WO2019171902A1 - Composition durcissable, film durci, élément optique, élément d'imagerie à semi-conducteurs, et filtre coloré - Google Patents

Composition durcissable, film durci, élément optique, élément d'imagerie à semi-conducteurs, et filtre coloré Download PDF

Info

Publication number
WO2019171902A1
WO2019171902A1 PCT/JP2019/005476 JP2019005476W WO2019171902A1 WO 2019171902 A1 WO2019171902 A1 WO 2019171902A1 JP 2019005476 W JP2019005476 W JP 2019005476W WO 2019171902 A1 WO2019171902 A1 WO 2019171902A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
curable composition
resin
cured film
compound
Prior art date
Application number
PCT/JP2019/005476
Other languages
English (en)
Japanese (ja)
Inventor
貴洋 大谷
浜田　大輔
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2020504884A priority Critical patent/JP7083887B2/ja
Publication of WO2019171902A1 publication Critical patent/WO2019171902A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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

Definitions

  • the present invention relates to a curable composition, a cured film, an optical element, a solid-state imaging element, and a color filter.
  • a method for producing a cured film used in a solid-state imaging device or the like is generally a method in which a curable composition layer is formed on a substrate and then cured. Typically, the curable composition layer is irradiated with light through a predetermined mask pattern, and then development processing is performed.
  • Patent Document 1 discloses a photopolymerizable resin laminate in which a photopolymerizable resin layer and the like are laminated, and the photopolymerizable resin layer has an alkali-soluble polymer and an ethylenically unsaturated bond.
  • a photopolymerizable resin laminate comprising a photopolymerizable resin composition containing a compound, a photopolymerizable initiator, and a black pigment is disclosed.
  • [1] Contains black color material, polymerizable compound, resin A, photopolymerization initiator, and polymerization inhibitor, A curable composition, wherein the resin A satisfies any one of an acid value of 120 to 350 mgKOH / g and a weight average molecular weight of 3000 to 7500.
  • [3] [1] or [2] further containing a resin B which is a resin different from the resin A and has one or more groups selected from the group consisting of an oxyalkylene group and an oxyalkylenecarbonyl group.
  • a curable composition capable of producing a cured film having excellent line width stability
  • the present invention can provide a cured film formed using such a curable composition, and a color filter, an optical element, and a solid-state imaging device having the cured film.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the notation in which neither substitution nor substitution is described includes a group containing a substituent as well as a group not containing a substituent.
  • the “alkyl group” includes not only an alkyl group not containing a substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
  • active light or “radiation” in the present specification means, for example, deep ultraviolet, extreme ultraviolet (EUV), X-ray, and electron beam.
  • light means actinic rays and radiation.
  • Exposure in this specification includes not only exposure with far ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified.
  • (meth) acrylate represents acrylate and methacrylate.
  • (meth) acryl represents acryl and methacryl.
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • (meth) acrylamide represents acrylamide and methacrylamide.
  • “monomer” and “monomer” are synonymous.
  • ppm means “parts-per-million (10 ⁇ 6 )”
  • ppb means “parts-per-bilion (10 ⁇ 9 )”
  • ppt Means “parts-per-trilition (10 ⁇ 12 )”.
  • the weight average molecular weight (Mw) is a polystyrene equivalent value determined by a GPC (Gel Permeation Chromatography) method.
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (4.6 mm ID ⁇ 15 cm, Tosoh Corporation) as columns and THF (tetrahydrofuran) as an eluent. ).
  • the curable composition of the present invention contains a black color material, a polymerizable compound, a resin A, a photopolymerization initiator, and a polymerization inhibitor.
  • the resin A has an acid value of 120 to 350 mg KOH / g (hereinafter also referred to as “requirement 1”) and a weight average molecular weight of 3000 to 7500 (hereinafter also referred to as “requirement 2”). It is a resin that satisfies one of the requirements.
  • a curable composition layer formed using a curable composition is usually cured through exposure and further developed. During the exposure, the irradiated light is diffracted and / or scattered, so that a slight amount of light leaks around the original exposure region, and the curable composition layer may be partially cured. As described above, the portion where the curable composition layer is partially cured around the original exposure region causes unintended enlargement of the cured film, and adversely affects the line width stability of the cured film.
  • the curable composition of the present invention contains a polymerization inhibitor, it is possible to reduce the occurrence of partial curing due to slight light leaking from the exposed area. Moreover, since the curable composition of this invention contains resin A which satisfy
  • the curable composition contains a black color material.
  • the black color material include one or more selected from the group consisting of black pigments and black dyes.
  • a black color material may be used individually by 1 type, and may use 2 or more types.
  • the content of the black color material in the curable composition is not particularly limited, but is preferably 1 to 99% by mass and more preferably 5 to 55% by mass with respect to the total solid content of the curable composition.
  • the total solid content of the curable composition intends a component that forms a cured film, and does not include a solvent. Moreover, if it is a component which forms a cured film, even if the property is a liquid state, it will be considered as solid content.
  • a plurality of colorants that cannot be used alone as a black color material may be combined and adjusted so as to be black as a whole to obtain a black color material.
  • a black pigment alone as a black pigment a plurality of pigments having colors other than black alone may be used in combination as a black pigment.
  • a black dye alone as a black dye a single dye having a color other than black may be used in combination as a black dye.
  • the black color material means a color material that has absorption over the entire wavelength range of 400 to 700 nm. More specifically, for example, a black color material that meets the evaluation standard Z described below is preferable.
  • a composition containing a coloring material, a transparent resin matrix (such as an acrylic resin) and a solvent and having a coloring material content of 60% by mass relative to the total solid content is prepared.
  • the obtained composition is applied onto a glass substrate so that the thickness of the dried coating film is 1 ⁇ m, thereby forming a coating film.
  • the light-shielding property of the coating film after drying is evaluated using a spectrophotometer (such as UV-3600 manufactured by Hitachi, Ltd.). If the maximum value of the transmittance at a wavelength of 400 to 700 nm of the coating film after drying is less than 10%, it can be determined that the color material is a black color material that meets the evaluation standard Z.
  • the black color material is preferably a black pigment from the viewpoint of obtaining a cured film having a reduced reflectance.
  • Various known black pigments can be used as the black pigment.
  • the black pigment may be an inorganic pigment or an organic pigment.
  • the black pigment a pigment that expresses black alone is preferable.
  • the black pigment is preferably a pigment that absorbs infrared rays, for example.
  • the black pigment that absorbs infrared rays has absorption in the wavelength region of the infrared region (preferably, wavelength 650 to 1300 nm), for example. It is also preferable to have a maximum absorption wavelength in the wavelength region of 675 to 900 nm.
  • Examples of inorganic pigments that absorb infrared rays and develop black alone include Group 4 metal elements such as titanium (Ti) and zirconium (Zr), and Group 5 such as vanadium (V) and niobium (Nb).
  • Metallic elements cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and silver (Ag)
  • Examples thereof include metal oxides, metal nitrides, and metal oxynitrides containing one or more metal elements selected from the group consisting of:
  • the inorganic pigment may be subjected to a surface modification treatment.
  • inorganic particles that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group can be mentioned, such as “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the metal oxide, the metal nitride, and the metal oxynitride may be used as particles in which other atoms are mixed.
  • it may be used as a metal nitride-containing particle that further contains an atom (preferably an oxygen atom and / or a sulfur atom) selected from Group 13 to 17 elements of the periodic table.
  • Carbon black is also mentioned as a pigment that absorbs infrared rays and develops black alone.
  • carbon black are commercially available C.I. I.
  • Organic pigments such as CI Pigment Black 1 and C.I. I.
  • inorganic pigments such as CI Pigment Black 7.
  • Carbon black whose surface is coated with a resin may be used as carbon black.
  • the nitride or oxide of a Group 4 metal element, or the nitride of a Group 5 metal element or Oxynitrides are preferred, titanium nitride or oxynitride, zirconium nitride or oxynitride, vanadium nitride or oxynitride, or niobium nitride or oxynitride, more preferably titanium nitride Or oxynitrides are more preferred.
  • the titanium nitride is titanium nitride, the zirconium nitride is zirconium nitride, the vanadium nitride is vanadium nitride, and the niobium nitride is niobium nitride.
  • the titanium oxynitride is titanium oxynitride, the zirconium oxynitride is zirconium oxynitride, the vanadium oxynitride is vanadium oxynitride, and the niobium oxynitride is oxynitride Niobium.
  • titanium nitride is intended for TiN, and may contain oxygen atoms that are unavoidable in production (for example, the surface of TiN particles are unintentionally oxidized).
  • titanium nitride means a compound having a diffraction angle 2 ⁇ of a peak derived from the (200) plane when CuK ⁇ rays are used as an X-ray source is 42.5 ° to 42.8 °.
  • titanium oxynitride is intended to be a compound having a diffraction angle 2 ⁇ of a peak derived from the (200) plane when CuK ⁇ rays are used as an X-ray source and exceeding 42.8 °.
  • the upper limit of the diffraction angle 2 ⁇ of titanium oxynitride is not particularly limited, but is preferably 43.5 ° or less.
  • titanium oxynitride include titanium black. More specifically, for example, low-order titanium oxide represented by TiO 2 , Ti n O 2n-1 (1 ⁇ n ⁇ 20), and / or or include forms containing TiN x O y titanium oxynitride represented by (0 ⁇ x ⁇ 2.0,0.1 ⁇ y ⁇ 2.0).
  • titanium nitride (the diffraction angle 2 ⁇ is 42.5 ° to 42.8 °) and titanium oxynitride (the diffraction angle 2 ⁇ is more than 42.8 °) are collectively referred to as titanium nitride.
  • the form will be described.
  • titanium nitride may be used as particles in which other atoms are mixed.
  • titanium nitride may be used as titanium nitride-containing particles that further contain atoms (preferably silicon atoms or sulfur atoms) selected from Group 13-17 elements of the periodic table.
  • the metal nitride which is a combination of metal nitride and metal oxynitride may be used as particles in which other atoms are further mixed.
  • the metal nitride may be used as a metal nitride-containing particle that further contains an atom (preferably a silicon atom or a sulfur atom) selected from Group 13 to 17 elements of the periodic table.
  • titanium nitride contains titanium oxide TiO 2
  • TiO 2 is white and causes a reduction in the light-shielding property of the light-shielding film obtained by curing the curable composition, it is preferably reduced to such an extent that it is not observed as a peak.
  • the crystallite size constituting the titanium nitride can be determined from the half width of the peak obtained by measuring the X-ray diffraction spectrum.
  • the crystallite size can be calculated using Scherrer's equation.
  • the crystallite size constituting the titanium nitride is preferably 50 nm or less, and more preferably 20 nm or more.
  • the cured film formed using the curable composition tends to have higher ultraviolet (especially i-line (wavelength 365 nm)) transmittance and is more curable. A composition is obtained.
  • the specific surface area of titanium nitride is not particularly limited, but can be determined by the BET (Brunauer, Emmett, Teller) method.
  • the specific surface area of the titanium nitride is preferably 5 ⁇ 100m 2 / g, more preferably 10 ⁇ 60m 2 / g.
  • the production method of the black pigment is not particularly limited, and a known production method can be used, and examples thereof include a gas phase reaction method.
  • the gas phase reaction method include an electric furnace method, a thermal plasma method, and the like.
  • the thermal plasma method is preferable in that impurities are less mixed, the particle diameter is easily uniformed, and productivity is high.
  • a method for generating thermal plasma is not particularly limited, and includes direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and there is little mixing of impurities from the electrodes. High frequency plasma is more preferred.
  • the specific method for producing the black pigment by the thermal plasma method is not particularly limited.
  • a method for producing titanium nitride a method of reacting titanium tetrachloride with ammonia gas in a plasma flame (JP-A-2-22110). No.), a method in which titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced as a carrier gas, and is nitrided and synthesized in the cooling process (Japanese Patent Laid-Open No. 61-11140), and ammonia gas is added to the periphery of the plasma. And a blowing method (Japanese Patent Laid-Open No. 63-85007).
  • the production method of the black pigment is not limited to the above, and the production method is not limited as long as a black pigment having desired physical properties is obtained.
  • a metal pigment (oxy) nitride as described above may be coated with a silicon-containing compound to form a black pigment.
  • the method for coating the (oxy) nitride of the metal atom is not particularly limited, and a known method can be used. For example, it is described in JP-A No. 53-33228, page 2, lower right to page 4, upper right. Method (using (acid) nitride of metal atom instead of titanium oxide), method described in paragraphs 0015 to 0043 of JP-A-2008-69193 ((acid) of metal atom instead of fine particle titanium dioxide) And the method described in paragraphs 0020 and 0124 to 0138 of JP-A No. 2016-74870 (using (acid) nitride of metal atom instead of metal oxide fine particles). And the above content is incorporated herein.
  • a curable composition contains titanium black
  • titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is still more preferable.
  • the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
  • titanium oxide and silica particles are dispersed using a disperser to obtain a dispersion, and this dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.) to thereby obtain titanium black particles mainly.
  • a dispersed material containing Si and Ti as components can be obtained.
  • the reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.
  • titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo).
  • silica particles examples include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik).
  • a dispersing agent may be used for the dispersion of titanium oxide and silica particles. Examples of the dispersant include those described as the dispersant described later.
