulas (1) to (3), respectively.
[ Chemical formula 4]
In the formulas (1) to (3), Z 1、Z2 and Z 3 each independently represent a hydroxyl group, an amino group or a 1-valent organic group. The organic group is not particularly limited, and specifically includes an alkyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, and the like.
The alkyl moiety in the alkyl group, alkoxy group, or alkyl thioether group represented by Z 1、Z2 and Z 3 may be any of linear, branched, and cyclic, and is preferably 1 to 30 carbon atoms. And, methylene in the alkoxy group may be substituted with-O-.
Among them, the organic group represented by Z 1、Z2 and Z 3 is preferably a group having a steric repulsion effect, more preferably an alkyl group or an alkoxy group having 5 to 24 carbon atoms, still more preferably a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms or an alkoxy group having 5 to 24 carbon atoms, from the viewpoint of improving dispersibility.
Each of the above groups may have a substituent (for example, an ethylenically unsaturated group such as a hydroxyl group or a (meth) acryloyloxy group).
In addition, in formula (1), when Z 1 is a hydroxyl group, the site represented by-COZ 1 in the formula may be anionized (-COO -). In this case, as the counter cation, a quaternary ammonium salt is exemplified.
In the formulas (1) and (2), n and m represent average addition numbers, and represent numbers equal to or greater than 3. Among these, the lower limit values of n and m are preferably 4 or more, more preferably 5 or more, and still more preferably 6 or more. The upper limit value of n and m is preferably 100 or less, more preferably 70 or less, further preferably 50 or less, and particularly preferably 30 or less.
In the formula (3), p represents an average addition number, and represents a number of 3 or more. Among these, the lower limit value of p is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, still more preferably 10 or more, particularly preferably 15 or more, and most preferably 20 or more. The upper limit value of p is preferably 100 or less, more preferably 70 or less, further preferably 50 or less, and particularly preferably 30 or less.
In the formulas (1) and (2), j and k each independently represent an integer of 2 to 10. The j and k in the formulas (1) and (2) are preferably an integer of 2 to 9, more preferably an integer of 2 to 7, still more preferably an integer of 4 to 6, and particularly preferably 5, from the viewpoint of further excellent viscosity stability and developability with time of the curable composition.
In formula (3), R 3 represents a branched or linear alkylene group. The number of carbon atoms of the alkylene group is preferably 2 to 10, more preferably 2 to 9, still more preferably 2 to 7, and particularly preferably 2 or 3. When p is 2 to 100, a plurality of R 3 may be the same or different.
The repeating unit A2 is preferably a repeating unit having an average addition number of 3 or more polyoxyalkylene carbonyl groups, more preferably a repeating unit represented by the above formula (1) or (2), and even more preferably a repeating unit represented by the above formula (1), from the viewpoint of further excellent effects of the present invention.
The resin a may contain 1 kind of repeating unit A2 alone or 2 or more kinds thereof.
The content of the repeating unit A2 in the resin a is 35 mass% or more, preferably 40 mass% or more, more preferably 50 mass% or more, and even more preferably 60 mass% or more, based on all the repeating units of the resin a. The upper limit is preferably 90 mass% or less, more preferably 80 mass% or less, and still more preferably 75 mass% or less. When 2 or more kinds of repeating units A2 are used simultaneously, the total content is preferably within the above range.
< Other repeating units (repeating unit A3) >)
The resin a may contain repeating units other than the repeating unit A1 and the repeating unit A2 (hereinafter also referred to as "repeating unit A3").
Examples of the other repeating unit include other repeating units having various functions other than the repeating units described above.
Examples of the other repeating unit include a hydrophobic repeating unit (hereinafter also referred to as "repeating unit a 31"), a repeating unit having a curable group (hereinafter also referred to as "repeating unit a 32"), a repeating unit having a functional group capable of interacting with a pigment or the like (hereinafter also referred to as "repeating unit a 33"), and a repeating unit derived from a radical monomer selected from acrylonitrile and methacrylonitrile.
(Repeating unit A31)
The resin a may contain a hydrophobic repeating unit (repeating unit a 31).
In one embodiment of the repeating unit A31, the repeating unit is derived from a compound (monomer) having a ClogP value of 1.2 or more, and among these, the repeating unit is preferably derived from a compound having a ClogP value of 1.2 to 8.
In this specification, clogP values are values calculated by the procedure "CLOGP" available from DAYLIGHT CHEMICAL Information System, inc. This procedure provides the value of "calculated log P" calculated by the Hansch, leo fragment method (see below). The fragmentation method is to divide a chemical structure into partial structures (fragments) based on the chemical structure of a compound, and calculate the logP value of the compound by summing up the logP contributions assigned to the fragments. Details of this are described in the following documents. In this specification, the ClogP value calculated by procedure CLOGP v 4.82.82 is used.
A.J.Leo,Comprehensive Medicinal Chemistry,Vol.4,C.Hansch,P.G.Sammnens,J.B.Taylor and C.A.Ramsden,Eds.,p.295,Pergamon Press,1990C.Hansch&A.J.Leo.SUbstituent Constants For Correlation Analysis in Chemistry and Biology.John Wiley&Sons.A.J.Leo.Calculating logPoct from structure.Chem.Rev.,93,1281-1306,1993.
Log p refers to the usual logarithm of partition coefficient P (Partition Coefficient) and is a physical property value expressed as a quantitative number for how an organic compound is partitioned in the balance of a two-phase system of oil (typically 1-octanol) and water, expressed by the following formula.
logP=log(Coil/Cwater)
Wherein Coil represents the molar concentration of the compound in the oil phase and Cwater represents the molar concentration of the compound in the water phase.
If the logP value increases positively with 0, the oil solubility increases, and if the absolute value increases negatively, the water solubility increases, and the water solubility of the organic compound has a negative correlation, and thus the value is widely used as a parameter for estimating the hydrophilicity/hydrophobicity of the organic compound.
Further, as another embodiment of the repeating unit a31, a repeating unit represented by the following formula (AX 2) is given.
[ Chemical formula 5]
Wherein R A4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
The number of carbon atoms of the alkyl group represented by R A4 is preferably 1 or 2, more preferably 1.
R A5 represents a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, and from the viewpoint of further excellent effect of the present invention, an aralkyl group having 7 to 18 carbon atoms is preferable.
The number of carbon atoms of the alkyl group represented by R A5 is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4. And, a linear alkyl group is preferable.
The number of carbon atoms of the aralkyl group represented by R A5 is preferably 7 to 18, more preferably 7 to 12, and still more preferably 7 to 10.
And, the alkyl group and the aralkyl group represented by R A5 may have a substituent. The substituent is not particularly limited, and examples thereof include a hydroxyl group.
The repeating unit a31 is preferably a repeating unit having a benzyl group, and more preferably a repeating unit derived from benzyl (meth) acrylate, from the viewpoint of further excellent effects of the present invention.
The resin a may contain 1 kind of repeating unit a31 alone or 2 or more kinds of repeating units.
The content of the repeating unit a31 in the resin a is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 40% by mass, based on the total repeating units of the resin a. When 2 or more kinds of repeating units a31 are used simultaneously, the total content is preferably within the above range.
(Repeating unit A32)
The resin a may contain a repeating unit (repeating unit a 32) having a curable group.
Examples of the curable group include an ethylenically unsaturated group (for example, (meth) acryl, vinyl, styryl, etc.), a cyclic ether group (for example, epoxy, oxetanyl, etc.), and the like. Among them, the curable group is preferably an ethylenically unsaturated group from the viewpoint of being capable of controlling polymerization in a radical reaction. As the ethylenically unsaturated group, (meth) acryl is preferable.
The specific structure of the repeating unit a32 is not particularly limited, and a repeating unit represented by the following formula (AX 3) is preferable.
[ Chemical formula 6]
Wherein R A11 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
The number of carbon atoms of the alkyl group represented by R A11 is preferably 1 to 3, more preferably 1.
L A11 represents a single bond, -COO-or-CONR A12-.RA12 has the same meaning as R A11, and the preferable mode is the same.
L A12 represents a single bond or a 2-valent linking group.
The type of the 2-valent linking group is not particularly limited, and examples thereof include a 2-valent aliphatic hydrocarbon group, a 2-valent aromatic hydrocarbon group, -O-, -S-, -SO 2-、-NRA13 -, -CO-, and a combination of 2 or more of these groups.
The aliphatic hydrocarbon group having a valence of 2 may be any of a linear, branched, and cyclic one. The number of carbon atoms is preferably 1 to 20, more preferably 1 to 10.
Examples of the aliphatic hydrocarbon group having a valence of 2 include an alkylene group, an alkenylene group, and an alkynylene group, and among these, an alkylene group is preferable.
The 2-valent aromatic hydrocarbon group is preferably a C6-10 hydrocarbon group, and examples thereof include phenylene groups.
The aliphatic hydrocarbon group having 2 valences and the aromatic hydrocarbon group having 2 valences may further have a substituent. Examples of the substituent include, but are not particularly limited to, acid groups such as carboxylic acid groups, sulfonic acid groups, phosphoric acid groups and phenolic hydroxyl groups, and hydroxyl groups.
The meaning of R A13 is the same as that of R A11, and the preferable mode is the same.
Among these, 2 or more kinds of groups selected from the group consisting of alkylene groups which may have a substituent, -O-and-CO-are preferably combined.
In the above formula (AX 3), the number of atoms other than hydrogen atoms in the moiety represented by-L A11-LA12 -is preferably, for example, less than 40.
W A11 represents a curable group.
Examples of the curable group represented by W A11 include the curable groups described above.
The resin a may contain 1 kind of repeating unit a32 alone or 2 or more kinds.
The content of the repeating unit a32 in the resin a is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 40% by mass, based on the total repeating units of the resin a. When 2 or more kinds of repeating units a32 are used simultaneously, the total content is preferably within the above range.
(Repeating unit A33)
The resin a may contain a repeating unit (repeating unit a 33) containing a functional group capable of forming an interaction with a pigment or the like.
Examples of the functional group capable of forming an interaction with a pigment or the like include a basic group, a ligand, and a functional group having reactivity.
Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, an amide group, and the like, and among them, a tertiary amino group is preferable from the viewpoint of good adsorption to a pigment and the like and high dispersibility.
The resin a may contain 1 kind of repeating unit containing a basic group alone or 2 or more kinds of repeating units.
The content of the repeating unit containing a basic group in the resin a is preferably 0.01 to 50% by mass, and more preferably 0.01 to 30% by mass in terms of suppression of development inhibition property, relative to all the repeating units of the resin a. When 2 or more kinds of repeating units containing a basic group are used simultaneously, the total content is preferably within the above range.
Examples of the ligand and the reactive functional group include an acetoacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, and an acid chloride, and among them, an acetoacetoxy group is preferable from the viewpoints of good adsorption onto a pigment or the like and high dispersibility of the pigment or the like.
Resin a may contain 1 kind of repeating unit containing a ligand alone or 2 or more kinds of repeating unit containing a ligand.
The content of the repeating unit containing a ligand in the resin a is preferably 0.01 to 50% by mass, more preferably 0.01 to 30% by mass, based on the total repeating units of the resin a. When 2 or more kinds of repeating units containing a ligand are used simultaneously, the total content is preferably within the above range.
The resin a may contain 1 kind of repeating unit containing a functional group having reactivity alone or 2 or more kinds of repeating units.
The content of the reactive functional group in the resin a is preferably 0.01 to 50% by mass, more preferably 0.01 to 30% by mass, based on the total repeating units of the resin a. When 2 or more reactive repeating units are used simultaneously, the total content is preferably within the above range.
The content of the resin a in the curable composition is not particularly limited, but is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 25% by mass, based on the total solid content of the curable composition.
The resin A may be used alone or in combination of 1 kind or 2 or more kinds. When 2 or more resins A are used simultaneously, the total content is preferably within the above range.
The acid value of the resin A is 50mgKOH/g or more, preferably 55mgKOH/g or more, and more preferably 60mgKOH/g or more from the viewpoint of securing developability with an alkali developer. The upper limit is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, still more preferably 100mgKOH/g or less, and particularly preferably 80mgKOH/g or less. In addition, when the content of the repeating unit including the acid group as a constituent of the resin a is changed, a resin having a desired acid value can be obtained.
The weight average molecular weight of the resin a is preferably 5,000 to 100,000, more preferably 6,000 to 80,000, further preferably 15,000 to 40,000, and most preferably 20,000 to 40,000.
The glass transition temperature of the resin A is preferably-20 to 100 ℃, more preferably-20 to 80 ℃, and even more preferably-10 to 60 ℃. The glass transition temperature can be measured by DSC 3500Sirius (manufactured by Netzsch Co.).
[ Resin B ]
The curable composition contains a resin B.
The resin B preferably does not contain a repeating unit having a group selected from the group consisting of a polyoxyalkylene group having an average addition number of 3 or more and a polyoxyalkylene carbonyl group having an average addition number of 3 or more.
