WO2018043085A1 - Curable compositon, cured film, color filter, solid imaging element, infrared sensor, process for producing cured film, and process for producing color filter - Google Patents

Curable compositon, cured film, color filter, solid imaging element, infrared sensor, process for producing cured film, and process for producing color filter Download PDF

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WO2018043085A1
WO2018043085A1 PCT/JP2017/028968 JP2017028968W WO2018043085A1 WO 2018043085 A1 WO2018043085 A1 WO 2018043085A1 JP 2017028968 W JP2017028968 W JP 2017028968W WO 2018043085 A1 WO2018043085 A1 WO 2018043085A1
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curable composition
group
cured film
metal nitride
content
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PCT/JP2017/028968
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French (fr)
Japanese (ja)
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純一 伊藤
倫弘 小川
金子　祐士
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富士フイルム株式会社
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Priority to KR1020197004692A priority Critical patent/KR102217044B1/en
Priority to JP2018537092A priority patent/JP6691604B2/en
Publication of WO2018043085A1 publication Critical patent/WO2018043085A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/065—Polyamides; Polyesteramides; Polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures

Definitions

  • the present invention relates to a curable composition, a cured film, a color filter, a solid-state imaging device, an infrared sensor, a method for producing a cured film, and a method for producing a color filter.
  • curable compositions containing light-shielding particles such as carbon black are known.
  • the curable composition containing the light-shielding particles as described above has been used in various applications, for example, in the production of a cured film contained in a liquid crystal display device, a solid-state imaging device, and the like. More specifically, a color filter used in a liquid crystal display device and a solid-state imaging device has a cured film called a black matrix on a glass substrate for the purpose of shielding light between colored pixels and improving contrast. Is used. Further, in the solid-state imaging device, a cured film is used for the purpose of preventing noise and improving image quality.
  • Such a solid-state imaging device generally includes a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, and a lens for forming a subject image on the solid-state imaging device. It is equipped with.
  • a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor
  • CMOS Complementary Metal-Oxide Semiconductor
  • Patent Document 1 discloses a photosensitive black resin composition containing a light shielding material, an alkali-soluble resin, a photopolymerization initiator, a reactive monomer, and an organic solvent, and at least as a light shielding material. There is described a photosensitive black resin composition containing titanium nitride particles and capable of forming a coating film having predetermined optical characteristics.
  • the present inventors formed a photosensitive black resin composition layer using the photosensitive black resin composition described in Patent Document 1, exposed the film, and then developed the patterned film. investigated. Although the above film has a high optical density (OD, optical density), it has been found that a residue is easily generated in an unexposed portion, and the pattern shape has not reached the level required recently.
  • OD optical density
  • the present invention provides a cured film that suppresses the generation of residues in unexposed areas and has an excellent pattern shape (hereinafter also referred to as “having the effect of the present invention”). Offering is an issue.
  • Another object of the present invention is to provide a cured film, a color filter, a solid-state imaging device, an infrared sensor, a cured film manufacturing method, and a color filter manufacturing method.
  • a curable composition containing metal nitride-containing particles, an oxime polymerization initiator, a polymerizable compound, and an acid anhydride [2] The curability according to [1], wherein the content ratio of the content of the acid anhydride to the content of the oxime polymerization initiator in the curable composition is 0.005 to 0.5. Composition. [3] The curable composition according to [1] or [2], wherein the acid anhydride contains two or more acid anhydride groups in one molecule. [4] The curable composition according to any one of [1] to [3], further comprising a polymerization inhibitor.
  • the content of the metal nitride-containing particles in the curable composition is 40% by mass or more based on the total solid content of the curable composition, according to any one of [1] to [8] The curable composition as described. [10] The content ratio of the content of the oxime polymerization initiator to the content of the metal nitride-containing particles in the curable composition is 0.03 to 0.2. [1] to [9 ] The curable composition in any one of. [11] The curable composition according to any one of [1] to [10], wherein the oxime polymerization initiator contains a nitro group. [12] The curable composition according to any one of [1] to [11], further comprising a solvent.
  • a curable composition layer forming step of forming a curable composition layer using the curable composition according to any one of [1] to [12], and a pattern on the curable composition layer An exposure process in which exposure is performed by irradiating actinic rays or radiation through a photomask having an opening, and a development process in which the cured curable composition layer is developed to form a cured film.
  • ADVANTAGE OF THE INVENTION According to this invention, generation
  • 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.
  • group (atomic group) in this specification the description which does not describe substitution and non-substitution includes what does not contain a substituent and what contains 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” means, for example, the emission line spectrum of a mercury lamp, extreme ultraviolet (EUV) represented by an excimer laser, X-ray, and electron beam. Etc. In the present specification, light means actinic rays and radiation.
  • exposure in this specification includes not only exposure by mercury lamp, excimer laser, deep ultraviolet ray, X-ray, EUV, but also drawing by particle beam such as electron beam and ion beam. To do.
  • (meth) acrylate represents an acrylate and a methacrylate.
  • (meth) acryl represents acryl and methacryl.
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • (meth) acrylamide represents acrylamide and methacrylamide.
  • “monomer” and “monomer” are synonymous.
  • a monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
  • the polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer.
  • the polymerizable group refers to a group that participates in a polymerization reaction.
  • the curable composition which concerns on embodiment of this invention contains metal nitride containing particle
  • the present inventors have found that the surface of metal nitride-containing particles tends to be basic.
  • the above characteristics are not necessarily caused only by a specific method for producing metal nitride-containing particles.
  • a specific manufacturing method will be described.
  • a method for producing titanium nitride-containing particles a method of reacting titanium tetrachloride with ammonia gas in a plasma flame (Japanese Patent Laid-Open No. 2-22110) is known.
  • ammonia gas is used to introduce nitrogen into the titanium compound, and therefore it is assumed that the surface of the produced titanium nitride-containing particles is likely to be basic.
  • the present inventors have also found that the oxime polymerization initiator has a property of being easily subjected to hydrolysis. Accordingly, when the metal nitride-containing particles and the oxime polymerization initiator are used in combination, hydrolysis of the oxime polymerization initiator may be promoted by the metal nitride-containing particles whose surface is basic. It is guessed.
  • the above tendency is remarkable when the curable composition contains a large amount of metal nitride-containing particles.
  • the photosensitive composition is used to form a photosensitive composition layer on the substrate, and when this is exposed, the pattern shape could get worse.
  • the region (upper layer region) close to the exposure surface of the photosensitive composition layer the opposite surface (substrate side surface, lower layer region) has a small amount of light reaching and is hard to be cured. Presumed to be from the body. This is presumed to be because light is more easily absorbed by a large amount of metal nitride-containing particles.
  • the photosensitive composition layer after exposure as described above is developed, the pattern of the lower layer region may be thinner than the upper layer region.
  • the curable composition according to the embodiment of the present invention includes an acid anhydride.
  • the acid anhydride reacts with water molecules that cause hydrolysis of the oxime polymerization initiator to generate an acid.
  • the curable composition has a function of removing water molecules that cause hydrolysis. Therefore, in the said curable composition, an oxime type polymerization initiator is hard to be hydrolyzed, As a result, it is estimated that the cured film obtained using the said curable composition has the outstanding pattern shape.
  • the acid generated when the acid anhydride removes water molecules moves to the upper layer region of the curable composition layer during exposure (particularly when heating is performed after exposure). It is presumed to have an action of promoting development during the subsequent alkali development. That is, when the curable composition contains an acid anhydride, the upper layer region of the curable composition layer formed thereby is more easily developed than the lower layer region, and thus the pattern shape obtained is Presumed to have improved. This is an unexpected synergistic effect due to the fact that the curable composition contains an acid anhydride.
  • an acid anhydride suppresses hydrolysis of the oxime polymerization initiator, and an unintended polymerization reaction due to decomposition of the oxime polymerization initiator, particularly in an unexposed portion. It was also found to suppress the above. This is an unexpected effect.
  • the curable composition according to the embodiment of the present invention it is presumed that the number of residues generated after development is suppressed in the unexposed area by the action of the above anhydride.
  • the curable composition which concerns on the said embodiment contains an acid anhydride.
  • the acid anhydride is not particularly limited as long as it has an action of removing water from the curable composition by reacting with and trapping with water, and a known acid anhydride can be used.
  • the content of the acid anhydride in the curable composition is not particularly limited, but is generally preferably 0.01 to 5% by mass with respect to the total solid content of the curable composition.
  • An acid anhydride may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of anhydride together, it is preferable that total content is in the said range.
  • an acid anhydride means a compound containing one or more acid anhydride groups in one molecule.
  • the content ratio of the content of acid anhydride to the content of metal nitride-containing particles described later in the curable composition is preferably 1.0 ⁇ 10 ⁇ 5 to 1.0, more preferably 0.0050 to 0.50.
  • the curable composition has a more excellent effect of the present invention.
  • a well-known acid anhydride group is mentioned.
  • the acid anhydride group include a carboxylic acid anhydride group derived from the same kind of acid, a phosphonic acid anhydride group, a sulfonic acid anhydride group, and the like, and an acid anhydride derived from two different acids. Groups.
  • the number of acid anhydride groups contained in the acid anhydride is not particularly limited, but two or more in one molecule is preferable in that the curable composition has more excellent effects of the present invention.
  • the upper limit of the number of acid anhydride groups contained in the acid anhydride is not particularly limited, but generally 4 or less is preferable.
  • the acid anhydride is not particularly limited.
  • disulfuric acid trifluoromethanesulfonic anhydride, dinitrogen pentoxide, diphosphoric acid, acetic anhydride, succinic anhydride, glutaric anhydride, phthalic anhydride, maleic anhydride 2-sulfobenzoic anhydride, p-toluenesulfonic anhydride, and the like.
  • a tetracarboxylic dianhydride represented by the formula (A1) is preferable in that the curable composition has more excellent effects of the present invention.
  • R 1 represents a tetravalent organic group.
  • the tetravalent organic group is not particularly limited, and examples thereof include an aliphatic or aromatic hydrocarbon group which may have a substituent having 1 to 40 carbon atoms.
  • Examples of the aliphatic hydrocarbon group include groups represented by the following formulas.
  • R a represents a nitrogen atom or CR b
  • R b represents a hydrogen atom or a monovalent organic group
  • n represents 0 or an integer of 1 or more
  • R a and R b may be the same or different, and a plurality of R b may be connected to each other to form a ring.
  • aromatic hydrocarbon group examples include groups represented by the following formulas.
  • tetracarboxylic dianhydride represented by the formula (A1) include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, meso-butane-1,2,3,4- Tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3- (carboxymethyl) -1,2 , 4-Cyclopentanetricarboxylic acid 1,4: 2,3-dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4 -(2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 3,4,9,10-perylene
  • tetracarboxylic dianhydride a compound represented by the following formula (A2) is more preferable in that the curable composition has more excellent effects of the present invention.
  • R 2 represents a single bond or a divalent linking group. Although it does not restrict
  • R b is as described above.
  • R 2 is preferably a single bond, —O— or —C ( ⁇ O) — from the viewpoint that the curable composition has the more excellent effects of the present invention.
  • Specific examples of the compound represented by the formula (A2) include, for example, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, diphenyl-3,3 ′, 4,4′-tetracarboxylic acid.
  • the molecular weight of the acid anhydride is not particularly limited, but the acid anhydride is likely to diffuse in the upper layer region of the curable composition layer in the heating step after exposure, and a cured film having a more excellent pattern shape is obtained by subsequent development. 100 to 800 are preferable, and 100 to 600 are more preferable in that they are easily obtained. In this paragraph, the molecular weight means a molecular weight that can be calculated from the structural formula.
  • the curable composition contains metal nitride-containing particles.
  • the metal nitride-containing particles mean particles containing metal atom nitrides.
  • the metal nitride-containing particles may contain metal atoms and atoms other than nitrogen atoms (for example, oxygen atoms), and the form thereof will be described later.
  • the content of the metal nitride-containing particles in the curable composition is not particularly limited, but is preferably 30% by mass or more based on the total solid content of the curable composition, and has a more excellent light-shielding property. Is more preferably 40% by mass or more. In addition, although it does not restrict
  • the content ratio of the content of the oxime polymerization initiator described later to the content of the metal nitride-containing particles in the curable composition hereinafter also referred to as “oxime polymerization initiator / metal nitride-containing particles”).
  • grain may be used individually by 1 type, or may use 2 or more types together. When two or more kinds of metal nitride-containing particles are used in combination, the total content is preferably within the above range.
  • the metal nitride-containing particles contain a metal atom nitride as described above.
  • the term “metal atom” is intended to mean a metal atom contained in a metal nitride-containing particle and present as a nitride. It does not restrict
  • Examples of the metal atom include transition metals, and a transition metal belonging to Group 3 to 11 is preferred in that it is easy to obtain a curable composition capable of obtaining a cured film having better light-shielding properties, Ti, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, or Pt are more preferable, Ti, Sc, V, Cr, Co, Cu, Y, Zr, Mo, Tc, Ru, Rh, Pd, Hf, Ta, W, Re, or Pt are more preferable, and Ti, V, Cr, Y, Zr, Nb, Hf, Ta, W, or Re is particularly preferable, and Ti, V, Nb, Ta, or Zr is most preferable.
  • the content of metal atoms in the metal nitride-containing particles is not particularly limited, but is preferably 50 to 80% by mass with respect to the total mass of the metal nitride-containing particles.
  • the content of metal atoms in the metal nitride-containing particles can be analyzed by ICP (Inductively Coupled Plasma) emission spectroscopy.
  • a metal atom may be used individually by 1 type, or may use 2 or more types together. When two or more metal atoms are used in combination, the total content is preferably within the above range.
  • the metal nitride-containing particles contain a metal atom nitride.
  • Metal nitride may be mixed with oxygen during its synthesis.
  • the content of oxygen atoms in the metal atom nitride is preferably 0.001 to 40 mass%, more preferably 0.001 to 35 mass%, more preferably 0.001 to the total mass of the metal atom nitride. More preferably, it is 30% by mass.
  • the oxygen atom content can be analyzed using an inert gas melting-infrared absorption method.
  • the nitride of a metal atom does not contain an oxygen atom substantially from the point which the cured film obtained by hardening
  • curing a curable composition has the more excellent light-shielding property. “Substantially free of oxygen atoms” means that oxygen atoms are not detected using the measurement method.
  • the metal nitride-containing particles preferably contain titanium nitride.
  • the titanium nitride is not particularly limited, and known titanium nitride can be used.
  • titanium nitride examples include low-order titanium oxide expressed by TiN, TiO 2 , Ti n O 2n-1 (1 ⁇ n ⁇ 20), and TiN x O y (0 ⁇ x ⁇ 2.0, 0.
  • the form containing the titanium oxynitride which can be represented by 1 ⁇ y ⁇ 2.0) is mentioned.
  • the diffraction angle 2 ⁇ of the peak derived from the (200) plane when CuK ⁇ ray is used as the X-ray source is generally preferably 42.5 ° to 43.5 °, and has more excellent light shielding properties. From the viewpoint of easily obtaining a curable composition capable of obtaining a cured film, 42.5 ° to 42.8 ° is more preferable, and 42.5 to 42.7 is even more preferable.
  • the diffraction angle 2 ⁇ of the peak derived from the (200) plane of the metal nitride-containing particles is preferably 42.5 ° or more and 43.5 ° or less, more preferably 42.5 ° or more and 42.8 or less, and 42.5 °. More preferably, the angle is 42.7 ° or less.
  • the metal nitride-containing particles contain 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 metal nitride-containing particles 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 metal nitride-containing particles is preferably 50 nm or less, preferably 20 nm or more, and more preferably 20 to 50 nm.
  • the light-shielding film formed using the curable composition tends to have a higher ultraviolet (particularly i-line (365 nm)) transmittance and has a higher photosensitivity. A thing is obtained.
  • the specific surface area of the metal nitride-containing particles is not particularly limited, but can be determined using a 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.
  • composite refers to particles in which metal nitride and metal fine particles are complexed or in a highly dispersed state.
  • composite means that particles are composed of both components of metal nitride and other metal, and “highly dispersed state” means that metal nitride and other metal nitride This means that the metals are present individually and the other metal particles are not aggregated but are uniformly and uniformly dispersed.
  • the material of the metal fine particles is not particularly limited, and for example, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, titanium , Bismuth, antimony and lead, and alloys thereof.
  • at least one selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and alloys thereof is preferable, from copper, silver, gold, platinum and tin, and alloys thereof. At least one selected is more preferable. From the viewpoint of better moisture resistance, silver is preferred.
  • the content of the metal fine particles in the metal nitride-containing particles is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less with respect to the total mass of the metal nitride-containing particles.
  • a method for producing the metal nitride-containing particles is not particularly limited, and a known method can be used.
  • Examples of the method for producing metal nitride-containing particles include a gas phase reaction method.
  • Examples of 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.
  • a specific method for producing a metal atom nitride by a thermal plasma method is not particularly limited.
  • a method for producing titanium nitride titanium tetrachloride is reacted with ammonia gas in a plasma flame (Japanese Patent Laid-Open No. Hei. 2-22110), 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. Sho 61-11140), and at the periphery of the plasma Examples include a method of blowing ammonia gas (Japanese Patent Laid-Open No. 63-85007).
  • the method for producing a metal atom nitride is not limited to the above, and the production method is not limited as long as a metal atom nitride having desired physical properties can be obtained.
  • the raw material containing metal atoms (hereinafter referred to as “metal raw material”) used for the production of metal nitride-containing particles is preferably a high-purity one. Although it does not restrict
  • Metal raw materials sometimes contain atoms other than metal atoms as impurities (hereinafter referred to as “impurity atoms”). Although it does not restrict
  • the metal raw material contains Si atoms, the content of Si atoms is preferably more than 0.002% by mass and less than 0.3% by mass with respect to the total mass of the metal raw material. .15% by mass is more preferable, and 0.02 to 0.1% by mass is even more preferable. When the content of Si atoms exceeds 0.002% by mass, the patterning property of the cured film is further improved.
  • the moisture in the metal raw material used for the production of the metal nitride-containing particles is preferably less than 1% by mass, more preferably less than 0.1% by mass, and substantially free of the total mass of the metal raw material. More preferably.
  • the method of causing the metal nitride-containing particles to contain Fe atoms is not particularly limited, and examples thereof include a method of introducing Fe atoms at the stage of obtaining a metal raw material. More specifically, when a metal raw material is manufactured by a crawl method or the like, a reaction vessel that is made of a material containing Fe atoms such as stainless steel (SUS) or a press for crushing the metal raw material is used. By using a material containing Fe atoms as the material of the mill and the grinder, Fe atoms can be attached to the surface of the titanium particles.
  • SUS stainless steel
  • Fe atoms can be contained in the metal nitride-containing particles.
  • the Fe atoms contained in the metal nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, and sulfides. , And oxysulfide may be included in any form.
  • Fe atoms contained in the metal nitride-containing particles may exist as impurities at the position of the crystal lattice, or may exist as impurities in the amorphous state at the crystal grain boundaries.
  • the content of Fe atoms in the metal nitride-containing particles is more than 0.001% by mass and preferably less than 0.4% by mass with respect to the total mass of the metal nitride-containing particles. Of these, 0.01 to 0.2% by mass is more preferable, and 0.02 to 0.1% by mass is even more preferable.
  • the content of Fe atoms in the metal nitride-containing particles is measured by ICP (Inductively Coupled Plasma) emission spectroscopy.
  • the metal nitride-containing particles preferably further contain Si atoms (silicon atoms). Thereby, the patterning property of a cured film improves more.
  • the reason why the patterning property is improved by containing Si atoms is considered to be the same as the above-described Fe atoms.
  • the content of Si atoms in the metal nitride-containing particles is more than 0.002% by mass, preferably less than 0.3% by mass, and preferably 0.01 to 0.15% by mass with respect to the total mass of the metal nitride-containing particles. % Is more preferable, and 0.02 to 0.1% by mass is still more preferable.
  • the content of Si atoms in the metal nitride-containing particles is measured by the same method as that for Fe atoms described above. Further, the method for incorporating the Si atoms into the metal nitride-containing particles is not particularly limited, and is the same as that already described as the method for introducing Fe atoms.
  • the curable composition contains an oxime polymerization initiator.
  • the oxime polymerization initiator is not particularly limited, and a known oxime polymerization initiator can be used.
  • the content of the oxime polymerization initiator in the curable composition is not particularly limited, but is generally preferably 0.5 to 30% by mass with respect to the total solid content of the curable composition, and the curable composition is From the viewpoint of having the effect of the present invention more excellent, 1 to 20% by mass is more preferable.
  • the content of the oxime polymerization initiator is preferably adjusted so that the anhydride / initiator already described is within a predetermined range.
  • an oxime polymerization initiator may be used individually by 1 type, or may use 2 or more types together. When two or more oxime polymerization initiators are used in combination, the total content is preferably within the above range.
  • the oxime polymerization initiator for example, 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 is used. it can.
  • the oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane-3-one.
  • IRGACURE OXE01 manufactured by BASF
  • IRGACURE OXE02 manufactured by BASF
  • IRGACURE OX03 manufactured by BASF
  • IRGACURE OXE04 manufactured by BASF
  • TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arcles NCI-831 and Adeka Arcles NCI-930 manufactured by ADEKA
  • N-1919 carboxyl ether skeleton-containing photoinitiator
  • NCI-730 ADEKA
  • oxime polymerization initiators other than those described above, compounds described in JP-T-2009-519904 in which oxime is linked to carbazole N-position; described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety
  • compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety ketoxime compounds described in International Patent Publication No. 2009-131189; triazine skeleton and oxime A compound described in US Pat. No.
  • the oxime polymerization initiator is preferably a compound represented by the following formula (OX-1). It should be noted that even if the N—O bond of the oxime polymerization initiator is an (E) oxime compound or a (Z) oxime compound, the (E) isomer and (Z) isomer It may be a mixture.
  • 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. 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 Compound (C-3); and the like. This content is incorporated herein.
  • 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 single bond (directly Bond) or a carbonyl group.
  • R 1, R 2, R 3 and R 4 have the same meanings as R 1, R 2, R 3 and R 4 in Formula (1)
  • R 5 is -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 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 single bond or a carbonyl group, and 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 number of 4 Represents a heterocyclic group of ⁇ 20, and X represents a single bond or a carbonyl group.
  • R 1, R 3 and R 4 have the same meanings as R 1, R 3 and R 4 in the formula (3)
  • R 5 is, -R 6, -OR 6, -SR 6, Represents —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 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 single bond or Represents a carbonyl group, and a represents an integer of 0 to 4.
  • R 1 and R 2 are preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or 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 single bond.
  • R 1 is preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or 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 single bond.
  • Specific examples of the compounds represented by the formulas (1) and (2) include compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466, for example. This content is incorporated herein.
  • the oxime-based polymerization initiator preferably contains a nitro group in that a curable composition having a more excellent effect of the present invention can be obtained.
  • the number of nitro groups contained in the oxime compound is not particularly limited, but is preferably 1 to 4, and preferably 1 or 2.
  • Specific examples of the oxime polymerization initiator containing a nitro group include, for example, NCI-831 (trade name, manufactured by ADEKA) having the following structure.
  • the oxime polymerization initiator preferably has a maximum absorption wavelength in the wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 to 480 nm, and further has a high absorbance at 365 nm and 405 nm. preferable.
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime polymerization initiator compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, from the viewpoint of sensitivity. More preferably, it is from 000 to 200,000.
  • a known method can be used. It is preferable to measure.
  • the photopolymerization initiator may be a bifunctional or trifunctional or higher compound.
  • Specific examples of such compounds include JP 2010-527339 A, JP 2011-524436 A, International Publication No. 2015/004565, Japanese Patent Publication No. 2016-532675, paragraphs 0417 to 0412, International Publication No. Dimers of oxime compounds described in paragraphs 0039 to 0055 of No. 2017/033680, compounds (E) and (G) described in JP 2013-522445 A, and International Publication No. 2016/034963 Examples of Cmpd 1 to 7 are described.
  • the curable composition contains a polymerizable compound.
  • the polymerizable compound means a compound containing a polymerizable group and a compound different from the anhydride.
  • the content of the polymerizable compound in the curable composition is not particularly limited, but is preferably 5 to 30% by mass and more preferably 10 to 25% by mass with respect to the total solid content of the curable composition.
  • 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 polymerizable compound is preferably a compound containing one or more groups containing an ethylenically unsaturated bond, more preferably a compound containing 2 or more, still more preferably a compound containing 3 or more, and a compound containing 5 or more Is particularly preferred.
  • the upper limit is preferably 15 or less.
  • the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • polymerizable compound for example, compounds described in paragraph 0050 of JP-A-2008-260927 and paragraph 0040 of JP-A-2015-68893 can be used, and the above contents are incorporated in this 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 having one or more groups containing an ethylenically unsaturated bond 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, and the contents thereof are incorporated herein.
  • Polymerizable compounds are 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 (KAYARAD D-310 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA as a commercial product; 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).
  • 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.
  • the preferable form of the polymerizable compound is 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 pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toa Gosei Co., Ltd.
  • the preferred acid value of the polymerizable compound containing an acid group is 0.1 to 40 mgKOH / g, more preferably 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.
  • Examples include ⁇ -caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as erythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ⁇ -caprolactone.
  • ⁇ -caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as erythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ⁇ -caprolactone.
  • Z-1 formula
  • 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 an integer of 0 to 10
  • 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.
  • formula (Z-4) or formula (Z-5) — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) — A form in which the terminal 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
  • a form that is a mixture with a compound having at least one hydrogen atom is preferred. 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 curable composition may contain an optional component other than the above.
  • the optional component include a dehydrating agent, a polymerization inhibitor, an alkali-soluble resin, a dispersant, a solvent, a silane coupling agent, an ultraviolet absorber, a surfactant, an adhesion improver, and a colorant.
  • the colorant means a colorant other than the metal nitride-containing particles.
  • the curable composition may contain a dehydrating agent.
  • a dehydrating agent intends a compound different from an acid anhydride. It does not restrict
  • orthoester compounds are more preferred as the dehydrating agent.
  • the orthoester compound is not particularly limited, and examples thereof include compounds described in paragraphs 0039 and 0040 of JP-A-2012-524759.
  • the content of the dehydrating agent in the curable composition is not particularly limited, but is generally preferably 0.01 to 5% by mass with respect to the total solid content in the curable composition.
  • the curable composition preferably contains a polymerization inhibitor.
  • the curable composition containing a polymerization inhibitor has better storage stability, and the generation of residues in unexposed areas is further suppressed.
  • the storage stability of a curable composition in this specification means the storage stability which can be evaluated by the method described in the Example. It does not restrict
  • the content of the polymerization inhibitor in the curable composition is not particularly limited, but is generally preferably 0.1 to 5% by mass with respect to the total solid content of the curable composition.
  • 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 polymerization inhibitor is not particularly limited, and a known compound used as a polymerization inhibitor can be used.
  • Examples of the compound used as a polymerization inhibitor include phenolic compounds, quinone compounds, hindered amine compounds, phenothiazine compounds, and nitrobenzene compounds.
  • phenol compound examples include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, 2,6-di-tert-butylphenol, 2,6-diphenol.
  • phenolic compound a phenolic compound represented by the formula (IH-1) is preferable.
  • R 1 to R 5 are each independently a hydrogen atom, alkyl group, alkenyl group, hydroxyl group, amino group, aryl group, alkoxy group, carboxylic acid group, alkoxycarbonyl group, or acyl. Represents a group. R 1 to R 5 may be connected to each other to form a ring.
  • R 1 to R 5 in formula (IH-1) are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group or an ethyl group), or an alkoxy group having 1 to 5 carbon atoms (eg, methoxy A alkenyl group having 2 to 4 carbon atoms (for example, a vinyl group), or a phenyl group.
  • R 1 and R 5 are each independently more preferably a hydrogen atom or a tert-butyl group
  • R 2 and R 4 are more preferably a hydrogen atom
  • R 3 is a hydrogen atom
  • an alkyl having 1 to 5 carbon atoms A group or an alkoxy group having 1 to 5 carbon atoms is more preferable.
  • Examples of the quinone compound include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.
  • Examples of the hindered amine compound include a polymerization inhibitor represented by the following formula (IH-2).
  • R 6 in formula (IH-2) represents a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. Of these, a hydrogen atom or a hydroxyl group is preferable, and a hydroxyl group is more preferable.
  • R 7 to R 10 each independently represents a hydrogen atom or an alkyl group.
  • the alkyl group represented by R 7 to R 10 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.
  • the curable composition preferably contains an alkali-soluble resin.
  • the alkali-soluble resin means a resin containing a group that promotes alkali solubility (alkali-soluble group).
  • the content of the alkali-soluble resin in the curable composition is not particularly limited, but is generally preferably 0.1 to 40% by mass with respect to the total solid content of the curable composition, and the curable composition is more excellent. In view of having the effect of the present invention, 1 to 20% by mass is more preferable.
  • Alkali-soluble resin may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of alkali-soluble resin together, it is preferable that total content is in the said range.
  • alkali-soluble resin examples include resins containing at least one alkali-soluble group in the molecule, such as polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, and (meth) acrylic. / (Meth) acrylamide copolymer resin, epoxy resin, polyimide resin and the like.
  • the alkali-soluble resin include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound.
  • unsaturated carboxylic acid Monocarboxylic acids, such as (meth) acrylic acid, crotonic acid, and vinyl acetic acid; Dicarboxylic acids, such as itaconic acid, maleic acid, and fumaric acid, or its acid Anhydrides; polyvalent carboxylic acid monoesters such as mono (2- (meth) acryloyloxyethyl) phthalate; and the like.
  • Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate.
  • compounds described in paragraph 0027 of JP 2010-97210 A and paragraphs 0036 to 0037 of JP 2015-68893 A can also be used, and the above contents are incorporated herein.
  • a copolymerizable ethylenically unsaturated compound that contains an ethylenically unsaturated group in the side chain may be used in combination.
  • a (meth) acrylic acid group is preferable.
  • An acrylic resin having an ethylenically unsaturated group in the side chain is obtained by, for example, adding an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to a carboxylic acid group of an acrylic resin containing a carboxylic acid group. Can also be obtained.
  • alkali-soluble resin examples include JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-54-92723, JP-A-59-.
  • alkali-soluble resin for example, compounds described in paragraphs 0225 to 0245 of JP-A-2016-75845 can be used, and the above contents are incorporated herein.
  • a polyimide precursor can also be used as the alkali-soluble resin.
  • the polyimide precursor is generally a resin obtained by subjecting a compound containing an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100 ° C., and means a compound different from the above acid anhydride.
  • resin containing the repeating unit represented by Formula (1) is mentioned, for example.
  • Examples of the structure of the polyimide precursor include an amic acid structure represented by the following formula (2), the following formula (3) in which the amic acid structure is partially imide ring-closed, and / or the following formula in which all imide rings are closed: The thing containing the imide structure shown by (4) is mentioned.
  • R 1 represents a tetravalent organic group having 2 to 22 carbon atoms
  • R 2 represents a divalent organic group having 1 to 22 carbon atoms
  • n is 1 or 2 Represents.
  • polyimide precursor examples include, for example, compounds described in paragraphs 0011 to 0031 of JP-A-2008-106250, compounds described in paragraphs 0022 to 0039 of JP-A-2016-122101, and JP-A Examples include the compounds described in paragraphs 0061 to 0092 of JP-A-2016-68401, and the above contents are incorporated herein.
  • the alkali-soluble resin contains at least one selected from the group consisting of a polyimide precursor and a polyimide resin, in that the pattern shape of the patterned cured film obtained using the curable composition is more excellent. Is preferred.
  • the polyimide resin containing an alkali-soluble group is not particularly limited, and a known polyimide resin containing an alkali-soluble group can be used. Examples of the polyimide resin include resins described in paragraph 0050 of JP-A-2014-137523, resins described in paragraph 0058 of JP-A-2015-187676, and JP-A-2014-106326. Examples include the resins described in paragraphs 0012 to 0013, and the above contents are incorporated herein.
  • the curable composition preferably contains a dispersant.
  • a dispersing agent and the alkali-soluble resin mentioned later intend a different component.
  • the content of the dispersant in the curable composition is not particularly limited, but is generally preferably 5 to 30% by mass with respect to the total solid content of the curable composition.
  • a dispersing agent may be used individually by 1 type, or may use 2 or more types together. When two or more dispersants are used in combination, the total content is preferably within the above range.
  • the dispersant for example, a known dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
  • the dispersant include polymer dispersants [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 type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
  • the polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
  • Polymer compound The polymer compound is adsorbed on the surface of the metal nitride-containing particles and acts to prevent re-aggregation of the dispersion. Therefore, terminal-modified polymers, graft polymers, block polymers, and the like that contain an anchor site to the pigment surface are preferred.
  • 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 the metal nitride-containing particles and the like, and the dispersion stability after aging ( Excellent stability over time. 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 metal nitride-containing particles and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to the metal nitride-containing particles and the like is lowered, and the dispersibility of the metal nitride-containing particles and the like tends to be lowered.
  • 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 preferred is 60-500.
  • 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, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide.
  • examples thereof include a structure and a polyether structure.
  • the graft chain was selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure in order to improve the interaction between the graft chain and the solvent, thereby increasing the dispersibility of the black pigment and the like.
  • a graft chain containing at least one kind is preferred, and a graft chain containing at least one of a polyester structure and a polyether structure is more preferred.
  • the macromonomer containing such a graft chain is not particularly limited, but a macromonomer containing a reactive double bond group can be suitably used.
  • AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.) Synthetic Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), Bremer PME-4000 (trade name, manufactured by NOF Corporation) and the like are preferable.
  • the dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. The dispersant may contain the above structure alone in one dispersant, or may contain a plurality of these structures in one dispersant.
  • the polycaprolactone structure means a structure containing a ring-opened structure of ⁇ -caprolactone as a repeating unit.
  • the polyvalerolactone structure means a structure containing a ring-opened structure of ⁇ -valerolactone as a repeating unit.
  • dispersant examples include, for example, compounds described in paragraphs 0035 to 0096 of JP-A-2015-34983, compounds described in paragraphs 0025 to 0105 of JP-A-2012-255148, and JP-A-2013-249417.
  • the curable composition preferably contains a solvent.
  • the content of the solvent is not particularly limited, but is preferably adjusted so that the total solid content of the curable composition is 5 to 40% by mass.
  • 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 content of a curable composition may become in the said range.
  • a well-known solvent can be used.
  • the solvent include water or an organic solvent.
  • 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, ethyl acetate, Examples include but are not limited to butyl acetate, methyl lactate, and ethyl lactate.
  • 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 carbon number 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 with hydrolyzable groups bonded) It is preferable that it does not contain, a fluorine atom, a silicon atom (however, excluding a 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 carbon More preferably, it does not contain a branched alkyl group of several or more.
  • the content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total solid content in the curable composition. 1.0 to 6% by mass is more preferable.
  • the said curable composition may contain 1 type of silane coupling agents individually, 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.
  • the curable composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine).
  • an 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-based ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) is 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, more preferably 0.01 to 10% by mass, and further preferably 0.1 to 5% by mass with respect to the total solid content of the curable composition. 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 fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
  • 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 uniform thickness with small thickness unevenness can be easily 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 (above DIC Corporation), Florad FC430, FC431, FC171 (Sumitomo 3M Limited), Surflon S-382, SC-101, SC- 103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (manufactured by Asahi Glass Co., Ltd.), 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-2011-89090.
  • the curable composition may contain a silane coupling agent as an adhesion improver.
  • the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. , Vinyltrimethoxysilane, vinyltriethoxysilane, and the like.
  • the content of the adhesion improver is not particularly limited, but is preferably 0.02 to 20% by mass with respect to the total solid content of the curable composition.
  • the curable composition may contain a colorant.
  • the colorant intends a colorant different from the metal nitride-containing particles.
  • the content of the colorant in the curable composition is not particularly limited, but generally 30 to 60% by mass is preferable.
  • colorant Various known pigments (colored pigments) and dyes (colored dyes) can be used as the colorant. When it contains a colorant, its content can be determined according to the optical properties of the light-shielding film obtained by curing. Other colorants may be used alone or in combination of two or more.
  • colorant examples include the colorants described in paragraphs 0027 to 0200 of JP2014-42375, paragraph 0031 of JP2008-260927A, and paragraphs 0015 to 0025 of JP2015-68893A. Which can be used and are incorporated herein by reference.
  • a pigment having infrared absorptivity can also be used.
  • a tungsten compound, a metal boride, and the like are preferable, and among them, a tungsten compound is more preferable in terms of excellent light-shielding properties at wavelengths in the infrared region.