  • the dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. What is demonstrated in the column of the organic solvent mentioned later is mentioned. Titanium black in which Si / Ti is adjusted to, for example, 0.05 or more can be produced, for example, by the method described in paragraphs 0005 and 0016 to 0021 of JP-A-2008-266045.
  • the composition containing this dispersion by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more).
  • a suitable range for example, 0.05 or more.
  • a residue contains the component derived from compositions, such as a titanium black particle and a resin component. The reason why the residue is reduced is not yet clear, but the above-mentioned dispersed material tends to have a small particle size (for example, a particle size of 30 nm or less).
  • titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light, and thus the above-described dispersion to be dispersed containing titanium black and Si atoms (preferably Si / Ti is in terms of mass).
  • a light-shielding film formed using a material having a thickness of 0.05 or more exhibits excellent light-shielding properties.
  • the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ). Whether or not the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more with respect to the dispersion to be contained in the cured film obtained by curing the composition Is determined using the method (2) described in paragraph 0035 of JP2013-249417A.
  • the above-described titanium black can be used.
  • materials used for introducing Si atoms into the dispersion will be described.
  • a Si-containing material such as silica may be used.
  • silica examples include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These can be selected and used as appropriate.
  • fine particle type silica examples include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
  • a plurality of pigments having a color other than black alone may be combined and used as a black pigment.
  • the pigment having a color other than black alone may be an inorganic pigment or an organic pigment.
  • chromatic pigments chromatic pigments
  • R (red), G (green), and B (blue) can also be used.
  • the inorganic pigment having a color other than black alone is not particularly limited, and a known inorganic pigment can be used.
  • the inorganic pigment include titanium oxide, chromium oxide, iron oxide, red lead, iron oxide red, yellow lead, zinc yellow (zinc yellow 1 type, zinc yellow 2 type), ultramarine blue, prussian blue (ferrocyanian).
  • the inorganic pigment may be subjected to a surface modification treatment. Examples thereof include inorganic pigments that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group, such as “KTP-09” series (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the organic pigment having a color other than black alone is selected from, for example, the following organic pigments.
  • the pigment may be used in combination with a dye described later.
  • a dye described later.
  • a pigment that expresses black alone and / or a pigment that has a color other than black alone red, green
  • chromatic pigments such as yellow, orange, purple, and blue
  • a tungsten compound, a metal boride, or the like can be used as a pigment having a color other than black by itself and absorbing infrared rays.
  • a tungsten compound is preferable from the viewpoint of excellent light blocking properties at wavelengths in the infrared region.
  • the tungsten compound is excellent in the light absorption wavelength region of the oxime polymerization initiator related to the curing efficiency by exposure and the translucency in the visible light region.
  • the average primary particle size of the black pigment is preferably 0.01 to 0.1 ⁇ m, more preferably 0.01 to 0.05 ⁇ m.
  • the black pigment is composed of a combination of plural kinds of pigments, it is preferable that one or more of the pigments constituting the black pigment are within the above range, and that all the pigments constituting the black pigment are within the above range. More preferred.
  • the average primary particle diameter of a pigment can be measured using a transmission electron microscope (Transmission Electron Microscope, TEM).
  • TEM Transmission Electron Microscope
  • a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
  • Maximum length of a particle image obtained using a transmission electron microscope (Dmax: maximum length at two points on the contour of the particle image), and maximum vertical length (DV-max: two straight lines parallel to the maximum length)
  • Dmax maximum length at two points on the contour of the particle image
  • DV-max maximum vertical length
  • the geometric mean value (Dmax ⁇ DV ⁇ max) 1 ⁇ 2 is taken as the particle diameter.
  • the particle diameter of 100 particles is measured by this method, and the arithmetic average value thereof is taken as the average particle diameter to obtain the average primary particle diameter of the pigment.
  • Black dye As the black dye, a dye that expresses black alone can be used. Furthermore, as described above, a single dye having a color other than black may be used in combination as a black dye. Examples of such coloring dyes include chromatic dyes (chromatic dyes) such as R (red), G (green), and B (blue), and paragraphs 0027 to 375 of JP-A-2014-42375. Colorants described in 0200 can also be used.
  • Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, US Pat. No. 4,808,501. No. 5, U.S. Pat. No. 5,667,920, U.S. Pat. No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6-194828.
  • dye currently disclosed by the gazette etc. can be used.
  • a compound etc. can be used.
  • a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A. Moreover, you may use the polymerizable dye which has polymerizability in a molecule
  • the black color material may further contain an infrared absorber as a color material having a color other than black by itself.
  • the infrared absorber means a compound having absorption in the wavelength region of the infrared region (preferably, wavelength 650 to 1300 nm).
  • a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm is preferable.
  • colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylenes.
  • Examples include compounds, dithiol metal complex compounds, and croconium compounds.
  • the phthalocyanine compound naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used. Embedded in the book.
  • the cyanine compound for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein.
  • the compound having the maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound.
  • the infrared absorber is preferably a compound that dissolves 1% by mass or more in 25 ° C. water, and more preferably a compound that dissolves 10% by mass or more in 25 ° C. water. By using such a compound, the solvent resistance is improved.
  • paragraphs 0049 to 0062 of JP 2010-222557 A can be referred to, the contents of which are incorporated herein.
  • the cyanine compounds and squarylium compounds are disclosed in 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 JP 2014-59550 A, and International Publication No. 2012/0074.
  • paragraphs 0029 to 0085 of JP-A-2015-40895 paragraphs 0022 to 0036 of JP-A-2014-126642, paragraphs 0011 to 0017 of JP-A-2014-148567, and JP-A-2015-157893.
  • Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP 2014-095007 A, paragraphs 0013 to 0047 of JP 2014-80487 A, paragraphs 0007 to 0028 of JP 2013-227403 A, and the like can be referred to. This content is incorporated herein.
  • the curable composition contains a polymerizable compound.
  • the polymerizable compound means a compound that polymerizes under the action of a photopolymerization initiator described later.
  • the content of the polymerizable compound in the curable composition is not particularly limited, but is preferably 5 to 30% by mass, more preferably 10 to 25% by mass with respect to the total solid content of the curable composition, 15 to 23 mass% is further more preferable.
  • a polymeric compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that total content is in the said range.
  • the molecular weight of the polymerizable compound is preferably 2000 or less.
  • the polymerizable compound is a group containing an ethylenically unsaturated bond (hereinafter, also simply referred to as “ethylenically unsaturated group”) from the viewpoint of obtaining a cured film having a moderately roughened surface and reduced reflectance.
  • ethylenically unsaturated group an ethylenically unsaturated bond
  • ethylenically unsaturated group is a group containing an ethylenically unsaturated bond from the viewpoint of obtaining a cured film having a moderately roughened surface and reduced reflectance.
  • ethylenically unsaturated group are preferably 1 to 15 compounds, more preferably 3 to 6 compounds, further preferably 4 to 5 compounds, and particularly preferably 4 compounds.
  • the content of the polymerizable compound which is a compound containing 4 to 5 (preferably 4) ethylenically unsaturated groups is determined based on the total polymerizable content in the curable composition.
  • the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • polymerizable compound for example, compounds described in paragraph 0050 of JP2008-260927A and paragraph 0040 of JP2015-68893A can be used, and the above contents are incorporated in the present specification. It is.
  • the polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof.
  • the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
  • the polymerizable compound is also preferably a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100 ° C. or higher under normal pressure.
  • compounds described in JP-A-2013-29760, paragraph 0227, and JP-A-2008-292970, paragraphs 0254 to 0257 can be referred to, the contents of which are incorporated herein.
  • Polymerizable compounds include dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product, manufactured by Nippon Kayaku), di Pentaerythritol penta (meth) acrylate (commercially available product is KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available products are KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., A-DPH- 12E, manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are mediated by an ethylene glycol residue or a propylene glycol residue (for example, SR454, SR499 commercially available from Sartomer) are
  • oligomer types can also be used.
  • NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd.
  • Preferred embodiments of the polymerizable compound are shown below.
  • the polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • a polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is more preferably pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.
  • the acid value of the polymerizable compound containing an acid group is preferably from 0.1 to 40 mgKOH / g, more preferably from 5 to 30 mgKOH / g.
  • the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development dissolution properties are good, and when it is 40 mgKOH / g or less, it is advantageous in production and / or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
  • the polymerizable compound is also preferably a compound containing a caprolactone structure.
  • the compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule.
  • trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta ⁇ -caprolactone-modified polyfunctional (meta ) Acrylates Among these, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferable.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • “*” represents a bond.
  • R 1 represents a hydrogen atom or a methyl group
  • “*” represents a bond
  • a compound represented by the following formula (Z-4) or (Z-5) can also be used.
  • each E independently represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) —.
  • Y represents each independently an integer of 0 to 10
  • each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
  • the total number of (meth) acryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40.
  • the total number of (meth) acryloyl groups is 5 or 6
  • each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
  • — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — represents an oxygen atom side.
  • a form in which the terminal of X is bonded to X is preferred.
  • the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
  • all six Xs are acryloyl groups
  • all six Xs are acryloyl groups
  • among six Xs The aspect which is a mixture with the compound whose at least 1 is a hydrogen atom is preferable. With such a configuration, the developability can be further improved.
  • the total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
  • pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
  • the polymerizable compound may contain a cardo skeleton.
  • a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable.
  • Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, oncoat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
  • the polymerizable compound has a double bond equivalent (content of ethylenically unsaturated group. More specifically, ethylenic unsaturation in the polymerizable compound from the point that the retention defect suppression property of the obtained cured film is more excellent.
  • the value obtained by dividing the number of groups by the molecular weight (g / mol) of the polymerizable compound is intended to be 7.0 mmol / g or more, and more preferably 11.0 mmol / g or more.
  • the upper limit is not particularly limited, but is generally 20.0 mmol / g or less.
  • the mass ratio of each polymerizable compound in the total polymerizable compound and each polymerizable compound It is preferable that the sum of the products of the compound and the double bond equivalent is within the above range.
  • the double bond equivalent may be referred to as “C ⁇ C value”.
  • require by calculating C C value
  • a solid component (black pigment or the like) in the curable composition is precipitated by a centrifugal separation method, and the remaining liquid component is collected. Furthermore, the polymerizable compound is separated from the obtained liquid component by a liquid chromatography method, and the structure of the polymerizable compound is specified by analysis using an NMR (nuclear magnetic resonance) method, a GPC method, or the like.
  • NMR nuclear magnetic resonance
  • GPC GPC method
  • the curable composition of the present invention contains resin A.
  • Resin A is a resin that satisfies any one of the requirements ((Requirement 1) that the acid value is 120 to 350 mgKOH / g) and ((Requirement 2) that the weight average molecular weight is 3000 to 7500). is there. Since the resin A satisfies one of the requirements 1 and 2, the curable composition of the present invention containing the resin A can obtain a cured film having good developability and excellent line width stability.
  • the resin A may be a resin that satisfies only one of the requirements 1 and 2, or a resin that satisfies both of them simultaneously. Among these, a resin that satisfies only one of the requirements 1 and 2 and does not satisfy the other requirement is preferable.
  • Resin A may contain a curable group.
  • the curable group include an ethylenically unsaturated group (for example, (meth) acryloyl group, vinyl group, and styryl group), and a cyclic ether group (for example, epoxy group, oxetanyl group, etc.)
  • an ethylenically unsaturated group is preferable as the curable group in that polymerization can be controlled by radical reaction.
  • the ethylenically unsaturated group is more preferably a (meth) acryloyl group.
  • Resin A is not particularly limited as long as it satisfies either requirement 1 or requirement 2, but preferably contains a repeating unit derived from a (meth) acrylic monomer.
  • the content of the repeating unit derived from the (meth) acrylic monomer of the resin A is preferably 10 mol% or more, more preferably 50 mol% or more, still more preferably 75 mol% or more, based on all repeating units. More than 90 mol% is particularly preferred.
  • a repeating unit derived from the (meth) acrylic monomer for example, a repeating unit represented by the following general formula (AA) is preferable.
  • R M represents a hydrogen atom or a methyl group.
  • L represents a single bond or a divalent linking group.