The resin B contains a repeating unit (repeating unit B1) derived from an alkyl (meth) acrylate, a repeating unit (repeating unit B2) having a hydroxyl group, and a repeating unit (repeating unit B3) having a carboxylic acid group, and the content of the repeating unit B1 is 60 mass% or more with respect to all the repeating units of the resin B. The resin B having the above structure improves adhesion of a cured film formed from the curable composition, and can form a phase separation structure by a difference in compatibility with the resin a.
The repeating units contained in the resin B will be described below.
< Repeating unit B1>
The resin B contains a repeating unit (repeating unit B1) derived from an alkyl (meth) acrylate.
The alkyl group bonded to the ester bond in the alkyl (meth) acrylate may be any of linear, branched and cyclic, and is preferably linear or branched from the viewpoint of further excellent effects of the present invention.
The number of carbon atoms of the alkyl group is preferably 1 or more, and from the viewpoint of further excellent effect of the present invention, it is preferably 4 or more. The upper limit value is preferably 20 or less, more preferably 12 or less, and further preferably 10 or less.
The alkyl group may or may not have a substituent, and is preferably not substituted from the viewpoint of further improving the effect of the present invention. When the alkyl group has a substituent, the substituent other than the hydroxyl group and the carboxylic acid group is preferable.
The resin B may contain 1 kind of repeating unit B1 alone or 2 or more kinds of repeating units.
The content of the repeating unit B1 in the resin B is 60 mass% or more, preferably 61 mass% or more, more preferably 65 mass% or more, still more preferably 70 mass% or more, and particularly preferably 80 mass% or more, based on all the repeating units of the resin B. The upper limit is not particularly limited, but is preferably 99 mass% or less, and more preferably 95 mass% or less. When 2 or more kinds of repeating units B1 are used simultaneously, the total content is preferably within the above range.
< Repeat unit B2>
The resin B contains a repeating unit (repeating unit B2) having a hydroxyl group.
The repeating unit B2 is a repeating unit different from the repeating unit B1 described above.
The repeating unit B2 preferably has no carboxylic acid group.
The number of hydroxyl groups in the repeating unit B2 may be 1 or more, and for example, 1 to 6 may be mentioned.
The specific structure of the repeating unit B2 is not particularly limited, and a repeating unit represented by the following formula (BX 1) is preferable.
[ Chemical formula 7]
R B1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
The number of carbon atoms of the alkyl group represented by R B1 is preferably 1 to 3, more preferably 1.
L B1 represents a single bond, -COO-or-CONR B2-.RB2 has the same meaning as R B1, and the preferable mode is the same.
L B2 represents a single bond or a 2-valent linking group.
The type of the 2-valent linking group is not particularly limited, and examples thereof include a 2-valent aliphatic hydrocarbon group, a 2-valent aromatic hydrocarbon group, -O-, -S-, -SO 2-、-NRB3 -, -CO-, and a combination of 2 or more of these groups.
The aliphatic hydrocarbon group having a valence of 2 may be any of a linear, branched, and cyclic one. The number of carbon atoms is preferably 1 to 20, more preferably 1 to 10.
Examples of the aliphatic hydrocarbon group having a valence of 2 include an alkylene group, an alkenylene group, and an alkynylene group, and among these, an alkylene group is preferable.
The 2-valent aromatic hydrocarbon group is preferably a C6-10 hydrocarbon group, and examples thereof include phenylene groups.
The aliphatic hydrocarbon group having 2 valences and the aromatic hydrocarbon group having 2 valences may further have a substituent. The substituent is not particularly limited, and examples thereof include a hydroxyl group.
The meaning of R B3 is the same as that of R B1, and the preferable mode is the same.
Among them, an alkylene group which may have a substituent or an alkylene group which may have a substituent and may contain a group selected from-O-and-CO-is preferable as the 2-valent linking group.
In the above formula (BX 1), the number of atoms other than hydrogen atoms in the moiety represented by-L B1-LB2 -is preferably, for example, less than 40.
W B1 represents a hydroxyl group or a curable group.
Examples of the curable group represented by W B1 include the curable groups described above.
W B1 preferably represents a hydroxyl group. When W B1 represents a curable group, the repeating unit B2 preferably has a hydroxyl group at a position other than W B1. Among them, it is preferable that the 2-valent linking group represented by L B2 is represented by the above-mentioned 2-valent linking group containing a hydroxyl group.
The repeating unit B2 is preferably a repeating unit derived from 2-ethylhydroxy (meth) acrylate from the viewpoint of further excellent effects of the present invention.
The resin B may contain 1 kind of repeating unit B2 alone or 2 or more kinds of repeating units.
The lower limit value of the content of the repeating unit B2 in the resin B is preferably 1 mass% or more, more preferably 2 mass% or more, and still more preferably 5 mass% or more, with respect to all the repeating units of the resin B. The upper limit value is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less. The content of the repeating unit B2 is preferably 1 to 50% by mass, more preferably 5 to 50% by mass, further preferably 5 to 40% by mass, particularly preferably 10 to 40% by mass, and most preferably 10 to 20% by mass, based on the total repeating units of the resin B. When 2 or more kinds of repeating units B2 are used simultaneously, the total content is preferably within the above range.
< Repeat unit B3>
The resin B contains a repeating unit (repeating unit B3) having a carboxylic acid group.
The repeating unit B3 is a repeating unit different from the repeating unit B1 and the repeating unit B2. The repeating unit B3 preferably has no hydroxyl group.
The number of carboxylic acid groups in the repeating unit B3 may be 1 or more, and may be, for example, 1 to 6.
The repeating unit B3 is specifically a repeating unit represented by the formula (AX 1) which is exemplified as the repeating unit A1 included in the resin a, and the same preferable embodiment is exemplified by a repeating unit in which the acid group represented by W A1 is a carboxylic acid group.
The resin B may contain 1 kind of repeating unit B3 alone or 2 or more kinds of repeating units.
The content of the repeating unit B3 in the resin B is preferably 5 to 40 mass%, more preferably 5 to 30 mass%, and even more preferably 10 to 30 mass% based on all the repeating units of the resin B. When 2 or more kinds of repeating units B3 are used simultaneously, the total content is preferably within the above range.
< Other repeating units (repeating unit B4) >)
The resin B may contain repeating units other than the repeating units B1 to B3 (hereinafter, also referred to as "repeating unit B4").
The other repeating unit may include other repeating units having various functions other than the repeating units described above.
Examples of the other repeating unit include a hydrophobic repeating unit (hereinafter, also referred to as "repeating unit B41").
Examples of the repeating unit B41 include repeating units derived from styrenes (e.g., styrene and α -methylstyrene) and repeating units similar to the repeating unit a31 included in the resin a.
The resin B may contain 1 kind of repeating unit B41 alone or 2 or more kinds of repeating units.
The content of the repeating unit B41 in the resin B is preferably 1 to 15 mass%, more preferably 5 to 15 mass%, based on the total repeating units of the resin B. When 2 or more kinds of repeating units B41 are used simultaneously, the total content is preferably within the above range.
The content of the resin B in the curable composition is not particularly limited, but is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 25% by mass, based on the total solid content of the curable composition.
The resin B may be used alone or in combination of 1 kind or 2 or more kinds. When 2 or more resins B are used simultaneously, the total content is preferably within the above range.
The acid value of the resin B is preferably 0mgKOH/g or more, more preferably 20mgKOH/g or more, still more preferably 40mgKOH/g or more, and particularly preferably 55mgKOH/g or more. The upper limit is preferably 150mgKOH/g or less, more preferably 100mgKOH/g or less, and still more preferably 90mgKOH/g or less. In addition, when the content of the repeating unit including the acid group as a constituent of the resin B is changed, a resin having a desired acid value can be obtained.
The weight average molecular weight of the resin B is preferably 5,000 to 100,000, more preferably 8,000 to 80,000, still more preferably 15,000 to 40,000, and particularly preferably 18,000 to 25,000.
The glass transition temperature of the resin B is preferably-20 to 120 ℃, more preferably-20 to 110 ℃, still more preferably-5 to 80 ℃, and still more preferably 0 to 70 ℃.
The glass transition temperature can be measured by DSC 3500Sirius (manufactured by Netzsch Co.).
[ Relation between the content of resin A and resin B ]
In the curable composition, the ratio of the content of the resin a to the total content of the resin a and the resin B (content ratio t1. Content of the resin a/total content of the resin a and the resin B) is 0.30 to 0.50, preferably 0.33 to 0.47, more preferably 0.35 to 0.45. When the content ratio T1 is within the above numerical range, the phase separation property of the resin a and the resin B is excellent, and the obtained cured product exhibits excellent low reflectivity to infrared light.
[ Polymerizable Compound ]
The curable composition contains a polymerizable compound.
In the present specification, the "polymerizable compound" refers to an organic compound (for example, an organic compound containing an ethylenically unsaturated group) that can be polymerized by the action of a photopolymerization initiator or the like described later.
When the curable composition contains a solvent, the polymerizable compound is preferably dissolved in the solvent.
The molecular weight (weight average molecular weight when having a molecular weight distribution) of the polymerizable compound is not particularly limited, and is preferably 2500 or less. The lower limit is preferably 100 or more.
The polymerizable compound is preferably a compound having an ethylenically unsaturated group (group having an ethylenically unsaturated bond).
That is, the curable composition preferably contains a low molecular compound containing an ethylenically unsaturated group as the polymerizable compound.
The polymerizable compound is preferably a compound having 1 or more ethylenically unsaturated bonds, more preferably a compound having 2 or more ethylenically unsaturated bonds, still more preferably a compound having 3 or more ethylenically unsaturated bonds, and particularly preferably a compound having 4 or more ethylenically unsaturated bonds. The upper limit is, for example, 15 or less. Examples of the ethylenically unsaturated group include vinyl, (meth) allyl and (meth) acryl.
Examples of the polymerizable compound include those described in [0050] of JP-A2008-260927 and [0040] of JP-A2015-068893, which are incorporated herein by reference.
The polymerizable compound may be any of monomers, prepolymers, oligomers, mixtures thereof, polymers thereof, and the like.
The polymerizable compound is preferably a3 to 15 functional (meth) acrylate compound, more preferably a3 to 6 functional (meth) acrylate compound.
The polymerizable compound preferably has a boiling point of 100 ℃ or more at normal pressure, which contains 1 or more ethylenically unsaturated groups. For example, the compounds described in paragraphs [0227] and [0254] to [0257] of JP-A2013-029760 and JP-A2008-292970 can be used, and these are incorporated herein.
The polymerizable compound is preferably dipentaerythritol triacrylate (manufactured as a commercial product, for example, KAYARAD D-330;Nippon Kayaku Co, ltd., as a commercial product, for example, KAYARAD D-320;Nippon Kayaku Co, ltd.,), dipentaerythritol penta (meth) acrylate (manufactured as a commercial product, for example, KAYARAD D-310;Nippon Kayaku Co, ltd.,), dipentaerythritol hexa (meth) acrylate (manufactured as a commercial product, for example, KAYARAD DPHA; nippon Kayaku co., ltd., a-DPH-12e; shin-NAKAMURA CHEMICAL co., ltd., as a commercial product), and the structure of these (meth) acryl-spaced ethylene glycol residues or propylene glycol residues (manufactured, for example, by Sartomer Company, inc. Commercially available SR454, SR 499). These oligomer types can also be used. Also, NK Ester A-TMMT (pentaerythritol tetraacrylate, SHIN-NAKAMURA CHEMICAL Co., ltd.) KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060 and KAYARAD DPEA-12 (all trade names, manufactured by Nippon Kayaku Co., ltd.) may be used. As the polymerizable compound, a urethane (meth) acrylate compound having both a (meth) acryloyl group and a urethane bond in the compound, or KAYARAD DPHA to 40H (trade name, manufactured by Nippon Kayaku co., ltd.) may be used, for example.
The following shows a preferred mode of the polymerizable compound.
The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group. The polymerizable compound containing an acid group is preferably an ester of an aliphatic polyhydroxyl compound and an unsaturated carboxylic acid, more preferably a polymerizable compound having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxyl compound, and even more preferably a compound in which the aliphatic polyhydroxyl compound is pentaerythritol and/or dipentaerythritol. Examples of commercial products include ARONIX TO-2349, M-305, M-510 and M-520 manufactured by TOAGOSEI CO., LTD.
The acid value of the acid group-containing polymerizable compound is preferably 0.1 to 40mgKOH/g, more preferably 5 to 30mgKOH/g. The polymerizable compound having an acid value of 0.1mgKOH/g or more has good development dissolution characteristics, and the polymerizable compound having an acid value of 40mgKOH/g or less is advantageous in production and/or handling. In addition, photopolymerization performance is good and curability is excellent.
Also preferred are compounds wherein the polymerizable compound comprises a caprolactone structure.
Examples of the compound containing a caprolactone structure include, but not limited to, epsilon-caprolactone-modified multifunctional (meth) acrylates obtained by esterifying a polyol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, and trimethylol melamine with (meth) acrylic acid and epsilon-caprolactone. Among them, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferable.
[ Chemical formula 8]
In the formula (Z-1), 6R are all groups represented by the following formula (Z-2) or 1 to 5 of 6R are groups represented by the following formula (Z-2), and the rest are groups represented by the following formula (Z-3).