  • a tungsten compound is preferable from the viewpoint of excellent light absorption wavelength region of an oxime polymerization initiator related to curing efficiency by exposure and transparency of visible light region.
  • Two or more of these pigments may be used in combination, or may be used in combination with a dye described later.
  • chromatic colors such as red, green, yellow, orange, purple and blue are added to black or infrared light-shielding pigments.
  • the form which mixes the pigment or the dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a purple pigment or dye with a black or infrared pigment, and it is more preferable to mix a red pigment with a black pigment or infrared pigment.
  • Organic pigment examples include, for example, Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 7,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,19
  • a pigment may be used individually by 1 type, or may use 2 or more types together.
  • Examples of the dye include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501.
  • US Pat. No. 5,667,920, US Pat. No. 505950, US Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6- Dyes disclosed in 194828 can be used.
  • pyrazole azo compounds When classified as chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, 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 colorant may further contain an infrared absorber.
  • the infrared absorber means a compound having absorption in the wavelength region in the infrared region (preferably, a wavelength of 650 to 1300 nm).
  • the infrared absorber is a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm.
  • Examples of 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, and quaterylenes.
  • phthalocyanine compound naphthalocyanine compound, iminium compound, cyanine compound, squalium compound and croconium compound
  • the compounds disclosed in paragraphs 0010 to 0081 of JP-A No. 2010-1111750 may be used.
  • 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 a 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 in 1% by mass or more in 25 ° C. water, and more preferably a compound that dissolves in 10% by mass or more in 25 ° C. water. By using such a compound, the solvent resistance is improved.
  • paragraph numbers 0049 to 0062 of JP 2010-222557 A can be referred to, and the contents thereof are incorporated in the present specification.
  • Cyanine compounds and squarylium compounds are disclosed in paragraphs 0022 to 0063 of WO 2014/088063, paragraphs 0053 to 0118 of WO 2014/030628, paragraphs 0028 to 0074 of JP 2014-59550 A, international Paragraph Nos. 0013 to 0091 of Japanese Patent Publication No. 2012/169447, Paragraph Nos. 0019 to 0033 of JP-A-2015-176046, Paragraph Nos.
  • JP-A-2014-63144 Paragraphs of JP-A-2014-52431 Nos. 0085 to 0150, paragraph numbers 0076 to 0124 of Japanese Patent Application Laid-Open No. 2014-44301, paragraph numbers 0045 to 0078 of Japanese Patent Application Laid-Open No. 2012-8532, paragraph numbers 0027 to 0067 of Japanese Patent Application Laid-Open No. 2015-172102, -172004, paragraph numbers 0029 to 0067, JP2015-40895, paragraphs 0029 to 0085, JP2014-126642, paragraphs 0022 to 0036, and JP2014-148567, paragraph 0011.
  • the infrared absorber is preferably at least one selected from the group consisting of compounds represented by the following formulas 1 to 3.
  • a 1 and A 2 each independently represent an aryl group, a heteroaryl group, or a group represented by the following Formula 1-A;
  • Formula 1-A Formula 1-A, Z 1A represents a nonmetallic atomic group that forms a nitrogen-containing heterocyclic ring,
  • R 2A represents an alkyl group, an alkenyl group, or an aralkyl group, d represents 0 or 1, and a wavy line Represents a connecting hand;
  • R 1a and R 1b each independently represent an alkyl group, an aryl group, or a heteroaryl group,
  • R 2 to R 5 each independently represents a hydrogen atom or a substituent, and
  • R 2 and R 3 , R 4 and R 5 may be bonded to each other to form a ring
  • R 6 and R 7 each independently represent a hydrogen atom, an alkyl group, an
  • the curable composition may contain a pigment derivative.
  • the pigment derivative is preferably a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group.
  • a pigment derivative having an acidic group or a basic group is preferable.
  • Particularly preferred are pigment derivatives having a basic group.
  • the combination of the resin (dispersant) and the pigment derivative described above is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.
  • organic pigment for constituting the pigment derivative examples include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
  • a sulfonic acid group a carboxylic acid group, and its salt
  • a carboxylic acid group and a sulfonic acid group are still more preferable, and a sulfonic acid group is especially preferable.
  • the basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.
  • the curable composition has an optical density (OD: Optical Density) per 2.5 ⁇ m in a wavelength region of 400 to 1100 nm of 2.5 or more in that the resulting cured film has better light-shielding properties. Is preferable, and 3.0 or more is more preferable.
  • the upper limit is not particularly limited, but is generally preferably 5.0 or less.
  • a cured film formed using a curable composition having the above characteristics can be preferably used as a light-shielding film (black matrix).
  • the optical density means an optical density measured by the method described in the examples.
  • the optical density per 1.5 ⁇ m film thickness in the wavelength region of 400 to 1100 nm is 2.5 or more.
  • the curable composition can be prepared by mixing the above-mentioned various components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, or a wet disperser).
  • a mixing method for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, or a wet disperser.
  • 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 through a filter for the purpose of removing foreign substances and / or reducing defects.
  • a filter can be used without particular limitation as long as it is for filtration.
  • a filter made of fluorine resin such as PTFE (polytetrafluoroethylene); polyamide resin such as nylon; polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP);
  • PTFE polytetrafluoroethylene
  • nylon polyamide resin
  • polyolefin resin including high density and ultra high molecular weight
  • polypropylene including high-density polypropylene
  • nylon is preferable as the filter material.
  • 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.
  • fine foreign substances such as impurities and aggregates contained in the pigment, can be reliably removed while suppressing filtration clogging of the pigment.
  • different filters may be combined. At that time, the filtering by the first filter may be performed only once or twice or more. When filtering two or more times in combination with different filters, it is preferable that the second and subsequent hole diameters are the same or larger than the first filtering hole diameter. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above.
  • 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 as the first filter described above can be used.
  • the pore size of the second filter is preferably about 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 not contained (below the detection limit of the measuring device). Most preferred).
  • the impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
  • a cured film can be formed with a curable composition.
  • the thickness of the cured film is not particularly limited, but is preferably 0.2 to 25 ⁇ m.
  • the above thickness is an average thickness, and is a value obtained by measuring the thicknesses of five or more arbitrary points of the cured film and arithmetically averaging them.
  • substrate, forming a coating film, performing a hardening process with respect to a coating film, and manufacturing a cured film is mentioned.
  • the method of the curing treatment is not particularly limited, and examples thereof include a photocuring treatment or a thermosetting treatment, and a photocuring treatment (particularly a curing treatment by irradiation with actinic rays or radiation) is preferable from the viewpoint of easy pattern formation. .
  • the cured film which concerns on embodiment of this invention is a cured film obtained by hardening
  • limit especially as a manufacturing method of a cured film It is preferable to have the following processes. -Curable composition layer formation process-Exposure process-Development process Hereinafter, 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
  • substrate is not restrict
  • a silicon substrate is mentioned, for example, When using as a color filter (including the color filter for solid-state image sensors), a glass substrate etc. are mentioned.
  • 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 can be applied.
  • the curable composition applied on the substrate is usually dried at 70 to 150 ° C. for 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 actinic rays or radiation through a photomask having a patterned opening. Exposure is preferably by irradiation with radiation. Examples of radiation that can be used for exposure include ultraviolet rays such as g-line, h-line, and i-line, and examples of the light source include a high-pressure mercury lamp.
  • the irradiation intensity is preferably 5 ⁇ 1500mJ / cm 2, more preferably 10 ⁇ 1000mJ / cm 2.
  • 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.
  • the development temperature is usually preferably 20-30 ° C., and the development time is preferably 20-90 seconds.
  • an alkaline aqueous solution for example, as an inorganic developer, an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, and sodium metasilicate has a concentration.
  • 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, in a concentration of 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass.
  • aqueous alkali solution dissolved so as to be%.
  • An appropriate amount of a water-soluble organic solvent such as methanol and ethanol, and / or a surfactant can be added to the alkaline aqueous solution, for example.
  • 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.
  • Other steps are not particularly limited and may be appropriately selected depending on the purpose. Examples of the other steps include a substrate surface treatment step, a preheating step (pre-baking step), and a post-heating step (post-baking step).
  • the heating temperature in the preheating step and the postheating step is preferably 80 to 300 ° C.
  • the upper limit is more preferably 220 ° C. or lower.
  • the lower limit is preferably 90 ° C. or higher.
  • the heating time in the preheating step and the postheating step is preferably 30 to 300 seconds.
  • Solid-state imaging device and solid-state imaging device contain the cured film.
  • the form in which the solid-state imaging device contains a cured film is not particularly limited. For example, a plurality of photodiodes, polysilicon, and the like constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate. And comprising the cured film of the present invention on the side of the support where the light receiving element is formed (for example, the portion other than the light receiving portion and / or the color adjustment pixel) or on the opposite side of the forming surface. The thing which was done is mentioned.
  • 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.
  • the cured film according to the embodiment 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 on 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.
  • the cured film according to the embodiment of the present invention can also be 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 according to the embodiment 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.
  • the cured film according to the embodiment 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
  • a black matrix contains the cured film which concerns on embodiment of this invention.
  • the black matrix may be contained in a color filter, a solid-state image sensor, and a liquid crystal display device.
  • As the black matrix those already described above; a black edge provided at the periphery of a display device such as a liquid crystal display device; a lattice shape between red, blue, and green pixels, and / or a stripe shape A black portion of the TFT; a dot-like and / or a linear black pattern for shielding a thin film transistor (TFT);
  • TFT thin film transistor
  • the black matrix improves the display contrast, and in the case of an active matrix liquid crystal display device using a thin film transistor (TFT), in order to prevent deterioration in image quality due to light current leakage, it has a high light shielding property (with an optical density OD). 3 or more).
  • TFT thin film transistor
  • 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-based resins and polyolefin-based resins; In view of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferable.
  • the color filter according to the embodiment of the present invention contains a cured film.
  • 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 in a substrate shape 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 in a substrate shape.
  • the resin composition for each color is not particularly limited, and a known resin composition can be used.
  • the metal nitride-containing particles correspond to each pixel. It is preferable to use a colorant that has been replaced with the above colorant.
  • 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 a resin composition for each color that contains red, green, and blue pigments.
  • the liquid crystal display device contains a cured film.
  • the form in which the liquid crystal display device contains a cured film is not particularly limited, but examples include a form containing a color filter containing the black matrix (cured film) already described.
  • liquid crystal display device for example, a mode provided with a pair of substrates arranged opposite to each other and a liquid crystal compound sealed between the substrates can be mentioned.
  • the substrate is as already described as the substrate for the black matrix.
  • liquid crystal display device for example, from the user side, a polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor)
  • TFT Thin Film Transistor
  • the liquid crystal display device is not limited to the above.
  • Display device (Junsho Ibuki) The liquid crystal display device described in the book “Industry Books Co., Ltd.” issued in 1989).
  • the infrared sensor which concerns on embodiment of this invention contains the said cured film.
  • the infrared sensor which concerns on the said embodiment is demonstrated using FIG.
  • reference numeral 310 is a solid-state image sensor.
  • the imaging region provided on the solid-state imaging device 310 is configured by combining the infrared absorption filter 311 and the color filter 312 according to the embodiment of the present invention.
  • the infrared absorption filter 311 transmits light in the visible light region (for example, light having a wavelength of 400 to 700 nm), and light in the infrared region (for example, light having a wavelength of 800 to 1300 nm, preferably light having a wavelength of 900 to 1200 nm).
  • it is a film that shields light with a wavelength of 900 to 1000 nm, and contains an infrared absorber (as already described as the form of the infrared absorber) as a colorant.
  • a membrane can be used.
  • the color filter 312 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed.
  • red (R), green (G), and blue (B) pixels are formed.
  • a color filter or the like is used, and its form is as already described.
  • a resin film 314 for example, a transparent resin film or the like
  • the infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared light having a specific wavelength, and is a colorant that absorbs light in the visible light region (for example, a perylene compound and / or bisbenzoic acid).
  • a cured film according to an embodiment of the present invention containing a furanone compound or the like and an infrared absorber (for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, or a polymethine compound) can be used.
  • the infrared transmission filter 313 preferably blocks light having a wavelength of 400 to 830 nm and transmits light having a wavelength of 900 to 1300 nm.
  • a micro lens 315 is disposed on the incident light h ⁇ side of the color filter 312 and the infrared transmission filter 313.
  • a planarization film 316 is formed so as to cover the microlens 315. In the embodiment shown in FIG.
  • the resin film 314 is disposed, but an infrared transmission filter 313 may be formed instead of the resin film 314. That is, the infrared transmission filter 313 may be formed on the solid-state image sensor 310.
  • the film thickness of the color filter 312 and the film thickness of the infrared transmission filter 313 are the same, but the film thickness of both may be different.
  • the color filter 312 is provided closer to the incident light h ⁇ than the infrared absorption filter 311, but the infrared absorption filter 311 and the color filter 312 are switched in order to absorb infrared rays.
  • the filter 311 may be provided closer to the incident light h ⁇ than the color filter 312.
  • the infrared absorption filter 311 and the color filter 312 are stacked adjacent to each other.
  • the two filters are not necessarily adjacent to each other, and other layers are provided between them. Also good.
  • this infrared sensor since image information can be captured simultaneously, motion sensing or the like that recognizes a target whose motion is to be detected is possible. Furthermore, since distance information can be acquired, an image including 3D information can be taken.
  • the solid-state imaging device includes a lens optical system, a solid-state imaging device, an infrared light emitting diode, and the like.
  • paragraphs 0032 to 0036 of JP2011-233983 can be referred to, and the contents thereof are incorporated in the present specification.
  • 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 identity authentication using facial image authentication; in-vehicle camera equipment; endoscopes, capsule endoscopes, And medical camera equipment such as catheters; biosensors, biosensors, military reconnaissance cameras, stereoscopic map cameras, weather and ocean observation cameras, land resource exploration cameras, and exploration cameras for space astronomy and deep space targets Optical filters and modules used in space equipment such as Light blocking member and the light-shielding film, further 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 suitable as an optical and optical film used in quantum dot displays. Moreover, it is suitable as a member which provides a light shielding function and an antireflection function.
  • quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. What has been described.
  • Metal nitride-containing particles were produced by the following methods.
  • Titanium nitride-containing particles TiN-1 were produced using the components shown in Table 1. First, Ti particles described in Table 1 were plasma-treated in Ar gas to obtain Ti nanoparticles. A state in which the above-mentioned Ti nanoparticles are allowed to stand under an Ar gas atmosphere under an O 2 concentration of 50 ppm or less and 30 ° C. for 24 hours, and then O 2 gas is introduced into the Ar gas atmosphere so that the O 2 concentration becomes 100 ppm. Then, the Ti nanoparticles were allowed to stand at 30 ° C. for 24 hours (the above is referred to as “pretreatment of Ti particles”).
  • Ti nanoparticles obtained under the condition of a yield of 10% using a TTSP separator manufactured by Hosokawa Micron were classified to obtain a powder of Ti nanoparticles.
  • the primary particle diameter of the obtained powder was 120 nm when the particle diameter of 100 particles was obtained by TEM (Transmission Electron Microscope) observation and further obtained by arithmetic average thereof.
  • the titanium nitride-containing particles TiN-1 were produced using an apparatus similar to the black composite fine particle production apparatus described in FIG. 1 of WO2010 / 147098.
  • a high frequency voltage of about 4 MHz and about 80 kVA is applied to the high frequency oscillation coil of the plasma torch, and argon gas 50 L / min and nitrogen as plasma gas are supplied from the plasma gas supply source.
  • a mixed gas of 50 L / min was supplied to generate an argon-nitrogen thermal plasma flame in the plasma torch.
  • 10 L / min carrier gas Ar gas was supplied from the spray gas supply source of the material supply apparatus.
  • the Ti nanoparticles obtained as described above and the additive particles shown in Table 1 are mixed so as to have the composition shown in Table 1, and together with the Ar gas as the carrier gas, the heat in the plasma torch It was fed into a plasma flame, and the fed particles were evaporated in a thermal plasma flame and highly dispersed in a gas phase. Further, nitrogen gas was used as the gas supplied into the chamber by the gas supply device. At this time, the flow rate of nitrogen gas in the chamber was 5 m / sec, and the supply amount of nitrogen gas was 1000 L / min. The pressure in the cyclone was 50 kPa, and the supply rate of each raw material from the chamber to the cyclone was 10 m / s (average value). In this way, titanium nitride-containing particles TiN-1 were obtained.
  • titanium nitride-containing particles TiN-1 With respect to the obtained titanium nitride-containing particles TiN-1, the contents of titanium (Ti) atoms, Fe (iron) atoms, and silicon (Si) atoms were measured by ICP (Inductively Coupled Plasma) emission spectroscopy. . The results are shown in Table 1.
  • ICP emission spectroscopic analysis an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
  • the nitrogen atom content was measured using an oxygen / nitrogen analyzer “EMGA-620W / C” (trade name) manufactured by Horiba, Ltd., and calculated by an inert gas melting-thermal conductivity method. The results are shown in Table 1.
  • titanium nitride-containing particles TiN-2 to TiN-4 which will be described later, the contents of Ti atoms, Fe atoms, silicon atoms, and nitrogen atoms are also set in the same manner as titanium nitride-containing particles TiN-1. It was measured. The results are shown in Table 1.
  • X-ray diffraction of titanium nitride-containing particles TiN-1 was measured by a wide-angle X-ray diffraction method (trade name “RU-200R” manufactured by Rigaku Corporation) with a powder sample placed in an aluminum standard sample holder.
  • the X-ray source is CuK ⁇ ray
  • the output is 50 kV / 200 mA
  • the slit system is 1 ° -1 ° -0.15 mm-0.45 mm
  • the measurement step (2 ⁇ ) is 0.02 °
  • the scan speed is It was 2 ° / min.
  • the diffraction angle of the peak derived from the TiN (200) plane observed in the vicinity of the diffraction angle 2 ⁇ (42.6 °) was measured.
  • the crystallite size constituting the particle was determined using Scherrer's equation.
  • the diffraction angle 2 ⁇ and crystallite size were measured in the same manner as the titanium nitride-containing particles TiN-1. The results are shown in Table 1. In any of the titanium nitride-containing particles, no X-ray diffraction peak attributed to TiO 2 was observed.
  • Titanium nitride-containing particles TiN-2 to TiN-4 were produced in the same manner as titanium nitride-containing particles TiN-1, except that the raw materials and compositions were as shown in Table 1.
  • TiN particles mean titanium nitride-containing particles.
  • ZrN zirconium nitride-containing particles, manufactured by Nippon Shin Metal Co., Ltd., trade name “ZrN-01”
  • VN vanadium nitride-containing particles, manufactured by Nippon Shin Metal Co., Ltd., trade name “VN-O”
  • NbN Niobium nitride-containing particles, manufactured by Nippon Shin Metal Co., Ltd., trade name “NbN-O”
  • Dispersant represented by the following formula “Mw” intends a weight average molecular weight.
  • Dispersant represented by the following formula
  • Dispersant 4 Dispersant represented by the following formula (weight average molecular weight: 240000)
  • each number in Table 3 represents the following components.
  • Acid anhydride 3 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (4,4′-biphthalic anhydride) (containing two acid anhydride groups in one molecule) )
  • Acid anhydride 4 4,4′-oxydiphthalic anhydride (contains two acid anhydride groups in one molecule)
  • Acid anhydride 5 3,4′-carbonyldiphthalic anhydride (containing two acid anhydride groups in one molecule)
  • Alkali-soluble resin 2 Polyimide precursor (polyamic acid) synthesized by the following method
  • the polyimide precursor (polyamic acid) was synthesized by the following method. First, 4,4′-diaminobenzanilide (0.475 molar equivalent), 3,3′-diaminodiphenylsulfone (0.475 molar equivalent), and bis (3-aminopropyl) tetramethyldisiloxane (0. (05 molar equivalents) together with 1700 g of N-methyl-2-pyrrolidone was placed in a reaction vessel to obtain a mixture. 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (0.98 molar equivalent) was added to the above mixture and reacted at 70 ° C. for 3 hours to obtain a reaction solution.
  • Phthalic anhydride (0.04 molar equivalent) was added to the above reaction solution, and the mixture was further reacted at 70 ° C. for 1 hour.
  • Polyamic acid A-1 (polymer concentration 17% by weight, imide ring closure rate 13%, molecular weight of repeating unit) 532) A solution was obtained.
  • the molecular weight of the repeating unit of polyamic acid A-1 was calculated in the following manner.
  • the molecular weight M1 of the repeating unit of the polyimide resin obtained by imidizing the polyamic acid A-1 is 496, and the number of moles n1 of the imino group and / or iminocarbonyl group contained in the repeating unit of the polyimide resin is 0. 475 moles.
  • Oxime polymerization initiator ⁇ Oxime polymerization initiator 1: IRGACURE OXE-02 (manufactured by BASF)
  • Oxime polymerization initiator 2 Adeka Arcles NCI-831 (manufactured by ADEKA, containing nitro group)
  • the obtained OD is the minimum OD at a wavelength of 400 to 1100 nm. That is, the cured film (film thickness: 1.5 ⁇ m) has an OD equal to or higher than the OD shown in Table 3 (Table 3 (Part 1) to Table 3 (Part 3)) in the entire wavelength range of 400 to 1100 nm.
  • Exposure sensitivity of curable composition (initial)> Each curable composition immediately after the preparation was applied onto a glass substrate using a spin coat and dried to form a curable composition layer having a thickness of 1.0 ⁇ m.
  • the spin coating conditions were as follows: first, rotation speed: 300 rpm (rotation per minute) for 5 seconds, and then 800 rpm for 20 seconds.
  • the drying conditions were 100 ° C. and 80 seconds.
  • the coating film obtained as described above was subjected to light having a wavelength of 365 nm through a pattern mask having a line and space of 1 ⁇ m to 10-1600 mJ / It was irradiated at an exposure dose of cm 2.
  • the curable composition layer after exposure was developed under the conditions of 25 ° C. and 60 seconds to obtain a patterned cured film.
  • the patterned cured film was rinsed with running water for 20 seconds and then air-dried.
  • the minimum exposure amount at which the pattern line width after development of the region irradiated with light was 1.0 ⁇ m or more was defined as exposure sensitivity, and this exposure sensitivity was defined as the initial exposure sensitivity.
  • Exposure sensitivity of curable composition (after time: after 30 days at 45 ° C.)> The curable composition immediately after preparation was sealed in a sealed container, held in a thermostatic chamber (EYELA / LTI-700) in which the internal temperature was set to 45 ° C., and taken out after 30 days. Using the extracted curable composition, the same test as that performed using the curable composition immediately after preparation was performed, and the exposure sensitivity was obtained. This was taken as the exposure sensitivity after time.
  • -Evaluation criteria- 5 A pattern was formed, and no residue was observed in the unexposed area.
  • 4 A pattern was formed, and 1 to 3 residues were observed in an unexposed area of 1.0 ⁇ m square.
  • 3 A pattern was formed, and 4 to 10 residues were observed in an unexposed area of 1.0 ⁇ m square.
  • 2 A pattern was formed, and 11 or more residues were observed in an unexposed area of 1.0 ⁇ m square. 1: No pattern was formed due to poor development.
  • ⁇ Curable composition layer forming step> A curable composition layer was formed on the silicon wafer so that the film thickness after drying was 1.5 ⁇ m.
  • the curable composition layer was formed using spin coating. The number of rotations of the spin coat was adjusted so as to achieve the above film thickness.
  • the applied curable composition layer was placed on a hot plate with the silicon wafer facing down and dried. The surface temperature of the hot plate was 100 ° C., and the drying time was 120 seconds.
  • the obtained curable composition layer was exposed under the following conditions.
  • the exposure was performed using an i-line stepper (trade name “FPA-3000iS +”, manufactured by Canon Inc.).
  • the curable composition layer was irradiated (exposed) with an exposure dose of 400 mJ / cm 2 (irradiation time 0.5 seconds) through a mask having a linear shape of 20 ⁇ m (width 20 ⁇ m, length 4 mm).
  • the curable composition layer after the exposure was placed on a hot plate with the silicon wafer facing down and dried.
  • the surface temperature of the hot plate was 100 ° C., and the drying time was 120 seconds.
  • the film thickness of the curable composition layer after drying was 1.5 ⁇ m.
  • TMAH tetramethylammonium hydroxide
  • ⁇ Post-bake process> The patterned cured film obtained above was heated at 220 ° C. for 300 seconds using a clean oven CLH-21CDH (manufactured by Koyo Thermo Co., Ltd.). Furthermore, the patterned cured film after heating was placed on a hot plate having a surface temperature of 220 ° C. and heated for 300 seconds.
  • the edge angle was more than 85 ° and less than 90 °. 4: The edge angle was more than 80 ° and less than 85 °. 3: The edge angle was more than 75 ° and less than 80 °. 2: The edge angle was more than 70 ° and 75 ° or less. 1: The edge angle was 70 ° or less.
  • the curable composition of Example 2 in which the acid anhydride contains two or more acid anhydride groups in one molecule is superior to the curable compositions of Examples 8 and 9. Further, a cured film having a pattern shape was obtained, and generation of a residue in an unexposed portion was further suppressed. Further, the curable composition of Example 5 containing a polymerization inhibitor has better storage stability than the curable composition of Example 2, and generation of residues in unexposed areas. was more suppressed. In addition, the curable composition of Example 2 in which the metal nitride-containing particles contain titanium nitride has a cured film having a more excellent pattern shape than the curable compositions of Examples 15 to 17. And the generation of residues in the unexposed areas was further suppressed.
  • Example 2 the hardening of Example 2 in which the metal nitride-containing particles contain titanium nitride and the diffraction angle 2 ⁇ of the peak derived from the (200) plane of the particles measured under predetermined conditions is 42.5 to 42.8.
  • the cured film obtained by comparing the curable compositions of Examples 19 and 20 had better light-shielding properties (high OD value).
  • the curable composition of Example 13 in which the content of metal nitride-containing particles in the curable composition is 40% by mass or more is obtained by comparing the curable composition of Example 14 with the curable composition of Example 14. Had better light-shielding properties.
  • the curable composition of Example 12 in which the oxime polymerization initiator contains a nitro group, yielded a cured film having a more excellent pattern shape as compared to the curable composition of Example 2. .
  • Metal Nitride-Containing Particle Dispersions 12 and 13 instead of titanium nitride-containing particles TiN-1, a mixture of titanium nitride-containing particles TiN-1 and carbon black (containing mass ratio (titanium nitride-containing particles TiN-1 / carbon black) is 35/5) is used.
  • a metal nitride-containing particle dispersion 12 was prepared in the same manner as the metal nitride-containing particle dispersion 1 except for the above.
  • titanium nitride-containing particles TiN-1 a mixture of titanium nitride-containing particles TiN-1 and an organic pigment (Irgaphor Black S0100CF, manufactured by BASF) (containing mass ratio (titanium nitride-containing particles TiN-1)
  • the metal nitride-containing particle dispersion 13 was prepared in the same manner as in the method for preparing the metal nitride-containing particle dispersion 1 except that 35/5) was used.
  • Examples 2-12 and 2-13 Preparation of curable composition
  • the metal nitride-containing particle dispersions 12 and 13 were used in place of the metal nitride-containing particle dispersion 1
  • the curable composition 2-12, 2-13 was prepared and evaluated in the same manner as described above, and the same results as in Example 2 were obtained.
  • a curable composition was prepared and evaluated in the same manner as in Example 5 except that PI-03 represented by the following formula was used instead of IRGACURE OXE-02 (manufactured by BASF). As a result, the same result as in Example 5 was obtained except that the pattern edge shape was 5.
  • PI-03 compound represented by the following formula, corresponding to oxime polymerization initiator
  • a curable composition was prepared and evaluated in the same manner as in Example 5 except that PI-04 represented by the following formula was used instead of IRGACURE OXE-02 (manufactured by BASF). As a result, the same results were obtained except that the storage stability was 1 and the pattern edge shape was 5.
  • PI-04 (corresponding to a compound represented by OE74 of WO2015 / 036910, an oxime polymerization initiator)
  • 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 ... Light shielding 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...

Abstract

The present invention addresses the problem of providing a curable composition which is inhibited from leaving a residue in unexposed areas and is capable of giving cured films having an excellent pattern shape. The present invention further addresses the problem of providing a cured film, a color filter, a solid imaging element, an infrared sensor, a process for producing the cured film, and a process for producing the color filter. The curable composition of the present invention comprises metal-nitride-containing particles, an oxime-based polymerization initiator, a polymerizable compound, and an acid anhydride.

Description

硬化性組成物、硬化膜、カラーフィルタ、固体撮像素子、赤外線センサ、硬化膜の製造方法、及び、カラーフィルタの製造方法Curable composition, cured film, color filter, solid-state imaging device, infrared sensor, method for producing cured film, and method for producing color filter
　本発明は、硬化性組成物、硬化膜、カラーフィルタ、固体撮像素子、赤外線センサ、硬化膜の製造方法、及び、カラーフィルタの製造方法に関する。 The present invention relates to a curable composition, a cured film, a color filter, a solid-state imaging device, an infrared sensor, a method for producing a cured film, and a method for producing a color filter.
　従来から、カーボンブラック等の遮光性粒子を含有する硬化性組成物が知られている。
　上記のような遮光性粒子を含有する硬化性組成物は、種々の用途に用いられ、例えば液晶表示装置及び固体撮像素子等が含有する硬化膜の製造に用いられてきた。
　より具体的には、液晶表示装置、及び、固体撮像素子に用いられるカラーフィルタには着色画素間の光を遮蔽し、コントラストを向上させる等の目的で、ガラス基板上にブラックマトリクスと呼ばれる硬化膜が用いられている。
　また、固体撮像素子では、ノイズ発生防止、及び、画質の向上等を目的として硬化膜が用いてられている。現在、携帯電話及びＰＤＡ（Ｐｅｒｓｏｎａｌ　Ｄｉｇｉｔａｌ　Ａｓｓｉｓｔａｎｔ）等の電子機器の携帯端末には、小型で薄型な固体撮像装置が搭載されている。このような固体撮像装置は、一般に、ＣＣＤ（Ｃｈａｒｇｅ　Ｃｏｕｐｌｅｄ　Ｄｅｖｉｃｅ）イメージセンサー及びＣＭＯＳ（Ｃｏｍｐｌｅｍｅｎｔａｒｙ　Ｍｅｔａｌ－Ｏｘｉｄｅ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ）イメージセンサー等の固体撮像素子と、固体撮像素子上に被写体像を形成するためのレンズと、を備えている。 Conventionally, curable compositions containing light-shielding particles such as carbon black are known.
The curable composition containing the light-shielding particles as described above has been used in various applications, for example, in the production of a cured film contained in a liquid crystal display device, a solid-state imaging device, and the like.
More specifically, a color filter used in a liquid crystal display device and a solid-state imaging device has a cured film called a black matrix on a glass substrate for the purpose of shielding light between colored pixels and improving contrast. Is used.
Further, in the solid-state imaging device, a cured film is used for the purpose of preventing noise and improving image quality. Currently, portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin solid-state imaging devices. Such a solid-state imaging device generally includes a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, and a lens for forming a subject image on the solid-state imaging device. It is equipped with.
　このような硬化性組成物として、特許文献１には、遮光材、アルカリ可溶性樹脂、光重合開始剤、反応性モノマー及び有機溶剤を含有する感光性黒色樹脂組成物であって、遮光材として少なくともチタン窒化物粒子を含有し、所定の光学特性を有する塗膜を形成することができる感光性黒色樹脂組成物、が記載されている。 As such a curable composition, Patent Document 1 discloses a photosensitive black resin composition containing a light shielding material, an alkali-soluble resin, a photopolymerization initiator, a reactive monomer, and an organic solvent, and at least as a light shielding material. There is described a photosensitive black resin composition containing titanium nitride particles and capable of forming a coating film having predetermined optical characteristics.
特開２０１０－９７２１０号公報JP 2010-97210 A
　本発明者らは、特許文献１に記載された感光性黒色樹脂組成物を用いて感光性黒色樹脂組成物層を形成し、これを露光し、その後現像して得られたパターン状の膜について検討した。上記の膜は高い光学濃度（ＯＤ、ｏｐｔｉｃａｌ　ｄｅｎｓｉｔｙ）を有するものの、未露光部に残渣が発生し易く、又、パターン形状が昨今要求される水準に達していないことを知見した。 The present inventors formed a photosensitive black resin composition layer using the photosensitive black resin composition described in Patent Document 1, exposed the film, and then developed the patterned film. investigated. Although the above film has a high optical density (OD, optical density), it has been found that a residue is easily generated in an unexposed portion, and the pattern shape has not reached the level required recently.
　そこで、本発明は、未露光部における残渣の発生が抑制され、かつ、優れたパターン形状を有する硬化膜が得られる（以下、「本発明の効果を有する」ともいう。）硬化性組成物の提供を課題とする。
　また、本発明は、硬化膜、カラーフィルタ、固体撮像素子、赤外線センサ、硬化膜の製造方法、及び、カラーフィルタの製造方法の提供も課題とする。 Therefore, the present invention provides a cured film that suppresses the generation of residues in unexposed areas and has an excellent pattern shape (hereinafter also referred to as “having the effect of the present invention”). Offering is an issue.
Another object of the present invention is to provide a cured film, a color filter, a solid-state imaging device, an infrared sensor, a cured film manufacturing method, and a color filter manufacturing method.
　本発明者らは、上記課題を達成すべく鋭意検討した結果、以下の構成により上記課題を達成することができることを見出した。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above-described problems can be achieved by the following configuration.
　［１］　金属窒化物含有粒子と、オキシム系重合開始剤と、重合性化合物と、酸無水物と、を含有する硬化性組成物。
　［２］　硬化性組成物中における、オキシム系重合開始剤の含有量に対する、酸無水物の含有量の含有質量比が、０．００５～０．５である、［１］に記載の硬化性組成物。
　［３］　酸無水物が、１分子中に２個以上の酸無水物基を含有する、［１］又は［２］に記載の硬化性組成物。
　［４］　更に、重合禁止剤を含有する、［１］～［３］のいずれかに記載の硬化性組成物。
　［５］　金属窒化物含有粒子がチタン窒化物を含有する、［１］～［４］のいずれかに記載の硬化性組成物。
　［６］　ＣｕＫα線をＸ線源とした場合の金属窒化物含有粒子の（２００）面に由来するピークの回折角２θが４２．５～４２．８°である、［５］に記載の硬化性組成物。
　［７］　更に、アルカリ可溶性樹脂を含有する、［１］～［６］のいずれかに記載の硬化性組成物。
　［８］　アルカリ可溶性樹脂が、ポリイミド前駆体、及び、ポリイミド樹脂からなる群から選択される少なくとも１種を含有する、［７］に記載の硬化性組成物。
　［９］　硬化性組成物中における、金属窒化物含有粒子の含有量が、硬化性組成物の全固形分に対して、４０質量％以上である、［１］～［８］のいずれかに記載の硬化性組成物。
　［１０］　硬化性組成物中における、金属窒化物含有粒子の含有量に対する、オキシム系重合開始剤の含有量の含有質量比が、０．０３～０．２である、［１］～［９］のいずれかに記載の硬化性組成物。
　［１１］　オキシム系重合開始剤がニトロ基を含有する、［１］～［１０］のいずれかに記載の硬化性組成物。
　［１２］　更に、溶剤を含有する、［１］～［１１］のいずれかに記載の硬化性組成物。
　［１３］　［１］～［１２］のいずれかに記載の硬化性組成物を硬化して得られる、硬化膜。
　［１４］　［１３］に記載の硬化膜を含有するカラーフィルタ。
　［１５］　［１３］に記載の硬化膜を含有する固体撮像素子。
　［１６］　［１３］に記載の硬化膜を含有する赤外線センサ。
　［１７］　［１］～［１２］のいずれかに記載の硬化性組成物を用いて硬化性組成物層を形成する、硬化性組成物層形成工程と、硬化性組成物層に、パターン状の開口部を備えるフォトマスクを介して、活性光線又は放射線を照射して露光する、露光工程と、露光後の硬化性組成物層を現像して、硬化膜を形成する、現像工程と、を含有する、硬化膜の製造方法。
　［１８］　［１７］に記載の硬化膜の製造方法を含有する、カラーフィルタの製造方法。 [1] A curable composition containing metal nitride-containing particles, an oxime polymerization initiator, a polymerizable compound, and an acid anhydride.
[2] The curability according to [1], wherein the content ratio of the content of the acid anhydride to the content of the oxime polymerization initiator in the curable composition is 0.005 to 0.5. Composition.
[3] The curable composition according to [1] or [2], wherein the acid anhydride contains two or more acid anhydride groups in one molecule.