  • the divalent linking group include a hydrocarbon group which may have a substituent (which may be linear or branched, and may have a cyclic structure. And the substituent is preferably a hydroxyl group. Among these, an alkylene group having 1 carbon atom is preferable.
  • X represents a hydrogen atom or a substituent.
  • substituents examples include an aromatic ring group (preferably a phenyl group), an alkyl group (preferably having a carbon number of 1 to 3), a (meth) acryloyl group, a (meth) acryloyloxy group, a hydroxyl group, and a carboxy group. It is done.
  • X is preferably a hydrogen atom or a phenyl group.
  • the repeating unit derived from the (meth) acrylic monomer contained in the resin A may be one kind, two kinds or more, and two kinds or more. It is preferable. When there are two or more, at least one is preferably a repeating unit derived from (meth) acrylic acid.
  • a repeating unit derived from benzyl (meth) acrylate is preferable.
  • Resin A preferably contains both the repeating unit derived from the benzyl (meth) acrylate and the repeating unit derived from the (meth) acrylic acid, the repeating unit derived from the benzyl (meth) acrylate, and the above More preferably, it consists only of a combination of repeating units derived from (meth) acrylic acid.
  • the resin A is preferably a copolymer of benzyl (meth) acrylate and (meth) acrylic acid.
  • Examples of other repeating units that are assumed to be contained in the main chain of the resin A include a repeating unit derived from a styrene monomer (such as hydroxystyrene) and a repeating unit derived from an ether dimer.
  • Examples of the ether dimer include a compound represented by the following general formula (ED1) and a compound represented by the following general formula (ED2).
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • ED2 general formula (ED2)
  • JP 2010-168539 A the description in JP 2010-168539 A can be referred to.
  • ether dimer for example, paragraph 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.
  • Resin A that satisfies Requirement 1
  • Resin A (resin A satisfying requirement 1) having an acid value of 120 to 350 mgKOH / g is prepared in an appropriate range.
  • the acid value of the resin satisfying the requirement 1 is preferably 170 to 300 mgKOH / g, more preferably 200 to 270 mgKOH / g, from the viewpoint of more excellent line width stability and undercut suppression of the obtained cured film.
  • the resin A satisfying the requirement 1 has a weight average molecular weight of preferably more than 7500, more preferably 8000 to 30000, and further preferably 10000 to 15000.
  • the resin A having a weight average molecular weight of 3000 to 7500 (resin A satisfying the requirement 2) is prepared in an appropriate molecular weight range.
  • the weight average molecular weight of the resin satisfying the requirement A is preferably from 3000 to 6500, more preferably from 3000 to 5000, more preferably from 4000 to 2000, because the cured film has more excellent line width stability, undercut suppression and residue suppression. 5000 is more preferable.
  • the acid value of the resin A satisfying the requirement 2 is preferably less than 120 mgKOH / g, more preferably 30 to 110 mgKOH / g, and more preferably 60 to 100 mgKOH / g.
  • Resin A may be used individually by 1 type, or may use 2 or more types together.
  • the curable composition may contain both the resin A satisfying the requirement 1 and the resin A satisfying the requirement 2.
  • the content of the resin A in the curable composition is not particularly limited, but is preferably 1 to 30% by mass and more preferably 5 to 15% by mass with respect to the total solid content of the curable composition. When using 2 or more types of resin A, it is preferable that total content is in the said range.
  • the presence or absence of the resin A in the curable composition and the content thereof can be measured by the following method.
  • a solid component (black pigment or the like) in the curable composition is precipitated by a centrifugal separation method, and the remaining liquid component is collected. Further, from the obtained liquid component, a component having a weight average molecular weight of more than 2000 is separated by GPC method, and this is used as a resin to be measured.
  • the resin is defined as resin A satisfying requirement 2, and the content relative to the total solid content of the curable composition is obtained.
  • the acid value is measured by an ordinary method (such as JISK5601-2-1 or JISK0070) to confirm whether the acid value is 120 to 350 mgKOH / g.
  • an ordinary method such as JISK5601-2-1 or JISK0070
  • the content of A can be determined. Further, the content of the resin A in the curable composition may be obtained by calculation when the blending of the curable composition and the acid value and the weight average molecular weight of the raw material to be used are known.
  • the curable composition may contain a resin other than the resin A described above.
  • the resin other than the resin A include a resin B from the viewpoint of obtaining a cured film having a reduced reflectance.
  • the resin B is a resin different from the resin A, and is a resin having one or more groups selected from the group consisting of oxyalkylene groups and oxyalkylenecarbonyl groups.
  • the resin B is preferably a resin that acts as a so-called pigment dispersant.
  • the content of the resin B in the curable composition is not particularly limited, but is preferably 2 to 40% by mass and more preferably 5 to 30% by mass with respect to the total solid content of the curable composition.
  • Resin B may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of resin B together, it is preferable that total content is in the said range.
  • the form in which at least one group selected from the group consisting of an oxyalkylene group and an oxyalkylenecarbonyl group in resin B is present is not particularly limited.
  • the alkylene moiety in the oxyalkylene group and oxyalkylenecarbonyl group may have a substituent, may be linear or branched, and may have a cyclic structure. Especially, it is preferable that the said alkylene part is unsubstituted.
  • the number of carbon atoms of the alkylene portion in the oxyalkylene group is preferably 1 to 10, and more preferably 2 to 3. Further, the number of carbon atoms of the alkylene moiety in the oxyalkylenecarbonyl group is preferably 2 to 8, and more preferably 4 to 6.
  • the resin B has a polyoxyalkylene structure in which a plurality of oxyalkylene groups are continuously bonded (preferably 3 or more, more preferably 10 or more) or a plurality of oxyalkylenecarbonyl groups (preferably 3). Or more, more preferably 10 or more) preferably having a bonded polyoxyalkylenecarbonyl structure.
  • Resin B is a polymer compound [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer Combined and naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, pigment derivative, and the like.
  • the polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
  • the polymer compound may contain a curable group.
  • the curable group include an ethylenically unsaturated group (for example, (meth) acryloyl group, vinyl group, styryl group, etc.), a cyclic ether group (for example, epoxy group, oxetanyl group, etc.) and the like.
  • an ethylenically unsaturated group is preferable as the curable group in that polymerization can be controlled by radical reaction.
  • the ethylenically unsaturated group is more preferably a (meth) acryloyl group.
  • the resin containing a curable group may contain an oxyalkylene group (preferably a polyoxyalkylene structure) and / or an oxyalkylene carbonyl group (preferably a polyoxyalkylene carbonyl structure) in the main chain.
  • the graft chain is an oxyalkylene group (preferably a polyoxyalkylene structure) and / or an oxyalkylenecarbonyl group (preferably a polyoxyalkylene structure). (Oxyalkylenecarbonyl structure) may be contained.
  • the said graft chain contains an oxyalkylene carbonyl group.
  • the polymer compound preferably contains a structural unit containing a graft chain.
  • structural unit is synonymous with “repeating unit”. Since the polymer compound containing a structural unit containing such a graft chain has an affinity for a solvent by the graft chain, the dispersibility of pigments, etc., and the dispersion stability after time (stability over time) It is excellent. Further, due to the presence of the graft chain, the polymer compound containing the structural unit containing the graft chain has an affinity with a polymerizable compound or other resin that can be used in combination. As a result, it becomes difficult to produce a residue by alkali development.
  • the graft chain When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to the pigment or the like is lowered, and the dispersibility of the pigment or the like tends to be lowered. Therefore, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and the number of atoms excluding hydrogen atoms. More preferably, it is 60 to 500.
  • the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
  • the graft chain preferably contains a polymer structure.
  • a polymer structure include a poly (meth) acrylate structure (for example, poly (meth) acrylic structure), a polyester structure (preferably, polyoxyalkylenecarbonyl). Structure), polyurethane structure, polyurea structure, polyamide structure, and polyether structure (preferably, polyoxyalkylene structure).
  • the graft chain is composed of a polyoxyalkylene carbonyl structure, a polyoxyalkylene structure, and a poly (meth) acrylate structure.
  • a graft chain containing at least one selected from the group is preferred, and a graft chain containing at least one of a polyoxyalkylenecarbonyl structure and a polyoxyalkylene structure is more preferred.
  • the macromonomer containing such a graft chain (a monomer having a polymer structure and bound to the main chain of the copolymer to constitute the graft chain) is not particularly limited, but includes a reactive double bond group.
  • the containing macromonomer can be used conveniently.
  • AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.), AS-6 (trade name, manufactured by Toagosei Co., Ltd.) Synthetic Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), or Bremer PME-4000 (trade name, manufactured by NOF Corporation) is preferable.
  • the resin B preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester, and includes polymethyl acrylate and polymethacrylic acid. More preferably, it contains at least one structure selected from the group consisting of methyl and chain polyester, and includes a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. More preferably, it contains at least one structure selected from the group consisting of:
  • the resin B is a resin other than the resin A and has the above structure in one resin B as long as it has at least one group selected from the group consisting of an oxyalkylene group and an oxyalkylenecarbonyl group.
  • the resin B contained alone may be used, or the resin B containing a plurality of these structures in one resin B may be used.
  • the polycaprolactone structure refers to a structure containing a ring-opened structure of ⁇ -caprolactone as a repeating unit.
  • the polyvalerolactone structure refers to a structure containing a ring-opened structure of ⁇ -valerolactone as a repeating unit. These correspond to one embodiment of the polyoxyalkylene carbonyl structure.
  • Specific examples of the repeating unit constituting the polycaprolactone structure contained in the resin B include a repeating unit in which j and k in the following formula (1) and the following formula (2) are 5.
  • the repeating unit which comprises the polyvalerolactone structure which resin B contains the repeating unit whose j and k in following formula (1) and following formula (2) are 4 is mentioned.
  • Specific examples of the repeating unit constituting the polymethyl acrylate structure contained in the resin B include a repeating unit in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group.
  • the resin B contains, as specific examples of the repeating units constituting the polymethyl methacrylate structure is X 5 is a methyl group in the formula (4) include the repeating units R 4 is a methyl group .
  • the polymer compound preferably contains a structural unit represented by any of the following formulas (1) to (4) as a structural unit containing a graft chain. It is more preferable to contain the structural unit represented by either (1A), the following formula (2A), the following formula (3A), the following formula (3B), or the following (4).
  • the polymer compound preferably contains at least one of structural units represented by any of the following formulas (1) to (3).
  • the structural unit represented by Formula (1) and the structural unit represented by Formula (2) are structural units containing an oxyalkylene carbonyl group.
  • the structural unit represented by Formula (3) is a structural unit containing an oxyalkylene group.
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
  • W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
  • X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group.
  • X 1 , X 2 , X 3 , X 4 , and X 5 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (the number of carbon atoms) from the viewpoint of restrictions on synthesis. It is preferably each independently a hydrogen atom or a methyl group, more preferably a methyl group.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
  • Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following linking groups (Y-1) to (Y-21). It is done.
  • a and B each represent a binding site in formulas (1) to (4). Of the structures shown below, (Y-2) or (Y-13) is more preferable because of the ease of synthesis.
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a monovalent organic group.
  • the structure of the organic group is not particularly limited, and specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group Etc.
  • a group containing a steric repulsion effect is particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 carbon atoms.
  • an alkyl group or an alkoxy group having ⁇ 24 is preferable, and among them, 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 is particularly preferable. Groups are more preferred.
  • the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.
  • n, m, p, and q are each independently an integer of 1 to 500.
  • j and k each independently represent an integer of 2 to 8.
  • J and k in the formulas (1) and (2) are preferably integers of 4 to 6, and more preferably 5, from the viewpoint of the temporal stability and developability of the composition.
  • n and m are preferably integers of 10 or more, and more preferably 20 or more.
  • the resin B contains a polycaprolactone structure and a polyvalerolactone structure
  • the sum of the number of repetitions of the polycaprolactone structure and the number of repetitions of the polyvalerolactone is preferably an integer of 10 or more, An integer is more preferable.
  • R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
  • R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure.
  • R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group.
  • the alkyl group may be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms.
  • a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is still more preferable.
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
  • the polymer compound can contain structural units containing graft chains that have two or more different structures. That is, in the molecule of the polymer compound, structural units represented by the formulas (1) to (4) having different structures from each other may be contained, and in the formulas (1) to (4), n, m , P, and q each represent an integer of 2 or more, in Formulas (1) and (2), j and k may contain structures different from each other in the side chain, and Formula (3) And (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
  • the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of temporal stability and developability of the composition.
  • a structural unit represented by Formula (2) it is more preferable that it is a structural unit represented by following formula (2A) from a viewpoint of temporal stability of a composition and developability.