[ Chemical formula 9]
In the formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and x represents a bonding position.
[ Chemical formula 10]
In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and "×" represents a bonding position.
Examples of the polymerizable compound having a caprolactone structure include a compound commercially available from Nippon Kayaku co, ltd, as KAYARAD DPCA series, DPCA-20 (a compound in which m=1 in the formulae (Z-1) to (Z-3) and r 1 are all hydrogen atoms), DPCA-30 (a compound in which m=1 in the formulae (Z-1) to (Z-3) and m=3 and r 1 are all hydrogen atoms), DPCA-60 (a compound in which m=1 in the formulae (Z-1) to (Z-3) and m=6 and r 1 are all hydrogen atoms in the formulae (Z-2) and DPCA-120 (a compound in which m=2 in the formulae (Z-1) and r 3482 are all hydrogen atoms) and m=2 and r=6 are all hydrogen atoms in the formulae (Z-2). Further, as a commercially available product containing a caprolactone-structure polymerizable compound, there is also mentioned TOAGOSEI co., ltd. Manufactured M-350 (trade name) (trimethylolpropane triacrylate).
The polymerizable compound represented by the following formula (Z-4) or formula (Z-5) can also be used.
[ Chemical formula 11]
In the formula (Z-4) and the formula (Z-5), E represents- ((CH 2)yCH2 O) -or- ((CH 2)yCH(CH3) O) -, y represents an integer of 0 to 10, and X represents a (meth) acryloyl group, a hydrogen atom or a carboxylic acid group.
In the formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, m represents an integer of 0 to 10, and the total number of m is an integer of 0 to 40.
In the formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, n represents an integer of 0 to 10, and the total number of n is an integer of 0 to 60.
In the formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
The total of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8.
In the formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
The total of n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12.
Further, the- ((CH 2)yCH2 O) -or- ((CH 2)yCH(CH3) O) -in the formula (Z-4) or (Z-5) is preferably such that the terminal on the oxygen atom side is bonded to X.
The compounds represented by the formula (Z-4) or the formula (Z-5) may be used singly or in combination of 1 kind or 2 or more kinds. In particular, it is preferable that 6X groups in the formula (Z-5) are all acryl groups, and that 6X groups in the formula (Z-5) are all a mixture of a compound having acryl groups and a compound having at least 1 hydrogen atom among 6X groups. As such a structure, the developability can be further improved.
The total content of the compounds represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, more preferably 50% by mass or more.
Among the compounds represented by the formula (Z-4) or the formula (Z-5), pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferable.
The polymerizable compound may contain a carbomer skeleton.
The polymerizable compound having a carbopol (Cardo) skeleton is preferably a polymerizable compound having a 9, 9-bisaryl fluorene skeleton.
Examples of the polymerizable compound having a carbomer skeleton include ONCOAT FX series (NAGASE & co., ltd. Manufactured) and OGSOL series (Osaka GAS CHEMICALS co., ltd. Manufactured).
The polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core. Examples of such polymerizable compounds include NK ESTER A-9300 (SHIN-NAKAMURA CHEMICAL Co., ltd.).
The content of the ethylenically unsaturated groups in the polymerizable compound (which means a value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g/mol) of the polymerizable compound) is preferably 5.0mmol/g or more. The upper limit is preferably 20.0mmol/g or less.
The content of the polymerizable compound in the curable composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and still more preferably 20% by mass or more, based on the total solid content of the curable composition. The upper limit is preferably 60 mass% or less, more preferably 40 mass% or less, and even more preferably 35 mass% or less.
The polymerizable compound may be used alone or in combination of at least 2 kinds. When 2 or more polymerizable compounds are used simultaneously, the total amount of these is preferably in the above range.
[ Relation of the content of the polymerizable Compound in resin A, resin B ]
The ratio of the content of the polymerizable compound to the total content of the resin a, the resin B and the polymerizable compound (content ratio t2. The content of the polymerizable compound per the total content of the resin a, the resin B and the polymerizable compound) in the curable composition is 0.30 to 0.50, preferably 0.33 to 0.47, more preferably 0.35 to 0.45. When the content ratio T2 is within the above numerical range, the obtained cured film is excellent in adhesion and exhibits excellent low reflectivity to infrared light. When the content ratio T2 is less than 0.30, the adhesion of the obtained cured film is poor. On the other hand, when the content ratio T2 exceeds 0.50, the obtained cured film is poor in low reflectivity to infrared light.
[ Pigment ]
The curable composition contains a pigment.
Examples of the pigment include, but are not particularly limited to, black pigments, white pigments, and color pigments. Examples of the color pigment include red pigment, green pigment, blue pigment, yellow pigment, violet pigment, and orange pigment. Among these pigments, black pigments and white pigments are preferable, and black pigments are more preferable.
The pigment may be any of an inorganic pigment and an organic pigment. As the pigment, a material obtained by substituting an organic chromophore for a part of an inorganic pigment or an organic-inorganic pigment can also be used. The organic chromophore has an advantage of easy color design by substituting the inorganic pigment or the organic-inorganic pigment with the organic chromophore.
The curable composition may be used alone with 1 kind of pigment, or may be used in combination with 2 or more kinds.
For example, when a cured film of the curable composition is used as a light shielding film, the light shielding properties of the light shielding film can be adjusted by using a black pigment and a pigment other than the black pigment. When the light shielding film is used as a light attenuating film, it is easy to attenuate the wavelengths equally for light containing a wide wavelength component.
< Black pigment >
The curable composition preferably contains a black pigment.
In the present specification, the black pigment is a pigment having absorption over the entire wavelength range of 400 to 700nm, and for example, a black pigment which meets the evaluation criterion Z described below is preferable.
First, a composition containing a black pigment, a transparent resin matrix (acrylic resin or the like), and a solvent was prepared, the content of the black pigment relative to the total solid content being 60 mass%. The obtained composition was coated on a glass substrate until the film thickness of the cured film after drying became 1 μm to form a cured film. The light-shielding properties of the cured film after drying were evaluated using a spectrophotometer (Hitachi, ltd. Manufactured UV-3600, etc.). If the maximum transmittance of the dried cured film at a wavelength of 400 to 700nm is less than 10%, it can be determined that the black pigment is a black pigment suitable for the evaluation standard Z. In the evaluation criterion Z, the maximum value of the transmittance of the black pigment at the wavelength of 400 to 700nm of the cured film after drying is more preferably less than 8%, and still more preferably less than 5%.
As the black pigment, a plurality of pigments which cannot be used alone as the black pigment may be combined and adjusted to be black as a whole.
For example, a plurality of pigments having colors other than black when alone may be used as the black pigment.
The average particle diameter of the black pigment is preferably 250nm or less, more preferably 200nm or less, and still more preferably 150nm or less. The average particle diameter is preferably 1nm or more, more preferably 5nm or more, and even more preferably 20nm or more, from the viewpoint of further excellent handleability.
The average particle diameter is calculated by the following method.
The curable composition was diluted with Propylene Glycol Monomethyl Ether Acetate (PGMEA), and a measurement solution having a solid content concentration of 0.2 mass% was prepared. Next, data of the above measurement solution was read 50 times using a dynamic light scattering type particle size distribution measuring apparatus (LB-500 (trade name) manufactured by HORIBA, ltd.) according to JIS8826:2005, using a 2ml quartz cell for measurement at 25 ℃, and the obtained number-based particle sizes were arithmetically averaged to obtain an average particle size.
In addition, although the measurement solution is prepared using the curable composition in the above, the measurement may be performed using a color material dispersion in which a black pigment is dispersed. For example, when particles other than the black pigment are contained in the curable composition, the average particle diameter of the black pigment may be measured using a color material dispersion in which the black pigment used for preparing the curable composition is dispersed. When particles other than the black pigment are contained in the curable composition, the black pigment may be separated from the other particles by any method, and then the average particle diameter of the black pigment may be measured.
As the black pigment, a pigment that solely develops black is preferable. Further, a black pigment that is black alone and absorbs infrared rays may be used.
Here, the black pigment absorbing infrared rays has absorption in a wavelength region of an infrared region (preferably, a wavelength of 650 to 1300 nm). It is also preferable that the black pigment has a maximum absorption wavelength in a wavelength region of 675 to 900 nm.
As the black pigment, various known black pigments can be used. The black pigment may be an inorganic pigment or an organic pigment
From the viewpoint of more excellent effects of the present invention, the black pigment is preferably an inorganic pigment, and more preferably carbon black, metal nitride particles or metal oxynitride particles.
(Inorganic pigment)
The inorganic pigment that can be used as the black pigment is not particularly limited as long as it is particles that have light-shielding properties and contain an inorganic compound, and known inorganic pigments can be used.
Examples of the inorganic pigment include metal oxides, metal nitrides, and metal oxynitrides containing 1 or 2 or more metal elements selected from the group consisting of group 4 metal elements such as titanium (Ti) and zirconium (Zr), group 5 metal elements such as vanadium (V) and niobium (Nb), yttrium (Y), aluminum (Al), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and silver (Ag).
Among them, a metal oxide, a metal nitride, or a metal oxynitride containing 1 or 2 or more metal elements selected from titanium (Ti), zirconium (Zr), vanadium (V), yttrium (Y), aluminum (Al), and iron (Fe) is preferable. That is, the inorganic pigment may contain 2 or more metal atoms.
As the metal oxide, metal nitride, and metal oxynitride, particles mixed with other metal atoms may be further used, and for example, metal nitride particles containing an atom (preferably, an oxygen atom and/or a sulfur atom) selected from the group 13 to 17 elements of the periodic table may be further used.
The metal oxide, metal nitride, and metal oxynitride may be coated with an inorganic substance and/or an organic substance.
The inorganic substance includes metal atoms contained in the inorganic pigment.
The organic substance may be an organic substance having a hydrophobic group, and is preferably a silane compound.
The method for producing the metal nitride, the metal oxide, and the metal oxynitride is not particularly limited as long as a black pigment having desired physical properties can be obtained, and known production methods such as a gas phase reaction method can be used. The gas phase reaction method includes an electric furnace method, a thermal plasma method, and the like, but is preferably a thermal plasma method in view of less mixing of impurities, easy uniformity of particle size, and high productivity.
The surface modification treatment may be performed on the metal nitride, the metal oxide, and the metal oxynitride. For example, the surface modification treatment may be performed using a surface treatment agent having both a silicone group and an alkyl group. Examples of such inorganic particles include "KTP-09" (Shin-Ftsu Chemical Co., ltd.) and the like.
Among them, from the viewpoint of suppressing the occurrence of undercut when forming a cured film, a nitride or oxynitride of 1 or more metals selected from titanium, vanadium, zirconium, niobium and iron is more preferable, and a nitride or oxynitride of zirconium or a nitride or oxynitride of titanium (titanium black) is further preferable.
Titanium black is a black particle containing titanium oxynitride.
The titanium black may be modified as necessary to improve dispersibility and suppress aggregation. The titanium black may be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and may be treated with a water-repellent substance as described in japanese patent laid-open No. 2007-302836.
Examples of the method for producing titanium black include a method of reducing a mixture of titanium dioxide and metallic titanium by heating in a reducing atmosphere (Japanese patent application laid-open No. 49-005432), a method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a hydrogen-containing reducing atmosphere (Japanese patent application laid-open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonium (Japanese patent application laid-open No. 60-065069, japanese patent application laid-open No. 61-201610) and a method of adhering a vanadium compound to titanium dioxide or titanium hydroxide and reducing the titanium oxide at a high temperature in the presence of ammonium (Japanese patent application laid-open No. 61-201610).
The particle size of the titanium black is not particularly limited, but is preferably 10 to 45nm, more preferably 12 to 20nm. The specific surface area of the titanium black is not particularly limited, and the value measured by the BET (Brunauer, emmett, teller: brunol, emmett, taylor) method is preferably 5 to 150m 2/g, more preferably 20 to 100m 2/g, in order to achieve a predetermined water repellency after the surface treatment with the water repellent.
Examples of the titanium black include titanium black 10S, 12S, 13R, 13M-C, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), tilack D (trade name, ako Kasei Co., manufactured by Ltd.) and MT-150A (trade name, manufactured by TAYCA CORPORATION).
The curable composition preferably contains titanium black as a dispersed body containing titanium black and Si atoms. In this embodiment, titanium black is contained as a dispersed substance in the curable composition. The content ratio (Si/Ti) of Si atoms to Ti atoms in the dispersion is preferably 0.05 to 0.5, more preferably 0.07 to 0.4, in terms of mass conversion. Here, the above-mentioned dispersed matter includes both of a dispersed matter in which titanium black is in a state of primary particles and a dispersed matter in which titanium black is in a state of aggregates (secondary particles).
Further, when patterning a composition layer using the dispersion by photolithography or the like, it is difficult to leave residues in the removed portion if the Si/Ti of the dispersion is equal to or smaller than a predetermined value, and the light shielding ability is easily improved if the Si/Ti of the dispersion is equal to or smaller than a predetermined value.