[4] The curable composition according to any one of [1] to [3], further comprising a polymerization inhibitor.
[5] The curable composition according to any one of [1] to [4], wherein the metal nitride-containing particles contain titanium nitride.
[6] The hardening according to [5], wherein the diffraction angle 2θ of the peak derived from the (200) plane of the metal nitride-containing particles using CuKα rays as an X-ray source is 42.5 to 42.8 °. Sex composition.
[7] The curable composition according to any one of [1] to [6], further comprising an alkali-soluble resin.
[8] The curable composition according to [7], wherein the alkali-soluble resin contains at least one selected from the group consisting of a polyimide precursor and a polyimide resin.
[9] The content of the metal nitride-containing particles in the curable composition is 40% by mass or more based on the total solid content of the curable composition, according to any one of [1] to [8] The curable composition as described.
[10] The content ratio of the content of the oxime polymerization initiator to the content of the metal nitride-containing particles in the curable composition is 0.03 to 0.2. [1] to [9 ] The curable composition in any one of.
[11] The curable composition according to any one of [1] to [10], wherein the oxime polymerization initiator contains a nitro group.
[12] The curable composition according to any one of [1] to [11], further comprising a solvent.
[13] A cured film obtained by curing the curable composition according to any one of [1] to [12].
[14] A color filter containing the cured film according to [13].
[15] A solid-state imaging device containing the cured film according to [13].
[16] An infrared sensor containing the cured film according to [13].
[17] A curable composition layer forming step of forming a curable composition layer using the curable composition according to any one of [1] to [12], and a pattern on the curable composition layer An exposure process in which exposure is performed by irradiating actinic rays or radiation through a photomask having an opening, and a development process in which the cured curable composition layer is developed to form a cured film. A method for producing a cured film.
[18] A method for producing a color filter, comprising the method for producing a cured film according to [17].
　本発明によれば、未露光部における残渣の発生が抑制され、かつ、優れたパターン形状を有する硬化膜が得られる硬化性組成物を提供できる。
　また、本発明によれば、硬化膜、カラーフィルタ、固体撮像素子、赤外線センサ、硬化膜の製造方法、及び、カラーフィルタの製造方法も提供できる。 ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of the residue in an unexposed part can be suppressed and the curable composition from which the cured film which has the outstanding pattern shape can be obtained can be provided.
Moreover, according to this invention, the manufacturing method of a cured film, a color filter, a solid-state image sensor, an infrared sensor, a cured film, and the manufacturing method of a color filter can also be provided.
固体撮像装置の構成例を示す概略断面図である。It is a schematic sectional drawing which shows the structural example of a solid-state imaging device. 図１の撮像部を拡大して示す概略断面図である。It is a schematic sectional drawing which expands and shows the imaging part of FIG. 赤外線センサの構成例を示す概略断面図である。It is a schematic sectional drawing which shows the structural example of an infrared sensor.
　以下、本発明について詳細に説明する。
　以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
　なお、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　また、本明細書における基（原子団）の表記において、置換及び無置換を記していない表記は、置換基を含有しないものと共に置換基を含有するものをも包含するものである。例えば、「アルキル基」とは、置換基を含有しないアルキル基（無置換アルキル基）のみならず、置換基を含有するアルキル基（置換アルキル基）をも包含する。
　また、本明細書中における「活性光線」又は「放射線」とは、例えば、水銀灯の輝線スペクトル、及びエキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ：Ｅｘｔｒｅｍｅ　ｕｌｔｒａｖｉｏｌｅｔ）、Ｘ線、並びに電子線等を意味する。また本明細書において光とは、活性光線及び放射線を意味する。本明細書中における「露光」とは、特に断らない限り、水銀灯、エキシマレーザー、遠紫外線、Ｘ線、及び、ＥＵＶ等による露光のみならず、電子線及びイオンビーム等の粒子線による描画も包含する。
　また、本明細書において、「（メタ）アクリレート」はアクリレート及びメタアクリレートを表す。また、本明細書において、「（メタ）アクリル」はアクリル及びメタアクリルを表す。また、本明細書において、「（メタ）アクリロイル」は、アクリロイル及びメタクリロイルを表す。また、本明細書において、「（メタ）アクリルアミド」は、アクリルアミド及びメタアクリルアミドを表す。また、本明細書中において、「単量体」と「モノマー」とは同義である。単量体は、オリゴマー及びポリマーと区別され、重量平均分子量が２，０００以下の化合物をいう。本明細書中において、重合性化合物とは、重合性基を含有する化合物のことをいい、単量体であっても、ポリマーであってもよい。重合性基とは、重合反応に関与する基をいう。 Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, 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.
Moreover, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not contain a substituent and what contains a substituent. For example, 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).
In addition, in the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, extreme ultraviolet (EUV) represented by an excimer laser, X-ray, and electron beam. Etc. In the present specification, light means actinic rays and radiation. Unless otherwise specified, “exposure” in this specification includes not only exposure by mercury lamp, excimer laser, deep ultraviolet ray, X-ray, EUV, but also drawing by particle beam such as electron beam and ion beam. To do.
Moreover, in this specification, "(meth) acrylate" represents an acrylate and a methacrylate. In the present specification, “(meth) acryl” represents acryl and methacryl. In the present specification, “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “(meth) acrylamide” represents acrylamide and methacrylamide. In this specification, “monomer” and “monomer” are synonymous. A monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.
［硬化性組成物］
　本発明の実施形態に係る硬化性組成物は、金属窒化物含有粒子と、オキシム系重合開始剤と、重合性化合物と、酸無水物と、を含有する。上記硬化性組成物が本発明の効果を奏する機序は必ずしも明らかではないが、以下に、推測される機序を説明する。
　なお、本発明は以下の機序により効果が得られるものに制限されず、以下の機序以外の機序により本発明の効果が得られる場合にも、本発明の範囲に含まれるものとする。 [Curable composition]
The curable composition which concerns on embodiment of this invention contains metal nitride containing particle | grains, an oxime type polymerization initiator, a polymeric compound, and an acid anhydride. Although the mechanism by which the curable composition exhibits the effects of the present invention is not necessarily clear, the mechanism that is assumed will be described below.
In addition, this invention is not restrict | limited to what can obtain an effect by the following mechanisms, Even when the effect of this invention is acquired by mechanisms other than the following mechanisms, it shall be contained in the scope of the present invention. .
　昨今、カラーフィルタ、及び／又は、固体撮像素子等に用いられる硬化膜には、より高い遮光性が求められている。上記のような遮光性の高い硬化膜が得られる感光性組成物としては、遮光性粒子を多量に含有するもの、及び／又は、金属窒化物含有粒子を含有するものが知られている。
　遮光性粒子を多量に含有する感光性組成物は、遮光性粒子を多量に含有するため、得られる硬化膜は高い遮光性を示す。しかし、一方で、本発明者らは、上記のような感光性組成物は、露光時に、組成物中を光が透過しにくいため、感光性組成物の硬化が不十分となることがあることを知見している。
　一方、オキシム系重合開始剤を含有する感光性組成物は、優れた硬化性を有する。これは、オキシム系重合開始剤が、優れた感度、及び、優れた重合効率を有するためだと推測される。 In recent years, higher light-shielding properties are required for cured films used in color filters and / or solid-state imaging devices. As a photosensitive composition from which a cured film having a high light-shielding property as described above can be obtained, those containing a large amount of light-shielding particles and / or containing metal nitride-containing particles are known.
Since the photosensitive composition containing a large amount of light-shielding particles contains a large amount of light-shielding particles, the resulting cured film exhibits high light shielding properties. However, on the other hand, the present inventors have found that the photosensitive composition as described above may not sufficiently cure the photosensitive composition because light is not easily transmitted through the composition during exposure. I know.
On the other hand, the photosensitive composition containing an oxime polymerization initiator has excellent curability. This is presumably because the oxime polymerization initiator has excellent sensitivity and excellent polymerization efficiency.
　しかし、本発明者らは、特許文献１に記載された感光性組成物のように、金属窒化物含有粒子と、オキシム系重合開始剤と、を併用した場合、所望の効果が得られないことがあることを、新たに知見した。本発明者らは、上記現象について鋭意検討した結果、以下の理由であると推測している。 However, the present inventors cannot obtain the desired effect when the metal nitride-containing particles and the oxime polymerization initiator are used in combination as in the photosensitive composition described in Patent Document 1. I have newly discovered that there is. As a result of intensive studies on the above phenomenon, the present inventors speculate that the reason is as follows.
　金属窒化物含有粒子は、表面が塩基性になり易いことを本発明者らは知見している。
　上記特性は、必ずしも金属窒化物含有粒子の特定の製造方法にのみ原因するものではない。しかし、簡単のために、特定の製造方法をとりあげて説明する。例えば、チタン窒化物含有粒子の製造方法としては、プラズマ炎中で四塩化チタンとアンモニアガスを反応させる方法（特開平２－２２１１０号公報）等が知られている。上記製造方法においては、チタン化合物に窒素を導入するためにアンモニアガスを使用することから、製造されるチタン窒化物含有粒子の表面は塩基性となりやすいものと推測される。 The present inventors have found that the surface of metal nitride-containing particles tends to be basic.
The above characteristics are not necessarily caused only by a specific method for producing metal nitride-containing particles. However, for the sake of simplicity, a specific manufacturing method will be described. For example, as a method for producing titanium nitride-containing particles, a method of reacting titanium tetrachloride with ammonia gas in a plasma flame (Japanese Patent Laid-Open No. 2-22110) is known. In the above production method, ammonia gas is used to introduce nitrogen into the titanium compound, and therefore it is assumed that the surface of the produced titanium nitride-containing particles is likely to be basic.
　一方、オキシム系重合開始剤は、加水分解を受け易い性質を有することもまた、本発明者らは知見している。従い、金属窒化物含有粒子と、オキシム系重合開始剤とを併用する場合、表面が塩基性となっている金属窒化物含有粒子によって、オキシム系重合開始剤の加水分解が促進されることがあると推測される。 On the other hand, the present inventors have also found that the oxime polymerization initiator has a property of being easily subjected to hydrolysis. Accordingly, when the metal nitride-containing particles and the oxime polymerization initiator are used in combination, hydrolysis of the oxime polymerization initiator may be promoted by the metal nitride-containing particles whose surface is basic. It is guessed.
　上記の傾向は、硬化性組成物が多量の金属窒化物含有粒子を含有する際に顕著である。一般的な感光性組成物において、多量の金属窒化物含有粒子を含有する場合、上記感光性組成物を用いて、基板上に感光性組成物層を形成し、これを露光した場合、パターン形状が悪化することがあった。
　これは、感光性組成物層の露光面に近い領域（上層領域）と比較すると、その反対側の面（基板側の面、下層領域）では、到達する光の量が少なく、硬化しにくくなるからだと推測される。これは、多量の金属窒化物含有粒子によって、より光が吸収されやすいことに原因すると推測される。上記のような露光後の感光性組成物層を現像すると、上層領域と比較して、下層領域のパターンが細ることがあった。 The above tendency is remarkable when the curable composition contains a large amount of metal nitride-containing particles. When a general photosensitive composition contains a large amount of metal nitride-containing particles, the photosensitive composition is used to form a photosensitive composition layer on the substrate, and when this is exposed, the pattern shape Could get worse.
Compared with the region (upper layer region) close to the exposure surface of the photosensitive composition layer, the opposite surface (substrate side surface, lower layer region) has a small amount of light reaching and is hard to be cured. Presumed to be from the body. This is presumed to be because light is more easily absorbed by a large amount of metal nitride-containing particles. When the photosensitive composition layer after exposure as described above is developed, the pattern of the lower layer region may be thinner than the upper layer region.
　これに対し、本発明の実施形態に係る硬化性組成物は酸無水物を含有することを特徴の一つとする。酸無水物は、硬化性組成物中において、オキシム系重合開始剤の加水分解の原因となる水分子と反応し、酸を発生する。言い換えれば、上記硬化性組成物中において、加水分解の原因となる水分子を除去する機能を有する。
　そのため、上記硬化性組成物中においてはオキシム系重合開始剤が加水分解されにくく、結果として、上記硬化性組成物を用いて得られる硬化膜は優れたパターン形状を有するものと推測される。 On the other hand, the curable composition according to the embodiment of the present invention includes an acid anhydride. In the curable composition, the acid anhydride reacts with water molecules that cause hydrolysis of the oxime polymerization initiator to generate an acid. In other words, the curable composition has a function of removing water molecules that cause hydrolysis.
Therefore, in the said curable composition, an oxime type polymerization initiator is hard to be hydrolyzed, As a result, it is estimated that the cured film obtained using the said curable composition has the outstanding pattern shape.
　更に、酸無水物が水分子を除去することで発生した酸が、露光時（特に、露光後に、加熱を行った場合に顕著である。）に硬化性組成物層の上層領域に移動し、その後のアルカリ現像の際に、現像を促す作用を有すると推測される。
　つまり、硬化性組成物が酸無水物を含有することにより、これにより形成された硬化性組成物層の上層領域が、下層領域と比較してより現像されやすくなることにより、得られるパターン形状が良化したものと推測される。これは、上記硬化性組成物が酸無水物を含有することによる、予想し得なかった相乗効果である。 Furthermore, the acid generated when the acid anhydride removes water molecules moves to the upper layer region of the curable composition layer during exposure (particularly when heating is performed after exposure). It is presumed to have an action of promoting development during the subsequent alkali development.
That is, when the curable composition contains an acid anhydride, the upper layer region of the curable composition layer formed thereby is more easily developed than the lower layer region, and thus the pattern shape obtained is Presumed to have improved. This is an unexpected synergistic effect due to the fact that the curable composition contains an acid anhydride.
　また、本発明者らの検討によれば、酸無水物がオキシム系重合開始剤の加水分解を抑制することにより、特に未露光部において、オキシム系重合開始剤が分解することによる意図しない重合反応を抑制することもまた知見した。これは、予想し得ない効果である。本発明の実施形態に係る硬化性組成物は、上記の無水物の作用により、未露光部において、現像後に生ずる残渣の数が抑制されたものと推測される。 Further, according to the study by the present inventors, an acid anhydride suppresses hydrolysis of the oxime polymerization initiator, and an unintended polymerization reaction due to decomposition of the oxime polymerization initiator, particularly in an unexposed portion. It was also found to suppress the above. This is an unexpected effect. In the curable composition according to the embodiment of the present invention, it is presumed that the number of residues generated after development is suppressed in the unexposed area by the action of the above anhydride.
　以下では、硬化性組成物が含有する各成分について詳述する。 Hereinafter, each component contained in the curable composition will be described in detail.
〔酸無水物〕
　上記実施形態に係る硬化性組成物は酸無水物を含有する。酸無水物としては、水と反応し、トラップすることによって、硬化性組成物中から水を除去する作用を有していれば、特に制限されず、公知の酸無水物が使用できる。
　硬化性組成物中における酸無水物の含有量としては特に制限されないが、一般に、硬化性組成物の全固形分に対して０．０１～５質量％が好ましい。
　酸無水物は、１種を単独で用いても、２種以上を併用してもよい。２種以上の無水物を併用する場合には、合計含有量が上記範囲内であることが好ましい。
　なお、本明細書において、酸無水物とは、１分子中に１個以上の酸無水物基を含有する化合物を意味する。 [Acid anhydride]
The curable composition which concerns on the said embodiment contains an acid anhydride. The acid anhydride is not particularly limited as long as it has an action of removing water from the curable composition by reacting with and trapping with water, and a known acid anhydride can be used.
The content of the acid anhydride in the curable composition is not particularly limited, but is generally preferably 0.01 to 5% by mass with respect to the total solid content of the curable composition.
An acid anhydride may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of anhydride together, it is preferable that total content is in the said range.
In addition, in this specification, an acid anhydride means a compound containing one or more acid anhydride groups in one molecule.
　また、硬化性組成物中における、後述する金属窒化物含有粒子の含有量に対する、酸無水物の含有量の含有質量比（酸無水物の含有量／金属窒化物含有粒子の含有量、以下、単に「酸無水物／金属窒化物含有粒子」ともいう。）は、１．０×１０－５～１．０が好ましく、０．００５０～０．５０がより好ましい。
　酸無水物／金属窒化物含有粒子が０．００５０～０．５０の範囲内であると、硬化性組成物はより優れた本発明の効果を有する。 In addition, the content ratio of the content of acid anhydride to the content of metal nitride-containing particles described later in the curable composition (content of acid anhydride / content of metal nitride-containing particles, hereinafter, The simply “acid anhydride / metal nitride-containing particles”) is preferably 1.0 × 10 −5 to 1.0, more preferably 0.0050 to 0.50.
When the acid anhydride / metal nitride-containing particles are in the range of 0.0050 to 0.50, the curable composition has a more excellent effect of the present invention.
　酸無水物が含有する酸無水物基としては、特に制限されず、公知の酸無水物基が挙げられる。酸無水物基としては例えば、同種の酸から誘導されるカルボン酸無水物基、ホスホン酸無水物基、及び、スルホン酸無水物基等、並びに、異なる２種の酸から誘導される酸無水物基が挙げられる。
　酸無水物が含有する酸無水物基の数としては特に制限されないが、硬化性組成物がより優れた本発明の効果を有する点で、１分子中に２個以上が好ましい。酸無水物が含有する酸無水物基の数の上限値としては特に制限されないが、一般に４個以下が好ましい。 It does not restrict | limit especially as an acid anhydride group which an acid anhydride contains, A well-known acid anhydride group is mentioned. Examples of the acid anhydride group include a carboxylic acid anhydride group derived from the same kind of acid, a phosphonic acid anhydride group, a sulfonic acid anhydride group, and the like, and an acid anhydride derived from two different acids. Groups.
The number of acid anhydride groups contained in the acid anhydride is not particularly limited, but two or more in one molecule is preferable in that the curable composition has more excellent effects of the present invention. The upper limit of the number of acid anhydride groups contained in the acid anhydride is not particularly limited, but generally 4 or less is preferable.
　酸無水物としては、特に制限されないが、例えば、二硫酸、トリフルオロメタンスルホン酸無水物、五酸化二窒素、二リン酸、無水酢酸、無水コハク酸、無水グルタル酸、無水フタル酸、無水マレイン酸、２－スルホ安息香酸無水物、及び、ｐ－トルエンスルホン酸無水物等が挙げられる。 The acid anhydride is not particularly limited. For example, disulfuric acid, trifluoromethanesulfonic anhydride, dinitrogen pentoxide, diphosphoric acid, acetic anhydride, succinic anhydride, glutaric anhydride, phthalic anhydride, maleic anhydride 2-sulfobenzoic anhydride, p-toluenesulfonic anhydride, and the like.
　酸無水物としては、硬化性組成物がより優れた本発明の効果を有する点で、式（Ａ１）で表される、テトラカルボン酸二無水物が好ましい。
Figure JPOXMLDOC01-appb-C000001
 As the acid anhydride, a tetracarboxylic dianhydride represented by the formula (A1) is preferable in that the curable composition has more excellent effects of the present invention.
Figure JPOXMLDOC01-appb-C000001
　式（Ａ１）中、Ｒ１は４価の有機基を表す。４価の有機基としては特に制限されないが、炭素数１～４０の置換基を有してもよい脂肪族、又は、芳香族炭化水素基が挙げられる。脂肪族炭化水素基としては、例えば、以下の式で表される基等が挙げられる。 In formula (A1), R 1 represents a tetravalent organic group. The tetravalent organic group is not particularly limited, and examples thereof include an aliphatic or aromatic hydrocarbon group which may have a substituent having 1 to 40 carbon atoms. Examples of the aliphatic hydrocarbon group include groups represented by the following formulas.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　なお、上記式中、Ｒａは窒素原子、又は、ＣＲｂを表し、Ｒｂは水素原子、又は、一価の有機基を表し、ｎは０、又は、１以上の整数を表し、複数あるＲａ、及び、Ｒｂはそれぞれ同一でも異なってもよく、複数のＲｂは互いに連結して環を形成してもよい。 In the above formula, R a represents a nitrogen atom or CR b , R b represents a hydrogen atom or a monovalent organic group, n represents 0 or an integer of 1 or more, and there are a plurality. R a and R b may be the same or different, and a plurality of R b may be connected to each other to form a ring.
　芳香族炭化水素基として、例えば、以下の式で表される基等が挙げられる。 Examples of the aromatic hydrocarbon group include groups represented by the following formulas.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（Ａ１）で表されるテトラカルボン酸二無水物の具体例としては、例えば、１，２，３，４－シクロブタンテトラカルボン酸二無水物、ｍｅｓｏ－ブタン－１，２，３，４－テトラカルボン酸二無水物、１，２，３，４－シクロペンタンテトラカルボン酸二無水物、１，２，４，５－シクロヘキサンテトラカルボン酸二無水物、３－（カルボキシメチル）－１，２，４－シクロペンタントリカルボン酸１，４：２，３－二無水物、５－（２，５－ジオキソテトラヒドロフリル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸無水物、４－（２，５－ジオキソテトラヒドロフラン－３－イル）－１，２，３，４－テトラヒドロナフタレン－１，２－ジカルボン酸無水物、３，４，９，１０－ペリレンテトラカルボン酸二無水物、１，２，５，６－ナフタレンテトラカルボン酸二無水物、ビシクロ［２．２．２］オクト－７－エン－２，３，５，６－テトラカルボン酸二無水物、ジエチレントリアミン五酢酸二無水物、２，６－ジブロモナフタレン－１，４，５，８－テトラカルボン酸二無水物、エチレンジアミン四酢酸二無水物、オクタヒドロ－４ａ，８ｂ：４ｂ，８ａ－ビス（メタノオキシメタノ）ビフェニレン－９，１１，１２，１４－テトラオン、及び、１，２，３，４－テトラメチル－１，２，３，４－シクロブタンテトラカルボン酸二無水物等が挙げられるが、これらに制限されない。 Specific examples of the tetracarboxylic dianhydride represented by the formula (A1) include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, meso-butane-1,2,3,4- Tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3- (carboxymethyl) -1,2 , 4-Cyclopentanetricarboxylic acid 1,4: 2,3-dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4 -(2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic dianhydride 1,2,5,6-naphthalenetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, diethylenetriaminepentaacetic dianhydride 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, octahydro-4a, 8b: 4b, 8a-bis (methanooxymethano) biphenylene-9 , 11, 12, 14-tetraone, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, and the like, but are not limited thereto.
　テトラカルボン酸二無水物としては、硬化性組成物がより優れた本発明の効果を有する点で、以下の式（Ａ２）で表される化合物がより好ましい。 As the tetracarboxylic dianhydride, a compound represented by the following formula (A2) is more preferable in that the curable composition has more excellent effects of the present invention.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式（Ａ２）中、Ｒ２は単結合、又は、２価の連結基を表す。２価の連結基としては特に制限されないが、例えば、以下の式で表される基、及び、以下の式で表される基を複数組み合わせた基が挙げられる。 In formula (A2), R 2 represents a single bond or a divalent linking group. Although it does not restrict | limit especially as a bivalent coupling group, For example, the group represented by the following formula | equation and the group which combined multiple groups represented by the following formula | equation are mentioned.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　上記式中、Ｒｂは既に説明したとおりである。なかでも、硬化性組成物がより優れた本発明の効果を有する点で、Ｒ２としては、単結合、－Ｏ－、又は、－Ｃ（＝Ｏ）－が好ましい。 In the above formula, R b is as described above. Among these, R 2 is preferably a single bond, —O— or —C (═O) — from the viewpoint that the curable composition has the more excellent effects of the present invention.
　式（Ａ２）で表される化合物の具体例としては、例えば、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、ジフェニル－３，３’，４，４’－テトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物、４，４’－（エチン－１，２－ジイル）ジフタル酸無水物、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物、３，４’－オキシジフタル酸無水物、及び、４，４’－オキシジフタル酸無水物等が挙げられるが、これらに制限されない。 Specific examples of the compound represented by the formula (A2) include, for example, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, diphenyl-3,3 ′, 4,4′-tetracarboxylic acid. Dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 4,4 ′-(ethyne-1,2-diyl) diphthalic anhydride, 4,4 ′-(hexafluoro) Isopropylidene) diphthalic anhydride, 4,4 '-(4,4'-isopropylidenediphenoxy) diphthalic anhydride, 3,4'-oxydiphthalic anhydride, and 4,4'-oxydiphthalic anhydride However, it is not limited to these.
　酸無水物の分子量としては特に制限されないが、露光後の加熱工程で酸無水物が硬化性組成物層の上層領域により拡散し易く、その後の現像により、より優れたパターン形状を有する硬化膜が得られ易い点で、１００～８００が好ましく、１００～６００がより好ましい。なお、本段落において、分子量とは、構造式から計算できる分子量を意味する。 The molecular weight of the acid anhydride is not particularly limited, but the acid anhydride is likely to diffuse in the upper layer region of the curable composition layer in the heating step after exposure, and a cured film having a more excellent pattern shape is obtained by subsequent development. 100 to 800 are preferable, and 100 to 600 are more preferable in that they are easily obtained. In this paragraph, the molecular weight means a molecular weight that can be calculated from the structural formula.
〔金属窒化物含有粒子〕
　上記硬化性組成物は金属窒化物含有粒子を含有する。本明細書において、金属窒化物含有粒子とは、金属原子の窒化物を含有する粒子を意味する。また、金属窒化物含有粒子は、金属原子、及び、窒素原子以外の原子（例えば、酸素原子等）を含有してもよく、その形態は後述する。 [Metal nitride-containing particles]
The curable composition contains metal nitride-containing particles. In the present specification, the metal nitride-containing particles mean particles containing metal atom nitrides. The metal nitride-containing particles may contain metal atoms and atoms other than nitrogen atoms (for example, oxygen atoms), and the form thereof will be described later.
　上記硬化性組成物中における金属窒化物含有粒子の含有量としては特に制限されないが、硬化性組成物の全固形分に対して、３０質量％以上が好ましく、より優れた遮光性を有する硬化膜が得られる点で、４０質量％以上がより好ましい。
　なお、金属窒化物含有粒子の含有量の上限値としては特に制限されないが、一般に、７０質量％以下が好ましい。
　また、上記硬化性組成物中における金属窒化物含有粒子の含有量に対する後述するオキシム系重合開始剤の含有量の含有質量比（以下、「オキシム系重合開始剤／金属窒化物含有粒子」ともいう。）は、特に制限されないが、０．００１～０．４が好ましく、より優れた本発明の効果を有する硬化性組成物が得られる点で、０．０３～０．２がより好ましい。
　なお、金属窒化物含有粒子は、１種を単独で用いても、２種以上を併用してもよい。２種以上の金属窒化物含有粒子を併用する場合には、合計含有量が上記範囲内であることが好ましい。 The content of the metal nitride-containing particles in the curable composition is not particularly limited, but is preferably 30% by mass or more based on the total solid content of the curable composition, and has a more excellent light-shielding property. Is more preferably 40% by mass or more.
In addition, although it does not restrict | limit especially as an upper limit of content of metal nitride containing particle | grains, Generally 70 mass% or less is preferable.
The content ratio of the content of the oxime polymerization initiator described later to the content of the metal nitride-containing particles in the curable composition (hereinafter also referred to as “oxime polymerization initiator / metal nitride-containing particles”). )) Is not particularly limited, but is preferably 0.001 to 0.4, and more preferably 0.03 to 0.2 in that a curable composition having a more excellent effect of the present invention can be obtained.
In addition, a metal nitride containing particle | grain may be used individually by 1 type, or may use 2 or more types together. When two or more kinds of metal nitride-containing particles are used in combination, the total content is preferably within the above range.
　金属窒化物含有粒子は上記のとおり金属原子の窒化物を含有する。なお、本明細書において、単に「金属原子」というときは、金属窒化物含有粒子に含まれる金属原子であって、窒化物として存在する金属原子のことを意図する。
　金属原子として特に制限されず、公知の金属原子を用いることができる。金属原子としては、例えば、遷移金属が挙げられ、より優れた遮光性を有する硬化膜を得ることができる硬化性組成物を得られ易い点で、３～１１族の遷移金属が好ましく、Ｔｉ、Ｓｃ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、又はＰｔがより好ましく、Ｔｉ、Ｓｃ、Ｖ、Ｃｒ、Ｃｏ、Ｃｕ、Ｙ、Ｚｒ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、又はＰｔが更に好ましく、Ｔｉ、Ｖ、Ｃｒ、Ｙ、Ｚｒ、Ｎｂ、Ｈｆ、Ｔａ、Ｗ、又はＲｅが特に好ましく、Ｔｉ、Ｖ、Ｎｂ、Ｔａ、又は、Ｚｒが最も好ましい。 The metal nitride-containing particles contain a metal atom nitride as described above. In the present specification, the term “metal atom” is intended to mean a metal atom contained in a metal nitride-containing particle and present as a nitride.
It does not restrict | limit especially as a metal atom, A well-known metal atom can be used. Examples of the metal atom include transition metals, and a transition metal belonging to Group 3 to 11 is preferred in that it is easy to obtain a curable composition capable of obtaining a cured film having better light-shielding properties, Ti, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, or Pt are more preferable, Ti, Sc, V, Cr, Co, Cu, Y, Zr, Mo, Tc, Ru, Rh, Pd, Hf, Ta, W, Re, or Pt are more preferable, and Ti, V, Cr, Y, Zr, Nb, Hf, Ta, W, or Re is particularly preferable, and Ti, V, Nb, Ta, or Zr is most preferable.
　金属窒化物含有粒子中にける金属原子の含有量としては特に制限されないが、金属窒化物含有粒子の全質量に対して、５０～８０質量％が好ましい。なお、金属窒化物含有粒子における金属原子の含有量は、ＩＣＰ（Ｉｎｄｕｃｔｉｖｅｌｙ　Ｃｏｕｐｌｅｄ　Ｐｌａｓｍａ）発光分光分析法により分析することができる。
　なお、金属原子は、１種を単独で用いても、２種以上を併用してもよい。２種以上の金属原子を併用する場合には、合計含有量が上記範囲内であることが好ましい。 The content of metal atoms in the metal nitride-containing particles is not particularly limited, but is preferably 50 to 80% by mass with respect to the total mass of the metal nitride-containing particles. The content of metal atoms in the metal nitride-containing particles can be analyzed by ICP (Inductively Coupled Plasma) emission spectroscopy.
In addition, a metal atom may be used individually by 1 type, or may use 2 or more types together. When two or more metal atoms are used in combination, the total content is preferably within the above range.
　金属窒化物含有粒子は、金属原子の窒化物を含有する。金属原子の窒化物は、その合成時に酸素が混入することがある。
　金属原子の窒化物中の酸素原子の含有量は、金属原子の窒化物の全質量に対して、０．００１～４０質量％が好ましく、０．００１～３５質量％がより好ましく、０．００１～３０質量％が更に好ましい。酸素原子の含有量は、不活性ガス融解－赤外線吸収法を用いて分析できる。
　なお、金属原子の窒化物は、硬化性組成物を硬化して得られる硬化膜がより優れた遮光性を有する点で、実質的に酸素原子を含有しないことが好ましい。実質的に酸素原子を含有しない、とは、上記測定方法を用いて、酸素原子が検出されないことを意味する。 The metal nitride-containing particles contain a metal atom nitride. Metal nitride may be mixed with oxygen during its synthesis.
The content of oxygen atoms in the metal atom nitride is preferably 0.001 to 40 mass%, more preferably 0.001 to 35 mass%, more preferably 0.001 to the total mass of the metal atom nitride. More preferably, it is 30% by mass. The oxygen atom content can be analyzed using an inert gas melting-infrared absorption method.
In addition, it is preferable that the nitride of a metal atom does not contain an oxygen atom substantially from the point which the cured film obtained by hardening | curing a curable composition has the more excellent light-shielding property. “Substantially free of oxygen atoms” means that oxygen atoms are not detected using the measurement method.
　金属窒化物含有粒子はチタン窒化物を含有することが好ましい。チタン窒化物としては特に制限されず、公知のチタン窒化物を用いることができる。 The metal nitride-containing particles preferably contain titanium nitride. The titanium nitride is not particularly limited, and known titanium nitride can be used.
　チタン窒化物としては、例えば、ＴｉＮ、ＴｉＯ２、ＴｉｎＯ２ｎ－１（１≦ｎ≦２０）で表せる低次酸化チタン、及び、ＴｉＮｘＯｙ（０＜ｘ＜２．０，０．１＜ｙ＜２．０）で表せる酸窒化チタンを含有する形態が挙げられる。
　上記のチタン窒化物はＣｕＫα線をＸ線源とした場合の（２００）面に由来するピークの回折角２θは、一般に４２．５°～４３．５°が好ましく、より優れた遮光性を有する硬化膜を得ることができる硬化性組成物が得られ易い点で、４２．５°～４２．８°がより好ましく、４２．５～４２．７が更に好ましい。 Examples of the titanium nitride include low-order titanium oxide expressed by TiN, TiO 2 , Ti n O 2n-1 (1 ≦ n ≦ 20), and TiN x O y (0 <x <2.0, 0. The form containing the titanium oxynitride which can be represented by 1 <y <2.0) is mentioned.
In the above titanium nitride, the diffraction angle 2θ of the peak derived from the (200) plane when CuKα ray is used as the X-ray source is generally preferably 42.5 ° to 43.5 °, and has more excellent light shielding properties. From the viewpoint of easily obtaining a curable composition capable of obtaining a cured film, 42.5 ° to 42.8 ° is more preferable, and 42.5 to 42.7 is even more preferable.
　ＣｕＫα線をＸ線源として金属窒化物含有粒子のＸ線回折スペクトルを測定した場合において、最も強度の強いピークとしてＴｉＮは（２００）面に由来するピークが２θ＝４２．５°近傍に、ＴｉＯは（２００）面に由来するピークが２θ＝４３．４°近傍に観測される。一方、最も強度の強いピークではないがアナターゼ型ＴｉＯ２は（２００）面に由来するピークは２θ＝４８．１°近傍に、ルチル型ＴｉＯ２は（２００）面に由来するピークは２θ＝３９．２°近傍に観測される。よって、チタン窒化物が酸素原子を多く含有するほどピーク位置は４２．５°に対して高角度側にシフトする。 When the X-ray diffraction spectrum of the metal nitride-containing particles was measured using CuKα rays as an X-ray source, TiN was the strongest peak, and the peak derived from the (200) plane was in the vicinity of 2θ = 42.5 °, TiO A peak derived from the (200) plane is observed in the vicinity of 2θ = 43.4 °. On the other hand, although not the strongest peak, the peak derived from the (200) plane of anatase TiO 2 is in the vicinity of 2θ = 48.1 °, and the peak derived from the (200) plane of rutile TiO 2 is 2θ = 39. Observed around 2 °. Therefore, as the titanium nitride contains more oxygen atoms, the peak position shifts to a higher angle side with respect to 42.5 °.
　金属窒化物含有粒子の（２００）面に由来するピークの回折角２θは、４２．５°以上４３．５°以下が好ましく、４２．５°以上４２．８以下がより好ましく、４２．５°以上４２．７°以下が更に好ましい。
　金属窒化物含有粒子が、酸化チタンＴｉＯ２を含有する場合、最も強度の強いピークとしてアナターゼ型ＴｉＯ２（１０１）に由来するピークが２θ＝２５．３°近傍に、ルチル型ＴｉＯ２（１１０）に由来するピークが２θ＝２７．４°近傍に見られる。しかし、ＴｉＯ２は白色であり、硬化性組成物を硬化して得られる遮光膜の遮光性を低下させる要因となるため、ピークとして観察されない程度に低減されていることが好ましい。 The diffraction angle 2θ of the peak derived from the (200) plane of the metal nitride-containing particles is preferably 42.5 ° or more and 43.5 ° or less, more preferably 42.5 ° or more and 42.8 or less, and 42.5 °. More preferably, the angle is 42.7 ° or less.
When the metal nitride-containing particles contain titanium oxide TiO 2 , the peak derived from anatase TiO 2 (101) as the strongest peak is in the vicinity of 2θ = 25.3 °, and rutile TiO 2 (110). The peak derived from is seen in the vicinity of 2θ = 27.4 °. However, since 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.
　上記のＸ線回折スペクトルの測定により得られたピークの半値幅から、金属窒化物含有粒子を構成する結晶子サイズを求めることができる。結晶子サイズの算出はシェラーの式を用いて行うことができる。 The crystallite size constituting the metal nitride-containing particles 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.