  • the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or formula (3B) from the viewpoint of the temporal stability and developability of the composition. .
  • the polymer compound contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain.
  • the structural unit containing a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% by mass in terms of mass with respect to the total mass of the polymer compound. Preferably, it is contained in the range of 5 to 30% by mass.
  • the total content of the structural units represented by the above formulas (1) to (3) is preferably included in the range of 2 to 80% by mass with respect to the total mass of the polymer compound, and 5 to 25% by mass. It is more preferable that it is included in the range.
  • the structural unit containing a graft chain is included within this range, the dispersibility of the pigment is high, and the developability when forming a cured film is good.
  • a high molecular compound contains the hydrophobic structural unit different from the structural unit containing a graft chain (namely, it does not correspond to the structural unit containing a graft chain).
  • a hydrophobic structural unit is a structural unit which does not have an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).
  • the hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, and is a structural unit derived from a compound having a ClogP value of 1.2 to 8 It is more preferable. Thereby, the effect of this invention can be expressed more reliably.
  • ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In this specification, the ClogP value calculated by the program CLOGP v4.82 is used. A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B.
  • log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
  • logP log (Coil / Cwater)
  • Coil represents the molar concentration of the compound in the oil phase
  • Cwater represents the molar concentration of the compound in the aqueous phase.
  • the polymer compound preferably contains one or more structural units selected from structural units derived from monomers represented by the following formulas (i) to (iii) as hydrophobic structural units.
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or An alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.) is represented.
  • R 1 , R 2 and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • R 2 and R 3 are more preferably a hydrogen atom.
  • X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • L is a single bond or a divalent linking group.
  • a divalent aliphatic group for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group
  • divalent aromatic group for example, arylene group
  • Substituted arylene group divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Are aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (—CO—), and combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.
  • the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring.
  • Another heterocyclic ring, an aliphatic ring, or an aromatic ring may be condensed with the heterocyclic ring.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is aliphatic. Group, aromatic group, or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group.
  • L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z includes an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, and a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, and Substituted arylene groups, etc.), heterocyclic groups, or combinations thereof.
  • These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, wherein R 31 is an aliphatic group, an aromatic group Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.
  • the aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like are included.
  • bridged cyclic hydrocarbon ring examples include 2 such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.).
  • Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [4.3.1.1 2,5 ] undecane rings , And tetracyclo [4.4.0.1 2,5 .
  • the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
  • a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed, such as a perhydrophenalene ring, is also included.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
  • the carbon number of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
  • a heterocyclic group contains a 5-membered ring or a 6-membered ring as a heterocyclic ring.
  • Another heterocyclic ring, aliphatic ring or aromatic ring may be condensed with the heterocyclic ring.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is aliphatic. Group, aromatic group or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group.
  • the heterocyclic group does not have an acid group as a substituent.
  • R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1-6.
  • An alkyl group for example, a methyl group, an ethyl group, a propyl group, etc.
  • Z, or LZ is represented.
  • L and Z are as defined above.
  • R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L contains a single bond, an alkylene group, or an oxyalkylene structure.
  • a compound that is a divalent linking group, X is an oxygen atom or imino group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable.
  • R 1 is a hydrogen atom or a methyl group
  • L is an alkylene group
  • Z is an aliphatic group, a heterocyclic group, or an aromatic group. Compounds that are groups are preferred.
  • R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Compounds that are groups are preferred.
  • Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
  • Examples of typical compounds represented by formulas (i) to (iii) compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Incorporated into.
  • the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is in the above range, sufficient pattern formation can be obtained.
  • the polymer compound preferably further contains a structural unit containing a functional group capable of forming an interaction with a pigment or the like.
  • the functional group capable of forming an interaction with the pigment and the like include an acid group, a basic group, a coordination group, and a reactive functional group.
  • the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as the acid group, developability for pattern formation by alkali development can be imparted to the polymer compound. That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as the resin B that contributes to the dispersion of pigments and the like has alkali solubility in the composition.
  • the curable composition containing such a polymer compound has excellent light shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
  • a high molecular compound contains the structural unit containing an acid group
  • a high molecular compound becomes easy to become compatible with a solvent, and there exists a tendency for applicability
  • the acid group in the structural unit containing an acid group easily interacts with the pigment and the like, and the polymer compound stably disperses the pigment and the like, and the viscosity of the polymer compound that disperses the pigment and the like decreases. This is presumably because the polymer compound itself is easily dispersed stably.
  • the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the structural unit containing the graft chain or a different structural unit.
  • the structural unit containing a soluble group is a structural unit different from the hydrophobic structural unit described above (that is, does not correspond to the hydrophobic structural unit described above).
  • Examples of the acid group that is a functional group capable of forming an interaction with a pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and a carboxylic acid group, a sulfonic acid group, and
  • the phosphoric acid group is preferably at least one, and more preferably a carboxylic acid group.
  • Carboxylic acid groups have good adsorptive power to pigments and the like, and have high dispersibility. That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • the polymer compound may have one or more structural units containing an acid group.
  • the polymer compound may or may not contain a structural unit containing an acid group.
  • the content of the structural unit containing an acid group is calculated by mass conversion to the total mass of the polymer compound.
  • the content is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass from the viewpoint of suppressing damage to the image strength due to alkali development.
  • Examples of the basic group which is a functional group capable of forming an interaction with a pigment include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide
  • a preferable basic group is a tertiary amino group in that it has a good adsorptive power to pigments and has high dispersibility.
  • the polymer compound can contain one or more of these basic groups.
  • the polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is the total amount of the polymer compound in terms of mass. The amount is preferably 0.01 to 50% by weight, and more preferably 0.01 to 30% by weight from the viewpoint of inhibiting the development inhibition.
  • Examples of the coordinating group that is a functional group capable of forming an interaction with a pigment and the reactive functional group include, for example, acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride, and acidification Thing etc. are mentioned.
  • a preferred functional group is an acetylacetoxy group in that it has a good adsorptive power to pigments and has high dispersibility of pigments and the like.
  • the polymer compound may have one or more of these groups.
  • the polymer compound may or may not contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, but if it contains, the content of these structural units Is preferably 10 to 80% by mass in terms of mass, and more preferably 20 to 60% by mass from the viewpoint of inhibiting developability inhibition.
  • the polymer compound contains a functional group capable of forming an interaction with a pigment or the like other than the graft chain
  • the polymer compound only needs to contain a functional group capable of forming an interaction with the various pigments or the like, although how these functional groups are introduced is not particularly limited, the polymer compound is selected from structural units derived from monomers represented by the following formulas (iv) to (vi): It is preferable to contain more than one type of structural unit.
  • R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number 1 to 6 alkyl groups (for example, a methyl group, an ethyl group, and a propyl group) are represented.
  • R 11 , R 12 , and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently a hydrogen atom or methyl More preferably, it is a group.
  • R 12 and R 13 are each more preferably a hydrogen atom.
  • X 1 in the formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the formula (v) represents a methine group or a nitrogen atom.
  • L 1 represents a single bond or a divalent linking group.
  • the definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in the above-described formula (i).
  • L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L 1 may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n —, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z 1 represents a functional group capable of forming an interaction with a pigment other than the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, More preferably, it is an acid group.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl having 1 to 6 carbon atoms group (e.g., methyl group, ethyl group, and propyl group), - represents a Z 1, or -L 1 -Z 1.
  • L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples.
  • R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 11 , R 12 and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or a divalent oxyalkylene structure.
  • a compound in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group is preferable.
  • R 11 is a hydrogen atom or a methyl group
  • L 1 is an alkylene group
  • Z 1 is a carboxylic acid group
  • Y is a methine group. Is preferred.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, L 1 is a single bond or an alkylene group, and Z A compound in which 1 is a carboxylic acid group is preferred.
  • monomers represented by formulas (iv) to (vi).
  • monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction containing a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride.
  • reaction product a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride Reaction product, a reaction product of a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and trimellitic anhydride, a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride Reaction products with acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4 Hydroxyphenyl methacrylamide.
  • the content of the structural unit containing a functional group capable of forming an interaction with the pigment, etc. is the total mass of the polymer compound from the viewpoint of the interaction with the pigment, the stability over time, and the permeability to the developer. On the other hand, it is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and still more preferably 10 to 70% by mass.
  • the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and a pigment as long as the effects of the present invention are not impaired.
  • Other structural units having various functions different from structural units containing functional groups capable of forming an interaction with the like for example, structural units containing functional groups having affinity with a solvent to be described later
  • Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
  • the polymer compound may use one or more of these other structural units, and its content is preferably 0 to 80% by mass, based on the total mass of the polymer compound, in terms of mass. 60 mass% or less is more preferable. When the content is in the above range, sufficient pattern formability is maintained.
  • the acid value of the polymer compound is preferably in the range of 10 to less than 110 mgKOH / g, more preferably in the range of 20 to 100 mgKOH / g, and still more preferably in the range of 30 to 70 mgKOH / g.
  • the acid value of the polymer compound is 110 mgKOH / g or less, pattern peeling during development when forming a cured film is more effectively suppressed.
  • the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable.
  • the acid value of a high molecular compound is 20 mgKOH / g or more, precipitation of a pigment etc. can be suppressed more, the number of coarse particles can be decreased more, and the temporal stability of a composition can be improved more.
  • the acid value can be calculated from, for example, the average content of acid groups in the compound.
  • the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of resin.
  • the weight average molecular weight of the polymer compound is preferably more than 7,000 and not more than 300,000, more preferably 8000 to 200,000, still more preferably 9000 to 100,000, and 10,000 to 50. Is particularly preferred.
  • the polymer compound can be synthesized based on a known method.
  • polymer compound examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, not corresponding to resin A, Polyethylene glycol distearate can also be used.
  • Specific examples of commercially available polymer compounds include “Solsperse 12000” manufactured by Nippon Lubrizol.
  • amphoteric resin containing an acid group and a basic group.
  • the amphoteric resin is preferably a resin having an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more. These polymer compounds may be used alone or in combination of two or more.
  • polymer compound As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.
  • a graft copolymer described in JP 2010-106268 A paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 in US2011 / 0124824) can be used. Is incorporated herein by reference. In addition to the above, it contains a side chain structure in which acidic groups in paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding paragraphs 0075 to 0133 of US2011 / 0279759) are bonded via a linking group.
  • Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.
  • the curable composition of this invention may contain resin which does not correspond to any of resin A and resin B.
  • the curable composition contains a photopolymerization initiator.
  • a photoinitiator if a superposition
  • the photopolymerization initiator for example, a photopolymerization initiator having photosensitivity from the ultraviolet region to the visible light region is preferable.
  • it may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and an initiator that initiates cationic polymerization according to the type of the polymerizable compound (radical polymerization initiator). It may be.
  • the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least 50 within a range of 300 to 800 nm (more preferably 330 to 500 nm).
  • the content of the photopolymerization initiator in the curable composition is not particularly limited, but is preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition.
  • a photoinitiator may be used individually by 1 type, or may use 2 or more types. When using 2 or more types of photoinitiators together, it is preferable that total content is in the said range.
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenones.
  • paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can be used as the photopolymerization initiator.
  • the hydroxyacetophenone compound for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can be used.
  • the aminoacetophenone compound for example, commercially available products IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade names, all manufactured by BASF) can be used.
  • aminoacetophenone compound a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source having a wavelength of 365 nm or a wavelength of 405 nm can also be used.
  • acylphosphine compound commercially available IRGACURE-819 or IRGACURE-TPO (trade name, both manufactured by BASF) can be used.
  • an oxime ester polymerization initiator As a photoinitiator, an oxime ester polymerization initiator (oxime compound) is more preferable.
  • oxime compound a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, or a compound described in JP-A-2006-342166 can be used.
  • Examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one.
  • J.H. C. S. Perkin II (1979) pp. 1653-1660) J.M. C. S.
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • IRGACURE-OXE03 manufactured by BASF
  • IRGACURE-OXE04 manufactured by BASF
  • TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arcles NCI-831 Adeka Arcles NCI-930
  • N-1919 carboxymethyl methacrylate
  • An initiator manufactured by ADEKA
  • oxime compounds other than those described above compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position; compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety; A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at a dye site; a ketoxime compound described in International Patent Publication No. 2009-131189; and a triazine skeleton and an oxime skeleton A compound described in US Pat. No.
  • the oxime compound is preferably a compound represented by the following formula (OX-1).
  • the N—O bond of the oxime compound may be an (E) oxime compound, a (Z) oxime compound, a mixture of (E) isomer and (Z) isomer. Good.
  • R and B each independently represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group.
  • the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
  • the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group.
  • these groups may have one or more substituents.
  • the substituent mentioned above may be further substituted by another substituent.
  • the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
  • the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group, and an aryl group or a heterocyclic group is More preferred. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
  • the divalent organic group 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 one or more substituents. Examples of the substituent include the above-described substituents.
  • An oxime compound containing a fluorine atom can also be used as a photopolymerization initiator.
  • Specific examples of the oxime compound containing a fluorine atom include compounds described in JP2010-262028; compounds 24 and 36 to 40 described in JP-T-2014-500852; and JP2013-164471A (C-3); and the like. This content is incorporated herein.
  • photopolymerization initiator compounds represented by the following general formulas (1) to (4) can also be used.
  • R 1 and R 2 are each independently 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 Represents an arylalkyl 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 fluorene group, and R 3 and R 4 are each independently Represents 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 carbonyl Indicates a group.
  • R 1, R 2, R 3 and, R 4 is, R 1, R 2, R 3 in the formula (1), and has the same meaning as R 4,
  • R 5 are, -R 6 , —OR 6 , —SR 6 , —COR 6 , —CONR 6 R 6 , —NR 6 COR 6 , —OCOR 6 , —COOR 6 , —SCOR 6 , —OCSR 6 , —COSR 6 , —CSOR 6 , —CN, a halogen atom, or a hydroxyl group
  • R 6 is 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 4 to 20 represents a heterocyclic group
  • X represents a direct bond or a carbonyl group
  • a represents an integer of 0 to 4.
  • 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 aryl group having 7 to 30 carbon atoms.
  • R 3 and R 4 each independently represents 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 carbon atom.
  • R 1, R 3 and, R 4 is, R 1, R 3 in the formula (3), and has the same meaning as R 4,
  • R 5 are, -R 6, -OR 6, -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , -CN, halogen atom,
  • R 6 represents 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.
  • X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
  • R 1 and R 2 are preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group.
  • R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group.
  • R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group.
  • R 1 is preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group.
  • R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group.
  • R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group.
  • X is preferably a direct bond.
  • Specific examples of the compounds represented by formula (1) and formula (2) include compounds described in paragraphs 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.
  • oxime compounds preferably used in the curable composition are shown below.
  • the oxime compound represented by the general formula (A) (hereinafter also referred to as “specific photopolymerization initiator”) is preferable from the viewpoint of more excellent peeling inhibition of the obtained cured film.
  • specific photopolymerization initiator IRGACURE-OXE03 (manufactured by BASF) can be mentioned.
  • the oxime compound the compound described in Table 1 of International Publication No. 2015-036910 can also be used, and the above contents are incorporated in the present specification.
  • the oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in a wavelength region of 360 to 480 nm, and further preferably has high absorbance at wavelengths of 365 nm and 405 nm. .
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200,000 from the viewpoint of sensitivity. More preferably, it is 000.
  • a known method can be used to determine the molar extinction coefficient of the compound.
  • the molar extinction coefficient is measured at a concentration of 0.01 g / L using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent. It is preferable. You may use a photoinitiator in combination of 2 or more type as needed.
  • the curable composition contains a polymerization inhibitor. It does not restrict
  • the polymerization inhibitor include phenol-based polymerization inhibitors (for example, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-ditert-butyl-4-methylphenol, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4-methoxynaphthol, etc .; hydroquinone polymerization inhibitors (for example, , Hydroquinone, 2,6-di-tert-butylhydroquinone, etc.); quinone polymerization inhibitors (eg, benzoquinone, etc.); free radical polymerization inhibitors (eg, 2,2,6,6-tetramethylpiperidine 1- Oxyl free radical,
  • Nitrobenzene-based polymerization inhibitor e.g., nitrobenzene, 4-nitrotoluene, etc.
  • phenothiazine-based polymerization inhibitor e.g., phenothiazine, 2-methoxy phenothiazine, etc.
  • a phenol polymerization inhibitor or a free radical polymerization inhibitor is preferable in that the curable composition has a more excellent effect.
  • the effect of the polymerization inhibitor is remarkable when used together with a resin containing a curable group.
  • the content of the polymerization inhibitor in the curable composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass with respect to the total solid content of the curable composition, preferably 0.001 to 0.2. % By mass is more preferable, and 0.008 to 0.05% by mass is even more preferable.
  • a polymerization inhibitor may be used individually by 1 type, or may use 2 or more types together. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.
  • the ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the curable composition is more than 0.0005.
  • 0.0006 to 0.02 is more preferable, and 0.0006 to 0.005 is still more preferable.
  • the curable composition may contain a surfactant.
  • Surfactant contributes to the applicability
  • the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the curable composition.
  • Surfactant may be used individually by 1 type, or may use 2 or more types together. When two or more surfactants are used in combination, the total amount is preferably within the above range.
  • surfactant examples include a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant.
  • the liquid properties (particularly fluidity) of the curable composition are further improved. That is, in the case of forming a film using a curable composition containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid. The applicability to the coated surface is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with small thickness unevenness can be more suitably formed.
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass.
  • a fluorosurfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and / or liquid-saving properties, and has good solubility in the curable composition. .
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, and F781 (above, manufactured by DIC); Florard FC430, FC431, and FC171 (above, manufactured by Sumitomo 3M); Surflon S-382, SC-101, SC -103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (above, manufactured by Asahi Glass); and PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.
  • a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A No. 2011-89090.
  • the curable composition may contain an ultraviolet absorber.
  • an ultraviolet absorber As the ultraviolet absorber, salicylate, benzophenone, benzotriazole, substituted acrylonitrile and triazine ultraviolet absorbers can be used.
  • compounds of paragraphs 0137 to 0142 corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
  • a diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) and the like are also preferably used.
  • the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
  • the content of the ultraviolet absorber is preferably 0.001 to 15% by mass with respect to the total solid content of the curable composition.
  • the curable composition may contain a silane coupling agent.
  • a silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule.
  • 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 a hydrolysis reaction and / or a condensation reaction.
  • Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group.
  • the hydrolyzable group contains a carbon atom
  • the number of carbon atoms is preferably 6 or less, and more preferably 4 or less.
  • an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
  • the silane coupling agent improves the adhesion between the substrate and the cured film, so fluorine atoms and silicon atoms (however, excluding silicon atoms to which hydrolyzable groups are bonded) Is preferably not included, fluorine atom, silicon atom (excluding the silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, and It is desirable not to include a branched alkyl group having 3 or more carbon atoms.
  • the content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass with respect to the total solid content in the curable composition.
  • the said curable composition may contain the silane coupling agent individually by 1 type, and may contain 2 or more types. When a curable composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.
  • silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Examples include vinyltrimethoxysilane and vinyltriethoxysilane.
  • the curable composition preferably contains a solvent.
  • the solvent is not particularly limited and a known solvent can be used.
  • 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 is 10 to 90% by mass, and 15 to 50% by mass. More preferably, it is adjusted.
  • solid content intends components other than a solvent.
  • a solvent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of solvent together, it is preferable to adjust so that the total solid of a curable composition may become in the said range.
  • Examples of the solvent include water and an organic solvent.
  • Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, 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 ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol mono Chill 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, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, butyl acetate, Examples include, but are not limited to, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.
  • the curable composition is preferably prepared by first preparing a dispersion composition in which a black color material is dispersed, and further mixing the obtained dispersion composition with other components to obtain a curable composition.
  • the dispersion composition is preferably prepared by mixing a black color material, resin B, and a solvent.
  • it is also preferable to make a dispersion composition contain a polymerization inhibitor.
  • the dispersion composition can be prepared by mixing the above components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, or the like).
  • each component may be blended at once, or each component may be blended sequentially after being dissolved or dispersed in a solvent.
  • the order of input and the working conditions when blending are not particularly limited.
  • the curable composition is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects.
  • a filter if it is a filter conventionally used for the filtration use etc., it can be used without being specifically limited. Examples include filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (containing high density and ultra high molecular weight). It is done. Among these materials, polypropylene (containing high density polypropylene) and nylon are preferable.
  • the pore size of the filter is preferably 0.1 to 7.0 ⁇ m, more preferably 0.2 to 2.5 ⁇ m, still more preferably 0.2 to 1.5 ⁇ m, and particularly preferably 0.3 to 0.7 ⁇ m.
  • different filters may be combined.
  • the filtering by the first filter may be performed only once or may be performed twice or more.
  • the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering.
  • the pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it can select from the various filters which Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (former Japan Microlith Co., Ltd.), KITZ micro filter, etc. provide, for example.
  • As the second filter a filter formed of the same material or the like as the first filter described above can be used.
  • the pore size of the second filter is preferably 0.2 to 10.0 ⁇ m, more preferably 0.2 to 7.0 ⁇ m, and still more preferably 0.3 to 6.0 ⁇ m.
  • a curable composition does not contain impurities, such as a metal, the metal salt containing a halogen, an acid, and an alkali.
  • the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.
  • the impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