In order to change the Si/Ti of the dispersion (for example, to 0.05 or more), the following method can be used. First, titanium oxide and silica particles are dispersed by using a dispersing machine to obtain a dispersion, and the mixture is subjected to a reduction treatment at a high temperature (for example, 850 to 1000 ℃) to obtain a dispersion containing Si and Ti with titanium black particles as a main component. The Si/Ti-modified titanium black can be produced by the method described in paragraphs [0005] to [0016] to [0021] of Japanese patent application laid-open No. 2008-266045.
The content ratio (Si/Ti) of Si atoms to Ti atoms in the dispersion can be measured by, for example, the method (2-1) or the method (2-3) described in paragraphs [0054] to [0056] of International publication No. 2011/049090.
In the dispersion containing titanium black and Si atoms, the titanium black described above can be used. In addition, in order to adjust dispersibility, colorability, and the like, the dispersion may be used as a black pigment composed of a composite oxide of 1 or 2 or more metals selected from Cu, fe, mn, V, ni, and the like, cobalt oxide, iron oxide, carbon black, aniline black, and the like, in combination with titanium black. In this case, it is preferable that the dispersion of titanium black occupies 50 mass% or more of the total dispersion.
Carbon black is also a black inorganic pigment.
Examples of the carbon black include furnace black, channel black, thermal black, acetylene black, and lamp black.
As the carbon black, carbon black produced by a known method such as an oil furnace method can be used, and commercially available carbon black can be used.
Examples of the commercial product of carbon black include inorganic pigments such as c.i. pigment black 7.
The carbon black is preferably a surface-treated carbon black. The surface treatment can change the particle surface state of the carbon black and can improve the dispersion stability in the curable composition. Examples of the surface treatment include a coating treatment with a resin, a surface treatment with an acid group, and a surface treatment with a silane coupling agent.
The carbon black is preferably carbon black coated with a resin. By coating the particle surface of carbon black with an insulating resin, the light shielding property and the insulating property of the cured film can be improved. Further, by reducing the leakage current or the like, the reliability of the image display device or the like can be improved. Therefore, the cured film is suitable for applications requiring light shielding properties and insulation properties.
Examples of the coating resin include epoxy resin, polyamide, polyamideimide, novolak resin, phenol resin, urea resin, melamine resin, polyurethane, diallyl phthalate resin, alkylbenzene resin, polystyrene, polycarbonate, polybutylene terephthalate and modified polyphenylene ether.
The content of the coating resin is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, based on the total amount of the carbon black and the coating resin, from the viewpoint of further excellent light shielding property and insulation property of the cured film.
Examples of the inorganic pigment used as the black pigment include zirconium used in Japanese patent application laid-open No. 2017-222559, international publication No. 2019/130772, international publication No. 2019/059359 and Japanese patent application laid-open No. 2009-091205, which are incorporated herein by reference.
(Organic pigment)
The organic pigment used as the black pigment is not particularly limited as long as it is particles having light-shielding properties and containing an organic compound, and known organic pigments can be used.
In the present invention, examples of the organic pigment include bis-benzofuranone compounds, azomethine compounds, perylene compounds and azo compounds, and bis-benzofuranone compounds or perylene compounds are preferable.
Examples of the bis-benzofuranone compound include compounds described in japanese patent application laid-open No. 2010-534726, japanese patent application laid-open No. 2012-515233, and japanese patent application laid-open No. 2012-515234. The bis-benzofuranone compound is available as "Irgaphor Black" (trade name) manufactured by BASF corporation.
As the perylene compound, there may be mentioned a compound described in Japanese patent application laid-open No. 62-001753 and Japanese patent application laid-open No. 63-026784. Perylene compounds can be obtained as c.i. pigment blacks 21, 30, 31, 32, 33 and 34.
The content of the pigment is preferably 10 to 90% by mass, more preferably 25 to 80% by mass, further preferably 30 to 70% by mass, and particularly preferably 30 to 60% by mass, based on the total solid content of the curable composition. The curable composition may contain only 1 pigment or 2 or more pigments. When it contains 2 or more, these total amounts are preferably within the above-mentioned range.
[ Photopolymerization initiator ]
The curable composition contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and a known photopolymerization initiator can be used.
The photopolymerization initiator is preferably a photopolymerization initiator having photosensitivity in the ultraviolet region to the visible light region, for example. The active agent may be an active agent that generates a reactive radical by reacting with a photosensitizing agent that is excited by light, or may be an initiator that initiates cationic polymerization depending on the type of polymerizable compound.
The photopolymerization initiator is preferably a so-called radical polymerization initiator.
Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, and the like), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbisimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, hydroxyacetophenone, and the like.
Specific examples of photopolymerization initiators include, for example, JP-A-2013-029760, paragraphs 0265 to 0268, which are incorporated herein by reference.
Examples of the photopolymerization initiator include an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in JP-A-4225898.
Examples of the hydroxyacetophenone compound include Omnirad-184, omnirad-1173, omnirad-500, omnirad-2959, and Omnirad-127 (trade names, all manufactured by IGM RESINS B.V.).
As the aminoacetophenone compound, for example, commercial products Omnirad-907, omnirad-369 or Omnirad-379EG (trade name: manufactured by IGM RESINS B.V.) are mentioned. Examples of the aminoacetophenone compound include those described in JP 2009-191179A having an absorption wavelength matching with an equivalent light source having a wavelength of 365nm or 405 nm.
Examples of the acylphosphine compound include commercially available Omnirad-819 and Omnirad-TPO (trade name, manufactured by IGM RESINS B.V. Co.).
(Oxime Compound)
As the photopolymerization initiator, an oxime ester-based polymerization initiator (oxime compound) is preferable. In particular, oxime compounds are preferable because they have high sensitivity and high polymerization efficiency, and the content of pigments in the curable composition is easily set to be high.
Examples of the oxime compound include a compound described in Japanese patent application laid-open No. 2001-233836, a compound described in Japanese patent application laid-open No. 2000-080068, and a compound described in Japanese patent application laid-open No. 2006-342166.
Examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyiminopropane-1-one, 2-benzoyloxyiminopropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyiminopropane-1-phenylpropane-1-one.
Examples of the compounds include J.C.S. Perkin II (1979) pp.1653-1660, J.C. S. Perkin II (1979) pp.156-162, journal of Photopolymer SCIENCE AND Technology (1995) pp.202-232, japanese patent application laid-open No. 2000-066385, japanese patent application laid-open No. 2000-080068, japanese patent application laid-open No. 2004-534797, and Japanese patent application laid-open No. 2006-342166.
Examples of the commercial products include IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), and IRGACURE-OXE04 (manufactured by BASF). Also, there may be mentioned TR-PBG-304 (Changzhou Tronly New Electronic Materials CO., LTD.; manufactured), ADEKA ARKLS NCI-730, ADEKA ARKLS NCI-831, ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), and N-1919 (a photoinitiator containing a carbazole/oxime ester skeleton (manufactured by ADEKA CORPORATION)). Further, omnirad1316 (IGM RESINS b.v.) is also exemplified.
Examples of the oxime compounds other than the above include compounds described in japanese patent application laid-open No. 2009-519904 in which an oxime is linked to the carbazole N-position, compounds described in us patent No. 7626957 in which a hetero substituent is introduced at the benzophenone position, compounds described in japanese patent application laid-open No. 2010-015025 and us patent application laid-open No. 2009-292039 in which a nitro group is introduced at the pigment position, ketoxime compounds described in japanese patent application laid-open No. 2009-131189 and compounds described in us patent No. 7556910 in which a triazine skeleton and an oxime skeleton are contained in the same molecule, and compounds described in japanese patent application laid-open No. 2009-221114 in which absorption at 405nm is extremely high and sensitivity to a g-ray light source is excellent.
For example, refer to paragraphs 0274 to 0275 of Japanese patent application laid-open No. 2013-029760, which is incorporated herein by reference.
Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. The n—o bond of the oxime compound may be an oxime compound of the (E) form, an oxime compound of the (Z) form, or a mixture of the (E) form and the (Z) form.
[ Chemical formula 12]
In the formula (OX-1), R and B each independently represent a 1-valent substituent, A represents a 2-valent organic group, and Ar represents an aryl group.
In the formula (OX-1), the substituent represented by R is preferably a nonmetallic atom having a valence of 1.
Examples of the nonmetallic atom having a valence of 1 include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthio carbonyl group, an arylthio carbonyl group, and the like. These groups may have 1 or more substituents. The above substituent may be substituted with another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In the formula (OX-1), the substituent having a valence of 1 represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group, more preferably an aryl group or a heterocyclic group. These groups may have 1 or more substituents. As the substituent, the above-described substituent can be exemplified.
In the formula (OX-1), the organic group having a valence of 2 represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group or an alkynylene group. These groups may have 1 or more substituents. As the substituent, the above-described substituent can be exemplified.
As the photopolymerization initiator, an oxime compound containing a fluorine atom can be also mentioned. Examples of the oxime compound containing a fluorine atom include compounds described in JP-A2010-26261028, compounds 24, 36 to 40 described in JP-A2014-500852, and compound (C-3) described in JP-A2013-164471. This content is incorporated into the present specification.
The polymerization initiator may be a compound represented by the following formulas (1) to (4).
[ Chemical formula 13]
[ Chemical formula 14]
In the formula (1), R 1 and R 2 each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, and when R 1 and R 2 are phenyl groups, the phenyl groups may be bonded to each other to form a fluorenyl group, and R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.
In the formula (2), R 1、R2、R3 and R 4 have the same meaning as R 1、R2、R3 and R 4 in the formula (1), R 5 represents -R6、-OR6、-SR6、-COR6、-CONR6R6、-NR6COR6、-OCOR6、-COOR6、-SCOR6、-OCSR6、-COSR6、-CSOR6、-CN、 a halogen atom or a hydroxyl group, R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
In the formula (3), R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.
In the formula (4), R 1、R3 and R 4 have the same meaning as R 1、R3 and R 4 in the formula (3), R 5 represents -R6、-OR6、-SR6、-COR6、-CONR6R6、-NR6COR6、-OCOR6、-COOR6、-SCOR6、-OCSR6、-COSR6、-CSOR6、-CN、 a halogen atom or a hydroxyl group, R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
Examples of the compounds represented by the formula (1) and the formula (2) include compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated into the present specification.
The photopolymerization initiator is also preferably a compound represented by the following formula (1).
[ Chemical formula 15]
In the formula (1), R represents a group represented by the following formula (1 a),
[ Chemical formula 16]
In the formula (1 a), n represents an integer of 1 to 5. m represents an integer of 1 to 6. * Indicating the bonding location.
M is preferably 3 or 4.
The compound represented by the formula (1) can be synthesized by a synthesis method described in, for example, japanese patent application laid-open No. 2012-519191.
Specific examples of oxime compounds preferably used in the curable composition are shown below.
Examples of the oxime compound include those shown in Table 1 of International publication No. 2015-036910, which is incorporated herein by reference.
[ Chemical formula 17]
[ Chemical formula 18]
[ Chemical formula 19]
The oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 to 500nm, more preferably has a maximum absorption wavelength in a wavelength region of 360 to 480nm, and still more preferably has a high absorbance at 365nm and 405 nm.
From the viewpoint of sensitivity, the molar absorptivity of the oxime compound at 365nm or 405nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and still more preferably 5,000 to 200,000.
The molar absorptivity of the compound can be measured using a known method, for example, preferably by an ultraviolet-visible spectrophotometer (Cary-5 spectrometer manufactured by Varian Co.) and using ethyl acetate at a concentration of 0.01 g/L.
The photopolymerization initiator may be used in combination of 2 or more kinds as needed.
Further, as the photopolymerization initiator, a compound described in paragraph 0052 of JP-A2008-260927, paragraphs 0033 to 0037 of JP-A2010-097210, and paragraph 0044 of JP-A2015-068893 can be used, and the contents are incorporated in the present specification.
The photopolymerization initiator is preferably an oxime ester-based polymerization initiator from the viewpoint of further excellent effects of the present invention.
The content of the photopolymerization initiator in the curable composition is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, and even more preferably 1.5 to 8% by mass, based on the total solid content of the curable composition.
The photopolymerization initiator may be used alone or in combination of 1 or more than 2. When 2 or more photopolymerization initiators are used simultaneously, the total amount of these is preferably within the above range.
[ Surfactant ]
The curable composition may contain a surfactant. The surfactant helps to improve the coatability of the curable composition.
As the surfactant, for example, silicone surfactants a fluorine-based surfactant, a nonionic surfactant, a a fluorine-based surfactant nonionic surfactant.
Among them, silicone surfactants are preferred from the viewpoint of further excellent effects of the present invention.
Examples of the silicone surfactant include linear polymers composed of siloxane bonds, and modified siloxane polymers having organic groups introduced into side chains and/or terminal ends.