　金属窒化物含有粒子を構成する結晶子サイズとしては、５０ｎｍ以下が好ましく、２０ｎｍ以上が好ましく、２０～５０ｎｍがより好ましい。結晶子サイズが２０～５０ｎｍであると、硬化性組成物を用いて形成される遮光膜は、紫外線（特にｉ線（３６５ｎｍ））透過率がより高くなりやすく、より感光性が高い硬化性組成物が得られる。 The crystallite size constituting the metal nitride-containing particles is preferably 50 nm or less, preferably 20 nm or more, and more preferably 20 to 50 nm. When the crystallite size is 20 to 50 nm, the light-shielding film formed using the curable composition tends to have a higher ultraviolet (particularly i-line (365 nm)) transmittance and has a higher photosensitivity. A thing is obtained.
　金属窒化物含有粒子の比表面積については特に制限されないが、ＢＥＴ（Ｂｒｕｎａｕｅｒ，Ｅｍｍｅｔｔ，Ｔｅｌｌｅｒ）法を用いて求られる。チタン窒化物の比表面積は、５～１００ｍ２／ｇが好ましく、１０～６０ｍ２／ｇがより好ましい。 The specific surface area of the metal nitride-containing particles is not particularly limited, but can be determined using a 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.
　また、金属窒化物は、他の金属微粒子と複合化していてもよい。
　本明細書において、複合化とは、金属窒化物と金属微粒子が複合化しているか、高度に分散した状態にある粒子のことをいう。ここで、「複合化している」とは、金属窒化物と他の金属の両成分によって粒子が構成されていることを意味し、「高度に分散した状態」とは、金属窒化物と他の金属がそれぞれ個別で存在し、他の金属の粒子が凝集せず均一、一様に分散していることを意味する。
　金属微粒子の材料としては特に限定されず、例えば、銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウム、イリジウム、ルテニウム、オスミウム、マンガン、モリブデン、タングステン、ニオブ、タンタル、カルシウム、チタン、ビスマス、アンチモン及び鉛、並びにこれらの合金、から選ばれる少なくとも一種が挙げられる。中でも、銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウム及びイリジウム、並びにこれらの合金から選ばれる少なくとも１種が好ましく、銅、銀、金、白金及び錫、並びにこれらの合金から選ばれる少なくとも一種がより好ましい。耐湿性により優れる観点から、銀であることが好ましい。
　金属窒化物含有粒子における上記金属微粒子の含有量としては、金属窒化物含有粒子の全質量に対して５質量％以上５０質量％以下が好ましく、１０質量％以上３０質量％以下がより好ましい。 The metal nitride may be combined with other metal fine particles.
In this specification, “composite” refers to particles in which metal nitride and metal fine particles are complexed or in a highly dispersed state. Here, “composite” means that particles are composed of both components of metal nitride and other metal, and “highly dispersed state” means that metal nitride and other metal nitride This means that the metals are present individually and the other metal particles are not aggregated but are uniformly and uniformly dispersed.
The material of the metal fine particles is not particularly limited, and for example, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, titanium , Bismuth, antimony and lead, and alloys thereof. Among these, at least one selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and alloys thereof is preferable, from copper, silver, gold, platinum and tin, and alloys thereof. At least one selected is more preferable. From the viewpoint of better moisture resistance, silver is preferred.
The content of the metal fine particles in the metal nitride-containing particles is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less with respect to the total mass of the metal nitride-containing particles.
（金属窒化物含有粒子の製造方法）
　金属窒化物含有粒子の製造方法としては特に制限されず、公知の方法を使用できる。金属窒化物含有粒子の製造方法としては、例えば、気相反応法が挙げられる。気相反応法としては、電気炉法、及び、熱プラズマ法等が挙げられるが、不純物の混入が少なく、粒子径が揃いやすく、また、生産性が高い点で、熱プラズマ法が好ましい。
　熱プラズマ法において、熱プラズマを発生させる方法としては、特に制限されず、直流アーク放電、多層アーク放電、高周波（ＲＦ）プラズマ、及び、ハイブリッドプラズマ等が挙げられ、電極からの不純物の混入が少ない高周波プラズマがより好ましい。
　熱プラズマ法による金属原子の窒化物の具体的な製造方法としては、特に制限されないが、例えば、チタン窒化物の製造方法として、プラズマ炎中で四塩化チタンとアンモニアガスを反応させる方法（特開平２－２２１１０号公報）、チタン粉末を高周波熱プラズマにより蒸発させ窒素をキャリアガスとして導入し冷却過程にて窒化させ合成する方法（特開昭６１－１１１４０号公報）、及び、プラズマの周縁部にアンモニアガスを吹き込む方法（特開昭６３－８５００７号）等が挙げられる。
　ただし、金属原子の窒化物の製造方法としては、上記に制限されるものではなく、所望とする物性を有する金属原子の窒化物が得られれば、製造方法は制限されない。 (Method for producing metal nitride-containing particles)
A method for producing the metal nitride-containing particles is not particularly limited, and a known method can be used. Examples of the method for producing metal nitride-containing particles include a gas phase reaction method. Examples of 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.
In the thermal plasma method, 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.
A specific method for producing a metal atom nitride by a thermal plasma method is not particularly limited. For example, as a method for producing titanium nitride, titanium tetrachloride is reacted with ammonia gas in a plasma flame (Japanese Patent Laid-Open No. Hei. 2-22110), 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. Sho 61-11140), and at the periphery of the plasma Examples include a method of blowing ammonia gas (Japanese Patent Laid-Open No. 63-85007).
However, the method for producing a metal atom nitride is not limited to the above, and the production method is not limited as long as a metal atom nitride having desired physical properties can be obtained.
　金属窒化物含有粒子の製造に用いられる、金属原子を含有する原料（以下「金属原料」という。）は、高純度のものが好ましい。金属原料の純度としては特に制限されないが、金属原子の純度が、９９．９９質量％以上が好ましく、９９．９９９質量％以上がより好ましい。 The raw material containing metal atoms (hereinafter referred to as “metal raw material”) used for the production of metal nitride-containing particles is preferably a high-purity one. Although it does not restrict | limit especially as purity of a metal raw material, 99.99 mass% or more is preferable and the purity of a metal atom is more preferable 99.999 mass% or more.
　金属原料は、金属原子以外の原子を不純物として含有することがある（以下、「不純物原子」という。）。不純物原子としては特に制限されないが、Ｆｅ原子、及び、Ｓｉ原子等が挙げられる。
　金属原料がＳｉ原子を含有する場合には、Ｓｉ原子の含有量が、金属原料の全質量に対して、０．００２質量％を超え、０．３質量％未満が好ましく、０．０１～０．１５質量％がより好ましく、０．０２～０．１質量％が更に好ましい。Ｓｉ原子の含有量が０．００２質量％超だと、硬化膜のパターニング性がより向上する。また、Ｓｉ原子の含有量が０．３質量％未満だと、得られる金属窒化物含有粒子の最表層の極性が安定し、金属窒化物含有粒子を分散させる際、金属窒化物含有粒子への分散剤の吸着性が良化して、金属窒化物含有粒子の未分散物が低減することで、パーティクル発生を抑制する効果があると考えられる。
　また、金属窒化物含有粒子の製造に使用する金属原料中の水分は、金属原料の全質量に対して、１質量％未満が好ましく、０．１質量％未満がより好ましく、実質的に含まないことが更に好ましい。 Metal raw materials sometimes contain atoms other than metal atoms as impurities (hereinafter referred to as “impurity atoms”). Although it does not restrict | limit especially as an impurity atom, Fe atom, Si atom, etc. are mentioned.
When the metal raw material contains Si atoms, the content of Si atoms is preferably more than 0.002% by mass and less than 0.3% by mass with respect to the total mass of the metal raw material. .15% by mass is more preferable, and 0.02 to 0.1% by mass is even more preferable. When the content of Si atoms exceeds 0.002% by mass, the patterning property of the cured film is further improved. Moreover, when the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the obtained metal nitride-containing particles is stabilized, and when the metal nitride-containing particles are dispersed, It is considered that the adsorbability of the dispersing agent is improved and the non-dispersed material of the metal nitride-containing particles is reduced, thereby suppressing the generation of particles.
Further, the moisture in the metal raw material used for the production of the metal nitride-containing particles is preferably less than 1% by mass, more preferably less than 0.1% by mass, and substantially free of the total mass of the metal raw material. More preferably.
　ここで、金属窒化物含有粒子にＦｅ原子を含有させる方法としては、特に制限されず、例えば、金属原料を得る段階において、Ｆｅ原子を導入する方法等が挙げられる。より詳細には、クロール法等により金属原料を製造する際に、反応容器としてステンレス鋼（ＳＵＳ）などのＦｅ原子を含有する材料から構成されるものを用いたり、金属原料を破砕する際のプレス機及び粉砕機の材料としてＦｅ原子を含有するものを用いたりすることによって、チタン粒子の表面にＦｅ原子を付着させることができる。
　また、金属窒化物含有粒子の製造において熱プラズマ法を用いる場合には、原料である金属原子の他に、Ｆｅ粒子、Ｆｅ酸化物などの成分を添加して、これらを熱プラズマ法によって窒化することによって、金属窒化物含有粒子にＦｅ原子を含有させることができる。
　なお、金属窒化物含有粒子中に含まれているＦｅ原子は、イオン、金属化合物（錯化合物も含む）、金属間化合物、合金、酸化物、複合酸化物、窒化物、酸窒化物、硫化物、及び、酸硫化物等、いずれの形態で含まれていてもよい。また、金属窒化物含有粒子中に含有されるＦｅ原子は、結晶格子間位置の不純物として存在していてもよいし、結晶粒界にアモルファス状態で不純物として存在していてもよい。 Here, the method of causing the metal nitride-containing particles to contain Fe atoms is not particularly limited, and examples thereof include a method of introducing Fe atoms at the stage of obtaining a metal raw material. More specifically, when a metal raw material is manufactured by a crawl method or the like, a reaction vessel that is made of a material containing Fe atoms such as stainless steel (SUS) or a press for crushing the metal raw material is used. By using a material containing Fe atoms as the material of the mill and the grinder, Fe atoms can be attached to the surface of the titanium particles.
In addition, when the thermal plasma method is used in the production of metal nitride-containing particles, components such as Fe particles and Fe oxide are added in addition to the metal atoms as raw materials, and these are nitrided by the thermal plasma method. As a result, Fe atoms can be contained in the metal nitride-containing particles.
The Fe atoms contained in the metal nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, and sulfides. , And oxysulfide may be included in any form. In addition, Fe atoms contained in the metal nitride-containing particles may exist as impurities at the position of the crystal lattice, or may exist as impurities in the amorphous state at the crystal grain boundaries.
　金属窒化物含有粒子中におけるＦｅ原子の含有量は、金属窒化物含有粒子全質量に対して、０．００１質量％を超え、０．４質量％未満が好ましい。なかでも、０．０１～０．２質量％がより好ましく、０．０２～０．１質量％が更に好ましい。ここで、金属窒化物含有粒子中におけるＦｅ原子の含有量は、ＩＣＰ（Ｉｎｄｕｃｔｉｖｅｌｙ　Ｃｏｕｐｌｅｄ　Ｐｌａｓｍａ；高周波誘導結合プラズマ）発光分光分析法により測定される。 The content of Fe atoms in the metal nitride-containing particles is more than 0.001% by mass and preferably less than 0.4% by mass with respect to the total mass of the metal nitride-containing particles. Of these, 0.01 to 0.2% by mass is more preferable, and 0.02 to 0.1% by mass is even more preferable. Here, the content of Fe atoms in the metal nitride-containing particles is measured by ICP (Inductively Coupled Plasma) emission spectroscopy.
　金属窒化物含有粒子は、更にＳｉ原子（ケイ素原子）を含有することが好ましい。これにより、硬化膜のパターニング性がより向上する。Ｓｉ原子を含有することによりパターニング性が向上する理由としては、上述したＦｅ原子と同様と考えられる。
　金属窒化物含有粒子中におけるＳｉ原子の含有量は、金属窒化物含有粒子全質量に対して、０．００２質量％を超え、０．３質量％未満が好ましく、０．０１～０．１５質量％がより好ましく、０．０２～０．１質量％が更に好ましい。金属窒化物含有粒子中におけるＳｉ原子の含有量は、上述したＦｅ原子と同様の方法によって測定される。
　また、金属窒化物含有粒子にＳｉ原子を含有させる方法としては、特に限定されず、Ｆｅ原子を導入する方法として既に説明したのと同様である。 The metal nitride-containing particles preferably further contain Si atoms (silicon atoms). Thereby, the patterning property of a cured film improves more. The reason why the patterning property is improved by containing Si atoms is considered to be the same as the above-described Fe atoms.
The content of Si atoms in the metal nitride-containing particles is more than 0.002% by mass, preferably less than 0.3% by mass, and preferably 0.01 to 0.15% by mass with respect to the total mass of the metal nitride-containing particles. % Is more preferable, and 0.02 to 0.1% by mass is still more preferable. The content of Si atoms in the metal nitride-containing particles is measured by the same method as that for Fe atoms described above.
Further, the method for incorporating the Si atoms into the metal nitride-containing particles is not particularly limited, and is the same as that already described as the method for introducing Fe atoms.
〔オキシム系重合開始剤〕
　上記硬化性組成物は、オキシム系重合開始剤を含有する。オキシム系重合開始剤としては特に制限されず、公知のオキシム系重合開始剤を使用できる。
　上記硬化性組成物中におけるオキシム系重合開始剤の含有量としては特に制限されないが、硬化性組成物の全固形分に対して、一般に０．５～３０質量％が好ましく、硬化性組成物がより優れた本発明の効果を有する点で、１～２０質量％がより好ましい。
　また、上記オキシム系重合開始剤の含有量としては、既に説明した、無水物／開始剤が、所定の範囲内となるよう、調整されることが好ましい。
　なお、オキシム系重合開始剤は、１種を単独で用いても、２種以上を併用してもよい。２種以上のオキシム系重合開始剤を併用する場合には、合計含有量が上記範囲内であることが好ましい。 [Oxime polymerization initiator]
The curable composition contains an oxime polymerization initiator. The oxime polymerization initiator is not particularly limited, and a known oxime polymerization initiator can be used.
The content of the oxime polymerization initiator in the curable composition is not particularly limited, but is generally preferably 0.5 to 30% by mass with respect to the total solid content of the curable composition, and the curable composition is From the viewpoint of having the effect of the present invention more excellent, 1 to 20% by mass is more preferable.
Further, the content of the oxime polymerization initiator is preferably adjusted so that the anhydride / initiator already described is within a predetermined range.
In addition, an oxime polymerization initiator may be used individually by 1 type, or may use 2 or more types together. When two or more oxime polymerization initiators are used in combination, the total content is preferably within the above range.
　オキシム系重合開始剤の具体例としては、例えば、特開２００１－２３３８４２号公報記載の化合物、特開２０００－８００６８号公報記載の化合物、又は特開２００６－３４２１６６号公報記載の化合物を用いることができる。
　オキシム系化合物としては、例えば、３－ベンゾイロキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイロキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、及び２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オン等が挙げられる。
　また、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐｐ．１６５３－１６６０）、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年）ｐｐ．１５６－１６２、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年）ｐｐ．２０２－２３２、特開２０００－６６３８５号公報記載の化合物、特開２０００－８００６８号公報、特表２００４－５３４７９７号公報、及び特開２００６－３４２１６６号公報の各公報に記載の化合物等も挙げられる。
　市販品ではＩＲＧＡＣＵＲＥ　ＯＸＥ０１（ＢＡＳＦ社製）、ＩＲＧＡＣＵＲＥ　ＯＸＥ０２（ＢＡＳＦ社製）、ＩＲＧＡＣＵＲＥ　ＯＸＥ０３（ＢＡＳＦ社製）、又はＩＲＧＡＣＵＲＥ　ＯＸＥ０４（ＢＡＳＦ社製）も好適に用いられる。また、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ－８３１及びアデカアークルズＮＣＩ－９３０（ＡＤＥＫＡ社製）、Ｎ－１９１９（カルバゾール・オキシムエステル骨格含有光開始剤（ＡＤＥＫＡ社製）、及び、ＮＣＩ－７３０（ＡＤＥＫＡ社製）等も用いることができる。 As specific examples of the oxime polymerization initiator, for example, 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 is used. it can.
Examples of the oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane-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.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162. Examples thereof include compounds described in 202-232, JP-A No. 2000-66385, JP-A No. 2000-80068, JP-T 2004-534797, and JP-A No. 2006-342166. .
IRGACURE OXE01 (manufactured by BASF), IRGACURE OXE02 (manufactured by BASF), IRGACURE OX03 (manufactured by BASF), or IRGACURE OXE04 (manufactured by BASF) are also suitably used as commercial products. In addition, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA), N-1919 (carbazole oxime ester skeleton-containing photoinitiator) (ADEKA) and NCI-730 (ADEKA) can also be used.
　また上記記載以外のオキシム系重合開始剤として、カルバゾールＮ位にオキシムが連結した特表２００９－５１９９０４号公報に記載の化合物；ベンゾフェノン部位にヘテロ置換基が導入された米国特許第７６２６９５７号公報に記載の化合物；色素部位にニトロ基が導入された特開２０１０－１５０２５号公報及び米国特許公開２００９－２９２０３９号記載の化合物；国際公開特許２００９－１３１１８９号公報に記載のケトオキシム系化合物；トリアジン骨格とオキシム骨格を同一分子内に含有する米国特許７５５６９１０号公報に記載の化合物；４０５ｎｍに吸収極大を有しｇ線光源に対して良好な感度を有する特開２００９－２２１１１４号公報記載の化合物；等を用いてもよい。
　好ましくは、例えば、特開２０１３－２９７６０号公報の段落０２７４～０２７５を参酌することができ、この内容は本願明細書に組み込まれる。
　具体的には、オキシム系重合開始剤としては、下記式（ＯＸ－１）で表される化合物が好ましい。なお、オキシム系重合開始剤のＮ－Ｏ結合が（Ｅ）体のオキシム系化合物であっても、（Ｚ）体のオキシム系化合物であっても、（Ｅ）体と（Ｚ）体との混合物であってもよい。 Further, as oxime polymerization initiators other than those described above, compounds described in JP-T-2009-519904 in which oxime is linked to carbazole N-position; described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety; ketoxime compounds described in International Patent Publication No. 2009-131189; triazine skeleton and oxime A compound described in US Pat. No. 7,556,910 containing a skeleton in the same molecule; a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source; May be.
Preferably, for example, paragraphs 0274 to 0275 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime polymerization initiator is preferably a compound represented by the following formula (OX-1). It should be noted that even if the N—O bond of the oxime polymerization initiator is an (E) oxime compound or a (Z) oxime compound, the (E) isomer and (Z) isomer It may be a mixture.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式（ＯＸ－１）中、Ｒ及びＢは各々独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表す。
　式（ＯＸ－１）中、Ｒで表される一価の置換基としては、一価の非金属原子団であることが好ましい。
　一価の非金属原子団としては、アルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環基、アルキルチオカルボニル基、及び、アリールチオカルボニル基等が挙げられる。また、これらの基は、１以上の置換基を有していてもよい。また、前述した置換基は、更に他の置換基で置換されていてもよい。
　置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基又はアリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、及び、アリール基等が挙げられる。
　式（ＯＸ－１）中、Ｂで表される一価の置換基としては、アリール基、複素環基、アリールカルボニル基、又は、複素環カルボニル基が好ましい。これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
　式（ＯＸ－１）中、Ａで表される二価の有機基としては、炭素数１～１２のアルキレン基、シクロアルキレン基、又は、アルキニレン基が好ましい。これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。 In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of 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. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent 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.
In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In the formula (OX-1), 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.
　光重合開始剤として、フッ素原子を含有するオキシム系化合物も使用できる。フッ素原子を含有するオキシム系化合物の具体例としては、特開２０１０－２６２０２８号公報記載の化合物；特表２０１４－５００８５２号公報記載の化合物２４、３６～４０；特開２０１３－１６４４７１号公報記載の化合物（Ｃ－３）；等が挙げられる。この内容は本明細書に組み込まれる。 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 Compound (C-3); and the like. This content is incorporated herein.
　光重合開始剤として、下記式（１）～（４）で表される化合物も使用できる。 As the photopolymerization initiator, compounds represented by the following formulas (1) to (4) can also be used.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　式（１）において、Ｒ１及びＲ２は、それぞれ独立に、炭素数１～２０のアルキル基、炭素数４～２０の脂環式炭化水素基、炭素数６～３０のアリール基、又は、炭素数７～３０のアリールアルキル基を表し、Ｒ１及びＲ２がフェニル基の場合、フェニル基同士が結合してフルオレン基を形成してもよく、Ｒ３及びＲ４は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数４～２０の複素環基を表し、Ｘは、単結合（直接結合）又はカルボニル基を示す。 In Formula (1), 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 single bond (directly Bond) or a carbonyl group.
　式（２）において、Ｒ１、Ｒ２、Ｒ３及びＲ４は、式（１）におけるＲ１、Ｒ２、Ｒ３及びＲ４と同義であり、Ｒ５は、－Ｒ６、－ＯＲ６、－ＳＲ６、－ＣＯＲ６、－ＣＯＮＲ６Ｒ６、－ＮＲ６ＣＯＲ６、－ＯＣＯＲ６、－ＣＯＯＲ６、－ＳＣＯＲ６、－ＯＣＳＲ６、－ＣＯＳＲ６、－ＣＳＯＲ６、－ＣＮ、ハロゲン原子又は水酸基を表し、Ｒ６は、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数４～２０の複素環基を表し、Ｘは、単結合又はカルボニル基を表し、ａは０～４の整数を表す。 In the formula (2), R 1, R 2, R 3 and R 4 have the same meanings as R 1, R 2, R 3 and R 4 in Formula (1), R 5 is -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 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 single bond or a carbonyl group, and a represents an integer of 0 to 4.
　式（３）において、Ｒ１は、炭素数１～２０のアルキル基、炭素数４～２０の脂環式炭化水素基、炭素数６～３０のアリール基、又は、炭素数７～３０のアリールアルキル基を表し、Ｒ３及びＲ４は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数４～２０の複素環基を表し、Ｘは、単結合又はカルボニル基を示す。 In Formula (3), R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an 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 number of 4 Represents a heterocyclic group of ˜20, and X represents a single bond or a carbonyl group.
　式（４）において、Ｒ１、Ｒ３及びＲ４は、式（３）におけるＲ１、Ｒ３及びＲ４と同義であり、Ｒ５は、－Ｒ６、－ＯＲ６、－ＳＲ６、－ＣＯＲ６、－ＣＯＮＲ６Ｒ６、－ＮＲ６ＣＯＲ６、－ＯＣＯＲ６、－ＣＯＯＲ６、－ＳＣＯＲ６、－ＯＣＳＲ６、－ＣＯＳＲ６、－ＣＳＯＲ６、－ＣＮ、ハロゲン原子又は水酸基を表し、Ｒ６は、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数４～２０の複素環基を表し、Ｘは、単結合又はカルボニル基を表し、ａは０～４の整数を表す。 In the formula (4), R 1, R 3 and R 4 have the same meanings as R 1, R 3 and R 4 in the formula (3), R 5 is, -R 6, -OR 6, -SR 6, Represents —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 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, and X represents a single bond or Represents a carbonyl group, and a represents an integer of 0 to 4.
　上記式（１）及び式（２）において、Ｒ１及びＲ２は、それぞれ独立に、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、シクロヘキシル基又はフェニル基が好ましい。Ｒ３はメチル基、エチル基、フェニル基、トリル基又はキシリル基が好ましい。Ｒ４は炭素数１～６のアルキル基又はフェニル基が好ましい。Ｒ５はメチル基、エチル基、フェニル基、トリル基又はナフチル基が好ましい。Ｘは単結合が好ましい。
　また、上記式（３）及び（４）において、Ｒ１は、それぞれ独立に、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、シクロヘキシル基又はフェニル基が好ましい。Ｒ３はメチル基、エチル基、フェニル基、トリル基又はキシリル基が好ましい。Ｒ４は炭素数１～６のアルキル基又はフェニル基が好ましい。Ｒ５はメチル基、エチル基、フェニル基、トリル基又はナフチル基が好ましい。Ｘは単結合が好ましい。
　式（１）及び式（２）で表される化合物の具体例としては、例えば、特開２０１４－１３７４６６号公報の段落番号００７６～００７９に記載された化合物が挙げられる。この内容は本明細書に組み込まれることとする。 In the above formulas (1) and (2), R 1 and R 2 are preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or 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 single bond.
In the above formulas (3) and (4), R 1 is preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or 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 single bond.
Specific examples of the compounds represented by the formulas (1) and (2) include compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466, for example. This content is incorporated herein.
　オキシム系重合開始剤としては、より優れた本発明の効果を有する硬化性組成物が得られる点で、ニトロ基を含有することが好ましい。
　オキシム系化合物が含有するニトロ基の数としては、特に制限されないが、１～４個が好ましく、１個、又は、２個が好ましい。
　ニトロ基を含有するオキシム系重合開始剤の具体例としては、例えば、以下の構造を有する、ＮＣＩ－８３１（商品名、ＡＤＥＫＡ社製）等が挙げられる。 The oxime-based polymerization initiator preferably contains a nitro group in that a curable composition having a more excellent effect of the present invention can be obtained.
The number of nitro groups contained in the oxime compound is not particularly limited, but is preferably 1 to 4, and preferably 1 or 2.
Specific examples of the oxime polymerization initiator containing a nitro group include, for example, NCI-831 (trade name, manufactured by ADEKA) having the following structure.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　以下にオキシム系重合開始剤の具体例を示す。 Specific examples of the oxime polymerization initiator are shown below.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-I000011
　オキシム系重合開始剤は、３５０～５００ｎｍの波長領域に極大吸収波長を有するものが好ましく、３６０～４８０ｎｍの波長領域に極大吸収波長を有するものがより好ましく、３６５ｎｍ及び４０５ｎｍの吸光度が高いものが更に好ましい。
　オキシム系重合開始剤化合物の３６５ｎｍ又は４０５ｎｍにおけるモル吸光係数は、感度の観点から、１，０００～３００，０００であることが好ましく、２，０００～３００，０００であることがより好ましく、５，０００～２００，０００であることが更に好ましい。
　化合物のモル吸光係数は、公知の方法を用いることができるが、例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 The oxime polymerization initiator preferably has a maximum absorption wavelength in the wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 to 480 nm, and further has a high absorbance at 365 nm and 405 nm. preferable.
The molar extinction coefficient at 365 nm or 405 nm of the oxime polymerization initiator compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, from the viewpoint of sensitivity. More preferably, it is from 000 to 200,000.
For the molar extinction coefficient of the compound, a known method can be used. It is preferable to measure.
　光重合開始剤は、２官能又は３官能以上の化合物を使用してもよい。そのような化合物の具体例としては、特表２０１０－５２７３３９号公報、特表２０１１－５２４４３６号公報、国際公開第２０１５／００４５６５号、特表２０１６－５３２６７５号公報の０４１７～０４１２段落、国際公開第２０１７／０３３６８０号の００３９～００５５段落に記載されたオキシム化合物の２量体、特表２０１３－５２２４４５号公報に記載された化合物（Ｅ）及び（Ｇ）、並びに、国際公開第２０１６／０３４９６３号に記載されているＣｍｐｄ１～７が挙げられる。 The photopolymerization initiator may be a bifunctional or trifunctional or higher compound. Specific examples of such compounds include JP 2010-527339 A, JP 2011-524436 A, International Publication No. 2015/004565, Japanese Patent Publication No. 2016-532675, paragraphs 0417 to 0412, International Publication No. Dimers of oxime compounds described in paragraphs 0039 to 0055 of No. 2017/033680, compounds (E) and (G) described in JP 2013-522445 A, and International Publication No. 2016/034963 Examples of Cmpd 1 to 7 are described.
〔重合性化合物〕
　上記硬化性組成物は、重合性化合物を含有する。本明細書において重合性化合物とは、重合性基を含有する化合物を意図し、無水物とは異なる化合物を意図する。
　硬化性組成物中における重合性化合物の含有量としては特に制限されないが、硬化性組成物の全固形分に対して５～３０質量％が好ましく、１０～２５質量％がより好ましい。
　重合性化合物は１種を単独で用いても、２種以上を併用してもよい。２種以上の重合性化合物を併用する場合には、合計含有量が上記範囲内であることが好ましい。 (Polymerizable compound)
The curable composition contains a polymerizable compound. In the present specification, the polymerizable compound means a compound containing a polymerizable group and a compound different from the anhydride.
The content of the polymerizable compound in the curable composition is not particularly limited, but is preferably 5 to 30% by mass and more preferably 10 to 25% by mass with respect to the total solid content of the curable composition.
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.
　重合性化合物は、エチレン性不飽和結合を含有する基を１個以上含有する化合物が好ましく、２個以上含有する化合物がより好ましく、３個以上含有する化合物が更に好ましく、５個以上含有する化合物が特に好ましい。上限は、例えば、１５個以下が好ましい。エチレン性不飽和結合を含有する基としては、例えば、ビニル基、（メタ）アリル基、及び、（メタ）アクリロイル基等が挙げられる。 The polymerizable compound is preferably a compound containing one or more groups containing an ethylenically unsaturated bond, more preferably a compound containing 2 or more, still more preferably a compound containing 3 or more, and a compound containing 5 or more Is particularly preferred. For example, the upper limit is preferably 15 or less. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
　重合性化合物としては、例えば、特開２００８－２６０９２７号公報の００５０段落、及び、特開２０１５－６８８９３号公報の００４０段落に記載されている化合物が使用でき、上記の内容は本明細書に組み込まれる。 As the polymerizable compound, for example, compounds described in paragraph 0050 of JP-A-2008-260927 and paragraph 0040 of JP-A-2015-68893 can be used, and the above contents are incorporated in this specification. It is.
　重合性化合物は、例えば、モノマー、プレポリマー、オリゴマー、及び、これらの混合物、並びに、これらの多量体等の化学的形態のいずれであってもよい。
　重合性化合物は、３～１５官能の（メタ）アクリレート化合物であることが好ましく、３～６官能の（メタ）アクリレート化合物であることがより好ましい。 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.
　重合性化合物は、エチレン性不飽和結合を含有する基を１個以上含有する、常圧下で１００℃以上の沸点を持つ化合物も好ましい。例えば、特開２０１３－２９７６０号公報の段落０２２７、特開２００８－２９２９７０号公報の段落０２５４～０２５７に記載の化合物を参酌でき、この内容は本願明細書に組み込まれる。 The polymerizable compound is also preferably a compound having one or more groups containing an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure. For example, compounds described in JP-A-2013-29760, paragraph 0227, and JP-A-2008-292970, paragraphs 0254 to 0257 can be referred to, and the contents thereof are incorporated herein.
　重合性化合物は、ジペンタエリスリトールトリアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬社製）、ジペンタエリスリトールテトラアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬社製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬社製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬社製、Ａ－ＤＰＨ－１２Ｅ；新中村化学社製）、及びこれらの（メタ）アクリロイル基がエチレングリコール残基又はプロピレングリコール残基を介している構造（例えば、サートマー社から市販されている、ＳＲ４５４、ＳＲ４９９）が好ましい。これらのオリゴマータイプも使用できる。また、ＮＫエステルＡ－ＴＭＭＴ（ペンタエリスリトールテトラアクリレート、新中村化学社製）、及び、ＫＡＹＡＲＡＤ　ＲＰ－１０４０（日本化薬社製）等も使用できる。
　以下に好ましい重合性化合物の形態を示す。 Polymerizable compounds are 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 (KAYARAD D-310 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA as a commercial product; 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). These oligomer types can also be used. Further, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can also be used.
The preferable form of the polymerizable compound is shown below.
　重合性化合物は、カルボン酸基、スルホン酸基、及び、リン酸基等の酸基を有してもよい。酸基を含有する重合性化合物としては、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルが好ましく、脂肪族ポリヒドロキシ化合物の未反応の水酸基に非芳香族カルボン酸無水物を反応させて酸基を持たせた重合性化合物がより好ましく、更に好ましくは、このエステルにおいて、脂肪族ポリヒドロキシ化合物がペンタエリスリトール及び／又はジペンタエリスリトールであるものである。市販品としては、例えば、東亜合成社製の、アロニックスＴＯ－２３４９、Ｍ－３０５、Ｍ－５１０、及び、Ｍ－５２０等が挙げられる。 The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. As the polymerizable compound containing an 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 pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toa Gosei Co., Ltd.
　酸基を含有する重合性化合物の好ましい酸価としては、０．１～４０ｍｇＫＯＨ／ｇであり、より好ましくは５～３０ｍｇＫＯＨ／ｇである。重合性化合物の酸価が０．１ｍｇＫＯＨ／ｇ以上であれば、現像溶解特性が良好であり、４０ｍｇＫＯＨ／ｇ以下であれば、製造及び／又は取扱い上、有利である。更には、光重合性能が良好で、硬化性に優れる。 The preferred acid value of the polymerizable compound containing an acid group is 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. When 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.
　重合性化合物は、カプロラクトン構造を含有する化合物も好ましい。
　カプロラクトン構造を含有する化合物としては、分子内にカプロラクトン構造を含有する限り特に制限されないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、トリメチロールメラミン等の多価アルコールと、（メタ）アクリル酸及びε－カプロラクトンとをエステル化することにより得られる、ε－カプロラクトン変性多官能（メタ）アクリレートが挙げられる。なかでも下記式（Ｚ－１）で表されるカプロラクトン構造を含有する化合物が好ましい。 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. Examples include ε-caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as erythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone. Of these, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　式（Ｚ－１）中、６個のＲは全てが下記式（Ｚ－２）で表される基であるか、又は６個のＲのうち１～５個が下記式（Ｚ－２）で表される基であり、残余が下記式（Ｚ－３）で表される基である。 In the formula (Z-1), all six R are groups represented by the following formula (Z-2), or 1 to 5 of the six R are represented by the following formula (Z-2) And the remainder is a group represented by the following formula (Z-3).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式（Ｚ－２）中、Ｒ１は水素原子又はメチル基を示し、ｍは１又は２の数を示し、「＊」は結合手を示す。 In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　式（Ｚ－３）中、Ｒ１は水素原子又はメチル基を示し、「＊」は結合手を示す。 In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
　カプロラクトン構造を含有する重合性化合物は、例えば、日本化薬からＫＡＹＡＲＡＤ　ＤＰＣＡシリーズとして市販されており、ＤＰＣＡ－２０（上記式（Ｚ－１）～（Ｚ－３）においてｍ＝１、式（Ｚ－２）で表される基の数＝２、Ｒ１が全て水素原子である化合物）、ＤＰＣＡ－３０（同式、ｍ＝１、式（Ｚ－２）で表される基の数＝３、Ｒ１が全て水素原子である化合物）、ＤＰＣＡ－６０（同式、ｍ＝１、式（Ｚ－２）で表される基の数＝６、Ｒ１が全て水素原子である化合物）、ＤＰＣＡ－１２０（同式においてｍ＝２、式（Ｚ－２）で表される基の数＝６、Ｒ１が全て水素原子である化合物）等が挙げられる。 Polymerizable compounds containing a caprolactone structure are commercially available, for example, from Nippon Kayaku as the KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3), -2) = the number of groups represented by 2 and R 1 is all hydrogen atoms), DPCA-30 (formula, m = 1, the number of groups represented by formula (Z-2) = 3) , Compounds in which R 1 is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, compounds in which R 1 is all hydrogen atoms), DPCA-120 (a compound in which m = 2 in the formula, the number of groups represented by formula (Z-2) = 6, and all R 1 are hydrogen atoms).
　重合性化合物は、下記式（Ｚ－４）又は（Ｚ－５）で表される化合物も使用できる。 As the polymerizable compound, a compound represented by the following formula (Z-4) or (Z-5) can also be used.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式（Ｚ－４）及び（Ｚ－５）中、Ｅは、各々独立に、－（（ＣＨ２）ｙＣＨ２Ｏ）－、又は（（ＣＨ２）ｙＣＨ（ＣＨ３）Ｏ）－を表し、ｙは、各々独立に０～１０の整数を表し、Ｘは、各々独立に、（メタ）アクリロイル基、水素原子、又はカルボン酸基を表す。
　式（Ｚ－４）中、（メタ）アクリロイル基の合計は３個又は４個であり、ｍは各々独立に０～１０の整数を表し、各ｍの合計は０～４０の整数である。
　式（Ｚ－５）中、（メタ）アクリロイル基の合計は５個又は６個であり、ｎは各々独立に０～１０の整数を表し、各ｎの合計は０～６０の整数である。 In formulas (Z-4) and (Z-5), each E independently represents — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) —. Y represents an integer of 0 to 10, and X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
In the formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.
In formula (Z-5), 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.