  • a curable composition layer (composition layer) formed using the curable composition can be cured to obtain a patterned cured film.
  • limit especially as a manufacturing method of a cured film
  • each process is demonstrated.
  • a curable composition layer formation process is a process of forming a curable composition layer using the said curable composition.
  • a process of forming a curable composition layer using a curable composition the process of apply
  • the type of the substrate is not particularly limited, but when used as a solid-state imaging device, for example, a silicon substrate is used, and when used as a color filter (including a color filter for a solid-state imaging device), a glass substrate or the like is used. .
  • the curable composition on the substrate various coating methods such as spin coating, slit coating, ink jet method, spray coating, spin coating, cast coating, roll coating, and screen printing are applied. be able to.
  • the curable composition applied on the substrate is usually dried at 70 to 150 ° C. for about 1 to 4 minutes to form a curable composition layer.
  • the curable composition layer formed in the curable composition layer forming step is exposed by irradiating with actinic rays or radiation, and the curable composition layer irradiated with light is cured.
  • the light irradiation method is not particularly limited, but light irradiation is preferably performed through a photomask having a patterned opening.
  • the exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferable, and a high-pressure mercury lamp is preferable as a light source.
  • the irradiation intensity is preferably 5 ⁇ 1500mJ / cm 2, more preferably 10 ⁇ 1000mJ / cm 2.
  • a curable composition contains a thermal-polymerization initiator, you may heat a curable composition layer in the said exposure process.
  • the heating temperature is not particularly limited, but is preferably 80 to 250 ° C.
  • the heating time is not particularly limited, but is preferably 30 to 300 seconds.
  • the method for producing a cured film may not include the post-heating step.
  • development processing is performed to elute the light non-irradiated portion in the exposure step into the developer.
  • An alkaline developer may be used as the developer.
  • an organic alkali developer is preferably used.
  • the development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
  • Examples of the alkaline aqueous solution (alkali developer) include inorganic alkali developers and organic alkali developers.
  • an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, and sodium metaoxalate is used at a concentration of 0.001 to 10% by mass (preferably An alkaline aqueous solution dissolved so as to be 0.005 to 0.5% by mass).
  • Organic alkaline developers include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline , Pyrrole, piperidine, and alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene at a concentration of 0.001 to 10% by mass (preferably 0.005 to 0.5% by mass) %) Dissolved in an alkaline aqueous solution.
  • a water-soluble organic solvent such as methanol and ethanol, and / or a surfactant, for example, can be added to the alkaline aqueous solution.
  • a developer composed of such an alkaline aqueous solution is used, the cured film is generally washed (rinsed) with pure water after development.
  • the manufacturing method of a cured film may contain another process.
  • the other steps include a substrate surface treatment step, a preheating step (pre-baking step), and a post-heating step (post-baking step).
  • pre-baking step pre-baking step
  • post-baking step post-heating step
  • a manufacturing method of the said cured film it is preferable to contain the process (post-heating process) of heating the curable composition layer after exposure between an exposure process and a image development process.
  • the heating temperature in the preheating step and the postheating step is preferably 80 to 250 ° C.
  • the upper limit is more preferably 200 ° C. or less, and further preferably 150 ° C. or less.
  • the lower limit is more preferably 90 ° C. or higher.
  • the heating time in the preheating step and the postheating step is preferably 30 to 300 seconds.
  • the upper limit is more preferably 240 seconds and even more preferably 180 seconds or less.
  • the lower limit is more preferably 60 seconds or more.
  • the cured film obtained using the curable composition of the present invention has an excellent light-shielding property, and has an optical density (OD: Optical Density) per film thickness of 1.0 ⁇ m in a wavelength region of 400 to 1200 nm of 2. 0.0 or more is preferable, and 3.0 or more is more preferable.
  • the upper limit is not particularly limited, but is generally preferably 10 or less.
  • the cured film can be preferably used as a light shielding film. In this specification, the optical density per 1.0 ⁇ m thickness in the wavelength region of 400 to 1200 nm is 3.0 or more.
  • a method of measuring the optical density of a cured film first, a cured film is formed on a glass substrate, and measured using a transmission densitometer (X-rite 361T (visual) densitometer). The film thickness at the location is also measured, and the optical density per predetermined film thickness is calculated.
  • the cured film preferably has a surface uneven structure. By doing so, the reflectance of the cured film can be reduced when the cured film is a light shielding film. Even if the surface of the cured film itself has an uneven structure, another layer may be provided on the cured film to provide the uneven structure.
  • the shape of the surface concavo-convex structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 ⁇ m to 1.5 ⁇ m.
  • the reflectance of the cured film is preferably less than 7%, more preferably less than 5%, and still more preferably less than 3%.
  • the method for producing the surface uneven structure is not particularly limited.
  • a cured film or other layer by a method containing an organic filler and / or an inorganic filler in a cured film or other layer, a lithography method utilizing exposure and development, or an etching method, a sputtering method, a nanoimprint method, etc. A method of roughening the surface of the layer may be used.
  • the method of reducing the reflectance of the cured film includes a method of providing a low refractive index layer on the cured film, a method of providing a plurality of layers having different refractive indexes (for example, high refractive index layers), and And a method of forming a low optical density layer and a high optical density layer described in JP-A-2015-1654.
  • the cured film is composed of portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as printer multifunction devices and scanners; surveillance cameras, barcode readers, cash Industrial equipment such as automated teller machines (ATMs), high-speed cameras, and devices with personal authentication using facial image authentication; in-vehicle camera equipment; endoscopes, capsule endoscopes, And medical camera equipment such as catheters; and biosensors, biosensors, military reconnaissance cameras, stereoscopic map cameras, weather and ocean observation cameras, land resource exploration cameras, and space astronomy and deep space targets Space equipment such as exploration cameras; etc.
  • Light blocking member and the light-shielding film of the optical filter and the module is used, yet is suitable for anti-reflection member and the antireflection film.
  • the cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode).
  • the cured film is suitable for members that provide a light shielding function or an antireflection function, in addition to optical filters and optical films used in micro LEDs and micro OLEDs.
  • Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.
  • the cured film is also suitable as an optical filter and an optical film used for quantum dot sensors and quantum dot solid-state imaging devices. Moreover, it is suitable as a member which provides a light shielding function and an antireflection function. Examples of the quantum dot sensor and the quantum dot solid-state imaging device include those described in US Patent Application Publication No. 2012/37789 and International Publication No. 2008/131313 pamphlet.
  • the cured film is also preferably used for a light shielding member and / or a light shielding film of a headlight unit used for a vehicle headlamp such as an automobile. Moreover, it is also preferable to use it for an antireflection member, an antireflection film, or the like.
  • the cured film obtained using the curable composition of the present invention is also preferably used as a so-called light-shielding film.
  • a light shielding film is also preferably used for a solid-state imaging device.
  • a light shielding film is one of the preferable forms in the cured film obtained using the curable composition of this invention. That is, the cured film of the present invention is also preferably a light shielding film.
  • the manufacturing method of the cured film which is a light shielding film can be similarly performed by the method described as the manufacturing method of the above-described cured film.
  • a light-shielding film can be produced by applying a curable composition to a substrate to form a curable composition layer, and exposing and developing.
  • the present invention also includes an invention of an optical element.
  • the optical element of the present invention is an optical element having the cured film (light-shielding film).
  • the optical element include an optical element used in an optical apparatus such as a camera, binoculars, a microscope, and a semiconductor exposure apparatus.
  • the said optical element is a solid-state image sensor mounted in a camera etc., for example.
  • the solid-state imaging device of the present invention contains the cured film (light-shielding film).
  • the form in which the solid-state image sensor includes a cured film (light-shielding film) is not particularly limited.
  • a plurality of photodiodes that form a light receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on a substrate.
  • a light receiving element made of polysilicon or the like, and having a cured film on the light receiving element forming surface side of the support (for example, a portion other than the light receiving portion and / or a color adjusting pixel) or the opposite side of the forming surface.
  • the solid-state imaging device contains the solid-state imaging element.
  • the solid-state imaging device 100 includes a rectangular solid-state imaging element 101 and a transparent cover glass 103 that is held above the solid-state imaging element 101 and seals the solid-state imaging element 101. Yes. Further, a lens layer 111 is provided on the cover glass 103 with a spacer 104 interposed therebetween.
  • the lens layer 111 includes a support body 113 and a lens material 112. The lens layer 111 may have a configuration in which the support 113 and the lens material 112 are integrally formed.
  • the peripheral region of the lens layer 111 is shielded from light by providing a light shielding film 114.
  • a cured film obtained using the curable composition of the present invention can also be used as the light shielding film 114.
  • the solid-state imaging device 101 photoelectrically converts an optical image formed by the imaging unit 102 serving as a light receiving surface thereof and outputs it as an image signal.
  • the solid-state imaging device 101 includes a laminated substrate 105 in which two substrates are laminated.
  • the laminated substrate 105 includes a rectangular chip substrate 106 and a circuit substrate 107 having the same size, and the circuit substrate 107 is laminated on the back surface of the chip substrate 106.
  • the material of the substrate used as the chip substrate 106 is not particularly limited, and a known material can be used.
  • An imaging unit 102 is provided at the center of the surface of the chip substrate 106. Further, when stray light is incident on the peripheral area of the imaging unit 102, dark current (noise) is generated from a circuit in the peripheral area. Therefore, the peripheral area is shielded from light by providing a light shielding film 115. A cured film obtained using the curable composition is preferably used as the light shielding film 115.
  • a plurality of electrode pads 108 are provided on the surface edge of the chip substrate 106.
  • the electrode pad 108 is electrically connected to the imaging unit 102 via a signal line (not shown) provided on the surface of the chip substrate 106 (which may be a bonding wire).
  • External connection terminals 109 are provided on the back surface of the circuit board 107 at positions substantially below the electrode pads 108, respectively. Each external connection terminal 109 is connected to an electrode pad 108 via a through electrode 110 that vertically penetrates the multilayer substrate 105. Each external connection terminal 109 is connected to a control circuit that controls driving of the solid-state image sensor 101, an image processing circuit that performs image processing on an image signal output from the solid-state image sensor 101, and the like via a wiring (not shown). Has been.
  • the imaging unit 102 is configured by each unit provided on a substrate 204 such as a light receiving element 201, a color filter 202, and a microlens 203.
  • the color filter 202 includes a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm.
  • the cured film obtained using the curable composition of the present invention can also be used as the black matrix 205bm.
  • a p-well layer 206 is formed on the surface layer of the substrate 204.
  • light receiving elements 201 which are n-type layers and generate and store signal charges by photoelectric conversion, are arranged in a square lattice pattern.
  • a vertical transfer path 208 made of an n-type layer is formed via a readout gate portion 207 on the surface layer of the p-well layer 206.
  • a vertical transfer path 208 belonging to an adjacent pixel is formed on the other side of the light receiving element 201 via an element isolation region 209 made of a p-type layer.
  • the read gate unit 207 is a channel region for reading signal charges accumulated in the light receiving element 201 to the vertical transfer path 208.
  • a gate insulating film 210 made of an ONO (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 204.
  • a vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed on the gate insulating film 210 so as to cover the vertical transfer path 208, the read gate portion 207, and the element isolation region 209.
  • the vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to perform charge transfer, and a read electrode that drives the read gate unit 207 to read signal charges.
  • the signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path (not shown) and an output unit (floating diffusion amplifier), and then output as a voltage signal.
  • a light shielding film 212 is formed on the vertical transfer electrode 211 so as to cover the surface thereof.
  • the light shielding film 212 has an opening at a position directly above the light receiving element 201 and shields light from other areas.
  • a cured film obtained using the curable composition of the present invention can also be used as the light shielding film 212.
  • an insulating film 213 made of BPSG (borophosphosilicate glass), an insulating film (passivation film) 214 made of P-SiN, and a transparent intermediate layer made of a planarizing film 215 made of transparent resin or the like are provided on the light shielding film 212.
  • BPSG borophosphosilicate glass
  • passivation film insulating film
  • a transparent intermediate layer made of a planarizing film 215 made of transparent resin or the like are provided. ing.
  • the color filter 202 is formed on the intermediate layer.
  • the cured film obtained using the curable composition of the present invention is also preferably contained in a black matrix.
  • the black matrix may be contained in an image display device such as a color filter, a solid-state imaging device, and a liquid crystal display device.
  • an image display device such as a color filter, a solid-state imaging device, and a liquid crystal display device.