Examples of Silicone surfactants include DOWSIL (registered trademark) series of DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (Dow Corning Toray Co., ltd., manufactured );X-22-4952、X-22-4272、X-22-6266、KF-351A、K354L、KF-355A、KF-945、KF-640、KF-642、KF-643、X-22-6191、X-22-4515、KF-6000、KF-6004、KP-323、KP-341、KF-6001 and KF-6002 (Shin-Etsu Silicone Co., ltd., manufactured), F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (Momentive performance Materials Inc., manufactured), and BYK307, BYK323, and BYK330 (BYK Co., LTD, manufactured).
In a preferred embodiment of the silicone surfactant, from the viewpoint of the more excellent effect of the present invention, an aromatic group-modified silicone surfactant (an aromatic group-containing silicone surfactant) is preferred, and a phenyl-modified silicone surfactant (a phenyl-containing silicone surfactant) is more preferred.
Examples of the fluorine-based surfactant include MEGAFACE F171、MEGAFACE F172、MEGAFACE F173、MEGAFACE F176、MEGAFACE F177、MEGAFACE F141、MEGAFACE F142、MEGAFACE F143、MEGAFACE F144、MEGAFACE R30、MEGAFACE F437、MEGAFACEF475、MEGAFACE F479、MEGAFACE F482、MEGAFACE F554 and MEGAFACE F780 (manufactured by DIC CORPORATION, supra), fluorine FC430, fluorine FC431, and fluorine FC171 (manufactured by Sumitomo 3M Limited, supra) and Surflon KH-40 (manufactured by ltd, supra), and PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA Solutions inc, supra).
The fluorine-based surfactant may be a block polymer, and examples thereof include compounds described in JP 2011-089090A.
When the curable composition contains a surfactant, the content of the surfactant in the curable composition is not particularly limited, but from the viewpoint of further excellent effects of the present invention, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 0.5% by mass, and even more preferably 0.01 to 0.1% by mass, relative to the total solid content of the curable composition.
The surfactant may be used alone or in combination of at least 2 kinds. When 2 or more surfactants are used simultaneously, the total amount is preferably within the above range.
[ Solvent ]
The curable composition may contain a solvent.
The solvent is not particularly limited, and a known solvent can be used, and examples thereof include an organic solvent and water.
The solid content in the curable composition is preferably 10 to 90 mass%, more preferably 10 to 50 mass%, and even more preferably 15 to 50 mass% based on the total mass of the curable composition. That is, the content of the solvent in the curable composition is not particularly limited, but is preferably adjusted so that the solid content of the curable composition becomes the above content.
The solvent may be used alone or in combination of 1 or more than 2. When 2 or more solvents are used simultaneously, the total solid content of the curable composition is preferably adjusted to be within the above range.
Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol diethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N-dimethylformamide, dimethyl sulfoxide, γ -butyrolactone, ethyl acetate, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, ethyl lactate, 3-methoxybutanol, 1, 3-butanediol, 2, 3-butanediol, propylene glycol, ethylene glycol, dimethyl sulfoxide, and γ -valerolactone, but are not limited thereto.
[ Epoxy group-containing Compound (sealing agent) ]
The curable composition may contain a compound containing an epoxy group.
Examples of the epoxy group-containing compound include compounds having 1 or more epoxy groups, and preferably compounds having 2 or more epoxy groups. The number of epoxy groups is preferably 1 to 100. The upper limit may be, for example, 10 or less, or 5 or less. The lower limit is preferably 2 or more.
The epoxy group-containing compound is a component different from the dispersant, the alkali-soluble resin, and the polymerizable compound.
The epoxy equivalent of the epoxy group-containing compound (=molecular weight of the epoxy group-containing compound/number of epoxy groups) is preferably 500 g/equivalent or less, more preferably 100 to 400 g/equivalent or less, and still more preferably 100 to 300 g/equivalent.
The epoxy group-containing compound may be a low molecular compound (for example, having a molecular weight of less than 2000) or a high molecular compound (macromolecule) (for example, having a molecular weight of 2000 or more, and in the case of a polymer, a weight average molecular weight of 2000 or more). The weight average molecular weight of the epoxy group-containing compound is preferably 200 to 100000, more preferably 500 to 50000. The upper limit of the weight average molecular weight is more preferably 10000 or less, still more preferably 5000 or less, and particularly preferably 3000 or less.
As the epoxy group-containing compound, commercially available ones can be used. Examples thereof include EHPE3150 (manufactured by Daicel Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., ltd.), EPICLON N-695 (manufactured by DIC), CELLOXIDE 2021P (manufactured by Daicel Corporation), and the like.
Examples of the epoxy group-containing compound include those described in paragraphs 0034 to 0036 of Japanese patent application laid-open No. 2013-011689, and in paragraphs 0147 to 0156 of Japanese patent application laid-open No. 2014-043556 and in paragraphs 0085 to 0092 of Japanese patent application laid-open No. 2014-089408. These are incorporated into this specification.
When the curable composition contains an epoxy group-containing compound, the content of the epoxy group-containing compound in the curable composition is preferably 0.001 to 10% by mass, more preferably 0.01 to 8% by mass, and even more preferably 0.01 to 6% by mass, based on the total solid content in the curable composition.
The epoxy group-containing compound may be used alone or in combination of 1 kind or 2 or more kinds. When the curable composition contains 2 or more epoxy group-containing compounds, the total content thereof is preferably within the above range.
[ Silane coupling agent (sealing agent) ]
The curable composition may contain a silane coupling agent.
When a cured film is formed on a substrate, the silane coupling agent functions as an adhesive agent that improves adhesion between the substrate and the cured film.
The silane coupling agent refers to a compound having a hydrolyzable group and a functional group other than the hydrolyzable group in the molecule. Further, a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by hydrolysis and/or condensation. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and an alkenyloxy group. When the hydrolyzable group contains a carbon atom, the number of carbon atoms is preferably 6 or less, more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
In order to improve the adhesion between the substrate and the cured film when forming the cured film on the substrate, the silane coupling agent preferably does not contain a fluorine atom or a silicon atom (excluding a silicon atom bonded to a hydrolyzable group), and preferably does not contain a fluorine atom, a silicon atom (excluding a silicon atom bonded to a hydrolyzable group), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, and a branched alkyl group having 3 or more carbon atoms.
The silane coupling agent may contain an ethylenically unsaturated group such as a (meth) acryloyl group. When an ethylenically unsaturated group is contained, the number thereof is preferably 1 to 10, more preferably 4 to 8. In addition, silane coupling agents containing an ethylenically unsaturated group (e.g., compounds having a molecular weight of 2000 or less containing a hydrolyzable group and an ethylenically unsaturated group) are not among the polymerizable compounds.
As the silane coupling agent, for example, examples thereof include 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, and 3-glycidoxypropyl methyl dimethoxy silane 3-glycidoxypropyl methyl diethoxysilane, vinyl trimethoxy silane, vinyl triethoxysilane, and the like.
When the curable composition contains a silane coupling agent, the content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and even more preferably 1.0 to 6% by mass, based on the total solid content in the curable composition.
The silane coupling agent may be contained in an amount of 1 or 2 or more. When the curable composition contains 2 or more silane coupling agents, the total thereof may be within the above range.
[ Ultraviolet absorber ]
The curable composition may contain an ultraviolet absorber. Thus, the pattern shape of the cured film formed by exposure can be made to be a more excellent (fine) shape.
Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers. Further, examples of the compounds include the compounds of paragraphs 0137 to 0142 (paragraphs 0251 to 0254 of corresponding US 2012/0068292) of japanese patent application publication 2012-068418, which are incorporated herein by reference.
In addition, diethylamino-phenylsulfonyl ultraviolet absorbers (DAITO CHEMICAL CO., LTD., manufactured by LTD. Trade name: UV-503) and the like can be mentioned.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP 2012-032556A.
When the curable composition contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and even more preferably 0.1 to 5% by mass, based on the total solid content of the curable composition.
[ Dye ]
The curable composition may contain a dye.
As the dye, a known dye can be used, and examples thereof include a black dye and a color dye. Examples of the color dye include red dye, green dye, blue dye, yellow dye, violet dye and orange dye.
Among them, a black dye is preferable.
As the black dye, for example, a dye that develops black alone can be used, and for example, a pyrazole azo compound, a pyrrole methylene compound, an aniline azo compound, a triphenylmethane compound, an anthraquinone compound, a benzylidene compound, an oxonol (oxonol) compound, a pyrazolotriazole azo compound, a pyridone azo compound, a cyanine compound, a phenothiazine compound, a pyrrolopyrazole azomethine compound, and the like can be used.
Examples of the black dye include compounds described in Japanese patent application laid-open No. 64-90403, japanese patent application laid-open No. 64-91102, japanese patent application laid-open No. 01-94301, japanese patent application laid-open No. 06-11614, japanese patent application laid-open No. 2592207, U.S. patent 4808501, U.S. patent 5667920, U.S. patent 505950, U.S. patent 5667920, japanese patent application laid-open No. 05-333207, japanese patent application laid-open No. 06-35183, japanese patent application laid-open No. 06-51115, and Japanese patent application laid-open No. 06-194828.
Examples of the black dye include dyes specified in the color index (c.i.) of solvent black 27 to 47, and preferably dyes specified in the c.i. of solvent black 27, 29 or 34.
Examples of commercial products of these Black dyes include Spilon Black MH, black BH (manufactured by Hodogaya Chemical co., ltd. Above), VALIFAST Black3804, 3810, 3820, 3830 (manufactured by ORIENT CHEMICAL INDUSTRIES co., ltd. Above), sayinyl Black RLSN (manufactured by CLARIANT CHEMICALS) and KAYASETBlack K-R, K-BL (manufactured by Nippon Kayaku co., ltd. Above). Further, a polymerizable dye having a polymerizability in a molecule may be used, and as a commercially available product, for example, the RDW series manufactured by Wako Pure Chemical Industries, ltd.
Also, a pigment polymer may be used as the black dye. Examples of the dye multimer include compounds described in JP 2011-213925A and JP 2013-042097A.
Further, as described above, a plurality of dyes having colors other than black alone may be used as the black dye. As such a coloring dye, for example, a dye described in paragraphs 0027 to 0200 of jp 2014-42375 can be used in addition to a color-based dye (color dye) such as R (red), G (green) and B (blue).
[ Infrared absorber ]
The curable composition may further comprise an infrared absorber.
The infrared absorber is a compound having absorption in a wavelength region of an infrared region (preferably, a wavelength of 650 to 1300 nm). The infrared absorber is preferably a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm.
Examples of the colorant having such spectroscopic characteristics include a pyrrolopyrrole compound, a copper compound, a cyanine compound, a phthalocyanine compound, an imine compound, a thiol complex compound, a transition metal oxide compound, a squaric acid compound, a naphthalocyanine compound, a quartilene (quaterrene) compound, a dithiol metal complex compound, and a Ketone onium compound.
As the phthalocyanine compound, naphthalocyanine compound, imine compound, cyanine compound, squaric acid compound, and Ketone onium compound, those disclosed in paragraphs 0010 to 0081 of JP-A2010-111750 can be used, and the contents are incorporated herein. For example, the cyanine compound can be referred to "functional dye, shirtz/tsuga/north-tail tsuga/Ping Daoheng, shiny, kodansha ltd.", and this content is incorporated in the present specification.
As the colorant having the above-mentioned spectroscopic characteristics, a compound disclosed in paragraphs 0004 to 0016 of japanese unexamined patent application publication No. 07-164729 and/or a compound disclosed in paragraphs 0027 to 0062 of japanese unexamined patent application publication No. 2002-146254, and near infrared absorbing particles comprising crystallites of oxides of Cu and/or P and having a number average agglomerated particle size of 5 to 200nm disclosed in paragraphs 0034 to 0067 of japanese unexamined patent application publication No. 2011-164583 can also be used.
The compound having a wavelength region of 675 to 900nm in which the wavelength is greatly absorbed is preferably at least 1 selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squaric acid compounds, phthalocyanine compounds and naphthalocyanine compounds.
The infrared absorber is preferably a compound which is dissolved in water at 25 ℃ in an amount of 1 mass% or more, and more preferably a compound which is dissolved in water at 25 ℃ in an amount of 10 mass% or more. By using this compound, solvent resistance is improved.
The pyrrolopyrrole compound can be referred to paragraphs 0049 to 0062 of Japanese patent application laid-open No. 2010-222557, and this content is incorporated herein by reference. The cyanine compound and the squaric acid compound can be prepared by referring to paragraphs 0022 to 0063 of International publication No. 2014/088063, paragraphs 0053 to 0118 of International publication No. 2014/030628, paragraphs 0028 to 0074 of International publication No. 2014 to 59550, paragraphs 0013 to 0091 of International publication No. 2012/169447, paragraphs 0019 to 0033 of Japanese patent application publication No. 2015-0036, paragraphs 0053 to 0099 of Japanese patent application publication No. 2014-63144, paragraphs 0085 to 0150 of Japanese patent application publication No. 2014-52431, paragraphs 0076 to 0124 of Japanese patent application publication No. 2012-44301, paragraphs 0045 to 0078 of Japanese patent application publication No. 2012-8532, paragraphs 0027 to 0067 of Japanese patent application publication No. 20155-172102, paragraphs 0029 to 0067 of Japanese patent application publication No. 2015-0085, paragraphs 0029 to 20145, paragraphs 5 to 20124-20124, paragraphs 5 to 20124-20148, and paragraphs 20120 to 2013 to 20145 and 2013 to 20120, and paragraphs 2013 to 20120 and 2015 to 2015.