　式（Ｚ－４）中、ｍは、０～６の整数が好ましく、０～４の整数がより好ましい。
　また、各ｍの合計は、２～４０の整数が好ましく、２～１６の整数がより好ましく、４～８の整数が更に好ましい。
　式（Ｚ－５）中、ｎは、０～６の整数が好ましく、０～４の整数がより好ましい。
　また、各ｎの合計は、３～６０の整数が好ましく、３～２４の整数がより好ましく、６～１２の整数が更に好ましい。
　また、式（Ｚ－４）又は式（Ｚ－５）中の－（（ＣＨ２）ｙＣＨ２Ｏ）－又は（（ＣＨ２）ｙＣＨ（ＣＨ３）Ｏ）－は、酸素原子側の末端がＸに結合する形態が好ましい。 In the formula (Z-4), 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.
In the formula (Z-5), 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.
In formula (Z-4) or formula (Z-5), — ((CH 2 ) y CH 2 O) — or ((CH 2 ) y CH (CH 3 ) O) — A form in which the terminal is bonded to X is preferred.
　式（Ｚ－４）又は式（Ｚ－５）で表される化合物は１種単独で用いてもよいし、２種以上併用してもよい。特に、式（Ｚ－５）において、６個のＸ全てがアクリロイル基である形態、式（Ｚ－５）において、６個のＸ全てがアクリロイル基である化合物と、６個のＸのうち、少なくとも１個が水素原子ある化合物との混合物である形態が好ましい。このような構成とすることにより、現像性をより向上できる。 The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in formula (Z-5), all six Xs are acryloyl groups, in formula (Z-5), all six Xs are acryloyl groups, and among six Xs, A form that is a mixture with a compound having at least one hydrogen atom is preferred. With such a configuration, the developability can be further improved.
　また、式（Ｚ－４）又は式（Ｚ－５）で表される化合物の重合性化合物中における全含有量としては、２０質量％以上が好ましく、５０質量％以上がより好ましい。
　式（Ｚ－４）又は式（Ｚ－５）で表される化合物の中でも、ペンタエリスリトール誘導体及び／又はジペンタエリスリトール誘導体がより好ましい。 Further, 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.
Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
　また、重合性化合物は、カルド骨格を含有してもよい。
　カルド骨格を含有する重合性化合物としては、９，９－ビスアリールフルオレン骨格を含有する重合性化合物が好ましい。
　カルド骨格を含有する重合性化合物としては、限定されないが、例えば、オンコートＥＸシリーズ（長瀬産業社製）及びオグソール（大阪ガスケミカル社製）等が挙げられる。 The polymerizable compound may contain a cardo skeleton.
As the polymerizable compound containing 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.).
〔任意成分〕
　上記硬化性組成物は、上記以外の任意成分を含有していてもよい。任意成分としては、例えば、脱水剤、重合禁止剤、アルカリ可溶性樹脂、分散剤、溶剤、シランカップリング剤、紫外線吸収剤、界面活性剤、密着性改良剤、及び、着色剤等が挙げられる。なお、着色剤とは、金属窒化物含有粒子以外の着色剤を意味する。以下では、各成分について詳述する。 [Optional ingredients]
The curable composition may contain an optional component other than the above. Examples of the optional component include a dehydrating agent, a polymerization inhibitor, an alkali-soluble resin, a dispersant, a solvent, a silane coupling agent, an ultraviolet absorber, a surfactant, an adhesion improver, and a colorant. The colorant means a colorant other than the metal nitride-containing particles. Below, each component is explained in full detail.
＜脱水剤＞
　上記硬化性組成物は、脱水剤を含有してもよい。本明細書において、脱水剤とは酸無水物とは異なる化合物を意図する。
　脱水剤としては特に制限されず、公知の脱水剤を用いることができる。なかでも、脱水剤としてはオルトエステル化合物がより好ましい。オルトエステル化合物としては特に制限されないが、例えば、特表第２０１２－５２４７５９号公報の００３９段落、及び、００４０段落に記載の化合物が挙げられる。
　硬化性組成物中における脱水剤の含有量としては特に制限されないが、一般に硬化性組成物中の全固形分に対して０．０１～５質量％が好ましい。 <Dehydrating agent>
The curable composition may contain a dehydrating agent. In this specification, a dehydrating agent intends a compound different from an acid anhydride.
It does not restrict | limit especially as a dehydrating agent, A well-known dehydrating agent can be used. Of these, orthoester compounds are more preferred as the dehydrating agent. The orthoester compound is not particularly limited, and examples thereof include compounds described in paragraphs 0039 and 0040 of JP-A-2012-524759.
The content of the dehydrating agent in the curable composition is not particularly limited, but is generally preferably 0.01 to 5% by mass with respect to the total solid content in the curable composition.
＜重合禁止剤＞
　上記硬化性組成物は、重合禁止剤を含有することが好ましい。重合禁止剤を含有する硬化性組成物は、より優れた保存安定性を有し、かつ、未露光部における残渣の発生がより抑制される。なお、本明細書において硬化性組成物の保存安定性とは、実施例に記載した方法により評価できる保存安定性を意味する。
　重合禁止剤としては特に制限されず、公知の重合禁止剤を使用できる。
　硬化性組成物中における重合禁止剤の含有量としては特に制限されないが、一般に硬化性組成物の全固形分に対して０．１～５質量％が好ましい。
　なお、重合禁止剤は、１種を単独で用いても、２種以上を併用してもよい。２種以上の重合禁止剤を併用する場合には、合計含有量が上記範囲内であることが好ましい。 <Polymerization inhibitor>
The curable composition preferably contains a polymerization inhibitor. The curable composition containing a polymerization inhibitor has better storage stability, and the generation of residues in unexposed areas is further suppressed. In addition, the storage stability of a curable composition in this specification means the storage stability which can be evaluated by the method described in the Example.
It does not restrict | limit especially as a polymerization inhibitor, A well-known polymerization inhibitor can be used.
The content of the polymerization inhibitor in the curable composition is not particularly limited, but is generally preferably 0.1 to 5% by mass with respect to the total solid content of the curable composition.
In addition, 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.
　重合禁止剤としては、特に制限されず、重合禁止剤として用いられる公知の化合物を使用できる。重合禁止剤として用いられる化合物としては、例えば、フェノール系化合物、キノン系化合物、ヒンダードアミン系化合物、フェノチアジン系化合物、及び、ニトロベンゼン系化合物等が挙げられる。 The polymerization inhibitor is not particularly limited, and a known compound used as a polymerization inhibitor can be used. Examples of the compound used as a polymerization inhibitor include phenolic compounds, quinone compounds, hindered amine compounds, phenothiazine compounds, and nitrobenzene compounds.
　上記フェノール系化合物としては、例えば、フェノール、４－メトキシフェノール、ヒドロキノン、２－ｔｅｒｔ－ブチルヒドロキノン、カテコール、４－ｔｅｒｔ－ブチル－カテコール、２，６－ジ－ｔｅｒｔ－ブチルフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－エチルフェノール、４－ヒドロキシメチル－２，６－ジ－ｔｅｒｔ－ブチルフェノール、ペンタエリスリトールテトラキス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシヒドロシンナメート）、４－メトキシ－１－ナフトール、及び１，４－ジヒドロキシナフタレン等が挙げられる。 Examples of the phenol compound include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, 2,6-di-tert-butylphenol, 2,6-diphenol. -Tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, pentaerythritol tetrakis (3,5-di- tert-butyl-4-hydroxyhydrocinnamate), 4-methoxy-1-naphthol, 1,4-dihydroxynaphthalene and the like.
　フェノール系化合物としては、式（ＩＨ－１）で示されるフェノール系化合物が好ましい。 As the phenolic compound, a phenolic compound represented by the formula (IH-1) is preferable.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　式（ＩＨ－１）中、Ｒ１～Ｒ５は、それぞれ独立して、水素原子、アルキル基、アルケニル基、水酸基、アミノ基、アリール基、アルコキシ基、カルボン酸基、アルコキシカルボニル基、又はアシル基を表す。Ｒ１～Ｒ５はそれぞれ連結して環を形成してもよい。 In formula (IH-1), R 1 to R 5 are each independently a hydrogen atom, alkyl group, alkenyl group, hydroxyl group, amino group, aryl group, alkoxy group, carboxylic acid group, alkoxycarbonyl group, or acyl. Represents a group. R 1 to R 5 may be connected to each other to form a ring.
　式（ＩＨ－１）中のＲ１～Ｒ５としては、水素原子、炭素数１～５のアルキル基（例えば、メチル基及びエチル基等）、炭素数１～５のアルコキシ基（例えば、メトキシ基及びエトキシ基等）、炭素数２～４のアルケニル基（例えば、ビニル基等）、又はフェニル基が好ましい。
　なかでも、Ｒ１及びＲ５はそれぞれ独立して、水素原子又はｔｅｒｔ－ブチル基がより好ましく、Ｒ２及びＲ４は水素原子がより好ましく、Ｒ３は水素原子、炭素数１～５のアルキル基又は炭素数１～５のアルコキシ基がより好ましい。 R 1 to R 5 in formula (IH-1) are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group or an ethyl group), or an alkoxy group having 1 to 5 carbon atoms (eg, methoxy A alkenyl group having 2 to 4 carbon atoms (for example, a vinyl group), or a phenyl group.
Among them, R 1 and R 5 are each independently more preferably a hydrogen atom or a tert-butyl group, R 2 and R 4 are more preferably a hydrogen atom, R 3 is a hydrogen atom, and an alkyl having 1 to 5 carbon atoms. A group or an alkoxy group having 1 to 5 carbon atoms is more preferable.
　上記キノン系化合物としては、例えば、１，４－ベンゾキノン、１，２－ベンゾキノン、及び１，４－ナフトキノン等が挙げられる。 Examples of the quinone compound include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.
　ヒンダードアミン系化合物としては、例えば、下記式（ＩＨ－２）で表わされる重合禁止剤が挙げられる。 Examples of the hindered amine compound include a polymerization inhibitor represented by the following formula (IH-2).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　式（ＩＨ－２）中のＲ６は、水素原子、水酸基、アミノ基、アルコキシ基、アルコキシカルボニル基、又はアシル基を表す。なかでも、水素原子又は水酸基が好ましく、水酸基がより好ましい。
　また、式（ＩＨ－２）中のＲ７～Ｒ１０は、それぞれ独立して、水素原子又はアルキル基を表す。Ｒ７～Ｒ１０が表すアルキル基としては、炭素数１～５のアルキル基が好ましく、メチル基又はエチル基がより好ましい。 R 6 in formula (IH-2) represents a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. Of these, a hydrogen atom or a hydroxyl group is preferable, and a hydroxyl group is more preferable.
In the formula (IH-2), R 7 to R 10 each independently represents a hydrogen atom or an alkyl group. The alkyl group represented by R 7 to R 10 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.
＜アルカリ可溶性樹脂＞
　硬化性組成物はアルカリ可溶性樹脂を含有することが好ましい。本明細書において、アルカリ可溶性樹脂とは、アルカリ可溶性を促進する基（アルカリ可溶性基）を含有する樹脂を意味する。
　硬化性組成物中におけるアルカリ可溶性樹脂の含有量としては特に制限されないが、一般に硬化性組成物の全固形分に対して、０．１～４０質量％が好ましく、硬化性組成物がより優れた本発明の効果を有する点で、１～２０質量％がより好ましい。
　アルカリ可溶性樹脂は１種を単独で用いても、２種以上を併用してもよい。２種以上のアルカリ可溶性樹脂を併用する場合には、合計含有量が上記範囲内であることが好ましい。 <Alkali-soluble resin>
The curable composition preferably contains an alkali-soluble resin. In the present specification, the alkali-soluble resin means a resin containing a group that promotes alkali solubility (alkali-soluble group).
The content of the alkali-soluble resin in the curable composition is not particularly limited, but is generally preferably 0.1 to 40% by mass with respect to the total solid content of the curable composition, and the curable composition is more excellent. In view of having the effect of the present invention, 1 to 20% by mass is more preferable.
Alkali-soluble resin may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of alkali-soluble resin together, it is preferable that total content is in the said range.
　アルカリ可溶性樹脂としては、分子中に少なくとも１つのアルカリ可溶性基を含有する樹脂が挙げられ、例えば、ポリヒドロキシスチレン樹脂、ポリシロキサン樹脂、（メタ）アクリル樹脂、（メタ）アクリルアミド樹脂、（メタ）アクリル／（メタ）アクリルアミド共重合体樹脂、エポキシ系樹脂、及び、ポリイミド樹脂等が挙げられる。 Examples of the alkali-soluble resin include resins containing at least one alkali-soluble group in the molecule, such as polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, and (meth) acrylic. / (Meth) acrylamide copolymer resin, epoxy resin, polyimide resin and the like.
　アルカリ可溶性樹脂の具体例としては、不飽和カルボン酸とエチレン性不飽和化合物の共重合体が挙げられる。
　不飽和カルボン酸としては特に制限されないが、（メタ）アクリル酸、クロトン酸、及び、ビニル酢酸等のモノカルボン酸類；イタコン酸、マレイン酸、及び、フマル酸等などのジカルボン酸、又は、その酸無水物；フタル酸モノ（２－（メタ）アクリロイロキシエチル）等の多価カルボン酸モノエステル類；等が挙げられる。 Specific examples of the alkali-soluble resin include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound.
Although it does not restrict | limit especially as unsaturated carboxylic acid, Monocarboxylic acids, such as (meth) acrylic acid, crotonic acid, and vinyl acetic acid; Dicarboxylic acids, such as itaconic acid, maleic acid, and fumaric acid, or its acid Anhydrides; polyvalent carboxylic acid monoesters such as mono (2- (meth) acryloyloxyethyl) phthalate; and the like.
　共重合可能なエチレン性不飽和化合物としては、（メタ）アクリル酸メチル等が挙げられる。また、特開２０１０－９７２１０号公報の００２７段落、及び、特開２０１５－６８８９３号公報の００３６～００３７段落に記載の化合物も使用でき、上記の内容は本明細書に組み込まれる。 Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate. In addition, compounds described in paragraph 0027 of JP 2010-97210 A and paragraphs 0036 to 0037 of JP 2015-68893 A can also be used, and the above contents are incorporated herein.
　また、共重合可能なエチレン性不飽和化合物であって、側鎖にエチレン性不飽和基を含有する化合物を組み合わせて用いてもよい。エチレン性不飽和基としては、（メタ）アクリル酸基が好ましい。側鎖にエチレン性不飽和基を有するアクリル樹脂は、例えば、カルボン酸基を含有するアクリル樹脂のカルボン酸基に、グリシジル基又は脂環式エポキシ基を含有するエチレン性不飽和化合物を付加反応させても得られる。 Also, a copolymerizable ethylenically unsaturated compound that contains an ethylenically unsaturated group in the side chain may be used in combination. As the ethylenically unsaturated group, a (meth) acrylic acid group is preferable. An acrylic resin having an ethylenically unsaturated group in the side chain is obtained by, for example, adding an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to a carboxylic acid group of an acrylic resin containing a carboxylic acid group. Can also be obtained.
　アルカリ可溶性樹脂としては、例えば、特開昭５９－４４６１５号、特公昭５４－３４３２７号、特公昭５８－１２５７７号、特公昭５４－２５９５７号、特開昭５４－９２７２３号、特開昭５９－５３８３６号、及び、特開昭５９－７１０４８号に記載されている側鎖にカルボン酸基を含有するラジカル重合体；欧州特許第９９３９６６号、欧州特許第１２０４０００号、及び、特開２００１－３１８４６３号等の各公報に記載されているアルカリ可溶性基を含有するアセタール変性ポリビニルアルコール系バインダー樹脂；ポリビニルピロリドン；ポリエチレンオキサイド；アルコール可溶性ナイロン、及び、２，２－ビス－（４－ヒドロキシフェニル）－プロパンとエピクロロヒドリンとの反応物であるポリエーテル等；国際公開第２００８／１２３０９７号に記載のポリイミド樹脂；等を使用できる。 Examples of the alkali-soluble resin include JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-54-92723, JP-A-59-. Radical polymers containing a carboxylic acid group in the side chain described in JP-A No. 53836 and JP-A-59-71048; European Patent No. 993966, European Patent No. 1204000, and JP-A No. 2001-318463 An acetal-modified polyvinyl alcohol binder resin containing an alkali-soluble group described in each of the above publications; polyvinyl pyrrolidone; polyethylene oxide; alcohol-soluble nylon; and 2,2-bis- (4-hydroxyphenyl) -propane Polyether, etc., which is a reaction product with epichlorohydrin; International Publication No. It can be used, and the like; polyimide resin described in JP 008/123097.
　アルカリ可溶性樹脂としては、例えば、特開２０１６－７５８４５号公報の０２２５～０２４５段落に記載の化合物を使用でき、上記内容は本明細書に組み込まれる。 As the alkali-soluble resin, for example, compounds described in paragraphs 0225 to 0245 of JP-A-2016-75845 can be used, and the above contents are incorporated herein.
　アルカリ可溶性樹脂としては、ポリイミド前駆体も使用できる。ポリイミド前駆体は、一般に、酸無水物基を含有する化合物とジアミン化合物とを４０～１００℃下において付加重合反応することにより得られる樹脂であり、上記酸無水物とは異なる化合物を意味する。
　ポリイミド前駆体としては、例えば、式（１）で表される繰り返し単位を含有する樹脂が挙げられる。ポリイミド前駆体の構造としては、例えば、下記式（２）で示されるアミック酸構造と、アミック酸構造が一部イミド閉環してなる下記式（３）、及び／又は、全てイミド閉環した下記式（４）で示されるイミド構造を含有するものが挙げられる。 A polyimide precursor can also be used as the alkali-soluble resin. The polyimide precursor is generally a resin obtained by subjecting a compound containing an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100 ° C., and means a compound different from the above acid anhydride.
As a polyimide precursor, resin containing the repeating unit represented by Formula (1) is mentioned, for example. Examples of the structure of the polyimide precursor include an amic acid structure represented by the following formula (2), the following formula (3) in which the amic acid structure is partially imide ring-closed, and / or the following formula in which all imide rings are closed: The thing containing the imide structure shown by (4) is mentioned.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　上記式（１）～（４）において、Ｒ１は炭素数２～２２の４価の有機基を表し、Ｒ２は炭素数１～２２の２価の有機基を表し、ｎは１又は２を表す。 In the above formulas (1) to (4), R 1 represents a tetravalent organic group having 2 to 22 carbon atoms, R 2 represents a divalent organic group having 1 to 22 carbon atoms, and n is 1 or 2 Represents.
　上記ポリイミド前駆体の具体例としては、例えば、特開２００８－１０６２５０号公報の００１１～００３１段落に記載の化合物、特開２０１６－１２２１０１号公報の００２２～００３９段落に記載の化合物、及び、特開２０１６－６８４０１号公報の００６１～００９２段落に記載の化合物等が挙げられ、上記の内容は本明細書に組み込まれる。 Specific examples of the polyimide precursor include, for example, compounds described in paragraphs 0011 to 0031 of JP-A-2008-106250, compounds described in paragraphs 0022 to 0039 of JP-A-2016-122101, and JP-A Examples include the compounds described in paragraphs 0061 to 0092 of JP-A-2016-68401, and the above contents are incorporated herein.
　アルカリ可溶性樹脂は、硬化性組成物を用いて得られるパターン状の硬化膜のパターン形状がより優れる点で、ポリイミド前駆体、及び、ポリイミド樹脂からなる群から選択される少なくとも１種を含有することが好ましい。
　アルカリ可溶性基を含有するポリイミド樹脂としては、特に制限されず、公知のアルカリ可溶性基を含有するポリイミド樹脂を用いることができる。上記ポリイミド樹脂としては、例えば、特開２０１４－１３７５２３号公報の００５０段落に記載された樹脂、特開２０１５－１８７６７６号公報の００５８段落に記載された樹脂、及び、特開２０１４－１０６３２６号公報の００１２～００１３段落に記載された樹脂等が挙げられ、上記の内容は本明細書に組み込まれる。 The alkali-soluble resin contains at least one selected from the group consisting of a polyimide precursor and a polyimide resin, in that the pattern shape of the patterned cured film obtained using the curable composition is more excellent. Is preferred.
The polyimide resin containing an alkali-soluble group is not particularly limited, and a known polyimide resin containing an alkali-soluble group can be used. Examples of the polyimide resin include resins described in paragraph 0050 of JP-A-2014-137523, resins described in paragraph 0058 of JP-A-2015-187676, and JP-A-2014-106326. Examples include the resins described in paragraphs 0012 to 0013, and the above contents are incorporated herein.
＜分散剤＞
　上記硬化性組成物は分散剤を含有することが好ましい。本明細書において、分散剤と、後述するアルカリ可溶性樹脂とは、異なる成分を意図する。
　硬化性組成物中における分散剤の含有量としては特に制限されないが、一般に硬化性組成物の全固形分に対して５～３０質量％が好ましい。
　分散剤は、１種を単独で用いても、２種以上を併用してもよい。２種以上の分散剤を併用する場合には、合計含有量が上記範囲内であることが好ましい。 <Dispersant>
The curable composition preferably contains a dispersant. In this specification, a dispersing agent and the alkali-soluble resin mentioned later intend a different component.
The content of the dispersant in the curable composition is not particularly limited, but is generally preferably 5 to 30% by mass with respect to the total solid content of the curable composition.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together. When two or more dispersants are used in combination, the total content is preferably within the above range.
　分散剤としては、例えば、公知の分散剤を適宜選択して用いることができる。なかでも、高分子化合物が好ましい。
　分散剤としては、高分子分散剤〔例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ（メタ）アクリレート、（メタ）アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物〕、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、及び、顔料誘導体等を挙げることができる。
　高分子化合物は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、及びブロック型高分子に分類することができる。 As the dispersant, for example, a known dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
Examples of the dispersant include polymer dispersants [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 type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
The polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
（高分子化合物）
　高分子化合物は、金属窒化物含有粒子の表面に吸着し、被分散体の再凝集を防止するように作用する。そのため、顔料表面へのアンカー部位を含有する、末端変性型高分子、グラフト型高分子、及び、ブロック型高分子等が好ましい。 (Polymer compound)
The polymer compound is adsorbed on the surface of the metal nitride-containing particles and acts to prevent re-aggregation of the dispersion. Therefore, terminal-modified polymers, graft polymers, block polymers, and the like that contain an anchor site to the pigment surface are preferred.
　高分子化合物は、グラフト鎖を含有する構造単位を含有することが好ましい。なお、本明細書において、「構造単位」とは「繰り返し単位」と同義である。
　このようなグラフト鎖を含有する構造単位を含有する高分子化合物は、グラフト鎖によって溶剤との親和性を有するために、金属窒化物含有粒子等の分散性、及び、経時後の分散安定性（経時安定性）に優れる。また、グラフト鎖の存在により、グラフト鎖を含有する構造単位を含有する高分子化合物は重合性化合物又はその他の併用可能な樹脂等との親和性を有する。結果として、アルカリ現像で残渣を生じにくくなる。
　グラフト鎖が長くなると立体反発効果が高くなり金属窒化物含有粒子等の分散性は向上する。一方、グラフト鎖が長すぎると金属窒化物含有粒子等への吸着力が低下して、金属窒化物含有粒子等の分散性は低下する傾向となる。このため、グラフト鎖は、水素原子を除いた原子数が４０～１００００であるものが好ましく、水素原子を除いた原子数が５０～２０００であるものがより好ましく、水素原子を除いた原子数が６０～５００であるものが更に好ましい。
　ここで、グラフト鎖とは、共重合体の主鎖の根元（主鎖から枝分かれしている基において主鎖に結合する原子）から、主鎖から枝分かれしている基の末端までを示す。 The polymer compound preferably contains a structural unit containing a graft chain. In the present specification, “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 the metal nitride-containing particles and the like, and the dispersion stability after aging ( Excellent stability over time. 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.
When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the metal nitride-containing particles and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to the metal nitride-containing particles and the like is lowered, and the dispersibility of the metal nitride-containing particles and the like tends to be lowered. For this reason, 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 preferred is 60-500.
Here, 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.
　グラフト鎖は、ポリマー構造を含有することが好ましく、このようなポリマー構造としては、例えば、ポリ（メタ）アクリレート構造（例えば、ポリ（メタ）アクリル構造）、ポリエステル構造、ポリウレタン構造、ポリウレア構造、ポリアミド構造、及び、ポリエーテル構造等が挙げられる。
　グラフト鎖と溶剤との相互作用性を向上させ、それにより黒色顔料等の分散性を高めるために、グラフト鎖は、ポリエステル構造、ポリエーテル構造及びポリ（メタ）アクリレート構造からなる群から選ばれた少なくとも１種を含有するグラフト鎖が好ましく、ポリエステル構造及びポリエーテル構造の少なくともいずれかを含有するグラフト鎖がより好ましい。 The graft chain preferably contains a polymer structure. Examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide. Examples thereof include a structure and a polyether structure.
The graft chain was selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure in order to improve the interaction between the graft chain and the solvent, thereby increasing the dispersibility of the black pigment and the like. A graft chain containing at least one kind is preferred, and a graft chain containing at least one of a polyester structure and a polyether structure is more preferred.
　このようなグラフト鎖を含有するマクロモノマーとしては、特に限定されないが、反応性二重結合性基を含有するマクロモノマーを好適に使用できる。 The macromonomer containing such a graft chain is not particularly limited, but a macromonomer containing a reactive double bond group can be suitably used.
　高分子化合物が含有するグラフト鎖を含有する構造単位に対応し、高分子化合物の合成に好適に用いられる市販のマクロモノマーとしては、ＡＡ－６（商品名、東亜合成社製）、ＡＡ－１０（商品名、東亜合成社製）、ＡＢ－６（商品名、東亜合成社製）、ＡＳ－６（商品名、東亜合成社製）、ＡＮ－６（商品名、東亜合成社製）、ＡＷ－６（商品名、東亜合成社製）、ＡＡ－７１４（商品名、東亜合成社製）、ＡＹ－７０７（商品名、東亜合成社製）、ＡＹ－７１４（商品名、東亜合成社製）、ＡＫ－５（商品名、東亜合成社製）、ＡＫ－３０（商品名、東亜合成社製）、ＡＫ－３２（商品名、東亜合成社製）、ブレンマーＰＰ－１００（商品名、日油社製）、ブレンマーＰＰ－５００（商品名、日油社製）、ブレンマーＰＰ－８００（商品名、日油社製）、ブレンマーＰＰ－１０００（商品名、日油社製）、ブレンマー５５－ＰＥＴ－８００（商品名、日油社製）、ブレンマーＰＭＥ－４０００（商品名、日油社製）、ブレンマーＰＳＥ－４００（商品名、日油社製）、ブレンマーＰＳＥ－１３００（商品名、日油社製）、ブレンマー４３ＰＡＰＥ－６００Ｂ（商品名、日油社製）等が挙げられる。なかでも、ＡＡ－６（商品名、東亜合成社製）、ＡＡ－１０（商品名、東亜合成社製）、ＡＢ－６（商品名、東亜合成社製）、ＡＳ－６（商品名、東亜合成社製）、ＡＮ－６（商品名、東亜合成社製）、及び、ブレンマーＰＭＥ－４０００（商品名、日油社製）等が好ましい。 Corresponding to the structural unit containing a graft chain contained in the polymer compound, commercially available macromonomers suitably used for the synthesis of the polymer compound include AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10. (Trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AW -6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.) AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-32 (trade name, manufactured by Toa Gosei Co., Ltd.), Blemmer PP-100 (trade name, NOF Corporation) Blemmer PP-500 (trade name, manufactured by NOF Corporation), Blemmer PP-800 ( Product name, manufactured by NOF Corporation), BLEMMER PP-1000 (trade name, manufactured by NOF CORPORATION), BLEMMER 55-PET-800 (trade name, manufactured by NOF CORPORATION), BLEMMER PME-4000 (trade name, manufactured by NOF Corporation) ), BLEMMER PSE-400 (trade name, manufactured by NOF Corporation), BLEMMER PSE-1300 (trade name, manufactured by NOF Corporation), BLEMMER 43PAPE-600B (trade name, manufactured by NOF Corporation) and the like. Among them, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.) Synthetic Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), Bremer PME-4000 (trade name, manufactured by NOF Corporation) and the like are preferable.
　上記分散剤は、ポリアクリル酸メチル、ポリメタクリル酸メチル及び環状又は鎖状のポリエステルからなる群より選択される少なくとも１種の構造を含有することが好ましい。より好ましくは、上記分散剤は、ポリアクリル酸メチル、ポリメタクリル酸メチル及び鎖状のポリエステルからなる群より選択される少なくとも１種の構造を含有する。更に好ましくは、上記分散剤は、ポリアクリル酸メチル構造、ポリメタクリル酸メチル構造、ポリカプロラクトン構造及びポリバレロラクトン構造からなる群より選択される少なくとも１種の構造を含有する。分散剤は、一の分散剤中に上記構造を単独で含有してもよいし、一の分散剤中にこれらの構造を複数含有してもよい。
　ここで、ポリカプロラクトン構造とは、ε－カプロラクトンを開環した構造を繰り返し単位として含有するものをいう。ポリバレロラクトン構造とは、δ－バレロラクトンを開環した構造を繰り返し単位として含有するものをいう。 The dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. The dispersant may contain the above structure alone in one dispersant, or may contain a plurality of these structures in one dispersant.
Here, the polycaprolactone structure means a structure containing a ring-opened structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure means a structure containing a ring-opened structure of δ-valerolactone as a repeating unit.
　上記分散剤の具体例としては、例えば、特開２０１５－３４９８３号公報の００３５～００９６段落に記載の化合物、特開２０１２－２５５１４８号公報の００２５～０１０５段落に記載の化合物、特開２０１３－２４９４１７号公報の０１２７～０１２９段落の化合物、特開２０１０－１０６２６８号公報の００３７～０１１５段落（対応するＵＳ２０１１／０１２４８２４の段落００７５～０１３３欄）に記載の化合物、特開２０１１－１５３２８３号公報の００２８～００８４段落（対応するＵＳ２０１１／０２７９７５９の段落００７５～０１３３欄）の酸性基が連結基を介して結合してなる側鎖構造を含有する構成成分を含有する化合物、特開２０１６－１０９７６３号公報の００３３～００４９段落に記載された化合物を使用でき、上記内容は本明細書に組み込まれる。 Specific examples of the dispersant include, for example, compounds described in paragraphs 0035 to 0096 of JP-A-2015-34983, compounds described in paragraphs 0025 to 0105 of JP-A-2012-255148, and JP-A-2013-249417. Compounds in paragraphs 0127 to 0129 of JP-A No. 10-26268, compounds described in paragraphs 0037 to 0115 of JP 2010-106268 A (corresponding to columns 0075 to 0133 in US 2011/0124824), and 0028 to JP-A No. 2011-153283. Compound containing a constituent component containing a side chain structure in which an acidic group in paragraph 0084 (corresponding to US 2011/0279759, paragraphs 0075 to 0133) is bonded via a linking group, 0033 of JP 2016-109763 A Uses compounds described in paragraphs 0049 to 0049 Can, the contents of which are incorporated herein.
＜溶剤＞
　上記硬化性組成物は、溶剤を含有することが好ましい。硬化性組成物が溶剤を含有する場合、溶剤の含有量としては特に制限されないが、硬化性組成物の全固形分が５～４０質量％となるよう調整されることが好ましい。
　溶剤は、１種を単独で用いても、２種以上を併用してもよい。２種以上の溶剤を併用する場合には、硬化性組成物の全固形分が上記範囲内となるよう調整されることが好ましい。 <Solvent>
The curable composition preferably contains a solvent. When the curable composition contains a solvent, the content of the solvent is not particularly limited, but is preferably adjusted so that the total solid content of the curable composition is 5 to 40% by mass.
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 content of a curable composition may become in the said range.
　溶剤の種類としては特に制限されず、公知の溶剤を使用できる。溶剤としては例えば、水、又は、有機溶剤が挙げられる。
　有機溶剤としては、例えば、アセトン、メチルエチルケトン、シクロヘキサン、酢酸エチル、エチレンジクロライド、テトラヒドロフラン、トルエン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、アセチルアセトン、シクロヘキサノン、シクロペンタノン、ジアセトンアルコール、エチレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、３－メトキシプロパノール、メトキシメトキシエタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、３－メトキシプロピルアセテート、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、γ－ブチロラクトン、酢酸エチル、酢酸ブチル、乳酸メチル、及び、乳酸エチル等が挙げられるが、これらに制限されない。 It does not restrict | limit especially as a kind of solvent, A well-known solvent can be used. Examples of the solvent include water or 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, γ-butyrolactone, ethyl acetate, Examples include but are not limited to butyl acetate, methyl lactate, and ethyl lactate.
＜シランカップリング剤＞
　硬化性組成物はシランカップリング剤を含有してもよい。
　シランカップリング剤とは、分子中に加水分解性基とそれ以外の官能基とを含有する化合物である。なお、アルコキシ基等の加水分解性基は、ケイ素原子に結合している。
　加水分解性基とは、ケイ素原子に直結し、加水分解反応及び／又は縮合反応によってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基、及びアルケニルオキシ基が挙げられる。加水分解性基が炭素原子を含有する場合、その炭素数は６以下が好ましく、４以下がより好ましい。特に、炭素数４以下のアルコキシ基又は炭素数４以下のアルケニルオキシ基が好ましい。
　また、基板上に硬化膜を形成する場合、シランカップリング剤は基板と硬化膜間の密着性を向上させるため、フッ素原子及びケイ素原子（ただし、加水分解性基が結合したケイ素原子は除く）を含まないことが好ましく、フッ素原子、ケイ素原子（ただし、加水分解性基が結合したケイ素原子は除く）、ケイ素原子で置換されたアルキレン基、炭素数８以上の直鎖アルキル基、及び、炭素数３以上の分鎖アルキル基は含まないことがより好ましい。 <Silane coupling agent>
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. When the hydrolyzable group contains a carbon atom, the carbon number is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
In addition, when forming a cured film on the substrate, the silane coupling agent improves the adhesion between the substrate and the cured film, so fluorine atoms and silicon atoms (however, excluding silicon atoms with hydrolyzable groups bonded) It is preferable that it does not contain, a fluorine atom, a silicon atom (however, excluding a 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 carbon More preferably, it does not contain a branched alkyl group of several or more.
　上記硬化性組成物中におけるシランカップリング剤の含有量は、硬化性組成物中の全固形分に対して、０．１～１０質量％が好ましく、０．５～８質量％がより好ましく、１．０～６質量％が更に好ましい。
　上記硬化性組成物は、シランカップリング剤を１種単独で含有してもよく、２種以上を含有してもよい。硬化性組成物がシランカップリング剤を２種以上含有する場合は、その合計が上記範囲内であればよい。 The content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total solid content in the curable composition. 1.0 to 6% by mass is more preferable.
The said curable composition may contain 1 type of silane coupling agents individually, 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.
＜紫外線吸収剤＞
　硬化性組成物は、紫外線吸収剤を含有してもよい。これにより、硬化膜のパターンの形状をより優れた（精細な）ものにできる。
　紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、及びトリアジン系の紫外線吸収剤を使用できる。これらの具体例としては、特開２０１２－０６８４１８号公報の段落０１３７～０１４２（対応するＵＳ２０１２／００６８２９２の段落０２５１～０２５４）の化合物が使用でき、これらの内容が援用でき、本明細書に組み込まれる。
　他にジエチルアミノ－フェニルスルホニル系紫外線吸収剤（大東化学社製、商品名：ＵＶ－５０３）なども好適に用いられる。
　紫外線吸収剤としては、特開２０１２－３２５５６号公報の段落０１３４～０１４８に例示される化合物が挙げられる。
　紫外線吸収剤の含有量は、硬化性組成物の全固形分に対して、０．００１～１５質量％が好ましく、０．０１～１０質量％がより好ましく、０．１～５質量％が更に好ましい。
＜界面活性剤＞
　硬化性組成物は、界面活性剤を含有してもよい。界面活性剤は、硬化性組成物の塗布性向上に寄与する。 <Ultraviolet absorber>
The curable composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine).
As the ultraviolet absorber, salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine ultraviolet absorbers can be used. As specific examples of these, 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. .
In addition, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) is also preferably used.
Examples of 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, more preferably 0.01 to 10% by mass, and further preferably 0.1 to 5% by mass with respect to the total solid content of the curable composition. preferable.
<Surfactant>
The curable composition may contain a surfactant. Surfactant contributes to the applicability | paintability improvement of a curable composition.
　上記硬化性組成物が、界面活性剤を含有する場合、界面活性剤の含有量としては、硬化性組成物の全固形分に対して、０．００１～２．０質量％が好ましい。
　界面活性剤は、１種を単独で用いても、２種以上を併用してもよい。界面活性剤を２種以上併用する場合は、合計量が上記範囲内であることが好ましい。 When the curable composition contains a surfactant, 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.