  • As the black matrix those already described above; a black edge provided at the peripheral portion of an image display device such as a liquid crystal display device; a lattice between red, blue, and green pixels, and / or stripes A black part of the shape; a dot-like and / or a linear black pattern for TFT (thin film transistor) light shielding; and the like.
  • the black matrix improves the display contrast, and in the case of an active matrix driving type liquid crystal display device using thin film transistors (TFTs), in order to prevent image quality deterioration due to light current leakage, it has a high light shielding property (with an optical density OD). 3 or more).
  • TFTs thin film transistors
  • the production method of the black matrix is not particularly limited, but can be produced by the same method as the production method of the cured film.
  • a curable composition can be applied to a substrate to form a curable composition layer, and exposed and developed to produce a patterned cured film (black matrix).
  • the thickness of the cured film used as the black matrix is preferably 0.1 to 4.0 ⁇ m.
  • the material of the substrate is not particularly limited, but preferably has a transmittance of 80% or more with respect to visible light (wavelength 400 to 800 nm).
  • Specific examples of such materials include glass such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resins and polyolefin resins; and the like. In view of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferable.
  • the cured film obtained using the curable composition of the present invention is also preferably contained in a color filter.
  • the form in which the color filter contains a cured film is not particularly limited, and examples thereof include a color filter including 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.
  • a color filter containing a black matrix can be produced, for example, by the following method.
  • a coating film (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of a color filter is formed in an opening of a patterned black matrix formed on a substrate.
  • the resin composition for each color is not particularly limited, and a known resin composition can be used.
  • the black pigment is replaced with a colorant corresponding to each pixel. Things may be used.
  • it exposes with respect to the resin composition layer through the photomask which has a pattern corresponding to the opening part of a black matrix.
  • the colored pixels can be formed in the openings of the black matrix by baking.
  • a color filter having red, green, and blue pixels can be manufactured by performing a series of operations using, for example, resin compositions for each color containing red, green, and blue pigments.
  • the color filter as described above is also preferably used for a liquid crystal display device, for example.
  • a liquid crystal display device for example.
  • a curable composition was prepared using the components shown below.
  • Dispersion composition and black dye solution The following dispersion composition (dispersion) and black dye solution were prepared and used for the preparation of the curable composition.
  • A-1 Titanium black dispersion (A-1)
  • a titanium black dispersion (A-1) was obtained using the following raw materials. ⁇ Titanium black (a-1) (details will be described later) ⁇ Resin (X-1) (equivalent to Resin B) ⁇ PGMEA (propylene glycol monomethyl ether acetate)
  • the structure of the resin (X-1) is as follows.
  • the acid value was 58 and the weight average molecular weight was 32,000.
  • subjected to each repeating unit shows the molar ratio of each unit.
  • Resin (X-1) (5.5 parts by mass) was added to titanium black (a-1) (20 parts by mass), and PGMEA was further added so that the solid content concentration was 35% by mass.
  • the obtained dispersion was sufficiently stirred with a stirrer and premixed.
  • the obtained dispersion was subjected to a dispersion treatment using NPM Pilot manufactured by Shinmaru Enterprises under the following dispersion conditions to obtain a titanium black dispersion (A-1).
  • a uniform mixture aqueous solution was obtained by treatment at several 1360 rpm and a rotational speed of 1047 rpm for 20 minutes.
  • This aqueous solution is filled in a quartz container, heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), then the atmosphere is replaced with nitrogen, and ammonia gas is kept at 100 mL / min for 5 hours at the same temperature.
  • the nitriding reduction treatment was carried out by flowing.
  • the recovered powder was pulverized in a mortar to obtain titanium black (a-1) containing Si atoms and having a powdery specific surface area of 73 m 2 / g.
  • a carbon black dispersion (A-2) was obtained using the raw materials shown below.
  • ⁇ Coated carbon black (details will be described later)
  • Resin (X-1) (equivalent to Resin B, the same as that used for the preparation of titanium black dispersion (A-1))
  • Solsperse 12000 (pigment derivative, manufactured by Lubrizol)
  • PGMEA propylene glycol monomethyl ether acetate
  • Resin (X-1) (4.5 parts by mass) and Solsperse 12000 (1 part by mass) are added to the coated carbon black (20 parts by mass), and the solid content concentration is further 35% by mass.
  • PGMEA was added.
  • the obtained mixed liquid was sufficiently stirred with a stirrer and premixed.
  • the dispersion was subjected to a dispersion treatment under the following dispersion conditions using an Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. to obtain a dispersion composition. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a carbon black dispersion (A-2).
  • Carbon black was produced by a normal oil furnace method. However, as the raw material oil, an ethylene bottom oil having a small Na content, Ca content, and S content was used, and combustion was performed using gas fuel. Furthermore, pure water treated with an ion exchange resin was used as the reaction stop water. Using a homomixer, the obtained carbon black (540 g) was stirred with pure water (14500 g) at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry.
  • the slurry was transferred to a container with a screw type stirrer, and toluene (600 g) in which an epoxy resin “Epicoat 828” (manufactured by Japan Epoxy Resin) (60 g) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, the entire amount of carbon black dispersed in water moved to the toluene side and became particles of about 1 mm. Next, after draining with a 60 mesh wire net, the separated particles were put into a vacuum dryer and dried at 70 ° C. for 7 hours to remove toluene and water. The resin coating amount of the obtained coated carbon black was 10% by mass with respect to the total amount of carbon black and resin.
  • a black dye solution (A-3) was obtained using the following raw materials. ⁇ VALIFAST BLACK 3804 (black dye, manufactured by Orient Chemical Industries) ⁇ PGMEA (propylene glycol monomethyl ether acetate)
  • a black dye solution (A-3) was prepared by adding PGMEA (73.2 parts by mass) to VALIFAST BLACK 3804 (manufactured by Orient Chemical Industries) (26.8 parts by mass) and dissolving it.
  • Resin solutions (B-1) to (B-9) containing a resin represented by the following structure 1 or structure 2 were used for the preparation of the curable composition.
  • the numbers given to each repeating unit (X and Y are also numbers) intend the content (molar ratio) in the resin of each repeating unit.
  • the ratio of X and Y was appropriately changed so that the acid value of each resin would be the value shown in Table 1.
  • C-1 IRGACURE OXE-03 (manufactured by BASF)
  • C-2 IRGACURE OXE-02 (BASF)
  • C-3 IRGACURE 369 (BASF)
  • C-1 and C-2 are oxime ester polymerization initiators.
  • C-1 has the following structure.
  • D-1 a compound represented by “C— (CH 2 OOC—CH ⁇ CH 2 ) 4 ”.
  • D-2 the following compound (5-6 functional, double bond equivalent 10.1 mmol / g)
  • D-3 The following compound (tetrafunctional, double bond equivalent 7.6 mmol / g)
  • the value of the above “functionality” indicates the number of ethylenically unsaturated groups that one molecule of the polymerizable compound has.
  • the double bond equivalent (the weighted average value of the double bond equivalents of the hexafunctional polymerizable compound and the pentafunctional polymerizable compound) as a whole of D-2 is 10.1 mmol / g.
  • the exposure amount was adjusted so that the average value (the average value of 100 points) of the width (line width) of the line portion of the pattern obtained after development was 50 ⁇ m.
  • a developing device AD-1200, manufactured by Mikasa
  • development was performed by a paddle method for 15 seconds with a developer (CD-2060, manufactured by FUJIFILM Electronics Materials). Further, it was washed with pure water for 30 seconds using a shower nozzle to form a patterned cured film (also simply referred to as “pattern”) on the substrate.
  • the line width of the pattern was measured using an optical microscope (100 points), and the line width variation (3 ⁇ ) was evaluated from the following viewpoints.
  • a pattern was formed on the substrate in the same manner as in the line width measurement test. Using a scanning electron microscope (S-4800 (Hitachi High-Technologies Corporation)), the portion of the substrate where the curable composition layer was removed in the development process was observed and evaluated from the following viewpoints.
  • A Level where no residue is observed and no problem
  • B Partial residue is observed but there is no problem in practical use
  • C Level in which a large amount of residue is observed and practical problem
  • a cured film-formed substrate having a cured film on the substrate was produced in the same manner as in the line width measurement test except that light was irradiated without using a mask during exposure. Measured by using a spectroscope manufactured by JASCO Corporation (product name: V7200, combined with an absolute reflectance measurement unit) and incident light with a wavelength of 500 nm on an incident angle of 5 ° on the produced cured film forming substrate.
  • the reflectance was evaluated from the following viewpoints. A smaller reflectance is preferable.
  • A The rate of change in reflectivity is less than 5%, and there is no problem.
  • B A problem level when the reflectance change rate is 5% or more.
  • A The change rate of the line width is less than 5% and no problem.
  • B A problem level when the change rate of the line width is 5% or more.
  • the following table shows the composition of the curable compositions used in each Example and Comparative Example, and the test results. In addition, in the compounds of Comparative Examples 1 and 4, a pattern could not be formed.
  • the “content” column indicates the content (% by mass) of each component in each curable composition.
  • the description of “balance” as the content of the solvent indicates that a necessary amount of the solvent was added so that the total content of each component described in the table was 100. For example, it shows that the curable composition of Example 1 contains 63% by mass of the titanium black dispersion (A-1).
  • the column “Resin acid value” indicates the acid value of the resin contained in the resin solution used in the curable composition.
  • the column of “molecular weight of resin” indicates the weight average molecular weight of the resin contained in the resin solution used in the curable composition.
  • the column “Resin B” indicates whether or not the curable composition contains the resin B.
  • the case where the above requirements were satisfied was designated as A, and the case where the above requirements were not satisfied was designated as B.
  • the column of “oxime photopolymerization initiator” indicates whether or not the photopolymerization initiator contained in the curable composition is an oxime ester polymerization initiator. The case where the above requirements were satisfied was designated as A, and the case where the above requirements were not satisfied was designated as B.
  • the column of “specific photopolymerization initiator” indicates whether or not the photopolymerization initiator contained in the curable composition is a specific polymerization initiator.
  • the case where the above requirements were satisfied was designated as A, and the case where the above requirements were not satisfied was designated as B.
  • the column “type of black color material” indicates the type of black color material contained in the curable composition.
  • TB is intended for titanium black (titanium nitride)
  • CB is intended for carbon black
  • black dye is intended for black dye.
  • the column “number of functional groups of polymerizable compound” indicates the number of ethylenically unsaturated groups that the polymerizable compound contained in the curable composition has.
  • the curable composition of the present invention if used, a cured film (containing a patterned cured film) having excellent line width stability can be formed. Moreover, in the curable composition of Comparative Example 5 containing no polymerization inhibitor, there was no problem with the temporal stability of the line width of the resulting cured film, but there was a problem with the temporal stability of the reflectance. On the other hand, the curable composition of the present invention containing a polymerization inhibitor also had good stability over time of the reflectance of the resulting cured film. When the curable composition contained the resin B, it was confirmed that the reflectance of the cured film was more excellent (comparison between Examples 5 and 6).
  • the reflectance of the cured film is more excellent (comparison with Examples 5 and 6). Further, when the black pigment is titanium black (titanium nitride), the cured film is peeled off. It was confirmed that the inhibitory properties were more excellent (comparison between Examples 1 and 5).
  • the acid value of the resin A satisfying the requirement 1 is 170 to 300 mgKOH / g, it was confirmed that the cured film had more excellent line width stability, undercut suppression, and reflectance (Example 1 and Comparison with 8).
  • the weight average molecular weight of the resin A satisfying Requirement 2 is 6500 or less, the residual suppression of the cured film is more excellent (comparison with Examples 9 and 10).
  • the weight average molecular weight is 3000 to 5000, the line width of the cured film It was confirmed that the stability, the undercut suppressing property, and the reflectance were more excellent (comparison between Examples 1 and 9).
  • the photopolymerizable compound is an oxime photopolymerization initiator, the cured film has more excellent line width stability and undercut suppression (comparison with Examples 3 and 12), and is a specific photopolymerization initiator. Further, it was confirmed that the cured film was more excellent in inhibition of peeling (comparison between Examples 1 and 3).
  • the cured film has more excellent reflectivity (comparison between Example 7 and other examples), and further the double bond of the polymerizable compound When the equivalent was 11.0 mmol / g or more, it was confirmed that the line width stability, the undercut suppressing property, the peeling suppressing property, and the reflectance of the cured film were more excellent (Comparison with Examples 1 and 11). ).
  • DESCRIPTION OF SYMBOLS 100 Solid-state imaging device 101 ... Solid-state image sensor 102 ... Imaging part 103 ... Cover glass 104 ... Spacer 105 ... Laminated substrate 106 ... Chip substrate 107 ... Circuit board 108 ... Electrode pad 109 ... External connection terminal 110 ... Penetration electrode 111 ... Lens layer 112 ... Lens material 113 ... Supports 114, 115 ... Curing film 201 ... Light receiving element 202 ... Color filter 201 ... Light receiving element 202 ... Color filter 203 ... Micro lens 204 ... Substrate 205b ... Blue pixel 205r ... Red pixel 205g ... Green pixel 205bm ... Black matrix 206... P well layer 207... Readout gate portion 208... Vertical transfer path 209. Over gate insulating film 211 ... vertical transfer electrodes 212 ... cured film 213 ... insulating film 215 ... flattening film