[ Other optional ingredients ]
The curable composition may further contain any other component than the above components. For example, polymerization inhibitors, sensitizers, co-sensitizers, crosslinking agents, curing accelerators, fillers, heat curing accelerators, plasticizers, diluents, and fat-sensitive agents may be used, and if necessary, known additives such as adhesion promoters and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension regulators, chain transfer agents, and the like) may be added to the substrate surface.
These components are described in, for example, paragraphs 0183 to 0228 of Japanese patent application laid-open No. 2012-003225 (paragraphs 0237 to 0309 of the specification of corresponding U.S. patent application publication No. 2013/0034812), paragraphs 0101 to 0102, 0103 to 0104, 0107 to 0109 and paragraphs 0159 to 0184 of Japanese patent application laid-open No. 2013-195480 of Japanese patent application laid-open No. 2008-250074, and the like, and are incorporated herein by reference.
[ Method for producing curable composition ]
Regarding the curable composition, it is preferable that a pigment-dispersed dispersion composition is first produced, and the obtained dispersion composition is further mixed with other components to produce a composition.
The dispersion composition is preferably prepared by mixing the pigment, the resin a and the solvent. It is also preferable to introduce a polymerization inhibitor into the dispersion composition.
The dispersion composition can be prepared by mixing the above-mentioned components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifying apparatus, a wet mill, a wet disperser, or the like).
After the preparation of the dispersion composition, the above-mentioned dispersion composition, resin B, polymerizable compound, photopolymerization initiator, and solvent can be mixed to prepare the composition.
In the preparation of the curable composition, the components may be blended together, or the components may be dissolved or dispersed in a solvent and then blended successively. The order of the addition and the working conditions at the time of the compounding are not particularly limited.
In order to remove foreign matters, reduce defects, and the like, the curable composition is preferably filtered by a filter. The filter may be used without any particular limitation as long as it is a filter conventionally used for filtration applications and the like. Examples thereof include filters based on fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins (including high density and ultra-high molecular weight) such as Polyethylene and Polypropylene (PP), and the like. Among them, polypropylene (including high density polypropylene) or nylon is preferable.
The pore diameter of the filter is preferably 0.1 to 7.0. Mu.m, more preferably 0.2 to 2.5. Mu.m, still more preferably 0.2 to 1.5. Mu.m, particularly preferably 0.3 to 0.7. Mu.m. When the content is within this range, it is possible to prevent the pigment (including the black pigment) from being clogged by filtration, and to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment.
The curable composition preferably contains no impurities such as metals, halogen-containing metal salts, acids, and bases. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably substantially none (the detection limit of the measuring apparatus or less).
The impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Flectric Corporation, agilent 7500cs type).
[ Method for producing cured film ]
In the present specification, the term "cured film" refers to a film formed by subjecting a composition layer formed using a curable composition to a curing treatment such as an exposure treatment.
Hereinafter, a method for producing a cured film will be described.
The method for producing the cured film preferably includes the following steps. Through the above steps, for example, a patterned cured film can be formed. In addition, when the cured film is not set in a pattern, the developing step may not be performed.
Hereinafter, each step will be described.
[ Procedure for Forming composition layer ]
In the composition layer forming step, a layer (composition layer) of the curable composition is formed by applying the curable composition to a support or the like before exposure. As the support, for example, a substrate for a solid-state image pickup device (light receiving device) in which an image pickup device (light receiving device) such as a CCD (Charge Coupled Device: charge coupled device) or CMOS (Complementary Metal-Oxide Semiconductor: complementary metal oxide semiconductor) is provided on a substrate (for example, a silicon substrate) can be used. Further, if necessary, an undercoat layer for improving adhesion to the upper layer, preventing diffusion of substances, planarizing the substrate surface, and the like may be provided on the support.
Examples of the method for applying the curable composition to the support include various coating methods such as a slit coating method, an inkjet method, a spin coating method, a casting coating method, a roll coating method, and a screen printing method. The film thickness of the composition layer is preferably 0.1 to 10. Mu.m, more preferably 0.2 to 5. Mu.m, still more preferably 0.2 to 3. Mu.m. The drying (pre-baking) of the composition layer applied to the support may be performed at a temperature of 50 to 140 ℃ for 10 to 300 seconds using a heating plate, an oven, or the like.
[ Exposure procedure ]
The exposure step is a step of exposing the composition layer formed in the composition layer forming step to actinic rays or radiation. Specifically, the exposure step is a step of exposing the composition layer formed in the composition layer forming step to actinic rays or radiation, and curing the irradiated region of the composition layer.
The method of irradiation is not particularly limited, and irradiation is preferably performed through a photomask having a patterned opening.
The exposure is preferably performed by irradiation with radiation, and particularly, ultraviolet rays such as g-rays, h-rays, and i-rays are preferable as radiation usable in the exposure, and a high-pressure mercury lamp is preferable as a light source. The irradiation intensity is preferably 5 to 1500mJ/cm 2, more preferably 10 to 1000mJ/cm 2.
In the exposure step, the composition layer may be heated in a subsequent heating step, which will be described later. In other words, in the exposure step, the method for producing a cured film may not include a post-heating step when the composition layer is heated.
[ Developing Process ]
The developing step is a step of performing a developing treatment on the exposed composition layer. By this step, the composition layer in the light-exposed region in the exposure step dissolves out, leaving only the light-cured portion. For example, in the exposure step, when light irradiation is performed through a photomask having a patterned opening, a patterned cured film can be obtained.
The type of the developing solution used in the developing step is not particularly limited, but an alkali developing solution that does not cause damage to the image pickup element, the circuit, and the like of the substrate is preferable.
The developing temperature is, for example, 20 to 30 ℃.
The development time is, for example, 20 to 90 seconds. In order to remove the residue, the treatment is sometimes carried out for 120 to 180 seconds in recent years. In order to further improve the residue removing property, the process of spin-drying the developer every 60 seconds and further supplying a new developer may be repeated.
The alkali developer is preferably an alkali aqueous solution prepared by dissolving an alkali compound in water to a concentration of 0.001 to 10 mass% (preferably 0.01 to 5 mass%).
Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1, 8-diazabicyclo [5.4.0] -7-undecene (among them, organic bases are preferable).
In addition, when used as an alkaline developer, a washing treatment is usually carried out with water after development.
[ Post baking ]
After the exposure step, a heat treatment (post baking) is preferably performed. Post baking is a post-development heat treatment for complete curing. The heating temperature is preferably 240 ℃ or less, more preferably 220 ℃ or less. The lower limit is not particularly limited, but is preferably 50 ℃ or higher, more preferably 100 ℃ or higher, in view of efficient and effective treatment.
Post-drying can be performed continuously or intermittently using a heating mechanism such as a heating plate, a convection oven (heated air circulation dryer), or a high-frequency heater.
The post-baking is preferably performed in an atmosphere having a low oxygen concentration. The oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, further preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. The lower limit is not particularly limited, but is practically 10 ppm by volume or more.
The post-baking by the heating may be changed to the curing by UV (ultraviolet) irradiation.
In this case, the curable composition preferably further contains a UV curing agent. The UV curing agent is preferably a UV curing agent capable of curing at a wavelength shorter than 365nm, which is an exposure wavelength of a polymerization initiator added for a photolithography step by normal i-ray exposure. Examples of the UV curing agent include Ciba IRGACURE 2959 (trade name). When UV irradiation is performed, the composition layer is preferably a material that cures at a wavelength of 340nm or less. The lower limit of the wavelength is not particularly limited, and is usually 220nm or more. The exposure amount of UV irradiation is preferably 100 to 5000mJ, more preferably 300 to 4000mJ, and even more preferably 800 to 3500mJ. In order to more effectively perform the low-temperature curing, the UV curing process is preferably performed after the photolithography process. The exposure light source preferably uses a mercury ozone-free lamp.
[ Physical Properties of cured film and use of cured film ]
The cured film obtained by curing the curable composition of the present invention is preferably used as a light shielding film. Hereinafter, preferable physical properties and applications when a cured film obtained by curing the curable composition of the present invention is used as a light shielding film will be described.
[ Physical Properties of light-blocking film and use of light-blocking film ]
From the viewpoint of excellent light-shielding properties, the light-shielding film preferably has an Optical Density (OD: optical Density) of 3.0 or more, more preferably 3.5 or more, per 5.0 μm film thickness in a wavelength region of 400 to 1100 nm. The upper limit is not particularly limited, but is usually preferably 10 or less.
In the present specification, an optical density of 3.0 or more per 5.0 μm film thickness in a wavelength region of 400 to 1100nm means an optical density of 3.0 or more per 5.0 μm film thickness in the entire region of 400 to 1100 nm. As a method for measuring the optical density of the light shielding film, first, a light shielding film is formed on a glass substrate and measured using a spectrophotometer (for example, U-4100 manufactured by HITACHI HIGH-Tech Corporation).
The film thickness of the light shielding film is, for example, preferably 0.1 to 6.0. Mu.m, more preferably 1.0 to 5.0. Mu.m, and still more preferably 1.0 to 2.5. Mu.m. Further, depending on the application, the light shielding film may be a thin film or a thick film as compared with the above range.
Further, from the viewpoint of excellent low reflectivity, the light shielding film preferably has a maximum reflectivity (incidence angle 5 °) of less than 5%, more preferably less than 3%, and even more preferably less than 1% per 5.0 μm film thickness in a wavelength region of 350 to 1200 nm. The lower limit is not particularly limited, but is usually 0% or more. As a method for measuring the maximum reflectance of the light shielding film, first, a light shielding film is formed on a glass substrate, and a reflectance spectrum of 5 ° with respect to an incident angle is obtained using a spectroscope (for example, a VAR unit of a spectroscope V7200 manufactured by JASCO Corporation), and the reflectance of light having a wavelength exhibiting the maximum reflectance in a wavelength region of 350 to 1200nm is obtained.
Further, from the viewpoint of excellent low reflectivity, the light shielding film preferably has a reflectance (reflectance at an incident angle of 5 ° and a light wavelength of 940 nm) of less than 5%, more preferably less than 3%, and even more preferably less than 1% per 5.0 μm film thickness in a wavelength region of 350 to 1200 nm. The lower limit is not particularly limited, but is usually 0% or more. As a method for measuring the reflectance of the light shielding film, first, the light shielding film is formed on a glass substrate, and a reflectance spectrum at an incident angle of 5 ° is obtained using a spectroscope (for example, a VAR unit of a spectroscope V7200 manufactured by JASCO Corporation), and the reflectance at a wavelength of 940nm is obtained.
The light shielding film is suitable for use in portable devices such as personal computers, tablet computers, cellular phones, smart phones, and digital cameras, OA (Office Automation: office automation) devices such as multifunctional printers and scanners, industrial devices such as monitoring cameras, bar code readers and automated teller machines (ATM: automated TELLER MACHINE), high-speed cameras, and devices having personal recognition functions using face recognition, in-vehicle camera devices, medical camera devices such as endoscopes, capsule endoscopes, and catheters, and space devices such as living sensors, biological sensors (Biosensor), military investigation cameras, stereoscopic map cameras, weather and marine observation cameras, terrestrial resource investigation cameras, and astronomical and deep space exploration cameras, and light shielding members and light shielding films of filters and modules used in such devices, and is further suitable for use in antireflection members and antireflection films.
The light shielding film can be used for micro LEDs (LIGHT EMITTING Diode: light emitting Diode) and micro OLEDs (Organic LIGHT EMITTING Diode: organic electroluminescent Diode) and the like. The light shielding film is suitable for a member that imparts a light shielding function or an antireflection function, in addition to a filter and an optical film used for the micro LED and the micro OLED.
Examples of the micro LED and the micro OLED include those described in japanese patent application laid-open No. 2015-500562 and japanese patent application laid-open No. 2014-533890.
The light shielding film is suitable as an optical and optical film used for a quantum dot sensor and a quantum dot solid-state imaging element. And is suitable as a member for imparting a light shielding function and an antireflection function. Examples of the quantum dot sensor and the quantum dot solid-state imaging element include those described in U.S. patent application publication No. 2012/37789 and international publication No. 2008/131313.
< Solid-state imaging element and solid-state imaging device >
The light shielding film is also preferably used for a solid-state imaging element.
In other words, the solid-state imaging device of the present invention is a solid-state imaging device having the light shielding film of the present invention.
The solid-state imaging device includes a light shielding film, and there is no particular limitation, and examples thereof include a solid-state imaging device including a light receiving element including a plurality of photodiodes, polysilicon, and the like, which constitute a light receiving region of the solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, and the like), on a substrate, and a light shielding film provided on a light receiving element formation surface side (for example, a portion other than the light receiving portion and/or a color adjustment pixel, and the like) of a support or on a side opposite to the formation surface.