　界面活性剤としては、例えば、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、及びシリコーン系界面活性剤等が挙げられる。 Examples of the surfactant include fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
　例えば、硬化性組成物がフッ素系界面活性剤を含有することで、硬化性組成物の液特性（特に、流動性）がより向上する。即ち、フッ素系界面活性剤を含有する硬化性組成物を用いて膜形成する場合においては、被塗布面と塗布液との界面張力を低下させることにより、被塗布面への濡れ性が改善され、被塗布面への塗布性が向上する。このため、少量の液量で数μｍ程度の薄膜を形成した場合であっても、厚みムラの小さい均一厚が形成しやすい点で有効である。 For example, when the curable composition contains a fluorosurfactant, 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 μm is formed with a small amount of liquid, it is effective in that a uniform thickness with small thickness unevenness can be easily formed.
　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好ましく、５～３０質量％がより好ましく、７～２５質量％が更に好ましい。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性及び／又は省液性の点で効果的であり、硬化性組成物中における溶解性も良好である。 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. .
　フッ素系界面活性剤としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ３９３、同ＫＨ－４０（以上、旭硝子（株）製）、ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（ＯＭＮＯＶＡ社製）等が挙げられる。
　フッ素系界面活性剤としてブロックポリマーも使用でき、具体例としては、例えば特開２０１１－８９０９０号公報に記載された化合物が挙げられる。 Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above DIC Corporation), Florad FC430, FC431, FC171 (Sumitomo 3M Limited), Surflon S-382, SC-101, SC- 103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (manufactured by Asahi Glass Co., Ltd.), 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-2011-89090.
＜密着性改良剤＞
　硬化性組成物は、密着性改良剤として、シランカップリング剤を含有してもよい。シランカップリング剤としては、例えば、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、ビニルトリメトキシシラン、及び、ビニルトリエトキシシラン等が挙げられる。
　密着性改良剤の含有量としては、特に制限されないが、硬化性組成物の全固形分に対して０．０２～２０質量％が好ましい。 <Adhesion improver>
The curable composition may contain a silane coupling agent as an adhesion improver. Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. , Vinyltrimethoxysilane, vinyltriethoxysilane, and the like.
The content of the adhesion improver is not particularly limited, but is preferably 0.02 to 20% by mass with respect to the total solid content of the curable composition.
＜着色剤＞
　硬化性組成物は着色剤を含有してもよい。本明細書において、着色剤とは、金属窒化物含有粒子とは異なる着色剤を意図する。
　硬化性組成物中における、着色剤の含有量としては特に制限されないが、一般に３０～６０質量％が好ましい。 <Colorant>
The curable composition may contain a colorant. In this specification, the colorant intends a colorant different from the metal nitride-containing particles.
The content of the colorant in the curable composition is not particularly limited, but generally 30 to 60% by mass is preferable.
　着色剤としては、各種公知の顔料（着色顔料）、及び、染料（着色染料）が使用できる。
　着色剤を含有する場合、その含有量は、硬化して得られる遮光膜の光学特性に応じて決定することができる。また、その他の着色剤は１種を単独で用いても、２種以上を併用してもよい。 Various known pigments (colored pigments) and dyes (colored dyes) can be used as the colorant.
When it contains a colorant, its content can be determined according to the optical properties of the light-shielding film obtained by curing. Other colorants may be used alone or in combination of two or more.
　着色剤としては、例えば、特開２０１４－４２３７５の段落００２７～０２００、特開２００８－２６０９２７号公報の００３１段落、及び、特開２０１５－６８８９３号公報の００１５～００２５段落に記載された着色剤が使用でき、上記の内容は本明細書に組み込まれる。 Examples of the colorant include the colorants described in paragraphs 0027 to 0200 of JP2014-42375, paragraph 0031 of JP2008-260927A, and paragraphs 0015 to 0025 of JP2015-68893A. Which can be used and are incorporated herein by reference.
　着色剤としては、赤外線吸収性を有する顔料も使用できる。
　赤外線吸収性を有する顔料としては、タングステン化合物、及び金属ホウ化物等が好ましく、なかでも、赤外領域の波長における遮光性に優れる点から、タングステン化合物がより好ましい。特に露光による硬化効率に関わるオキシム系重合開始剤の光吸収波長領域と、可視光線領域の透光性に優れる観点からタングステン化合物が好ましい。 As the colorant, a pigment having infrared absorptivity can also be used.
As the pigment having infrared absorptivity, a tungsten compound, a metal boride, and the like are preferable, and among them, a tungsten compound is more preferable in terms of excellent light-shielding properties at wavelengths in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of excellent light absorption wavelength region of an oxime polymerization initiator related to curing efficiency by exposure and transparency of visible light region.
　これらの顔料は、２種以上併用してもよく、また、後述する染料と併用してもよい。色味を調整するため、及び、所望の波長領域の遮光性を高めるため、例えば、黒色、又は赤外線遮光性を有する顔料に、赤色、緑色、黄色、オレンジ色、紫色、及びブルー等の有彩色顔料若しくは後述する染料を混ぜる形態が挙げられる。黒色、又は赤外線遮光性を有する顔料に、赤色顔料若しくは染料、又は、紫色顔料若しくは染料を混合することが好ましく、黒色、又は赤外線遮光性を有する顔料に赤色顔料を混合することがより好ましい。
　更に、後述する近赤外線吸収剤、赤外線吸収剤を加えてもよい。 Two or more of these pigments may be used in combination, or may be used in combination with a dye described later. In order to adjust the color tone and to improve the light-shielding property in a desired wavelength region, for example, chromatic colors such as red, green, yellow, orange, purple and blue are added to black or infrared light-shielding pigments. The form which mixes the pigment or the dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a purple pigment or dye with a black or infrared pigment, and it is more preferable to mix a red pigment with a black pigment or infrared pigment.
Furthermore, you may add the near-infrared absorber and infrared absorber which are mentioned later.
・有機顔料
　有機顔料としては、例えば、カラーインデックス（Ｃ．Ｉ．）ピグメントイエロー１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４等、
　Ｃ．Ｉ．ピグメントオレンジ　２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等、
　Ｃ．Ｉ．ピグメントレッド　１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２７０，２７２，２７９等；
　Ｃ．Ｉ．ピグメントグリーン　７，１０，３６，３７，５８，５９等；
　Ｃ．Ｉ．ピグメントバイオレット　１，１９，２３，２７，３２，３７，４２等；
　Ｃ．Ｉ．ピグメントブルー　１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，６０，６４，６６，７９，８０等；
が挙げられる。なお、顔料は１種を単独で用いても、２種以上を併用してもよい。 Organic pigment Examples of the organic pigment include, for example, Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 7,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc.
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc .;
C. I. Pigment green 7, 10, 36, 37, 58, 59, etc .;
C. I. Pigment violet 1, 19, 23, 27, 32, 37, 42, etc .;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc .;
Is mentioned. In addition, a pigment may be used individually by 1 type, or may use 2 or more types together.
（染料）
　染料としては、例えば特開昭６４－９０４０３号公報、特開昭６４－９１１０２号公報、特開平１－９４３０１号公報、特開平６－１１６１４号公報、特登２５９２２０７号、米国特許４８０８５０１号明細書、米国特許５６６７９２０号明細書、米国特許５０５９５０号明細書、米国特許５６６７９２０号明細書、特開平５－３３３２０７号公報、特開平６－３５１８３号公報、特開平６－５１１１５号公報、特開平６－１９４８２８号公報等に開示されている色素を使用できる。化学構造として区分すると、ピラゾールアゾ化合物、ピロメテン化合物、アニリノアゾ化合物、トリフェニルメタン化合物、アントラキノン化合物、ベンジリデン化合物、オキソノール化合物、ピラゾロトリアゾールアゾ化合物、ピリドンアゾ化合物、シアニン化合物、フェノチアジン化合物、ピロロピラゾールアゾメチン化合物等を使用できる。また、染料としては色素多量体を使用してもよい。色素多量体としては、特開２０１１－２１３９２５号公報、特開２０１３－０４１０９７号公報に記載されている化合物が挙げられる。また、分子内に重合性を有する重合性染料を使用してもよく、市販品としては、例えば、和光純薬株式会社製ＲＤＷシリーズが挙げられる。 (dye)
Examples of the dye include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501. US Pat. No. 5,667,920, US Pat. No. 505950, US Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6- Dyes disclosed in 194828 can be used. When classified as chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, 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 | numerator, As a commercial item, the RDW series by Wako Pure Chemical Industries, Ltd. is mentioned, for example.
（赤外線吸収剤）
　上記着色剤は、更に赤外線吸収剤を含有してもよい。
　赤外線吸収剤は、赤外領域（好ましくは、波長６５０～１３００ｎｍ）の波長領域に吸収を有する化合物を意味する。好ましくは、赤外線吸収剤は、波長６７５～９００ｎｍの波長領域に極大吸収波長を有する化合物が好ましい。
　このような分光特性を有する着色剤としては、例えば、ピロロピロール化合物、銅化合物、シアニン化合物、フタロシアニン化合物、イミニウム化合物、チオール錯体系化合物、遷移金属酸化物系化合物、スクアリリウム化合物、ナフタロシアニン化合物、クオタリレン化合物、ジチオール金属錯体系化合物、クロコニウム化合物等が挙げられる。
　フタロシアニン化合物、ナフタロシアニン化合物、イミニウム化合物、シアニン化合物、スクアリウム化合物及びクロコニウム化合物は、特開２０１０－１１１７５０号公報の段落００１０～００８１に開示の化合物を使用してもよく、この内容は本明細書に組み込まれる。シアニン化合物は、例えば、「機能性色素、大河原信／松岡賢／北尾悌次郎／平嶋恒亮・著、講談社サイエンティフィック」を参酌でき、この内容は本願明細書に組み込まれる。 (Infrared absorber)
The colorant may further contain an infrared absorber.
The infrared absorber means a compound having absorption in the wavelength region in the infrared region (preferably, a wavelength of 650 to 1300 nm). Preferably, the infrared absorber is a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm.
Examples of 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, and quaterylenes. Compounds, dithiol metal complex compounds, croconium compounds and the like.
As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squalium compound and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP-A No. 2010-1111750 may be used. Incorporated. As the cyanine compound, for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein.
　上記分光特性を有する着色剤として、特開平０７－１６４７２９号公報の段落０００４～００１６に開示の化合物及び／又は特開２００２－１４６２５４号公報の段落００２７～００６２に開示の化合物、特開２０１１－１６４５８３号公報の段落００３４～００６７に開示のＣｕ及び／又はＰを含む酸化物の結晶子からなり数平均凝集粒子径が５～２００ｎｍである近赤外線吸収粒子を使用できる。 As the colorant having the above-mentioned spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or compounds disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254, JP-A-2011-16483 The near-infrared absorbing particles comprising a crystallite of an oxide containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the publication can be used and having a number average aggregate particle size of 5 to 200 nm.
　波長６７５～９００ｎｍの波長領域に極大吸収波長を有する化合物としては、シアニン化合物、ピロロピロール化合物、スクアリリウム化合物、フタロシアニン化合物、及びナフタロシアニン化合物からなる群から選択される少なくとも１種が好ましい。
　また、赤外線吸収剤は、２５℃の水に１質量％以上溶解する化合物が好ましく、２５℃の水に１０質量％以上溶解する化合物がより好ましい。このような化合物を用いることで、耐溶剤性が良化する。
　ピロロピロール化合物は、特開２０１０－２２２５５７号公報の段落番号００４９～００６２を参酌でき、この内容は本明細書に組み込まれることとする。シアニン化合物及びスクアリリウム化合物は、国際公開第２０１４／０８８０６３号の段落番号００２２～００６３、国際公開第２０１４／０３０６２８号の段落番号００５３～０１１８、特開２０１４－５９５５０号公報の段落番号００２８～００７４、国際公開第２０１２／１６９４４７号の段落番号００１３～００９１、特開２０１５－１７６０４６号公報の段落番号００１９～００３３、特開２０１４－６３１４４号公報の段落番号００５３～００９９、特開２０１４－５２４３１号公報の段落番号００８５～０１５０、特開２０１４－４４３０１号公報の段落番号００７６～０１２４、特開２０１２－８５３２号公報の段落番号００４５～００７８、特開２０１５－１７２１０２号公報の段落番号００２７～００６７、特開２０１５－１７２００４号公報の段落番号００２９～００６７、特開２０１５－４０８９５号公報の段落番号００２９～００８５、特開２０１４－１２６６４２号公報の段落番号００２２～００３６、特開２０１４－１４８５６７号公報の段落番号００１１～００１７、特開２０１５－１５７８９３号公報の段落番号００１０～００２５、特開２０１４－０９５００７号公報の段落番号００１３～００２６、特開２０１４－８０４８７号公報の段落番号００１３～００４７、及び特開２０１３－２２７４０３号公報の段落番号０００７～００２８等を参酌でき、この内容は本明細書に組み込まれることとする。 The compound having a 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 in 1% by mass or more in 25 ° C. water, and more preferably a compound that dissolves in 10% by mass or more in 25 ° C. water. By using such a compound, the solvent resistance is improved.
As for the pyrrolopyrrole compound, paragraph numbers 0049 to 0062 of JP 2010-222557 A can be referred to, and the contents thereof are incorporated in the present specification. Cyanine compounds and squarylium compounds are disclosed in paragraphs 0022 to 0063 of WO 2014/088063, paragraphs 0053 to 0118 of WO 2014/030628, paragraphs 0028 to 0074 of JP 2014-59550 A, international Paragraph Nos. 0013 to 0091 of Japanese Patent Publication No. 2012/169447, Paragraph Nos. 0019 to 0033 of JP-A-2015-176046, Paragraph Nos. 0053 to 00099 of JP-A-2014-63144, Paragraphs of JP-A-2014-52431 Nos. 0085 to 0150, paragraph numbers 0076 to 0124 of Japanese Patent Application Laid-Open No. 2014-44301, paragraph numbers 0045 to 0078 of Japanese Patent Application Laid-Open No. 2012-8532, paragraph numbers 0027 to 0067 of Japanese Patent Application Laid-Open No. 2015-172102, -172004, paragraph numbers 0029 to 0067, JP2015-40895, paragraphs 0029 to 0085, JP2014-126642, paragraphs 0022 to 0036, and JP2014-148567, paragraph 0011. 0017, paragraph numbers 0010 to 0025 of JP-A-2015-157893, paragraph numbers 0013 to 0026 of JP-A-2014-095007, paragraph numbers 0013 to 0047 of JP-A-2014-80487, and JP-A-2013-13. No. 227403, paragraph numbers 0007 to 0028 and the like can be referred to, and the contents thereof are incorporated in this specification.
　赤外線吸収剤は、下記式１～３で表される化合物からなる群から選択される少なくとも１種が好ましい。
式１
Figure JPOXMLDOC01-appb-C000022
　式１中、Ａ１及びＡ２は、それぞれ独立に、アリール基、ヘテロアリール基又は下記式１－Ａで表される基を表す；
式１－Ａ
Figure JPOXMLDOC01-appb-C000023
　式１－Ａ、Ｚ１Ａは、含窒素複素環を形成する非金属原子団を表し、Ｒ２Ａは、アルキル基、アルケニル基、又はアラルキル基を表し、ｄは、０、又は１を表し、波線は連結手を表す；
式２
Figure JPOXMLDOC01-appb-C000024
　式２中、Ｒ１ａ及びＲ１ｂは、それぞれ独立に、アルキル基、アリール基、又はヘテロアリール基を表し、
　Ｒ２～Ｒ５は、それぞれ独立に、水素原子、又は置換基を表し、Ｒ２とＲ３、Ｒ４とＲ５は、それぞれ結合して環を形成していてもよく、
　Ｒ６、及びＲ７は、それぞれ独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、－ＢＲＡＲＢ、又は金属原子を表し、ＲＡ、及びＲＢは、各々独立に、水素原子、又は置換基を表し、
　Ｒ６は、Ｒ１ａ、又はＲ３と、共有結合、又は配位結合していてもよく、Ｒ７は、Ｒ１ｂ、又はＲ５と、共有結合、又は配位結合していてもよい
；式３
Figure JPOXMLDOC01-appb-C000025
　式３中、Ｚ１、及びＺ２は、それぞれ独立に、縮環してもよい５員、又は６員の含窒素複素環を形成する非金属原子団であり、
　Ｒ１０１、及びＲ１０２は、それぞれ独立に、アルキル基、アルケニル基、アルキニル基、アラルキル基、又はアリール基を表し、
　Ｌ１は、奇数個のメチンからなるメチン鎖を表し、
　ａ、及びｂは、それぞれ独立に、０、又は１であり、
　ａが０の場合は、炭素原子と窒素原子とが二重結合で結合し、ｂが０の場合は、炭素原子と窒素原子とが単結合で結合し、
　式中のＣｙで表される部位がカチオン部である場合、Ｘ１はアニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位がアニオン部である場合、Ｘ１はカチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中の
Ｃｙで表される部位の電荷が分子内で中和されている場合、ｃは０である。 The infrared absorber is preferably at least one selected from the group consisting of compounds represented by the following formulas 1 to 3.
Formula 1
Figure JPOXMLDOC01-appb-C000022
In Formula 1, A 1 and A 2 each independently represent an aryl group, a heteroaryl group, or a group represented by the following Formula 1-A;
Formula 1-A
Figure JPOXMLDOC01-appb-C000023
Formula 1-A, Z 1A represents a nonmetallic atomic group that forms a nitrogen-containing heterocyclic ring, R 2A represents an alkyl group, an alkenyl group, or an aralkyl group, d represents 0 or 1, and a wavy line Represents a connecting hand;
Formula 2
Figure JPOXMLDOC01-appb-C000024
In Formula 2, R 1a and R 1b each independently represent an alkyl group, an aryl group, or a heteroaryl group,
R 2 to R 5 each independently represents a hydrogen atom or a substituent, and R 2 and R 3 , R 4 and R 5 may be bonded to each other to form a ring,
R 6 and R 7 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR A R B , or a metal atom, and R A and R B each independently represent a hydrogen atom Represents an atom or substituent,
R 6 may be covalently or coordinated with R 1a or R 3, and R 7 may be covalently or coordinated with R 1b or R 5 ; Formula 3
Figure JPOXMLDOC01-appb-C000025
In Formula 3, Z 1 and Z 2 are each independently a nonmetallic atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocycle that may be condensed,
R 101 and R 102 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group,
L 1 represents a methine chain composed of an odd number of methines;
a and b are each independently 0 or 1,
When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond,
When the site represented by Cy in the formula is a cation moiety, X 1 represents an anion, c represents a number necessary for balancing the charge, and the site represented by Cy in the formula is an anion moiety. X 1 represents a cation, c represents a number necessary to balance the charge, and when the charge of the site represented by Cy in the formula is neutralized in the molecule, c is 0.
（顔料誘導体）
　硬化性組成物は、顔料誘導体を含有してもよい。顔料誘導体は、有機顔料の一部分を、酸性基、塩基性基又はフタルイミドメチル基で置換した構造を有する化合物が好ましい。顔料誘導体としては、着色剤Ａの分散性及び分散安定性の観点から、酸性基又は塩基性基を有する顔料誘導体が好ましい。特に好ましくは、塩基性基を有する顔料誘導体である。また、上述した樹脂（分散剤）と、顔料誘導体の組み合わせは、分散剤が酸性分散剤で、顔料誘導体が塩基性基を有する組み合わせが好ましい。 (Pigment derivative)
The curable composition may contain a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. As the pigment derivative, from the viewpoint of dispersibility and dispersion stability of the colorant A, a pigment derivative having an acidic group or a basic group is preferable. Particularly preferred are pigment derivatives having a basic group. Further, the combination of the resin (dispersant) and the pigment derivative described above is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.
　顔料誘導体を構成するための有機顔料としては、ジケトピロロピロール系顔料、アゾ系顔料、フタロシアニン系顔料、アントラキノン系顔料、キナクリドン系顔料、ジオキサジン系顔料、ペリノン系顔料、ペリレン系顔料、チオインジゴ系顔料、イソインドリン系顔料、イソインドリノン系顔料、キノフタロン系顔料、スレン系顔料、金属錯体系顔料等が挙げられる。
　また、顔料誘導体が有する酸性基としては、スルホン酸基、カルボン酸基及びその塩が好ましく、カルボン酸基及びスルホン酸基が更に好ましく、スルホン酸基が特に好ましい。顔料誘導体が有する塩基性基としては、アミノ基が好ましく、特に三級アミノ基が好ましい。 Examples of the organic pigment for constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
Moreover, as an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its salt are preferable, a carboxylic acid group and a sulfonic acid group are still more preferable, and a sulfonic acid group is especially preferable. The basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.
　上記硬化性組成物は、得られる硬化膜がより優れた遮光性を有する点で、４００～１１００ｎｍの波長領域における膜厚１．５μｍあたりの光学濃度（ＯＤ：Ｏｐｔｉｃａｌ　Ｄｎｓｉｔｙ）が、２．５以上が好ましく、３．０以上がより好ましい。なお、上限値は特に制限されないが、一般に５．０以下が好ましい。上記特性を有する硬化性組成物を用いて形成された硬化膜は、遮光膜（ブラックマトリクス）として好ましく使用できる。
　なお、本明細書において、光学濃度とは、実施例に記載された方法により測定した光学濃度を意味する。また、本明細書において、４００～１１００ｎｍの波長領域における膜厚１．５μｍあたりの光学濃度が、２．５以上とは、波長４００～１１００ｎｍの全域において、膜厚１．５μｍあたりの光学濃度が２．５以上であることを意味する。 The curable composition has an optical density (OD: Optical Density) per 2.5 μm in a wavelength region of 400 to 1100 nm of 2.5 or more in that the resulting cured film has better light-shielding properties. Is preferable, and 3.0 or more is more preferable. The upper limit is not particularly limited, but is generally preferably 5.0 or less. A cured film formed using a curable composition having the above characteristics can be preferably used as a light-shielding film (black matrix).
In the present specification, the optical density means an optical density measured by the method described in the examples. In this specification, the optical density per 1.5 μm film thickness in the wavelength region of 400 to 1100 nm is 2.5 or more. The optical density per 1.5 μm film thickness in the entire wavelength range of 400 to 1100 nm. It means that it is 2.5 or more.
〔硬化性組成物の製造方法〕
　硬化性組成物は、上述した各種成分を公知の混合方法（例えば、攪拌機、ホモジナイザー、高圧乳化装置、湿式粉砕機、又は、湿式分散機を用いた混合方法）により混合して調製できる。
　硬化性組成物の調製に際しては、各成分を一括配合してもよいし、各成分をそれぞれ、溶剤に溶解又は分散した後に逐次配合してもよい。また、配合する際の投入順序及び作業条件は特に制限されない。 [Method for producing curable composition]
The curable composition can be prepared by mixing the above-mentioned various components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, or a wet disperser).
In preparing the curable composition, each component may be blended at once, or each component may be blended sequentially after being dissolved or dispersed in a solvent. Moreover, the order of input and the working conditions when blending are not particularly limited.
　硬化性組成物は、異物の除去、及び／又は、欠陥の低減などの目的で、フィルタで濾過するのが好ましい。フィルタとしては、ろ過用であれば特に制限されず使用できる。例えば、ＰＴＦＥ（ポリテトラフルオロエチレン）等のフッ素樹脂；ナイロン等のポリアミド系樹脂；ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン系樹脂（高密度、超高分子量を含む）；等によるフィルタが挙げられる。なかでもフィルタの材料としてはポリプロピレン（高密度ポリプロピレンを含む）、又は、ナイロンが好ましい。
　フィルタの孔径は、０．１～７．０μｍが好ましく、０．２～２．５μｍがより好ましく、０．２～１．５μｍが更に好ましく、０．３～０．７μｍ特に好ましい。この範囲とすることにより、顔料のろ過詰まりを抑えつつ、顔料に含まれる不純物及び凝集物等、微細な異物を確実に除去できる。
　フィルタを使用する際、異なるフィルタを組み合わせてもよい。その際、第１のフィルタでのフィルタリングは、１回のみでもよいし、２回以上でもよい。異なるフィルタを組み合わせて２回以上フィルタリングする場合、１回目のフィルタリングの孔径より２回目以降の孔径が同じ、又は、大きい方が好ましい。また、上述した範囲内で異なる孔径の第１のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照できる。市販のフィルタとしては、例えば、日本ポール株式会社、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）又は株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択できる。
　第２のフィルタは、上述した第１のフィルタと同様の材料等で形成されたものを使用できる。第２のフィルタの孔径は、０．２～１０．０μｍ程度が好ましく、０．２～７．０μｍがより好ましく、０．３～６．０μｍが更に好ましい。
　硬化性組成物は、金属、ハロゲンを含む金属塩、酸、及び、アルカリ等の不純物を含有しないのが好ましい。これらの材料に含まれる不純物の含有量としては、１ｐｐｍ以下が好ましく、１ｐｐｂ以下がより好ましく、１００ｐｐｔ以下が更に好ましく、１０ｐｐｔ以下が特に好ましく、実質的に含有しないこと（測定装置の検出限界以下であること）が最も好ましい。
　なお、上記不純物は、誘導結合プラズマ質量分析装置（横河アナリティカルシステムズ製、Ａｇｉｌｅｎｔ　７５００ｃｓ型）により測定できる。 The curable composition is preferably filtered through a filter for the purpose of removing foreign substances and / or reducing defects. Any filter can be used without particular limitation as long as it is for filtration. For example, a filter made of fluorine resin such as PTFE (polytetrafluoroethylene); polyamide resin such as nylon; polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP); Among these, polypropylene (including high-density polypropylene) or nylon is preferable as the filter material.
The pore size of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, still more preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm. By setting it as this range, fine foreign substances, such as impurities and aggregates contained in the pigment, can be reliably removed while suppressing filtration clogging of the pigment.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or twice or more. When filtering two or more times in combination with different filters, it is preferable that the second and subsequent hole diameters are the same or larger than the first filtering hole diameter. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. 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 as the first filter described above can be used. The pore size of the second filter is preferably about 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, and still more preferably 0.3 to 6.0 μm.
It is preferable that 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 not contained (below the detection limit of the measuring device). Most preferred).
The impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
［硬化膜及びその製造方法］
　硬化性組成物により、硬化膜を形成できる。
　硬化膜の厚みは特に制限されないが、０．２～２５μｍが好ましい。
　上記厚みは平均厚みであり、硬化膜の任意の５点以上の厚みを測定し、それらを算術平均した値である。 [Curing film and manufacturing method thereof]
A cured film can be formed with a curable composition.
The thickness of the cured film is not particularly limited, but is preferably 0.2 to 25 μm.
The above thickness is an average thickness, and is a value obtained by measuring the thicknesses of five or more arbitrary points of the cured film and arithmetically averaging them.
　硬化膜の製造方法は特に制限されないが、上述した硬化性組成物を基板上に塗布して塗膜を形成して、塗膜に対して硬化処理を施し、硬化膜を製造する方法が挙げられる。
　硬化処理の方法は特に制限されず、光硬化処理又は熱硬化処理が挙げられ、パターン形成が容易である点から、光硬化処理（特に、活性光線又は放射線を照射することによる硬化処理）が好ましい。 Although the manufacturing method in particular of a cured film is not restrict | limited, The method of apply | coating the curable composition mentioned above on a board | substrate, forming a coating film, performing a hardening process with respect to a coating film, and manufacturing a cured film is mentioned. .
The method of the curing treatment is not particularly limited, and examples thereof include a photocuring treatment or a thermosetting treatment, and a photocuring treatment (particularly a curing treatment by irradiation with actinic rays or radiation) is preferable from the viewpoint of easy pattern formation. .
　本発明の実施形態に係る硬化膜は、上記硬化性組成物を用いて形成された硬化性組成物層を硬化して得られた硬化膜である。
　硬化膜の製造方法としては特に制限されないが、以下の工程を有することが好ましい。
・硬化性組成物層形成工程
・露光工程
・現像工程
　以下、各工程について説明する。 The cured film which concerns on embodiment of this invention is a cured film obtained by hardening | curing the curable composition layer formed using the said curable composition.
Although it does not restrict | limit especially as a manufacturing method of a cured film, It is preferable to have the following processes.
-Curable composition layer formation process-Exposure process-Development process Hereinafter, each process is demonstrated.
＜硬化性組成物層形成工程＞
　硬化性組成物層形成工程は、上記硬化性組成物を用いて、硬化性組成物層を形成する工程である。硬化性組成物を用いて、硬化性組成物層を形成する工程としては、例えば、基板上に、硬化性組成物を塗布して、硬化性組成物層を形成する工程が挙げられる。
　基板の種類は特に制限されないが、固体撮像素子として用いる場合は、例えば、ケイ素基板が挙げられ、カラーフィルタ（固体撮像素子用カラーフィルタを含む）として用いる場合には、ガラス基板等が挙げられる。
　基板上への硬化性組成物の塗布方法としては、スピンコート、スリット塗布、インクジェット法、スプレー塗布、回転塗布、流延塗布、ロール塗布、及び、スクリーン印刷法等の各種の塗布方法を適用できる。
　基板上に塗布された硬化性組成物は、通常、７０～１５０℃で、１～４分間乾燥され、硬化性組成物層が形成される。 <Curable composition layer forming step>
A curable composition layer formation process is a process of forming a curable composition layer using the said curable composition. As a process of forming a curable composition layer using a curable composition, the process of apply | coating a curable composition on a board | substrate and forming a curable composition layer is mentioned, for example.
Although the kind of board | substrate is not restrict | limited in particular, When using as a solid-state image sensor, a silicon substrate is mentioned, for example, When using as a color filter (including the color filter for solid-state image sensors), a glass substrate etc. are mentioned.
As a coating method of 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 can be applied. .
The curable composition applied on the substrate is usually dried at 70 to 150 ° C. for 1 to 4 minutes to form a curable composition layer.
＜露光工程＞
　露光工程では、硬化性組成物層形成工程において形成された硬化性組成物層に、パターン状の開口部を備えるフォトマスクを介して、活性光線又は放射線を照射して露光する工程である。
　露光は放射線の照射によるのが好ましく、露光に際して使用できる放射線としては、ｇ線、ｈ線、及び、ｉ線等の紫外線が挙げられ、光源としては高圧水銀灯が挙げられる。照射強度は５～１５００ｍＪ／ｃｍ２が好ましく、１０～１０００ｍＪ／ｃｍ２がより好ましい。 <Exposure process>
In the exposure step, the curable composition layer formed in the curable composition layer forming step is exposed by irradiating actinic rays or radiation through a photomask having a patterned opening.
Exposure is preferably by irradiation with radiation. Examples of radiation that can be used for exposure include ultraviolet rays such as g-line, h-line, and i-line, and examples of the light source include a high-pressure mercury lamp. The irradiation intensity is preferably 5 ~ 1500mJ / cm 2, more preferably 10 ~ 1000mJ / cm 2.
＜現像工程＞
　露光工程に次いで、現像処理（現像工程）を行い、露光工程における光未照射部分を現像液に溶出させる。これにより、光硬化した部分だけが残る。
　現像液としては、アルカリ現像液を用いてもよい。その場合は、有機アルカリ現像液を用いるのが好ましい。現像温度としては通常２０～３０℃が好ましく、現像時間は２０～９０秒が好ましい。
　アルカリ水溶液（アルカリ現像液）としては、例えば、無機系現像液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、及び、メタケイ酸ナトリウム等のアルカリ性化合物を、濃度が０．００１～１０質量％、好ましくは０．００５～０．５質量％となるように溶解したアルカリ水溶液が挙げられる。
　また、有機アルカリ現像液としては、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、及び、１，８－ジアザビシクロ－［５，４，０］－７－ウンデセン等のアルカリ性化合物を、濃度が０．００１～１０質量％、好ましくは０．００５～０．５質量％となるように溶解したアルカリ水溶液が挙げられる。
　アルカリ水溶液には、例えば、メタノール、エタノール等の水溶性有機溶剤、及び／又は、界面活性剤等を適量添加できる。なお、このようなアルカリ水溶液からなる現像液を使用した場合には、一般に現像後に硬化膜を純水で洗浄（リンス）する。 <Development process>
Subsequent to the exposure step, development processing (development step) is performed to elute the light non-irradiated portion in the exposure step into the developer. Thereby, only the photocured part remains.
An alkaline developer may be used as the developer. In that case, it is preferable to use an organic alkali developer. The development temperature is usually preferably 20-30 ° C., and the development time is preferably 20-90 seconds.
As an alkaline aqueous solution (alkali developer), for example, as an inorganic developer, an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, and sodium metasilicate has a concentration. Is an alkaline aqueous solution in which is dissolved in an amount of 0.001 to 10% by mass, preferably 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, in a concentration of 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass. %, An aqueous alkali solution dissolved so as to be%.
An appropriate amount of a water-soluble organic solvent such as methanol and ethanol, and / or a surfactant can be added to the alkaline aqueous solution, for example. When a developer composed of such an alkaline aqueous solution is used, the cured film is generally washed (rinsed) with pure water after development.
　なお、硬化膜の製造方法は、その他の工程を含有してもよい。
　その他の工程としては、特に制限はなく、目的に応じて適宜選択できる。
　その他の工程としては、例えば、基材の表面処理工程、前加熱工程（プリベーク工程）、後加熱工程（ポストベーク工程）等が挙げられる。
　上記前加熱工程、及び後加熱工程における加熱温度は、８０～３００℃が好ましい。
上限は、２２０℃以下がより好ましい。下限は９０℃以上が好ましい。
　前加熱工程及び後加熱工程における加熱時間は、３０～３００秒が好ましい。 In addition, the manufacturing method of a cured film may contain another process.
Other steps are not particularly limited and may be appropriately selected depending on the purpose.
Examples of the other steps include a substrate surface treatment step, a preheating step (pre-baking step), and a post-heating step (post-baking step).
The heating temperature in the preheating step and the postheating step is preferably 80 to 300 ° C.
The upper limit is more preferably 220 ° C. or lower. The lower limit is preferably 90 ° C. or higher.
The heating time in the preheating step and the postheating step is preferably 30 to 300 seconds.
［固体撮像装置、及び、固体撮像素子］
　本発明の実施形態に係る固体撮像装置、及び、固体撮像素子は、上記硬化膜を含有する。固体撮像素子が硬化膜を含有する形態としては特に制限されず、例えば、基板上に、固体撮像素子（ＣＣＤイメージセンサー、ＣＭＯＳイメージセンサー等）の受光エリアを構成する複数のフォトダイオード及びポリシリコン等からなる受光素子を有し、支持体の受光素子形成面側（例えば、受光部以外の部分及び／又は色調整用画素等）又は該形成面の反対側に本発明の硬化膜を備えて構成したものが挙げられる。
　固体撮像装置は、上記固体撮像素子を含有する。 [Solid-state imaging device and solid-state imaging device]
A solid-state imaging device and a solid-state imaging device according to an embodiment of the present invention contain the cured film. The form in which the solid-state imaging device contains a cured film is not particularly limited. For example, a plurality of photodiodes, polysilicon, and the like constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate. And comprising the cured film of the present invention on the side of the support where the light receiving element is formed (for example, the portion other than the light receiving portion and / or the color adjustment pixel) or on the opposite side of the forming surface. The thing which was done is mentioned.
The solid-state imaging device contains the solid-state imaging element.
　固体撮像装置、及び、固体撮像素子の構成例を図１～図２を参照して説明する。なお、図１～図２では、各部を明確にするため、相互の厚み及び／又は幅の比率は無視して一部誇張して表示している。
　図１に示すように、固体撮像装置１００は、矩形状の固体撮像素子１０１と、固体撮像素子１０１の上方に保持され、この固体撮像素子１０１を封止する透明なカバーガラス１０３とを備えている。更に、このカバーガラス１０３上には、スペーサー１０４を介してレンズ層１１１が重ねて設けられている。レンズ層１１１は、支持体１１３とレンズ材１１２とで構成されている。レンズ層１１１は、支持体１１３とレンズ材１１２とが一体成形された構成でもよい。レンズ層１１１の周縁領域に迷光が入射すると光の拡散によりレンズ材１１２での集光の効果が弱くなり、撮像部１０２に届く光が低減する。また、迷光によるノイズの発生も生じる。そのため、このレンズ層１１１の周縁領域は、遮光膜１１４が設けられて遮光されている。本発明の実施形態に係る硬化膜は上記遮光膜１１４としても用いることができる。 Configuration examples of the solid-state imaging device and the solid-state imaging device will be described with reference to FIGS. In FIG. 1 and FIG. 2, in order to clarify each part, the ratio of the thickness and / or width is disregarded and partly exaggerated.