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

L'invention fournit une composition durcissable qui permet de fabriquer un film durci d'une excellente stabilité de largeur de ligne. En outre, l'invention fournit un film durci formé à l'aide d'une telle composition durcissable, un filtre coloré possédant ce film durci, un élément optique, et un élément d'imagerie à semi-conducteurs. La composition durcissable comprend un matériau noir, une composition polymérysable, une résine (A), un initiateur de photopolymérisation et un inhibiteur de polymérisation. La résine (A) satisfait l'une des conditions suivantes : présenter un indice d'acide compris entre １２０ et ３５０ｍｇＫＯＨ／ｇ ; et présenter une masse moléculaire moyenne en poids comprise entre 3000 et 7500.
PCT/JP2019/005476 2018-03-08 2019-02-15 Composition durcissable, film durci, élément optique, élément d'imagerie à semi-conducteurs, et filtre coloré WO2019171902A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020504884A JP7083887B2 (ja) 2018-03-08 2019-02-15 硬化性組成物、硬化膜、光学素子、固体撮像素子、カラーフィルタ

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018042093 2018-03-08
JP2018-042093 2018-03-08

Publications (1)

Publication Number Publication Date
WO2019171902A1 true WO2019171902A1 (fr) 2019-09-12

Family

ID=67847181

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/005476 WO2019171902A1 (fr) 2018-03-08 2019-02-15 Composition durcissable, film durci, élément optique, élément d'imagerie à semi-conducteurs, et filtre coloré

Country Status (3)

Country Link
JP (1) JP7083887B2 (fr)
TW (1) TW201938596A (fr)
WO (1) WO2019171902A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021075174A1 (fr) * 2019-10-16 2021-04-22

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007304210A (ja) * 2006-05-09 2007-11-22 Fujifilm Corp 転写材料、カラーフィルタ、カラーフィルタの製造方法、並びに液晶表示装置
JP2013114008A (ja) * 2011-11-28 2013-06-10 Nichigo Morton Co Ltd 感光性樹脂組成物、及びこれを用いたフォトレジストフィルム
US20140162178A1 (en) * 2012-12-10 2014-06-12 Lg Display Co., Ltd. Photosensitive composition for display device, black matrix having the composition, and method of forming black matrix using the composition
WO2017208848A1 (fr) * 2016-05-31 2017-12-07 富士フイルム株式会社 Composition de résine photosensible, film de transfert, motif décoratif et panneau tactile
WO2018037913A1 (fr) * 2016-08-22 2018-03-01 富士フイルム株式会社 Composition pare-lumière, film pare-lumière, élément d'imagerie solide, filtre couleur, et dispositif d'affichage à cristaux liquides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007304210A (ja) * 2006-05-09 2007-11-22 Fujifilm Corp 転写材料、カラーフィルタ、カラーフィルタの製造方法、並びに液晶表示装置
JP2013114008A (ja) * 2011-11-28 2013-06-10 Nichigo Morton Co Ltd 感光性樹脂組成物、及びこれを用いたフォトレジストフィルム
US20140162178A1 (en) * 2012-12-10 2014-06-12 Lg Display Co., Ltd. Photosensitive composition for display device, black matrix having the composition, and method of forming black matrix using the composition
WO2017208848A1 (fr) * 2016-05-31 2017-12-07 富士フイルム株式会社 Composition de résine photosensible, film de transfert, motif décoratif et panneau tactile
WO2018037913A1 (fr) * 2016-08-22 2018-03-01 富士フイルム株式会社 Composition pare-lumière, film pare-lumière, élément d'imagerie solide, filtre couleur, et dispositif d'affichage à cristaux liquides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021075174A1 (fr) * 2019-10-16 2021-04-22
JP7288515B2 (ja) 2019-10-16 2023-06-07 富士フイルム株式会社 分散液、組成物、硬化膜、カラーフィルタ、光学素子、固体撮像素子及びヘッドライトユニット

Also Published As

Publication number Publication date
TW201938596A (zh) 2019-10-01
JPWO2019171902A1 (ja) 2021-02-04
JP7083887B2 (ja) 2022-06-13

Similar Documents

Publication Publication Date Title
WO2019176409A1 (fr) Procédé de fabrication de film durci et procédé de fabrication d'élément d'imagerie à semi-conducteurs
JP7109565B2 (ja) 遮光性組成物、硬化膜、遮光膜、固体撮像素子
WO2018066296A1 (fr) Composition de dispersion, composition durcissable, film durci, filtre coloré, élément d'imagerie à semi-conducteurs, dispositif d'imagerie à semi-conducteurs, capteur de rayons infrarouges, procédé de production d'une composition de dispersion, procédé de production d'une composition durcissable, et procédé de production d'un film durci
WO2018061583A1 (fr) Composition, film durci, filtre coloré, élément d'imagerie à semi-conducteurs, capteur de rayons infrarouges, capteur de rayons infrarouges proches, et capteur de proximité
WO2020017184A1 (fr) Composition de résine bloquant la lumière, film durci, filtre coloré, film bloquant la lumière, capteur d'image à l'état solide et dispositif d'affichage d'image
WO2018135249A1 (fr) Composition durcissable, film durci, filtre coloré, film de blocage de lumière, élément d'imagerie à semi-conducteur, dispositif d'affichage d'image, et procédé de fabrication de film durci
JP6994044B2 (ja) 硬化膜の製造方法、固体撮像素子の製造方法、画像表示装置の製造方法
WO2020059382A1 (fr) Film de protection contre la lumière, procédé de fabrication d'un film de protection contre la lumière, élément optique, élément d'imagerie à semi-conducteurs et unité de phare
WO2020059381A1 (fr) Composition de protection contre la lumière, film durci, filtre coloré, film de protection contre la lumière, élément optique, élément d'imagerie à semi-conducteurs et unité de phare
WO2017221620A1 (fr) Composition durcissable, film durci, filtre de couleur, film de blocage de lumière, élément d'imagerie à l'état solide, dispositif d'affichage d'image, procédé de production de film durci et composé thiol polyfonctionnel
JP6727344B2 (ja) 硬化性組成物、化合物、硬化膜、硬化膜の製造方法、カラーフィルタの製造方法、固体撮像素子、赤外線センサ
TWI751196B (zh) 含金屬氮化物粒子、分散組成物、硬化性組成物、硬化膜及它們的製造方法以及彩色濾光片、固體攝影元件、固體攝像裝置、紅外線感測器
JP6745977B2 (ja) 硬化性組成物、硬化膜、遮光膜、固体撮像素子、固体撮像装置、及び、硬化膜の製造方法
WO2017208771A1 (fr) Composition, film durci, filtre coloré, film de blocage de lumière, dispositif d'imagerie à semi-conducteurs, et dispositif d'affichage d'image
EP3412723B1 (fr) Composition de dispersion, composition durcissable, film bloquant la lumière, filtre coloré, et dispositif d'imagerie à semi-conducteurs
WO2019171902A1 (fr) Composition durcissable, film durci, élément optique, élément d'imagerie à semi-conducteurs, et filtre coloré
WO2019065456A1 (fr) Composition durcissable, film durci, dispositif d'imagerie à semi-conducteurs et procédé de fabrication de film durci
TWI836039B (zh) 組成物、硬化膜、濾色器、遮光膜、光學元件、固體攝像元件、頭燈單元、修飾二氧化矽粒子、修飾二氧化矽粒子的製造方法
KR20230033620A (ko) 조성물, 차광막, 고체 촬상 소자, 화상 표시 장치, 경화막의 제조 방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19763765

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020504884

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19763765

Country of ref document: EP

Kind code of ref document: A1