In addition, when the light shielding film is used as the light attenuating film, for example, if the light attenuating film is arranged so that a part of light enters the light receiving element after passing through the light attenuating film, the dynamic range of the solid-state imaging element can be improved.
The solid-state imaging device includes the solid-state imaging element described above.
< Image display device >
The light shielding film is also preferably applied to an image display device.
In other words, the image display device of the present invention is an image display device having the light shielding film of the present invention.
As a method of providing the light shielding film in the image display device, for example, a method of applying a color filter including a black matrix including the light shielding film to the image display device is given.
Next, a black matrix and a color filter including the black matrix will be described, and a liquid crystal display device including such a color filter will be described as a specific example of an image display device.
(Black matrix)
The light shielding film is also preferably contained in a black matrix. The black matrix may be included in an image display device such as a color filter, a solid-state imaging element, and a liquid crystal display device.
Examples of the black matrix include the black matrix described above, black edges provided at the peripheral edge of an image display device such as a liquid crystal display device, grid-like and/or linear black portions between red, blue and green pixels, dot-like and/or linear black patterns for shielding TFTs (thin film transistor: thin film transistors), and the like. The definition of the black matrix is described in, for example, the 'dictionary of terms of liquid crystal display manufacturing apparatus', 2 nd edition, NIKKAN KOGYO SHIMBUN, ltd.,1996, page 64.
In order to improve display contrast and to prevent degradation of image quality due to current leakage of light in the case of an active matrix driving type liquid crystal display device using a Thin Film Transistor (TFT), the black matrix preferably has high light-shielding properties (3 or more in terms of optical density OD).
The method for manufacturing the black matrix is not particularly limited, and can be manufactured by the same method as the method for manufacturing the light shielding film. Specifically, a curable composition can be applied to a substrate to form a composition layer, and then exposed to light and developed to produce a patterned light shielding film (black matrix). The thickness of the light shielding film (black matrix) is preferably 0.1 to 4.0 μm.
The substrate is not particularly limited, and preferably has a transmittance of 80% or more with respect to visible light (wavelength 400 to 800 nm). Examples of the material of the substrate include glass such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass, plastic such as polyester resin and polyolefin resin, and alkali-free glass and quartz glass from the viewpoints of chemical resistance and heat resistance.
(Color Filter)
The light shielding film is also preferably included in the color filter.
The color filter includes a light shielding film, and includes a color filter having a substrate and the black matrix. That is, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.
The color filter including the black matrix can be manufactured by, for example, the following method.
First, a coating film (composition layer) of a curable composition containing a pigment corresponding to each colored pixel of a color filter is formed on an opening of a patterned black matrix formed on a substrate. The composition for each color is not particularly limited, and a known composition can be used, and among the compositions described in the present specification, a composition in which a black pigment is replaced with a colorant corresponding to each pixel is preferably used.
Next, the composition layer is exposed to light through a photomask having a pattern corresponding to the opening of the black matrix. Then, after the unexposed portions are removed by development treatment, baking is performed to form colored pixels in the openings of the black matrix. For example, when a series of operations are performed using a composition for each color including red, green, and blue pigments, a color filter having red, green, and blue pixels can be manufactured.
(Liquid Crystal display device)
The light shielding film is also preferably included in a liquid crystal display device. The liquid crystal display device includes a light shielding film, and includes a color filter including the black matrix (light shielding film) described above.
As a liquid crystal display device, for example, a liquid crystal display device having a pair of substrates disposed opposite to each other and a liquid crystal compound sealed between the substrates is used. As the substrate, a substrate for a black matrix has been described.
Specific examples of the liquid crystal display device include a laminate including a polarizer, a substrate, a color filter, a transparent electrode layer, an alignment film, a liquid crystal layer, an alignment film, a transparent electrode layer, a TFT (Thin Film Transistor: thin film transistor) element, a substrate, a polarizer, and a backlight unit in this order from the user side.
The liquid crystal display device is not limited to the above, and examples thereof include those described in electronic display devices (zol wood Zhaofu, kogyo Chosakai Publishing co., ltd,1990 release) and display devices (isb, chapter Sangyotosyo inc., release 1989). Further, for example, a liquid crystal display device described in "next-generation liquid crystal display technology (edited by interior Tian Longnan, kogyo Chosakai Publishing co., ltd, 1994) is mentioned.
< Infrared sensor >
The light shielding film is also preferably included in an infrared sensor.
Next, a solid-state imaging device to which the above-described infrared sensor is applied will be described.
The solid-state imaging device includes a lens optical system, a solid-state imaging element, an infrared light emitting diode, and the like. Further, for each structure of the solid-state imaging device, reference may be made to paragraphs 0032 to 0036 of Japanese patent application laid-open No. 2011-233983, which is incorporated herein by reference.
< Cover glass, optical Filter >
The light shielding film is also preferably used for a filter and a cover glass to be incorporated in a solid-state imaging device. Examples of the filter include an IR cut filter. By forming the light shielding film on the peripheral portion of the filter and the cover glass, generation of flare and ghost can be suppressed.
The configurations of the above-described light-shielding film-equipped filter and solid-state imaging device, and the configurations of the above-described light-shielding film-equipped cover glass and solid-state imaging device in paragraphs 0009 to 0012 of Japanese patent application laid-open No. 2014-132333 are incorporated herein by reference in paragraphs 0017 to 0020, 0037 and 0040 of Japanese patent application laid-open No. 2021-092605.
Examples
The present invention will be described in further detail with reference to examples. The materials, amounts used, proportions, processing contents, processing steps and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the examples shown below.
[ [ Preparation of curable composition and evaluation (1) ]
[ Various ingredients used in the preparation of curable composition ]
Hereinafter, the components for preparing the curable composition will be described in detail.
[ Resin A ]
Table 1 shows the structure of resin A (resins A-1~A-15 and RA-1) shown in Table 3.
As the resins A-1~A-15 and RA-1, synthetic resins were used. Hereinafter, a synthetic example of the resin A-1 will be shown as an example. The resins A-2~A-15 and RA-1 were synthesized in the same manner as in the synthesis example of the resin A-1, except that the types and proportions of the raw material monomers were changed.
< Synthesis of resin A-1 >
20.0G of methacrylic acid (FUJIFILM Wako Pure Chemical Corporation, manufactured) and 130.0g of PME-1000 (manufactured by NOF CORPORATION) and 50.0g of benzyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) were added to 233% by mass of propylene glycol monomethyl ether acetate relative to the total mass of the raw material monomers, and the mixture was heated to 80℃under a nitrogen stream. Then, dodecanethiol in an amount of 2mol% relative to the total mass of the raw material monomers and a thermal polymerization initiator (V-601 manufactured by FUJIFILM Wako Pure Chemical Corporation) in an amount of 0.5 mass% relative to the total mass of the raw material monomers were added, and the mixture was stirred for 2 hours. Then, a thermal polymerization initiator (V-601 manufactured by FUJIFILM Wako Pure Chemical Corporation) was added in an amount of 0.5 mass% based on the total mass of the raw material monomers, and the mixture was stirred for 2 hours. Then, a thermal polymerization initiator (V-601 manufactured by FUJIFILM Wako Pure Chemical Corporation) was added in an amount of 0.5 mass% based on the total mass of the raw material monomers, and the mixture was heated to 90 ℃ and stirred for 2 hours, thereby synthesizing resin a-1.
The weight average molecular weight of the resin A-1~A-15 is 15,000-39,000.
Table 1 is shown below.
TABLE 1
TABLE 2
[ Resin B ]
Table 2 shows the structure of resin B (resin B-1~B-15 and RB-1 to RB-3) shown in Table 4.
As the resins B-1~B-15 and RB-1 to RB-3, synthetic resins were used. Hereinafter, a synthetic example of the resin B-1 is shown as an example. The resins B-2~B-15 and RB-1 to RB-3 were synthesized in the same manner as in the synthetic example of the resin B-1, except that the types and proportions of the raw material monomers were changed.
< Synthesis of resin B-1 >
A raw material monomer solution was prepared by mixing 172.0g of methyl methacrylate (FUJIFILM Wako Pure Chemical Corporation manufactured) with 20.0g of methacrylic acid (FUJIFILM Wako Pure Chemical Corporation manufactured) and 8.0g of 2-hydroxyethyl methacrylate (FUJIFILM Wako Pure Chemical Corporation manufactured). A mixed solution A was prepared by mixing 2mol% of a thermal polymerization initiator (V-601 produced by FUJIFILM Wako Pure Chemical Corporation) with respect to the total mass of the raw material monomers and 111 mass% of 1-methoxy-2-propanol with respect to the total mass of the raw material monomers. Then, a mixed solution B of the above raw material monomer mixed solution and 1-methoxy-2-propanol in an amount of 74 mass% based on the total mass of the above raw material monomers was prepared and heated to 80 ℃, then a mixed solution a was added dropwise to the mixed solution B over 2 hours (addition polymerization), and after the dropwise addition, the mixture was heated at 80 ℃ for 2 hours and further heated at 90 ℃ for 3 hours, whereby a resin B-1 was synthesized.
In addition, the weight average molecular weight of the resin B-1~B-15 is in the range of 12,000 to 30,000.
Table 2 is shown below.
TABLE 3
TABLE 4
TABLE 5
[ Polymerizable Compound ]
The polymerizable compound (C-1~C-3) shown in Table 4 is shown below.
C-1 NK Ester A-TMMT (SHIN-NAKAMURA CHEMICAL Co., ltd.; pentaerythritol tetraacrylate)
Kayarad DPHA (Nippon Kayaku co., ltd. Manufactured), a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate
C-3 NK Ester A-DPH-12E (SHIN-NAKAMURA CHEMICAL Co., ltd. Manufactured ethoxylated dipentaerythritol polyacrylate)
[ Pigment ]
The pigment (D-1~D-4) shown in Table 3 is shown below.
D-1:TiON (titanium oxynitride)
TiN (titanium nitride) D-2:
D-3:TiO 2 (titanium oxide)
D-4:CB (carbon black)
[ Photopolymerization initiator ]
The photopolymerization initiator (E-1~E-3) shown in Table 4 is shown below.
E-1 IRGACURE OXE02 (oxime ester-based polymerization initiator, manufactured by BASF Co., ltd.)
E-2:ADEKA ARKLS NCI-831E (ADEKA CORPORATION, oxime ester-based polymerization initiator)
E-3 Compound of the following structure (oxime ester-based polymerization initiator)
[ Chemical formula 20]
[ Heat-crosslinkable Compound ]
The thermally crosslinkable compound (F-1~F-3) shown in Table 4 is shown below.
F-1:CELLOXIDE 2021P (DAICEL CHEMICAL INDUSTRIES, LTD. production)
EOCN-1020 (Nippon Kayaku Co., ltd.)
F-3:EHPE-3150 (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.)
[ Surfactant ]
The surfactant (W-1) shown in Table 4 is shown below.
W-1: KF6001 (Shin-Etsu Chemical Co., ltd.)
[ Solvent ]
The solvents shown in tables 3 and 4 are shown below.
PGMEA propylene glycol monomethyl ether acetate
PGME 1-methoxy-2-propanol
Butyl acetate
[ Preparation of pigment Dispersion ]
After mixing the components shown in Table 3 in the amounts (parts by mass) shown in Table 3, 230 parts by mass of zirconia beads having a diameter of 0.3mm were added, and dispersion treatment was performed for 5 hours using a paint stirrer, and the beads were separated by filtration, whereby pigment dispersions (pigment dispersions 1 to 16) were produced. The mass parts of the resin A are described as mass parts of the resin solid components except the solvent described in < synthetic example of the resin A-1 >.
Table 3 is shown below.
TABLE 6
[ Preparation of curable composition ]
The curable compositions of examples and comparative examples were prepared by mixing the components shown in table 4 below in the amounts (parts by mass) shown in table 4. The mass parts of the pigment dispersion liquid are the mass parts of the resin B as the total amount of the solution containing the solvent, and the mass parts of the resin B are described as the mass parts of the resin solid components other than the solvent described in < synthetic example of the resin B-1 >.
Table 4 is shown below.
In table 4, "content ratio T1" represents the ratio [ a/(a+b) of the content of resin a to the total content of resin a and resin B. A is the content of the resin A, B is the content of the resin B.
In table 4, "content ratio T2" represents the ratio [ C/(a+b+c) of the content of the polymerizable compound to the total content of the resin a, the resin B, and the polymerizable compound. A is the content of the resin A, B is the content of the resin B, and C is the content of the polymerizable compound.
[ Evaluation ]
Evaluation of the curable composition was performed by the following method. The results are shown in table 5.
[ Evaluation of reflectivity ]
The curable compositions of examples and comparative examples were applied to a glass substrate by spin coating, and a coating film having a film thickness of 5.0 μm after exposure was produced. After pre-baking at 90℃for 120 seconds, the entire surface of the substrate was exposed to light using a UX-1000SM-EH04 (manufactured by Ushio Inc.) with an exposure of 1000mJ/cm 2 by a high-pressure mercury lamp (lamp power: 50mW/cm 2). The exposed substrate was post-baked at 220 ℃ for 300 seconds, thereby obtaining a substrate with a cured film.