As shown in FIG. 1, 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. When stray light is incident on the peripheral region of the lens layer 111, the effect of condensing light on the lens material 112 is weakened due to light diffusion, and light reaching the imaging unit 102 is reduced. In addition, noise is generated due to stray light. Therefore, the peripheral region of the lens layer 111 is shielded from light by providing a light shielding film 114. The cured film according to the embodiment of the present invention can also be used as the light shielding film 114.
　固体撮像素子１０１は、その受光面となる撮像部１０２結像した光学像を光電変換して、画像信号として出力する。この固体撮像素子１０１は、２枚の基板を積層した積層基板１０５を備えている。積層基板１０５は、同サイズの矩形状のチップ基板１０６及び回路基板１０７からなり、チップ基板１０６の裏面に回路基板１０７が積層されている。 The solid-state imaging device 101 photoelectrically converts an optical image formed on 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.
　チップ基板１０６として用いられる基板の材料としては特に制限されず、公知の材料を用いることができる。 The material of the substrate used as the chip substrate 106 is not particularly limited, and a known material can be used.
　チップ基板１０６の表面中央部には、撮像部１０２が設けられている。また、撮像部１０２の周縁領域に迷光が入射すると、この周縁領域内の回路から暗電流（ノイズ）が発生するため、この周縁領域は、遮光膜１１５が設けられて遮光されている。本発明の実施形態に係る硬化膜は遮光膜１１５として用いることもできる。 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. The cured film according to the embodiment of the present invention can also be used as the light shielding film 115.
　チップ基板１０６の表面縁部には、複数の電極パッド１０８が設けられている。電極パッド１０８は、チップ基板１０６の表面に設けられた図示しない信号線（ボンディングワイヤでも可）を介して、撮像部１０２に電気的に接続されている。 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).
　回路基板１０７の裏面には、各電極パッド１０８の略下方位置にそれぞれ外部接続端子１０９が設けられている。各外部接続端子１０９は、積層基板１０５を垂直に貫通する貫通電極１１０を介して、それぞれ電極パッド１０８に接続されている。また、各外部接続端子１０９は、図示しない配線を介して、固体撮像素子１０１の駆動を制御する制御回路、及び固体撮像素子１０１から出力される撮像信号に画像処理を施す画像処理回路等に接続されている。 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.
　図２に示すように、撮像部１０２は、受光素子２０１、カラーフィルタ２０２、マイクロレンズ２０３等の基板２０４上に設けられた各部から構成される。カラーフィルタ２０２は、青色画素２０５ｂ、赤色画素２０５ｒ、緑色画素２０５ｇ、及びブラックマトリクス２０５ｂｍを有している。本発明の実施形態に係る硬化膜は、ブラックマトリクス２０５ｂｍとして用いることもできる。 As shown in FIG. 2, 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 according to the embodiment of the present invention can also be used as the black matrix 205bm.
　基板２０４の材料としては、前述のチップ基板１０６と同様の材料を用いることができる。基板２０４の表層にはｐウェル層２０６が形成されている。このｐウェル層２６内には、ｎ型層からなり光電変換により信号電荷を生成して蓄積する受光素子２０１が正方格子状に配列形成されている。 As the material of the substrate 204, the same material as that of the above-described chip substrate 106 can be used. A p-well layer 206 is formed on the surface layer of the substrate 204. In the p-well layer 26, 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.
　受光素子２０１の一方の側方には、ｐウェル層２０６の表層の読み出しゲート部２０７を介して、ｎ型層からなる垂直転送路２０８が形成されている。また、受光素子２０１の他方の側方には、ｐ型層からなる素子分離領域２０９を介して、隣接画素に属する垂直転送路２０８が形成されている。読み出しゲート部２０７は、受光素子２０１に蓄積された信号電荷を垂直転送路２０８に読み出すためのチャネル領域である。 On one side of the light receiving element 201, 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.
　基板２０４の表面上には、ＯＮＯ（Ｏｘｉｄｅ－Ｎｉｔｒｉｄｅ－Ｏｘｉｄｅ）膜からなるゲート絶縁膜２１０が形成されている。このゲート絶縁膜２１０上には、垂直転送路２０８、読み出しゲート部２０７、及び素子分離領域２０９の略直上を覆うように、ポリシリコン又はアモルファスシリコンからなる垂直転送電極２１１が形成されている。垂直転送電極２１１は、垂直転送路２０８を駆動して電荷転送を行わせる駆動電極と、読み出しゲート部２０７を駆動して信号電荷読み出しを行わせる読み出し電極として機能する。信号電荷は、垂直転送路２０８から図示しない水平転送路及び出力部（フローティングディフュージョンアンプ）に順に転送された後、電圧信号として出力される。 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.
　垂直転送電極２１１上には、その表面を覆うように遮光膜２１２が形成されている。遮光膜２１２は、受光素子２０１の直上位置に開口部を有し、それ以外の領域を遮光している。本発明の実施形態に係る硬化膜は、遮光膜２１２として用いることもできる。
　遮光膜２１２上には、ＢＰＳＧ（ｂｏｒｏｐｈｏｓｐｈｏ　ｓｉｌｉｃａｔｅ　ｇｌａｓｓ）からなる絶縁膜２１３、Ｐ－ＳｉＮからなる絶縁膜（パシベーション膜）２１４、透明樹脂等からなる平坦化膜２１５からなる透明な中間層が設けられている。カラーフィルタ２０２は、中間層上に形成されている。 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. The cured film according to the embodiment of the present invention can also be used as the light shielding film 212.
On 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. ing. The color filter 202 is formed on the intermediate layer.
［ブラックマトリクス］
　ブラックマトリクスは、本発明の実施形態に係る硬化膜を含有する。ブラックマトリクスは、カラーフィルタ、固体撮像素子、及び、液晶表示装置に含有されることがある。
　ブラックマトリクスとしては、上記で既に説明したもの；液晶表示装置等の表示装置の周縁部に設けられた黒色の縁；赤、青、及び、緑の画素間の格子状、及び／又は、ストライプ状の黒色の部分；ＴＦＴ（ｔｈｉｎ　ｆｉｌｍ　ｔｒａｎｓｉｓｔｏｒ）遮光のためのドット状、及び／又は、線状の黒色パターン；等が挙げられる。このブラックマトリクスの定義については、例えば、菅野泰平著、「液晶ディスプレイ製造装置用語辞典」、第２版、日刊工業新聞社、１９９６年、ｐ．６４に記載がある。
　ブラックマトリクスは表示コントラストを向上させるため、また薄膜トランジスタ（ＴＦＴ）を用いたアクティブマトリックス駆動方式の液晶表示装置の場合には光の電流リークによる画質低下を防止するため、高い遮光性（光学濃度ＯＤで３以上）を有することが好ましい。 [Black matrix]
A black matrix contains the cured film which concerns on embodiment of this invention. The black matrix may be contained in a color filter, a solid-state image sensor, and a liquid crystal display device.
As the black matrix, those already described above; a black edge provided at the periphery of a display device such as a liquid crystal display device; a lattice shape between red, blue, and green pixels, and / or a stripe shape A black portion of the TFT; a dot-like and / or a linear black pattern for shielding a thin film transistor (TFT); For the definition of this black matrix, see Taihei Kanno, “Liquid Crystal Display Manufacturing Dictionary”, 2nd edition, Nikkan Kogyo Shimbun, 1996, p. 64.
The black matrix improves the display contrast, and in the case of an active matrix liquid crystal display device using a thin film transistor (TFT), in order to prevent deterioration in image quality due to light current leakage, it has a high light shielding property (with an optical density OD). 3 or more).
　ブラックマトリクスの製造方法としては特に制限されないが、上記の硬化膜の製造方法と同様の方法により製造することができる。具体的には、基板に硬化性組成物を塗布して、硬化性組成物層を形成し、露光、及び、現像してパターン状の硬化膜（ブラックマトリクス）を製造することができる。なお、ブラックマトリクスとして用いられる硬化膜の膜厚としては、０．１～４．０μｍが好ましい。 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. Specifically, 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 μm.
　上記基板の材料としては、特に制限されないが、可視光（波長：４００～８００ｎｍ）に対して８０％以上の透過率を有することが好ましい。このような材料としては、具体的には、例えば、ソーダライムガラス、無アルカリガラス、石英ガラス、及び、ホウケイ酸ガラス等のガラス；ポリエステル系樹脂、及び、ポリオレフィン系樹脂などのプラスチック；等が挙げられ、耐薬品性、及び、耐熱性の観点から、無アルカリガラス、又は、石英ガラス等が好ましい。 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-based resins and polyolefin-based resins; In view of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferable.
［カラーフィルタ］
　本発明の実施形態に係るカラーフィルタは、硬化膜を含有する。
　カラーフィルタが硬化膜を含有する形態としては、特に制限されないが、基板と、上記ブラックマトリクスと、を備えるカラーフィルタが挙げられる。すなわち、基板状に形成された上記ブラックマトリクスの開口部に形成された赤色、緑色、及び、青色の着色画素と、を備えるカラーフィルタが例示できる。 [Color filter]
The color filter according to the embodiment of the present invention contains a cured film.
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 in a substrate shape can be exemplified.
　ブラックマトリクス（硬化膜）を含有するカラーフィルタは、例えば、以下の方法により製造することができる。
　まず、基板状に形成されたパターン状のブラックマトリクスの開口部に、カラーフィルタの各着色画素に対応する顔料を含有した樹脂組成物の塗膜（樹脂組成物層）を形成する。なお、各色用樹脂組成物としては特に制限されず、公知の樹脂組成物を用いることができるが、本発明の実施形態に係る硬化性組成物において、金属窒化物含有粒子を、各画素に対応した着色剤に置き換えたものを用いることが好ましい。
　次に、樹脂組成物層に対して、ブラックマトリクスの開口部に対応したパターンを有するフォトマスクを介して露光する。次いで、現像処理により未露光部を除去した後、ベークすることでブラックマトリクスの開口部に着色画素を形成することができる。一連の操作を、例えば、赤色、緑色、及び、青色顔料を含有した各色用樹脂組成物を用いて行うことにより、赤色、緑色、及び、青色画素を有するカラーフィルタを製造することができる。 A color filter containing a black matrix (cured film) can be produced, for example, by the following method.
First, 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 in a substrate shape. The resin composition for each color is not particularly limited, and a known resin composition can be used. In the curable composition according to the embodiment of the present invention, the metal nitride-containing particles correspond to each pixel. It is preferable to use a colorant that has been replaced with the above colorant.
Next, 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. Next, after removing the unexposed portions by development processing, the colored pixels can be formed in the openings of the black matrix by baking. For example, a color filter having red, green, and blue pixels can be manufactured by performing a series of operations using a resin composition for each color that contains red, green, and blue pigments.
［液晶表示装置］
　本発明の実施形態に係る液晶表示装置は、硬化膜を含有する。液晶表示装置が硬化膜を含有する形態としては特に制限されないが、すでに説明したブラックマトリクス（硬化膜）を含有するカラーフィルタを含有する形態が挙げられる。 [Liquid Crystal Display]
The liquid crystal display device according to the embodiment of the present invention contains a cured film. The form in which the liquid crystal display device contains a cured film is not particularly limited, but examples include a form containing a color filter containing the black matrix (cured film) already described.
　本実施形態に係る液晶表示装置としては、例えば、対向して配置された一対の基板と、それらの基板の間に封入されている液晶化合物とを備える形態が挙げられる。上記基板としては、ブラックマトリクス用の基板として既に説明したとおりである。 As the liquid crystal display device according to the present embodiment, for example, a mode provided with a pair of substrates arranged opposite to each other and a liquid crystal compound sealed between the substrates can be mentioned. The substrate is as already described as the substrate for the black matrix.
　上記液晶表示装置の具体的な形態としては、例えば、使用者側から、偏光板／基板／カラーフィルタ／透明電極層／配向膜／液晶層／配向膜／透明電極層／ＴＦＴ（Ｔｈｉｎ　Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）素子／基板／偏光板／バックライトユニットをこの順に含有する積層体が挙げられる。 As a specific form of the liquid crystal display device, for example, from the user side, a polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) The laminated body which contains an element / board | substrate / polarizing plate / backlight unit in this order is mentioned.
　なお、本発明の実施形態に係る液晶表示装置としては、上記に制限されず、例えば「電子ディスプレイデバイス（佐々木　昭夫著、（株）工業調査会　１９９０年発行）」、「ディスプレイデバイス（伊吹　順章著、産業図書（株）平成元年発行）」などに記載されている液晶表示装置が挙げられる。また、例えば「次世代液晶ディスプレイ技術（内田　龍男編集、（株）工業調査会　１９９４年発行）」に記載されている液晶表示装置が挙げられる。 The liquid crystal display device according to the embodiment of the present invention is not limited to the above. For example, “Electronic display device (Akio Sasaki, published by Industrial Research Co., Ltd., 1990)”, “Display device (Junsho Ibuki) The liquid crystal display device described in the book "Industry Books Co., Ltd." issued in 1989). Further, for example, there is a liquid crystal display device described in “Next-generation liquid crystal display technology (Uchida, edited by Tatsuo, Kogyo Kenkyukai, published in 1994)”.
［赤外線センサ］
　本発明の実施形態に係る赤外線センサは、上記硬化膜を含有する。
　上記実施態様に係る赤外線センサについて、図３を用いて説明する。図３に示す赤外線センサ３００において、図番３１０は、固体撮像素子である。
　固体撮像素子３１０上に設けられている撮像領域は、赤外線吸収フィルタ３１１と本発明の実施形態に係るカラーフィルタ３１２とを組み合せて構成されている。
　赤外線吸収フィルタ３１１は、可視光線領域の光（例えば、波長４００～７００ｎｍの光）を透過し、赤外領域の光（例えば、波長８００～１３００ｎｍの光、好ましくは波長９００～１２００ｎｍの光、より好ましくは波長９００～１０００ｎｍの光）を遮蔽する膜であり、着色剤として赤外線吸収剤（赤外線吸収剤の形態としては既に説明したとおりである。）を含有する、本発明の実施形態に係る硬化膜を用いることができる。
　カラーフィルタ３１２は、可視光線領域における特定波長の光を透過及び吸収する画素が形成されたカラーフィルタであって、例えば、赤色（Ｒ）、緑色（Ｇ）、青色（Ｂ）の画素が形成されたカラーフィルタ等が用いられ、その形態は既に説明したとおりである。　赤外線透過フィルタ３１３と固体撮像素子３１０との間には、赤外線透過フィルタ３１３を透過した波長の光を透過させることができる樹脂膜３１４（例えば、透明樹脂膜など）が配置されている。
　赤外線透過フィルタ３１３は、可視光線遮蔽性を有し、かつ、特定波長の赤外線を透過させるフィルタであって、可視光線領域の光を吸収する着色剤（例えば、ペリレン化合物、及び／又は、ビスベンゾフラノン化合物等）と、赤外線吸収剤（例えば、ピロロピロール化合物、フタロシアニン化合物、ナフタロシアニン化合物、及び、ポリメチン化合物等）と、を含有する、本発明の実施形態に係る硬化膜を用いることができる。赤外線透過フィルタ３１３は、例えば、波長４００～８３０ｎｍの光を遮光し、波長９００～１３００ｎｍの光を透過させることが好ましい。
　カラーフィルタ３１２及び赤外線透過フィルタ３１３の入射光ｈν側には、マイクロレンズ３１５が配置されている。マイクロレンズ３１５を覆うように平坦化膜３１６が形成されている。
　図３に示す実施形態では、樹脂膜３１４が配置されているが、樹脂膜３１４に代えて赤外線透過フィルタ３１３を形成してもよい。すなわち、固体撮像素子３１０上に、赤外線透過フィルタ３１３を形成してもよい。
　また、図３に示す実施形態では、カラーフィルタ３１２の膜厚と、赤外線透過フィルタ３１３の膜厚が同一であるが、両者の膜厚は異なっていてもよい。
　また、図３に示す実施形態では、カラーフィルタ３１２が、赤外線吸収フィルタ３１１よりも入射光ｈν側に設けられているが、赤外線吸収フィルタ３１１と、カラーフィルタ３１２との順序を入れ替えて、赤外線吸収フィルタ３１１を、カラーフィルタ３１２よりも入射光ｈν側に設けてもよい。
　また、図３に示す実施形態では、赤外線吸収フィルタ３１１とカラーフィルタ３１２は隣接して積層しているが、両フィルタは必ずしも隣接している必要はなく、間に他の層が設けられていてもよい。
　この赤外線センサによれば、画像情報を同時に取り込むことができるため、動きを検知する対象を認識したモーションセンシングなどが可能である。更には、距離情報を取得できるため、３Ｄ情報を含んだ画像の撮影等も可能である。 [Infrared sensor]
The infrared sensor which concerns on embodiment of this invention contains the said cured film.
The infrared sensor which concerns on the said embodiment is demonstrated using FIG. In the infrared sensor 300 shown in FIG. 3, reference numeral 310 is a solid-state image sensor.
The imaging region provided on the solid-state imaging device 310 is configured by combining the infrared absorption filter 311 and the color filter 312 according to the embodiment of the present invention.
The infrared absorption filter 311 transmits light in the visible light region (for example, light having a wavelength of 400 to 700 nm), and light in the infrared region (for example, light having a wavelength of 800 to 1300 nm, preferably light having a wavelength of 900 to 1200 nm). Preferably, it is a film that shields light with a wavelength of 900 to 1000 nm, and contains an infrared absorber (as already described as the form of the infrared absorber) as a colorant. A membrane can be used.
The color filter 312 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed. For example, red (R), green (G), and blue (B) pixels are formed. A color filter or the like is used, and its form is as already described. Between the infrared transmission filter 313 and the solid-state imaging device 310, a resin film 314 (for example, a transparent resin film or the like) that can transmit light having a wavelength transmitted through the infrared transmission filter 313 is disposed.
The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared light having a specific wavelength, and is a colorant that absorbs light in the visible light region (for example, a perylene compound and / or bisbenzoic acid). A cured film according to an embodiment of the present invention containing a furanone compound or the like and an infrared absorber (for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, or a polymethine compound) can be used. For example, the infrared transmission filter 313 preferably blocks light having a wavelength of 400 to 830 nm and transmits light having a wavelength of 900 to 1300 nm.
A micro lens 315 is disposed on the incident light hν side of the color filter 312 and the infrared transmission filter 313. A planarization film 316 is formed so as to cover the microlens 315.
In the embodiment shown in FIG. 3, the resin film 314 is disposed, but an infrared transmission filter 313 may be formed instead of the resin film 314. That is, the infrared transmission filter 313 may be formed on the solid-state image sensor 310.
In the embodiment shown in FIG. 3, the film thickness of the color filter 312 and the film thickness of the infrared transmission filter 313 are the same, but the film thickness of both may be different.
In the embodiment shown in FIG. 3, the color filter 312 is provided closer to the incident light hν than the infrared absorption filter 311, but the infrared absorption filter 311 and the color filter 312 are switched in order to absorb infrared rays. The filter 311 may be provided closer to the incident light hν than the color filter 312.
In the embodiment shown in FIG. 3, the infrared absorption filter 311 and the color filter 312 are stacked adjacent to each other. However, the two filters are not necessarily adjacent to each other, and other layers are provided between them. Also good.
According to this infrared sensor, since image information can be captured simultaneously, motion sensing or the like that recognizes a target whose motion is to be detected is possible. Furthermore, since distance information can be acquired, an image including 3D information can be taken.
　次に、上記赤外線センサを適用した固体撮像装置について説明する。
　上記固体撮像装置は、レンズ光学系と、固体撮像素子と、赤外発光ダイオード等を含有する。なお、固体撮像装置の各構成については、特開２０１１－２３３９８３号公報の段落００３２～００３６を参酌することができ、この内容は本願明細書に組み込まれる。 Next, a solid-state imaging device to which the infrared sensor is applied will be described.
The solid-state imaging device includes a lens optical system, a solid-state imaging device, an infrared light emitting diode, and the like. Regarding each configuration of the solid-state imaging device, paragraphs 0032 to 0036 of JP2011-233983 can be referred to, and the contents thereof are incorporated in the present specification.
　また、上記硬化膜は、パーソナルコンピュータ、タブレット、携帯電話、スマートフォン、及び、デジタルカメラ等のポータブル機器；プリンタ複合機、及び、スキャナ等のＯＡ（Ｏｆｆｉｃｅ　Ａｕｔｏｍａｔｉｏｎ）機器；監視カメラ、バーコードリーダ、現金自動預け払い機（ＡＴＭ：automated teller machine）、ハイスピードカメラ、及び、顔画像認証を使用した本人認証機能を有する機器等の産業用機器；車載用カメラ機器；内視鏡、カプセル内視鏡、及び、カテーテル等の医療用カメラ機器；生体センサ、バイオセンサー、軍事偵察用カメラ、立体地図用カメラ、気象及び海洋観測カメラ、陸地資源探査カメラ、並びに、宇宙の天文及び深宇宙ターゲット用の探査カメラ等の宇宙用機器；等に使用される光学フィルタ及びモジュールの遮光部材及び遮光膜、更には反射防止部材及び反射防止膜に好適である。 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 identity authentication using facial image authentication; in-vehicle camera equipment; endoscopes, capsule endoscopes, And medical camera equipment such as catheters; biosensors, biosensors, military reconnaissance cameras, stereoscopic map cameras, weather and ocean observation cameras, land resource exploration cameras, and exploration cameras for space astronomy and deep space targets Optical filters and modules used in space equipment such as Light blocking member and the light-shielding film, further is suitable for anti-reflection member and the antireflection film.
　上記硬化膜は、マイクロＬＥＤ（Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）及びマイクロＯＬＥＤ（Ｏｒｇａｎｉｃ　Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）などの用途にも用いることができる。上記硬化膜は、マイクロＬＥＤ及びマイクロＯＬＥＤに使用される光学フィルタ及び光学フィルムのほか、遮光機能又は反射防止機能を付与する部材に対して好適である。
　マイクロＬＥＤ及びマイクロＯＬＥＤの例としては、特表２０１５－５００５６２号及び特表２０１４－５３３８９０に記載されたものが挙げられる。 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.
　上記硬化膜は、量子ドットディスプレイに使用される光学及び光学フィルムとして好適である。また、遮光機能及び反射防止機能を付与する部材として好適である。
　量子ドットディスプレイの例としては、米国特許出願公開第２０１３／０３３５６７７号、米国特許出願公開第２０１４／００３６５３６号、米国特許出願公開第２０１４／００３６２０３号、及び、米国特許出願公開第２０１４／００３５９６０号に記載されたものが挙げられる。 The cured film is suitable as an optical and optical film used in quantum dot displays. Moreover, it is suitable as a member which provides a light shielding function and an antireflection function.
Examples of quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. What has been described.
　以下に実施例に基づいて本発明を更に詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、及び、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更できる。従って、本発明の範囲は以下に示す実施例により限定的に解釈されるべきものではない。なお、％及び部は、特に断らない限り質量基準を意図する。 Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below. Note that% and parts are based on mass unless otherwise specified.
［金属窒化物含有粒子の作製］
　以下の方法により、金属窒化物含有粒子をそれぞれ作製した。 [Production of metal nitride-containing particles]
Metal nitride-containing particles were produced by the following methods.
〔チタン窒化物含有粒子ＴｉＮ－１の作製〕
　表１に記載の各成分を用いてチタン窒化物含有粒子ＴｉＮ－１を作製した。
　まず、表１に記載のＴｉ粒子をＡｒガス中においてプラズマ処理し、Ｔｉナノ粒子を得た。上記のＴｉナノ粒子を、Ａｒガス雰囲気下でＯ２濃度５０ｐｐｍ以下、３０℃の条件で２４時間静置した後、Ｏ２濃度が１００ｐｐｍとなるようにＡｒガス雰囲気にＯ２ガスを導入した状態で、Ｔｉナノ粒子を、３０℃で、２４時間静置した（以上を、「Ｔｉ粒子の前処理」とする。）。
　その後、ホソカワミクロン製ＴＴＳＰセパレータを用いて収率１０％となる条件で得られたＴｉナノ粒子を分級し、Ｔｉナノ粒子の粉末を得た。得られた粉末の一次粒径は、ＴＥＭ（Transmission Electron Microscope）観察によって１００個の粒子の粒子径を求め、更に、これらの算術平均により求めたところ、１２０ｎｍであった。
　チタン窒化物含有粒子ＴｉＮ－１は、国際公開第２０１０／１４７０９８号の図１に記載の黒色複合微粒子製造装置に準ずる装置を用いて製造した。
　具体的には、黒色複合微粒子製造装置において、プラズマトーチの高周波発振用コイルには、約４ＭＨｚ及び約８０ｋＶＡの高周波電圧を印加し、プラズマガス供給源からはプラズマガスとしてアルゴンガス５０Ｌ／ｍｉｎ及び窒素５０Ｌ／ｍｉｎの混合ガスを供給し、プラズマトーチ内にアルゴン－窒素熱プラズマ炎を発生させた。また、材料供給装置の噴霧ガス供給源からは１０Ｌ／ｍｉｎのキャリアガス（Ａｒガス）を供給した。
　そして、上記のようにして得られたＴｉナノ粒子、及び、表１に記載の添加粒子を、表１に記載の組成となるよう混合し、キャリアガスであるＡｒガスと共に、プラズマトーチ内の熱プラズマ炎中に供給し、供給した粒子を熱プラズマ炎中で蒸発させ、気相状態で高度に分散させた。
　また、気体供給装置によって、チャンバ内に供給される気体としては、窒素ガスを使用した。このときのチャンバ内の窒素ガスの流速は５ｍ／ｓｅｃとして、窒素ガスの供給量は１０００Ｌ／ｍｉｎとした。また、サイクロン内の圧力は５０ｋＰａとし、また、チャンバからサイクロンへの各原料の供給速度は、１０ｍ／ｓ（平均値）とした。
　このようにして、チタン窒化物含有粒子ＴｉＮ－１を得た。 [Production of titanium nitride-containing particles TiN-1]
Titanium nitride-containing particles TiN-1 were produced using the components shown in Table 1.
First, Ti particles described in Table 1 were plasma-treated in Ar gas to obtain Ti nanoparticles. A state in which the above-mentioned Ti nanoparticles are allowed to stand under an Ar gas atmosphere under an O 2 concentration of 50 ppm or less and 30 ° C. for 24 hours, and then O 2 gas is introduced into the Ar gas atmosphere so that the O 2 concentration becomes 100 ppm. Then, the Ti nanoparticles were allowed to stand at 30 ° C. for 24 hours (the above is referred to as “pretreatment of Ti particles”).
Thereafter, Ti nanoparticles obtained under the condition of a yield of 10% using a TTSP separator manufactured by Hosokawa Micron were classified to obtain a powder of Ti nanoparticles. The primary particle diameter of the obtained powder was 120 nm when the particle diameter of 100 particles was obtained by TEM (Transmission Electron Microscope) observation and further obtained by arithmetic average thereof.
The titanium nitride-containing particles TiN-1 were produced using an apparatus similar to the black composite fine particle production apparatus described in FIG. 1 of WO2010 / 147098.
Specifically, in the black composite fine particle manufacturing apparatus, a high frequency voltage of about 4 MHz and about 80 kVA is applied to the high frequency oscillation coil of the plasma torch, and argon gas 50 L / min and nitrogen as plasma gas are supplied from the plasma gas supply source. A mixed gas of 50 L / min was supplied to generate an argon-nitrogen thermal plasma flame in the plasma torch. Moreover, 10 L / min carrier gas (Ar gas) was supplied from the spray gas supply source of the material supply apparatus.
Then, the Ti nanoparticles obtained as described above and the additive particles shown in Table 1 are mixed so as to have the composition shown in Table 1, and together with the Ar gas as the carrier gas, the heat in the plasma torch It was fed into a plasma flame, and the fed particles were evaporated in a thermal plasma flame and highly dispersed in a gas phase.
Further, nitrogen gas was used as the gas supplied into the chamber by the gas supply device. At this time, the flow rate of nitrogen gas in the chamber was 5 m / sec, and the supply amount of nitrogen gas was 1000 L / min. The pressure in the cyclone was 50 kPa, and the supply rate of each raw material from the chamber to the cyclone was 10 m / s (average value).
In this way, titanium nitride-containing particles TiN-1 were obtained.
　得られたチタン窒化物含有粒子ＴｉＮ－１について、ＩＣＰ（Ｉｎｄｕｃｔｉｖｅｌｙ　Ｃｏｕｐｌｅｄ　Ｐｌａｓｍａ）発光分光分析法によって、チタン（Ｔｉ）原子、Ｆｅ（鉄）原子、及び、ケイ素（Ｓｉ）原子の含有量を測定した。結果を表１に示した。なお、ＩＣＰ発光分光分析法には、セイコーインスツルメンツ社製のＩＣＰ発光分光分析装置「ＳＰＳ３０００」（商品名）を用いた。
　また、窒素原子の含有量については、堀場製作所製の酸素・窒素分析装置「ＥＭＧＡ－６２０Ｗ／Ｃ」（商品名）を用いて測定し、不活性ガス融解－熱伝導度法により算出した。結果を表１に示した。
　なお、後述するチタン窒化物含有粒子ＴｉＮ－２～ＴｉＮ－４についても、チタン窒化物含有粒子ＴｉＮ－１と同様の方法によって、Ｔｉ原子、Ｆｅ原子、ケイ素原子、及び、窒素原子の含有量を測定した。結果を表１に示した。 With respect to the obtained titanium nitride-containing particles TiN-1, the contents of titanium (Ti) atoms, Fe (iron) atoms, and silicon (Si) atoms were measured by ICP (Inductively Coupled Plasma) emission spectroscopy. . The results are shown in Table 1. For the ICP emission spectroscopic analysis, an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
The nitrogen atom content was measured using an oxygen / nitrogen analyzer “EMGA-620W / C” (trade name) manufactured by Horiba, Ltd., and calculated by an inert gas melting-thermal conductivity method. The results are shown in Table 1.
For titanium nitride-containing particles TiN-2 to TiN-4, which will be described later, the contents of Ti atoms, Fe atoms, silicon atoms, and nitrogen atoms are also set in the same manner as titanium nitride-containing particles TiN-1. It was measured. The results are shown in Table 1.
　チタン窒化物含有粒子ＴｉＮ－１のＸ線回折は、粉末試料をアルミ製標準試料ホルダーに詰め、広角Ｘ線回折法（理学電機社製、商品名「ＲＵ－２００Ｒ」）により測定した。測定条件としては、Ｘ線源はＣｕＫα線とし、出力は５０ｋＶ／２００ｍＡ、スリット系は１°－１°－０．１５ｍｍ－０．４５ｍｍ、測定ステップ（２θ）は０．０２°、スキャン速度は２°／分とした。
　そして、回折角２θ（４２．６°）付近に観察されるＴｉＮ（２００）面に由来するピークの回折角を測定した。更に、この（２００）面に由来するピークの半値幅より、シェラーの式を用いて、粒子を構成する結晶子サイズを求めた。
　なお、以下のチタン窒化物含有粒子ＴｉＮ－２～ＴｉＮ－４についても、チタン窒化物含有粒子ＴｉＮ－１と同様の方法によって、回折角２θ、結晶子サイズを測定した。結果を表１に示す。なお、いずれのチタン窒化物含有粒子についても、ＴｉＯ２に起因するＸ線回折ピークは、全く見られなかった。 X-ray diffraction of titanium nitride-containing particles TiN-1 was measured by a wide-angle X-ray diffraction method (trade name “RU-200R” manufactured by Rigaku Corporation) with a powder sample placed in an aluminum standard sample holder. As measurement conditions, the X-ray source is CuKα ray, the output is 50 kV / 200 mA, the slit system is 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) is 0.02 °, and the scan speed is It was 2 ° / min.
And the diffraction angle of the peak derived from the TiN (200) plane observed in the vicinity of the diffraction angle 2θ (42.6 °) was measured. Furthermore, from the half width of the peak derived from the (200) plane, the crystallite size constituting the particle was determined using Scherrer's equation.
For the following titanium nitride-containing particles TiN-2 to TiN-4, the diffraction angle 2θ and crystallite size were measured in the same manner as the titanium nitride-containing particles TiN-1. The results are shown in Table 1. In any of the titanium nitride-containing particles, no X-ray diffraction peak attributed to TiO 2 was observed.
〔チタン窒化物含有粒子ＴｉＮ－２～ＴｉＮ－４の作製〕
　原料、及び、組成を表１に示したとおりとした以外は、チタン窒化物含有粒子ＴｉＮ－１と同様にして、チタン窒化物含有粒子ＴｉＮ－２～ＴｉＮ－４を製造した。 [Production of titanium nitride-containing particles TiN-2 to TiN-4]
Titanium nitride-containing particles TiN-2 to TiN-4 were produced in the same manner as titanium nitride-containing particles TiN-1, except that the raw materials and compositions were as shown in Table 1.
Figure JPOXMLDOC01-appb-T000026
　なお、表中、「ｗｔ％」は質量％を意図する。また、表中、「ＴｉＮ粒子」とは、チタン窒化物含有粒子を意図する。
Figure JPOXMLDOC01-appb-T000026
In the table, “wt%” intends mass%. In the table, “TiN particles” mean titanium nitride-containing particles.
［金属窒化物含有粒子分散液１～１１の作製］
　金属窒化物含有粒子、分散剤、及び、有機溶剤を、それぞれ表２に示した組成となるよう、攪拌機（ＩＫＡ社製ＥＵＲＯＳＴＡＲ）によって１５分間混合して、混合液を得た。次に、得られた混合液に対して、シンマルエンタープライゼス製のＮＰＭ－Ｐｉｌｏｔを使用して下記条件にて分散処理を行い、金属窒化物含有粒子分散液を得た。 [Preparation of metal nitride-containing particle dispersions 1 to 11]
The metal nitride-containing particles, the dispersant, and the organic solvent were mixed for 15 minutes with a stirrer (EUROSTAR manufactured by IKA) so that the compositions shown in Table 2 were obtained, thereby obtaining a mixed solution. Next, the obtained mixed solution was subjected to a dispersion treatment using NPM-Pilot made by Shinmaru Enterprises under the following conditions to obtain a metal nitride-containing particle dispersion.
＜分散条件＞
・ビーズ径：φ０．０５ｍｍ、（ニッカトー製ジルコニアビーズ、ＹＴＺ）
・ビーズ充填率：６５体積％
・ミル周速：１０ｍ／ｓｅｃ
・セパレータ周速：１３ｍ／ｓ
・分散処理する混合液量：１５ｋｇ
・循環流量（ポンプ供給量）：９０ｋｇ／ｈｏｕｒ
・処理液温度：１９～２１℃
・冷却水：水
・処理時間：２２時間程度 <Distribution conditions>
・ Bead diameter: 0.05mm, (Nikkato zirconia beads, YTZ)
・ Bead filling rate: 65% by volume
・ Mill peripheral speed: 10m / sec
・ Separator peripheral speed: 13m / s
・ Amount of liquid mixture to be dispersed: 15kg
・ Circulating flow rate (pump supply amount): 90 kg / hour
・ Processing liquid temperature: 19-21 ℃
・ Cooling water: Water ・ Processing time: About 22 hours
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　なお、表２における各略号は、以下の成分を示す。 In addition, each abbreviation in Table 2 indicates the following components.
（金属窒化物含有粒子）
・ＺｒＮ：ジルコニウム窒化物含有粒子、日本新金属株式会社製、商品名「ＺｒＮ－０１」
・ＶＮ：バナジウム窒化物含有粒子、日本新金属株式会社製、商品名「ＶＮ－Ｏ」
・ＮｂＮ：ニオブ窒化物含有粒子、日本新金属株式会社製、商品名「ＮｂＮ－Ｏ」 (Metal nitride-containing particles)
ZrN: zirconium nitride-containing particles, manufactured by Nippon Shin Metal Co., Ltd., trade name “ZrN-01”
VN: vanadium nitride-containing particles, manufactured by Nippon Shin Metal Co., Ltd., trade name “VN-O”
NbN: Niobium nitride-containing particles, manufactured by Nippon Shin Metal Co., Ltd., trade name “NbN-O”
（分散剤）
・分散剤１：ＢＹＫ社製、商品名「ＢＹＫ－１１１」 (Dispersant)
-Dispersant 1: Product name "BYK-111" manufactured by BYK
・分散剤２：下記式により表される分散剤
Figure JPOXMLDOC01-appb-C000028
　なお、「Ｍｗ」は重量平均分子量を意図する。 -Dispersant 2: Dispersant represented by the following formula
Figure JPOXMLDOC01-appb-C000028
“Mw” intends a weight average molecular weight.
・分散剤３：下記式により表される分散剤
Figure JPOXMLDOC01-appb-C000029
 -Dispersant 3: Dispersant represented by the following formula
Figure JPOXMLDOC01-appb-C000029
・分散剤４：下記式により表される分散剤（重量平均分子量：２４００００）
Figure JPOXMLDOC01-appb-C000030
 Dispersant 4: Dispersant represented by the following formula (weight average molecular weight: 240000)
Figure JPOXMLDOC01-appb-C000030
（溶剤）
・ＰＧＭＥＡ：プロピレングリコール１－モノメチルエーテル２－アセタート (solvent)
・ PGMEA: Propylene glycol 1-monomethyl ether 2-acetate
［実施例１～２６、及び、比較例１～５：硬化性組成物の調製］
　次に、表３に記載の組成となるよう、上記金属窒化物含有粒子分散液にその他の成分を混合し、各硬化性組成物を得た。なお、表３中における各成分の含有量はいずれも質量％を意図する。
　なお、各硬化性組成物の最終的な固形分は、３０質量％となるよう、有機溶剤で調整した。なお、固形分調整用の溶剤は、ＰＧＭＥＡ（propyleneglycol monomethyl ether acetate）を用いた。 [Examples 1 to 26 and Comparative Examples 1 to 5: Preparation of Curable Composition]
Next, other components were mixed in the metal nitride-containing particle dispersion so as to have the composition shown in Table 3, and each curable composition was obtained. In addition, all content of each component in Table 3 intends mass%.
In addition, the final solid content of each curable composition was adjusted with the organic solvent so that it might become 30 mass%. Note that PGMEA (propyleneglycol monomethyl ether acetate) was used as the solvent for adjusting the solid content.
　なお、表３中の各番号は以下の成分を表す。 In addition, each number in Table 3 represents the following components.
（酸無水物）
・酸無水物１：無水マレイン酸
・酸無水物２：無水フタル酸 (Acid anhydride)
-Acid anhydride 1: Maleic anhydride-Acid anhydride 2: Phthalic anhydride
・酸無水物３：３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（４，４’－ビフタル酸無水物）（１分子中に２個の酸無水物基を含有する。）
Figure JPOXMLDOC01-appb-C000031
 Acid anhydride 3: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (4,4′-biphthalic anhydride) (containing two acid anhydride groups in one molecule) )
Figure JPOXMLDOC01-appb-C000031
・酸無水物４：４，４’－オキシジフタル酸無水物（１分子中に２個の酸無水物基を含有する。）
Figure JPOXMLDOC01-appb-C000032
 Acid anhydride 4: 4,4′-oxydiphthalic anhydride (contains two acid anhydride groups in one molecule)
Figure JPOXMLDOC01-appb-C000032
・酸無水物５：３，４’－カルボニルジフタル酸無水物（１分子中に２個の酸無水物基を含有する。）
Figure JPOXMLDOC01-appb-C000033
 Acid anhydride 5: 3,4′-carbonyldiphthalic anhydride (containing two acid anhydride groups in one molecule)
Figure JPOXMLDOC01-appb-C000033
（アルカリ可溶性樹脂）
・アルカリ可溶性樹脂１：ベンジルメタクリレート／アクリル酸共重合体〔組成比：ベンジルメタクリレート／アクリル酸共重合体＝８０／２０（質量％）、Ｍｗ：２５０００〕 (Alkali-soluble resin)
Alkali-soluble resin 1: benzyl methacrylate / acrylic acid copolymer [composition ratio: benzyl methacrylate / acrylic acid copolymer = 80/20 (mass%), Mw: 25000]
・アルカリ可溶性樹脂２：以下の方法により合成したポリイミド前駆体（ポリアミック酸） Alkali-soluble resin 2: Polyimide precursor (polyamic acid) synthesized by the following method
　上記ポリイミド前駆体（ポリアミック酸）は、以下の方法により合成した。まず、４，４’－ジアミノベンズアニリド（０．４７５モル当量）、３，３’－ジアミノジフェニルスルフォン（０．４７５モル当量）、及び、ビス（３－アミノプロピル）テトラメチルジシロキサン（０．０５モル当量）を、Ｎ－メチル－２－ピロリドン１７００ｇと共に、反応容器に入れ、混合物を得た。上記混合物に、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（０．９８モル当量）を添加し、７０℃で３時間反応させ、反応液を得た。上記反応液に、無水フタル酸（０．０４モル当量）を添加し、更に７０℃で１時間反応させ、ポリアミック酸Ａ－１（ポリマー濃度１７重量％、イミド閉環率１３％、繰り返し単位の分子量５３２）溶液を得た。ここで、ポリアミック酸Ａ－１の繰り返し単位の分子量は下記要領にて計算されたものである。 The polyimide precursor (polyamic acid) was synthesized by the following method. First, 4,4′-diaminobenzanilide (0.475 molar equivalent), 3,3′-diaminodiphenylsulfone (0.475 molar equivalent), and bis (3-aminopropyl) tetramethyldisiloxane (0. (05 molar equivalents) together with 1700 g of N-methyl-2-pyrrolidone was placed in a reaction vessel to obtain a mixture. 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (0.98 molar equivalent) was added to the above mixture and reacted at 70 ° C. for 3 hours to obtain a reaction solution. Phthalic anhydride (0.04 molar equivalent) was added to the above reaction solution, and the mixture was further reacted at 70 ° C. for 1 hour. Polyamic acid A-1 (polymer concentration 17% by weight, imide ring closure rate 13%, molecular weight of repeating unit) 532) A solution was obtained. Here, the molecular weight of the repeating unit of polyamic acid A-1 was calculated in the following manner.
　繰り返し単位の分子量＝２×（２２７×０．４７５＋２４８×０．４７５＋２４９×０．０５＋２９４×０．９８）／（０．４７５＋０．４７５＋０．０５＋０．９８）＝５３２
　また、ポリアミック酸Ａ－１をイミド化して得られるポリイミド樹脂の繰り返し単位の分子量Ｍ１は４９６となり、ポリイミド樹脂の繰り返し単位に含まれるイミノ基、及び／又は、イミノカルボニル基のモル数ｎ１は０．４７５モルである。　 Molecular weight of repeating unit = 2 × (227 × 0.475 + 248 × 0.475 + 249 × 0.05 + 294 × 0.98) / (0.475 + 0.475 + 0.05 + 0.98) = 532
The molecular weight M1 of the repeating unit of the polyimide resin obtained by imidizing the polyamic acid A-1 is 496, and the number of moles n1 of the imino group and / or iminocarbonyl group contained in the repeating unit of the polyimide resin is 0. 475 moles.
（重合性化合物）
　下記式により表される重合性化合物
Figure JPOXMLDOC01-appb-C000034
 (Polymerizable compound)
The polymerizable compound represented by the following formula
Figure JPOXMLDOC01-appb-C000034
（オキシム系重合開始剤）
・オキシム系重合開始剤１：ＩＲＧＡＣＵＲＥ　ＯＸＥ－０２（ＢＡＳＦ社製）
・オキシム系重合開始剤２：アデカアークルズＮＣＩ－８３１（ＡＤＥＫＡ社製、ニトロ基を含有する。） (Oxime polymerization initiator)
・ Oxime polymerization initiator 1: IRGACURE OXE-02 (manufactured by BASF)
Oxime polymerization initiator 2: Adeka Arcles NCI-831 (manufactured by ADEKA, containing nitro group)
（重合禁止剤）
　・重合禁止剤：４－メトキシフェノール (Polymerization inhibitor)
・ Polymerization inhibitor: 4-methoxyphenol
（界面活性剤）
・界面活性剤１：下記式により表される界面活性剤（重量平均分子量（Ｍｗ）＝１５３１１）
　ただし、下記式において、式中（Ａ）及び（Ｂ）で表される構造単位はそれぞれ６２モル％、３８モル％である。式（Ｂ）で表される構造単位中、ａは、ｂ、ｃは、それぞれ、ａ＋ｃ＝１４、ｂ＝１７の関係を満たす。 (Surfactant)
Surfactant 1: Surfactant represented by the following formula (weight average molecular weight (Mw) = 15311)
However, in the following formula, the structural units represented by the formulas (A) and (B) are 62 mol% and 38 mol%, respectively. In the structural unit represented by the formula (B), a, b, and c satisfy the relationships of a + c = 14 and b = 17, respectively.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
・界面活性剤２：「ＬＣ９５１」、楠本化成社製 ・ Surfactant 2: “LC951”, manufactured by Enomoto Kasei Co., Ltd.
［評価］
　上記各硬化性組成物を、以下の方法で評価した。 [Evaluation]
Each said curable composition was evaluated with the following method.
〔光学濃度（ＯＤ：Ｏｐｔｉｃａｌ　ｄｅｎｓｉｃｔｙ）の測定〕
　上記硬化性組成物をガラス基板上に、乾燥後の膜厚が１．５μｍとなるよう塗布し、硬化性組成物層を得た。得られた硬化性組成物層を、ホットプレート上に、ガラス基板を下にして載置し、１００℃で、２分間、加熱し、乾燥させた。
　乾燥後の硬化性組成物層に対し、５００ｍＪ／ｃｍ２の照射量で露光し、硬化膜を得た。
　上記硬化膜について、Ｖ－７２００Ｆ（日本分光社製）を用いて、波長３８０～１１００ｎｍにおける光学濃度（ＯＤ）を測定した。結果を表３（表３（その１）～表３（その３））に示した。
　なお、得られたＯＤは、波長４００～１１００ｎｍにおける最小のＯＤである。すなわち、上記硬化膜（膜厚：１．５μｍ）は、波長４００～１１００ｎｍの全域において表３（表３（その１）～表３（その３））に示したＯＤ以上のＯＤを有する。 [Measurement of optical density (OD: Optical density)]
The said curable composition was apply | coated on the glass substrate so that the film thickness after drying might be set to 1.5 micrometers, and the curable composition layer was obtained. The obtained curable composition layer was placed on a hot plate with the glass substrate facing down, heated at 100 ° C. for 2 minutes, and dried.
The curable composition layer after drying was exposed with an irradiation amount of 500 mJ / cm 2 to obtain a cured film.
The cured film was measured for optical density (OD) at a wavelength of 380 to 1100 nm using V-7200F (manufactured by JASCO Corporation). The results are shown in Table 3 (Table 3 (Part 1) to Table 3 (Part 3)).
The obtained OD is the minimum OD at a wavelength of 400 to 1100 nm. That is, the cured film (film thickness: 1.5 μm) has an OD equal to or higher than the OD shown in Table 3 (Table 3 (Part 1) to Table 3 (Part 3)) in the entire wavelength range of 400 to 1100 nm.
〔保存安定性の評価〕
＜１．硬化性組成物の露光感度（初期）＞
　調製直後の各硬化性組成物を、ガラス基板上にスピンコートを用いて塗布し、乾燥して膜厚１．０μｍの硬化性組成物層を形成した。スピンコートの条件は、まず、回転数：３００ｒｐｍ（ｒｏｔａｔｉｏｎ　ｐｅｒ　ｍｉｎｕｔｅ）で、５秒間、次いで、８００ｒｐｍで２０秒間とした。また、乾燥条件は１００℃で８０秒とした。
　上記により得られた塗膜に対して、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を用いて、波長３６５ｎｍの光を、１μｍのラインアンドスペースを有するパターンマスクを通して１０～１６００ｍＪ／ｃｍ２の露光量で照射した。次に、６０％ＣＤ－２０００（富士フイルムエレクトロニクスマテリアルズ社製）現像液を使用して、露光後の硬化性組成物層を、２５℃、６０秒間の条件で現像し、パターン状の硬化膜を得た。その後、パターン状の硬化膜を流水で２０秒間リンスした後、エアー乾燥した。
　上記露光工程において、光が照射された領域の現像後のパターン線幅が、１．０μｍ以上となる最小の露光量を露光感度とし、この露光感度を初期の露光感度とした。 [Evaluation of storage stability]
<1. Exposure sensitivity of curable composition (initial)>
Each curable composition immediately after the preparation was applied onto a glass substrate using a spin coat and dried to form a curable composition layer having a thickness of 1.0 μm. The spin coating conditions were as follows: first, rotation speed: 300 rpm (rotation per minute) for 5 seconds, and then 800 rpm for 20 seconds. The drying conditions were 100 ° C. and 80 seconds.
Using the i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the coating film obtained as described above was subjected to light having a wavelength of 365 nm through a pattern mask having a line and space of 1 μm to 10-1600 mJ / It was irradiated at an exposure dose of cm 2. Next, using a 60% CD-2000 (produced by Fuji Film Electronics Materials) developer, the curable composition layer after exposure was developed under the conditions of 25 ° C. and 60 seconds to obtain a patterned cured film. Got. Thereafter, the patterned cured film was rinsed with running water for 20 seconds and then air-dried.
In the above exposure step, the minimum exposure amount at which the pattern line width after development of the region irradiated with light was 1.0 μm or more was defined as exposure sensitivity, and this exposure sensitivity was defined as the initial exposure sensitivity.
＜２．硬化性組成物の露光感度（経時後：４５℃で３０日間経過後）＞
　調製直後の硬化性組成物を密閉容器に封入し、器内温度が４５℃に設定された恒温器（ＥＹＥＬＡ／ＬＴＩ－７００）内に保持し、３０日間経過後に取り出した。取り出した硬化性組成物を用いて、調製直後の硬化性組成物を用いて行ったのと同様の試験を行い、露光感度を求めた。これを経時後の露光感度とした。 <2. Exposure sensitivity of curable composition (after time: after 30 days at 45 ° C.)>
The curable composition immediately after preparation was sealed in a sealed container, held in a thermostatic chamber (EYELA / LTI-700) in which the internal temperature was set to 45 ° C., and taken out after 30 days. Using the extracted curable composition, the same test as that performed using the curable composition immediately after preparation was performed, and the exposure sensitivity was obtained. This was taken as the exposure sensitivity after time.
＜評価＞
　初期の露光感度と、経時後の露光感度から、以下の式で求められる露光感度の変動率（％）を算出した。上記変動率（％）の値が小さいほど保存安定性が優れていることを示す。
（式）変動率＝（経時後の露光感度－初期の露光感度）／初期の露光感度×１００ <Evaluation>
From the initial exposure sensitivity and the exposure sensitivity after time, the fluctuation rate (%) of the exposure sensitivity obtained by the following formula was calculated. The smaller the value of the fluctuation rate (%), the better the storage stability.
(Expression) Fluctuation rate = (exposure sensitivity after time-initial exposure sensitivity) / initial exposure sensitivity × 100
〔未露光部残渣の評価〕
　上記の＜１．硬化性組成物の露光感度（初期）＞の試験において、現像後のパターン線幅が１．０μｍ以上となる最小の露光量で得られた硬化膜を、ガラス基板ごと２２０℃のオーブンで１時間加熱した。硬化膜を加熱した後、ガラス基板上の、露光工程において光が照射されなかった領域（未露光部）に存在する残渣の数をＳＥＭ（Ｓｃａｎｎｉｎｇ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ、倍率：２００００倍）にて観察し、未露光部残渣を評価した。評価は以下の基準により行い、結果を表３（表３（その１）～表３（その３））に示した。なお、実用上、評価「３」以上が好ましく、４及び５は優れた性能を有すると評価する。 [Evaluation of unexposed area residue]
<1. In a test of exposure sensitivity (initial)> of the curable composition, a cured film obtained with a minimum exposure amount at which the pattern line width after development was 1.0 μm or more was placed in an oven at 220 ° C. for 1 hour together with the glass substrate Heated. After heating the cured film, the number of residues present on the glass substrate in the region not exposed to light in the exposure process (unexposed portion) was observed with SEM (Scanning Electron Microscope, magnification: 20000 times), Unexposed residue was evaluated. Evaluation was performed according to the following criteria, and the results are shown in Table 3 (Table 3 (Part 1) to Table 3 (Part 3)). In practice, an evaluation of “3” or higher is preferable, and 4 and 5 are evaluated as having excellent performance.
－評価基準－
　５：パターンが形成され、未露光部には、残渣が全く観察されなかった。
　４：パターンが形成され、未露光部１．０μｍ四方に残渣が１～３個観察された。
　３：パターンが形成され、未露光部１．０μｍ四方に残渣が４～１０個観察された。
　２：パターンが形成され、未露光部１．０μｍ四方に残渣が１１個以上観察された。
　１：現像不良でパターン形成されなかった。 -Evaluation criteria-
5: A pattern was formed, and no residue was observed in the unexposed area.
4: A pattern was formed, and 1 to 3 residues were observed in an unexposed area of 1.0 μm square.
3: A pattern was formed, and 4 to 10 residues were observed in an unexposed area of 1.0 μm square.
2: A pattern was formed, and 11 or more residues were observed in an unexposed area of 1.0 μm square.
1: No pattern was formed due to poor development.
〔パターンエッジ形状の評価〕
　以下の方法により、各硬化性組成物を用いて形成したパターン状の硬化膜のパターンエッジ形状を評価した。 [Evaluation of pattern edge shape]
The pattern edge shape of the patterned cured film formed using each curable composition was evaluated by the following method.
＜硬化性組成物層形成工程＞
　シリコンウェハ上に、乾燥後の膜厚が１．５μｍになるように、硬化性組成物層を形成した。硬化性組成物層の形成は、スピンコートを用いて行った。上記膜厚となるよう、スピンコートの回転数を調整した。塗布後の硬化性組成物層を、シリコンウェハを下にしてホットプレート上に載置して乾燥した。ホットプレートの表面温度は１００℃で、乾燥時間は、１２０秒間とした。 <Curable composition layer forming step>
A curable composition layer was formed on the silicon wafer so that the film thickness after drying was 1.5 μm. The curable composition layer was formed using spin coating. The number of rotations of the spin coat was adjusted so as to achieve the above film thickness. The applied curable composition layer was placed on a hot plate with the silicon wafer facing down and dried. The surface temperature of the hot plate was 100 ° C., and the drying time was 120 seconds.
＜露光工程＞
　得られた硬化性組成物層を、以下の条件で露光した。
　露光は、ｉ線ステッパー（商品名「ＦＰＡ－３０００ｉＳ＋」、キャノン社製）を用いて行った。硬化性組成物層に対して、線形２０μｍ（幅２０μｍ、長さ４ｍｍ）を有するマスクを介して４００ｍＪ／ｃｍ２の露光量（照射時間０．５秒）で照射（露光）した。 <Exposure process>
The obtained curable composition layer was exposed under the following conditions.
The exposure was performed using an i-line stepper (trade name “FPA-3000iS +”, manufactured by Canon Inc.). The curable composition layer was irradiated (exposed) with an exposure dose of 400 mJ / cm 2 (irradiation time 0.5 seconds) through a mask having a linear shape of 20 μm (width 20 μm, length 4 mm).
＜加熱工程＞
　次いで、露光後の硬化性組成物層を、シリコンウェハを下にして、ホットプレート上に載置して乾燥した。ホットプレートの表面温度は１００℃で、乾燥時間は１２０秒間とした。乾燥後の硬化性組成物層の膜厚は１．５μｍだった。 <Heating process>
Next, the curable composition layer after the exposure was placed on a hot plate with the silicon wafer facing down and dried. The surface temperature of the hot plate was 100 ° C., and the drying time was 120 seconds. The film thickness of the curable composition layer after drying was 1.5 μm.
＜現像工程＞
　乾燥後の硬化性組成物層を、以下の条件により現像し、パターン状の硬化膜を得た。
　乾燥後の硬化性組成物層に対して、テトラメチルアンモニウムハイドロオキサイド（ＴＭＡＨ）０．３質量％水溶液を用いて、２３℃で、６０秒間のパドル現像を５回繰り返し、パターン状の硬化膜を得た。その後、スピンシャワーを用いてパターン状の硬化膜をリンスし、更に純水で洗浄した。 <Development process>
The dried curable composition layer was developed under the following conditions to obtain a patterned cured film.
Using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for the curable composition layer after drying, paddle development for 60 seconds at 23 ° C. is repeated 5 times to form a patterned cured film. Obtained. Thereafter, the patterned cured film was rinsed using a spin shower and further washed with pure water.
＜ポストベーク工程＞
　上記で得られたパターン状の硬化膜を、クリーンオーブンＣＬＨ－２１ＣＤＨ（光洋サーモ社製）を用いて２２０℃で３００秒間加熱した。
　更に、加熱後のパターン状の硬化膜を、表面温度２２０℃のホットプレートに載置し、３００秒間加熱した。 <Post-bake process>
The patterned cured film obtained above was heated at 220 ° C. for 300 seconds using a clean oven CLH-21CDH (manufactured by Koyo Thermo Co., Ltd.).
Furthermore, the patterned cured film after heating was placed on a hot plate having a surface temperature of 220 ° C. and heated for 300 seconds.
＜評価＞
　上記のパターン状の硬化膜を走査型電子顕微鏡で撮影し、２０μｍパターン断面のエッジ部分（短辺）と、ガラス基板とのなす角（以下、単に「エッジ角度」という。）を測定した。パターンエッジの形状を以下の基準により評価し、結果を表３（表３（その１）～表３（その３））に示した。なお、実用上、評価「３」以上が好ましい。 <Evaluation>
The patterned cured film was photographed with a scanning electron microscope, and the angle (hereinafter simply referred to as “edge angle”) formed by the edge portion (short side) of the cross section of the 20 μm pattern and the glass substrate was measured. The shape of the pattern edge was evaluated according to the following criteria, and the results are shown in Table 3 (Table 3 (Part 1) to Table 3 (Part 3)). In practice, an evaluation of “3” or higher is preferable.
－評価基準－
　５：エッジ角度が８５°超、９０°以下だった。
　４：エッジ角度が８０°超、８５°以下だった。
　３：エッジ角度が７５°超、８０°以下だった。
　２：エッジ角度が７０°超、７５°以下だった。
　１：エッジ角度が７０°以下だった。 -Evaluation criteria-
5: The edge angle was more than 85 ° and less than 90 °.
4: The edge angle was more than 80 ° and less than 85 °.
3: The edge angle was more than 75 ° and less than 80 °.
2: The edge angle was more than 70 ° and 75 ° or less.
1: The edge angle was 70 ° or less.
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000038
Figure JPOXMLDOC01-appb-T000038
　表３に示した結果から、金属窒化物含有粒子と、オキシム系重合開始剤と、重合性化合物と、酸無水物と、を含有する実施例１～２６の硬化性組成物は、本発明の効果を有していた。一方、比較例の硬化性組成物は、本発明の効果を有していなかった。
　また、硬化性組成物中におけるオキシム系重合開始剤の含有量に対する、酸無水物の含有量の含有質量比が０．００５～０．５である、実施例２の硬化性組成物は、実施例４、実施例２４、及び、実施例２５の硬化性組成物と比較してより優れたパターン形状を有する硬化膜が得られることがわかった。
　また、酸無水物が１分子中に２個以上の酸無水物基を含有する実施例２の硬化性組成物は、実施例８、及び、９の硬化性組成物と比較して、より優れたパターン形状を有する硬化膜が得られ、また、未露光部における残渣の発生がより抑制されていた。
　また、重合禁止剤を含有する実施例５の硬化性組成物は、実施例２の硬化性組成物と比較して、より優れた保存安定性を有し、かつ、未露光部における残渣の発生がより抑制されていた。
　また、金属窒化物含有粒子がチタン窒化物を含有する実施例２の硬化性組成物は、実施例１５～１７の硬化性組成物と比較して、より優れたパターン形状を有する硬化膜がえられ、かつ、未露光部における残渣の発生がより抑制されていた。
　また、金属窒化物含有粒子がチタン窒化物を含有し、所定条件で測定した粒子の（２００）面に由来するピークの回折角２θが４２．５～４２．８である、実施例２の硬化性組成物は、実施例１９及び実施例２０の硬化性組成物と比較して得られる硬化膜がより優れた遮光性（高いＯＤ値）を有していた。
　また、硬化性組成物中における金属窒化物含有粒子の含有量が４０質量％以上である実施例１３の硬化性組成物は、実施例１４の硬化性組成物と比較して、得られる硬化膜がより優れた遮光性を有していた。
　また、オキシム系重合開始剤がニトロ基を含有する、実施例１２の硬化性組成物は、実施例２の硬化性組成物と比較して、より優れたパターン形状を有する硬化膜が得られた。 From the results shown in Table 3, the curable compositions of Examples 1 to 26 containing metal nitride-containing particles, an oxime polymerization initiator, a polymerizable compound, and an acid anhydride were obtained according to the present invention. Had an effect. On the other hand, the curable composition of the comparative example did not have the effect of the present invention.
The curable composition of Example 2 in which the content ratio of the content of the acid anhydride to the content of the oxime polymerization initiator in the curable composition is 0.005 to 0.5 is It turned out that the cured film which has a more excellent pattern shape compared with the curable composition of Example 4, Example 24, and Example 25 is obtained.
Further, the curable composition of Example 2 in which the acid anhydride contains two or more acid anhydride groups in one molecule is superior to the curable compositions of Examples 8 and 9. Further, a cured film having a pattern shape was obtained, and generation of a residue in an unexposed portion was further suppressed.
Further, the curable composition of Example 5 containing a polymerization inhibitor has better storage stability than the curable composition of Example 2, and generation of residues in unexposed areas. Was more suppressed.
In addition, the curable composition of Example 2 in which the metal nitride-containing particles contain titanium nitride has a cured film having a more excellent pattern shape than the curable compositions of Examples 15 to 17. And the generation of residues in the unexposed areas was further suppressed.
Further, the hardening of Example 2 in which the metal nitride-containing particles contain titanium nitride and the diffraction angle 2θ of the peak derived from the (200) plane of the particles measured under predetermined conditions is 42.5 to 42.8. The cured film obtained by comparing the curable compositions of Examples 19 and 20 had better light-shielding properties (high OD value).
Further, the curable composition of Example 13 in which the content of metal nitride-containing particles in the curable composition is 40% by mass or more is obtained by comparing the curable composition of Example 14 with the curable composition of Example 14. Had better light-shielding properties.
In addition, the curable composition of Example 12, in which the oxime polymerization initiator contains a nitro group, yielded a cured film having a more excellent pattern shape as compared to the curable composition of Example 2. .
［金属窒化物含有粒子分散液１２、及び１３の作製］
　チタン窒化物含有粒子ＴｉＮ－１に代えて、チタン窒化物含有粒子ＴｉＮ－１と、カーボンブラックの混合物（含有質量比（チタン窒化物含有粒子ＴｉＮ－１／カーボンブラック）は３５／５）を用いたことを除いては金属窒化物含有粒子分散液１の作製方法と同様にして、金属窒化物含有粒子分散液１２を作製した。
　また、チタン窒化物含有粒子ＴｉＮ－１に代えて、チタン窒化物含有粒子ＴｉＮ－１と、有機顔料（Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ　Ｓ０１００ＣＦ、ＢＡＳＦ社製）の混合物（含有質量比（チタン窒化物含有粒子ＴｉＮ－１／有機顔料）は３５／５）を用いたことを除いては金属窒化物含有粒子分散液１の作製方法と同様にして、金属窒化物含有粒子分散液１３を作製した。 [Production of Metal Nitride-Containing Particle Dispersions 12 and 13]
Instead of titanium nitride-containing particles TiN-1, a mixture of titanium nitride-containing particles TiN-1 and carbon black (containing mass ratio (titanium nitride-containing particles TiN-1 / carbon black) is 35/5) is used. A metal nitride-containing particle dispersion 12 was prepared in the same manner as the metal nitride-containing particle dispersion 1 except for the above.
Further, instead of the titanium nitride-containing particles TiN-1, a mixture of titanium nitride-containing particles TiN-1 and an organic pigment (Irgaphor Black S0100CF, manufactured by BASF) (containing mass ratio (titanium nitride-containing particles TiN-1) The metal nitride-containing particle dispersion 13 was prepared in the same manner as in the method for preparing the metal nitride-containing particle dispersion 1 except that 35/5) was used.
［実施例２－１２、２－１３：硬化性組成物の作製］
　金属窒化物含有粒子分散液１に代えて、金属窒化物含有粒子分散液１２、及び、１３をそれぞれ用いたことを除いては、実施例２と同様にして、硬化性組成物２－１２、及び、２－１３を作製して、上記と同様の評価を行ったところ、実施例２と同様の結果が得られた。 [Examples 2-12 and 2-13: Preparation of curable composition]
In the same manner as in Example 2 except that the metal nitride-containing particle dispersions 12 and 13 were used in place of the metal nitride-containing particle dispersion 1, the curable composition 2-12, 2-13 was prepared and evaluated in the same manner as described above, and the same results as in Example 2 were obtained.
　ＩＲＧＡＣＵＲＥ　ＯＸＥ－０２（ＢＡＳＦ社製）に代えて、以下の式で表されるＰＩ－０３を用いたことを除いては実施例５と同様にして、硬化性組成物を作製し、評価を行ったところ、パターンエッジ形状が５になった他は実施例５と同様の結果が得られた。
・ＰＩ－０３（以下の式で表される化合物、オキシム系重合開始剤に該当する。） A curable composition was prepared and evaluated in the same manner as in Example 5 except that PI-03 represented by the following formula was used instead of IRGACURE OXE-02 (manufactured by BASF). As a result, the same result as in Example 5 was obtained except that the pattern edge shape was 5.
PI-03 (compound represented by the following formula, corresponding to oxime polymerization initiator)
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　ＩＲＧＡＣＵＲＥ　ＯＸＥ－０２（ＢＡＳＦ社製）に代えて、以下の式で表されるＰＩ－０４を用いたことを除いては実施例５と同様にして、硬化性組成物を作製し、評価を行ったところ、保存安定性が１に、パターンエッジ形状が５になった他は同様の結果が得られた。
・ＰＩ－０４（ＷＯ２０１５／０３６９１０　のＯＥ７４で表される化合物、オキシム系重合開始剤に該当する。） A curable composition was prepared and evaluated in the same manner as in Example 5 except that PI-04 represented by the following formula was used instead of IRGACURE OXE-02 (manufactured by BASF). As a result, the same results were obtained except that the storage stability was 1 and the pattern edge shape was 5.
PI-04 (corresponding to a compound represented by OE74 of WO2015 / 036910, an oxime polymerization initiator)
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　界面活性剤を用いなかったことを除いては実施例５と同様にして、硬化性組成物を作製し、評価を行ったところ、実施例５と同様の結果が得られた。 When a curable composition was prepared and evaluated in the same manner as in Example 5 except that the surfactant was not used, the same result as in Example 5 was obtained.
１００・・・固体撮像装置
１０１・・・固体撮像素子
１０２・・・撮像部
１０３・・・カバーガラス
１０４・・・スペーサー
１０５・・・積層基板
１０６・・・チップ基板
１０７・・・回路基板
１０８・・・電極パッド
１０９・・・外部接続端子
１１０・・・貫通電極
１１１・・・レンズ層
１１２・・・レンズ材
１１３・・・支持体
１１４、１１５・・・遮光膜
２０１・・・受光素子
２０２・・・カラーフィルタ
２０１・・・受光素子
２０２・・・カラーフィルタ
２０３・・・マイクロレンズ
２０４・・・基板
２０５ｂ・・・青色画素
２０５ｒ・・・赤色画素
２０５ｇ・・・緑色画素
２０５ｂｍ・・・ブラックマトリクス
２０６・・・ｐウェル層
２０７・・・読み出しゲート部
２０８・・・垂直転送路
２０９・・・素子分離領域
２１０・・・ゲート絶縁膜
２１１・・・垂直転送電極
２１２・・・遮光膜
２１３、２１４・・・絶縁膜
２１５・・・平坦化膜
５３・・・レンズ層
５４、５５・・・遮光パターン 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 ... Light shielding 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 ... light shielding film 213 ... insulating film 215 ... flattening film 53 ... lens layer 54, 55 ... light shielding pattern

Claims (18)

  1. 　金属窒化物含有粒子と、オキシム系重合開始剤と、重合性化合物と、酸無水物と、を含有する硬化性組成物。 A curable composition containing metal nitride-containing particles, an oxime polymerization initiator, a polymerizable compound, and an acid anhydride.
  2. 　前記硬化性組成物中における、前記オキシム系重合開始剤の含有量に対する、前記酸無水物の含有量の含有質量比が、０．００５～０．５である、請求項１に記載の硬化性組成物。 The curability according to claim 1, wherein the content ratio of the content of the acid anhydride to the content of the oxime polymerization initiator in the curable composition is 0.005 to 0.5. Composition.
  3. 　前記酸無水物が、１分子中に２個以上の酸無水物基を含有する、請求項１又は２に記載の硬化性組成物。 The curable composition according to claim 1 or 2, wherein the acid anhydride contains two or more acid anhydride groups in one molecule.
  4. 　更に、重合禁止剤を含有する、請求項１～３のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 3, further comprising a polymerization inhibitor.
  5. 　前記金属窒化物含有粒子がチタン窒化物を含有する、請求項１～４のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 4, wherein the metal nitride-containing particles contain titanium nitride.
  6. 　ＣｕＫα線をＸ線源とした場合の前記金属窒化物含有粒子の（２００）面に由来するピークの回折角２θが４２．５～４２．８°である、請求項５に記載の硬化性組成物。 6. The curable composition according to claim 5, wherein a diffraction angle 2θ of a peak derived from the (200) plane of the metal nitride-containing particles when CuKα rays are used as an X-ray source is 42.5 to 42.8 °. object.
  7. 　更に、アルカリ可溶性樹脂を含有する、請求項１～６のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 6, further comprising an alkali-soluble resin.
  8. 　前記アルカリ可溶性樹脂が、ポリイミド前駆体、及び、ポリイミド樹脂からなる群から選択される少なくとも１種を含有する、請求項７に記載の硬化性組成物。 The curable composition according to claim 7, wherein the alkali-soluble resin contains at least one selected from the group consisting of a polyimide precursor and a polyimide resin.
  9. 　前記硬化性組成物中における、前記金属窒化物含有粒子の含有量が、前記硬化性組成物の全固形分に対して、４０質量％以上である、請求項１～８のいずれか一項に記載の硬化性組成物。 The content of the metal nitride-containing particles in the curable composition is 40% by mass or more based on the total solid content of the curable composition. The curable composition as described.
  10. 　前記硬化性組成物中における、前記金属窒化物含有粒子の含有量に対する、前記オキシム系重合開始剤の含有量の含有質量比が、０．０３～０．２である、請求項１～９のいずれか一項に記載の硬化性組成物。 The content mass ratio of the content of the oxime polymerization initiator to the content of the metal nitride-containing particles in the curable composition is 0.03 to 0.2. The curable composition as described in any one.
  11. 　前記オキシム系重合開始剤がニトロ基を含有する、請求項１～１０のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 10, wherein the oxime polymerization initiator contains a nitro group.
  12. 　更に、溶剤を含有する、請求項１～１１のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 11, further comprising a solvent.
  13. 　請求項１～１２のいずれか一項に記載の硬化性組成物を硬化して得られる、硬化膜。 A cured film obtained by curing the curable composition according to any one of claims 1 to 12.
  14. 　請求項１３に記載の硬化膜を含有するカラーフィルタ。 A color filter containing the cured film according to claim 13.
  15. 　請求項１３に記載の硬化膜を含有する固体撮像素子。 A solid-state imaging device containing the cured film according to claim 13.
  16. 　請求項１３に記載の硬化膜を含有する赤外線センサ。 An infrared sensor containing the cured film according to claim 13.
  17. 　請求項１～１２のいずれか一項に記載の硬化性組成物を用いて硬化性組成物層を形成する、硬化性組成物層形成工程と、
    　前記硬化性組成物層に、パターン状の開口部を備えるフォトマスクを介して、活性光線又は放射線を照射して露光する、露光工程と、
    　前記露光後の前記硬化性組成物層を現像して、硬化膜を形成する、現像工程と、を含有する、硬化膜の製造方法。     A curable composition layer forming step of forming a curable composition layer using the curable composition according to any one of claims 1 to 12,
    An exposure step of exposing the curable composition layer by irradiating actinic rays or radiation through a photomask having a pattern-shaped opening; and
    The development method of developing the said curable composition layer after the said exposure, and forming the cured film, The manufacturing method of a cured film containing.
  18. 　請求項１７に記載の硬化膜の製造方法を含有する、カラーフィルタの製造方法。
          The manufacturing method of the color filter containing the manufacturing method of the cured film of Claim 17.
PCT/JP2017/028968 2016-08-30 2017-08-09 Curable compositon, cured film, color filter, solid imaging element, infrared sensor, process for producing cured film, and process for producing color filter WO2018043085A1 (en)

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