The substrate with a cured film was evaluated on the basis of the reflectance spectrum obtained at an angle of reflection of 5 ° by using a spectroscopic V7200 (trade name) VAR unit manufactured by JASCO Corporation to enter light having a wavelength of 350 to 1200nm at an angle of incidence of 5 °. Specifically, the reflectance of light having a wavelength of 940nm was evaluated as an evaluation criterion according to the following classification. In practical use, the evaluation is preferably "3" or more, and more preferably "4" or more.
(Evaluation criterion)
"5" Reflectivity less than 1%
"4" Is a reflectance of 1% or more and less than 3%
"3" The reflectivity is more than 3% and less than 5%
"2" Is a reflectance of 5% or more and less than 7%
"1" The reflectivity is 7% or more
[ Evaluation of Pattern adhesion ]
Each curable composition of examples and comparative examples was applied to an 8-inch silicon wafer previously sprayed with hexamethyldisilazane using a spin coater, and a coating film having a thickness of 5.0 μm after exposure was produced. Next, the obtained coating film was subjected to pre-baking at 100℃for 120 seconds, to prepare a substrate with a film.
The film in the produced film-equipped substrate was irradiated with light at a wavelength of 365nm through a mask having an island pattern of 50 μm square (a mask having 25 openings of 50 μm square) at an exposure of 50 to 1,700mJ/cm 2 using an i-ray step exposure apparatus FPA-i5+ (manufactured by Canon Inc.). After exposure, development was performed using an alkali developer CD-2000 (FUJIFILM Flectronic Materials co., ltd.) at 25 ℃ for 40 seconds. Then, after rinsing under running water for 30 seconds, spray drying was performed, thereby obtaining a substrate with a cured film.
Regarding the obtained island-like pattern of 50 μm square, the number of the obtained pattern was measured by observing from above the pattern using a scanning electron microscope (Hitachi, ltd. Manufactured S-9220). The minimum exposure required for the entire island pattern of 50 μm square to be bonded was obtained, and the adhesion was evaluated according to the following classification. If the evaluation is "3" or more, it is determined that there is no problem in practical use. In practical use, the evaluation is preferably "3" or more, and more preferably "4" or more.
(Evaluation criterion)
The minimum exposure is below 400mJ/cm 2.
"4" Is that the minimum exposure exceeds 400mJ/cm 2 and 900mJ/cm 2 or less.
"3" Is that the minimum exposure exceeds 900mJ/cm 2 and 1700mJ/cm 2 or less.
"2" Is capable of forming at least 1 island pattern of 50 μm square but not all patterns at an exposure of 50 to 170mJ/cm 2.
"1" In which an island pattern of 50 μm square cannot be formed at an exposure of 50 to 170mJ/cm 2.
[ Evaluation of development residue (unexposed portion residue) ]
Each curable composition of examples and comparative examples was applied to an 8-inch silicon wafer previously sprayed with hexamethyldisilazane using a spin coater, and a coating film having a thickness of 5.0 μm after exposure was produced. Next, the obtained coating film was subjected to pre-baking at 100℃for 120 seconds, to prepare a substrate with a film.
Further, light with a wavelength of 365nm was irradiated to the film in the produced film-attached substrate with an exposure of 50 to 1,700mJ/cm 2 through a pattern mask having a line and space of 50 μm using an i-ray step exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.). Next, the exposed film (cured film) was developed with a 60% cd-2000 (FUJIFILM Flectronic Materials co., ltd.) developer at 25 ℃ for 60 seconds, to obtain a patterned cured film. Then, the patterned cured film was rinsed with running water for 20 seconds, and then air-dried.
In the exposure step, the minimum exposure amount at which the line width of the developed pattern in the area irradiated with light becomes 50 μm or more is defined as exposure sensitivity, and the exposure sensitivity is defined as initial exposure sensitivity.
The cured film obtained with the minimum exposure amount at which the pattern line width after development became 50 μm or more was heated in an oven at 220 ℃ for 1 hour for each substrate. After the film was cured by heating, the number of residues present in the area (unexposed portion) where light was not irradiated was observed by SEM (Scanning Flectron Microscope: scanning electron microscope: 20000 times) in the exposure step on the substrate, and the development residues (unexposed portion residues) were evaluated according to the following classification. In practical use, the evaluation is preferably "3" or more, and more preferably "4" or more.
"5" No pattern was formed, and no residue was observed at all in the unexposed portion.
"4" In which no pattern was formed and 1 to 3 residues were observed at the 1.0 μm square of the unexposed portion.
"3" In which no pattern was formed and 4 to 10 residues were observed at the 1.0 μm square of the unexposed portion.
"2" In which no pattern was formed and 11 or more residues were observed at the unexposed portion at 1.0 μm square.
"1" Is poorly developed and unpatterned.
Table 5 is shown below.
TABLE 9
From the results shown in table 5, it was found that the cured film obtained by curing the curable composition of examples was excellent in low reflectivity to infrared light if the adhesion was excellent.
It was also confirmed that when the following condition A1 or the following condition A2 is satisfied (preferably, when the following condition B1 or the following condition B2 is satisfied), the cured film obtained by curing the curable composition is more excellent in low reflectivity to infrared light.
The requirement A1 the repeating unit A2 in the resin A contains a repeating unit having a polyoxyalkylene carbonyl group with an average addition number of 3 or more.
The requirement A2 the resin A contains a repeating unit having a polyoxyalkylene group with an average addition number of 10 or more, and the resin A contains a repeating unit having a benzyl group (preferably a repeating unit derived from benzyl (meth) acrylate).
The requirement B1 that the repeating unit A2 in the resin A contains a repeating unit having a polyoxyalkylene carbonyl group with an average addition number of 3 or more, and the number of carbon atoms of the ester-bonded alkyl group in the repeating unit B1 in the resin B is 4 or more.
The requirement B2 that the resin A contains a repeating unit having a polyoxyalkylene group with an average addition number of 10 or more (preferably a repeating unit derived from benzyl (meth) acrylate), and the number of carbon atoms of the ester-bonded alkyl group in the repeating unit B1 in the resin B is 4 or more.
Further, it was confirmed that when the curable composition contains a thermally crosslinkable compound, the adhesion of the cured film tends to be further improved.
Further, it was confirmed that when the resin a in the curable composition contains a repeating unit represented by the formula (a 11), the formula (a 12) or the formula (a 13) (in particular, a repeating unit represented by the formula (a 12)) as a repeating unit having an acid group, development residues tend to be further reduced.
[ [ Preparation of curable composition and evaluation (2) ]
[ Preparation of curable composition ]
Compositions 24 to 36 were prepared in the same manner as in example 20, except that the solvent (PGMEA: 12.60 parts by mass, PGME:12.52 parts by mass) in example 20 was changed to the solvent shown in table 6 below (mixed solvent in which solvents 1 to 4 were mixed in the combination shown in table 6). Then, the results of these were evaluated by the same evaluation method as in example 20, and the same evaluation result as in example 20 was obtained.
TABLE 10
[ Solvent ]
In addition, abbreviations of solvents shown in table 6 represent the following solvents.
PGMEA propylene glycol monomethyl ether acetate
PGME 1-methoxy-2-propanol
CyP cyclopentanone
CyH cyclohexanone
MB 3-methoxybutanol
1,3-BG 1, 3-butanediol
2,3-BG 2, 3-butanediol
PG propylene glycol
EG ethylene glycol
DMSO-dimethyl sulfoxide
GVL gamma valerolactone
DAA diacetone alcohol
[ [ Preparation of curable composition and evaluation (3) ]
[ Various ingredients used in the preparation of curable composition ]
Hereinafter, the components for preparing the curable composition will be described in detail.
[ Pigment Dispersion ]
Pigment dispersions 11 and 13 shown in table 8 are the same as pigment dispersions 11 and 13 used in table 4.
[ Resin B ]
The resins B (resin B-8, resin B-16 to resin B-19) shown in Table 8 are shown below.
Resin B-8 the same as resin B-8 used in Table 4.
Resins B-16 to B-19 the structure of resins B-16 to B-19 is shown in Table 7. Further, as the resins B-16 to B-19, synthetic resins were used. The resins B-16 to B-19 were synthesized in the same manner as in the synthesis example of the resin B-1, except that the types and proportions of the raw material monomers were changed.
The weight average molecular weight of the resins B-16 to B-19 is in the range of 18,000 to 39,000.
Table 7 is shown below.
TABLE 11
[ Polymerizable Compound ]
The polymerizable compounds (C-2, C-4~C-6) shown in Table 8 are shown below.
The same polymerizable compound C-2 as that used in Table 4 was used.
KAYARAD RP-1040 (Nippon Kayaku Co., ltd.) ethoxylated pentaerythritol tetraacrylate
C-5 KAYARAD DCPA-20 (manufactured by Nippon Kayaku Co., ltd., comprising a caprolactone-structured polymerizable compound)
OGSOLEA-0300 (Osaka GAS CHEMICALS Co., ltd.; polymerizable compound having 9, 9-bisaryl fluorene skeleton)
[ Photopolymerization initiator ]
The photopolymerization initiators (E-2, E-4~E-6) shown in Table 8 are shown below.
E-2 the photopolymerization initiator E-2 used in Table 4 was the same.
E-4 IRGACURE OXE01 (oxime ester-based polymerization initiator, manufactured by BASF Co., ltd.)
E-5 Omnirad1316 (TGM RESINS B.V. manufactured by oxime ester-based polymerization initiator)
E-6 Omnirad-2959 (IGM RESINS B.V. polymerization initiator of hydroxyacetophenone Compound series)
[ Heat-crosslinkable Compound ]
The thermally crosslinkable compound F-3 shown in Table 8 is the same as the thermally crosslinkable compound F-3 used in Table 4.
[ Solvent ]
PGME 1-methoxy-2-propanol
CyP cyclopentanone
[ Surfactant ]
The surfactant W-1 shown in Table 8 was the same as the surfactant W-1 used in Table 4.
[ Preparation of curable composition ]
The curable compositions of examples and comparative examples were prepared by mixing the components shown in table 8 below in the amounts (parts by mass) shown in table 8. The mass parts of the pigment dispersion liquid are the mass parts of the resin B as the total amount of the solution containing the solvent, and the mass parts of the resin B are described as the mass parts of the resin solid components other than the solvent described in < synthetic example of the resin B-1 >.
The above-described various evaluations were performed in the same manner using the obtained curable composition. The evaluation results are shown in table 8.
Table 8 is shown below.
In table 8, "content ratio T1" represents the ratio [ a/(a+b) of the content of resin a to the total content of resin a and resin B. A is the content of the resin A, B is the content of the resin B.
In table 8, "content ratio T2" represents the ratio [ C/(a+b+c) of the content of the polymerizable compound to the total content of the resin a, the resin B, and the polymerizable compound. A is the content of the resin A, B is the content of the resin B, and C is the content of the polymerizable compound.
TABLE 13
From the results shown in table 9, it was found that the cured film obtained by curing the curable composition of examples was excellent in low reflectivity to infrared light if the adhesion was excellent.
Further, according to the comparison of examples, it was confirmed that when the acid value of the resin B contained in the curable composition was 100mgKOH/g or less, the adhesion of the cured film tended to be further improved.
Claims (16)
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| JP2022-122125 | 2022-07-29 | ||
| JP2022122125 | 2022-07-29 | ||
| JP2023012023 | 2023-01-30 | ||
| JP2023-012023 | 2023-01-30 | ||
| PCT/JP2023/026726 WO2024024657A1 (en) | 2022-07-29 | 2023-07-21 | Curable composition, light-blocking film, solid-state imaging element, image display device, infrared sensor, and method for manufacturing cured film |
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| CN119452305A true CN119452305A (en) | 2025-02-14 |
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| CN202380049274.7A Pending CN119452305A (en) | 2022-07-29 | 2023-07-21 | Curable composition, light shielding film, solid-state imaging element, image display device, infrared sensor, and method for producing cured film |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20250020613A (en) |
| CN (1) | CN119452305A (en) |
| TW (1) | TW202411267A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6265093B2 (en) * | 2014-09-22 | 2018-01-24 | Jsr株式会社 | Colored composition, colored cured film, display element and solid-state image sensor |
| JP6824276B2 (en) * | 2016-08-30 | 2021-02-03 | 富士フイルム株式会社 | Photosensitive composition, cured film, optical filter, laminate, pattern formation method, solid-state image sensor, image display device and infrared sensor |
| JP7436620B2 (en) * | 2020-02-20 | 2024-02-21 | 富士フイルム株式会社 | Photosensitive compositions, films, optical filters, solid-state imaging devices, and image display devices |
| WO2022024554A1 (en) * | 2020-07-29 | 2022-02-03 | 富士フイルム株式会社 | Coloring composition, cured product, color filter, solid-state imaging device, image display device, and resin and method for producing same |
| JP7593002B2 (en) | 2020-08-04 | 2024-12-03 | 株式会社リコー | COMMUNICATION SYSTEM, COMMUNICATION METHOD, AND PROGRAM |
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