WO2021059846A1 - Near-infrared absorption composition, film, optical filter and manufacturing method thereof, solid-state imaging element, infrared sensor, camera module, and inkjet ink - Google Patents

Near-infrared absorption composition, film, optical filter and manufacturing method thereof, solid-state imaging element, infrared sensor, camera module, and inkjet ink Download PDF

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Publication number
WO2021059846A1
WO2021059846A1 PCT/JP2020/032332 JP2020032332W WO2021059846A1 WO 2021059846 A1 WO2021059846 A1 WO 2021059846A1 JP 2020032332 W JP2020032332 W JP 2020032332W WO 2021059846 A1 WO2021059846 A1 WO 2021059846A1
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group
ring
infrared
resin
present disclosure
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PCT/JP2020/032332
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French (fr)
Japanese (ja)
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峻輔 北島
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富士フイルム株式会社
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Priority to JP2021548447A priority Critical patent/JP7271692B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • 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 disclosure relates to a near-infrared absorbing composition, a film, an optical filter and a method for manufacturing the same, a solid-state image sensor, an infrared sensor, a camera module, and an inkjet ink.
  • an infrared cut filter, an infrared transmission filter and the like containing a near-infrared absorbing pigment are known.
  • a curable composition for obtaining an optical filter as described above for example, in Patent Document 1, a curable composition containing a near-infrared absorbing dye and a polymerizable monomer having a group having an unsaturated double bond.
  • the near-infrared absorbing dye is a compound having a ⁇ -conjugated plane containing an aromatic ring of a monocycle or a condensed ring, and contains the near-infrared absorbing dye in the total solid content of the curable composition.
  • the content of the polymerizable monomer having an amount of 10% by mass or more and having at least one group selected from an acid group and a hydroxyl group and a group having an unsaturated double bond in the total mass of the above-mentioned polymerizable monomer is 50. Curable compositions that are no more than% by weight are disclosed.
  • An object to be solved by one embodiment of the present disclosure is to provide a near-infrared absorption composition having excellent storage stability. Further, the problem to be solved by another embodiment of the present disclosure is a film using the near infrared absorption composition, an optical filter and a method for manufacturing the same, a solid-state image sensor, an infrared sensor, a camera module, and an inkjet ink. Is to provide.
  • the means for solving the above problems include the following aspects.
  • the binder resin contains at least one structural unit having a ring structure selected from the group consisting of an aromatic ring and an aliphatic ring, in an amount of 50 mol% to 90 mol with respect to all the structural units of the binder resin.
  • the near-infrared absorption composition according to ⁇ 1> which is a resin contained in%.
  • the near-infrared absorption composition according to ⁇ 2> wherein the aliphatic ring is a bicyclo ring or a tricyclo ring.
  • ⁇ 4> The near-infrared absorption composition according to ⁇ 2> or ⁇ 3>, wherein the aromatic ring is a benzene ring, a naphthalene ring, or a nitrogen-containing heteroaromatic ring.
  • ⁇ 5> Any one of ⁇ 1> to ⁇ 4>, wherein the binder resin contains a structural unit having an acid group in an amount of 10 mol% to 40 mol% with respect to all the structural units of the binder resin.
  • ⁇ 6> The near-infrared absorption composition according to any one of ⁇ 1> to ⁇ 5>, wherein the binder resin has a weight average molecular weight of 20,000 or less.
  • the resin having the basic group is at least one selected from the group consisting of a resin having a tertiary amino group in the side chain and a resin having a nitrogen atom in the main chain.
  • ⁇ 11> The near-infrared absorption composition according to any one of ⁇ 1> to ⁇ 10>, further comprising a polymerizable compound and a polymerization initiator.
  • ⁇ 12> A film comprising the near-infrared absorption composition according to any one of ⁇ 1> to ⁇ 11> or obtained by curing the near-infrared absorption composition.
  • ⁇ 13> An optical filter having the film according to ⁇ 12>.
  • ⁇ 14> The optical filter according to ⁇ 13>, which is an infrared cut filter or an infrared transmission filter.
  • ⁇ 15> A solid-state image sensor having the film according to ⁇ 12>.
  • ⁇ 16> An infrared sensor having the film according to ⁇ 12>.
  • ⁇ 17> A step of applying the near-infrared absorption composition according to ⁇ 11> onto a support to form a composition layer, and The step of exposing the composition layer in a pattern and A method for manufacturing an optical filter, which includes a step of developing and removing an unexposed portion to form a pattern.
  • ⁇ 18> A step of applying the near-infrared absorption composition according to ⁇ 11> onto a support to form a composition layer, and then curing to form a layer.
  • a near-infrared absorption composition having excellent storage stability is provided. Further, according to another embodiment of the present disclosure, a film using the near infrared absorption composition, an optical filter and a method for manufacturing the same, a solid-state image sensor, an infrared sensor, a camera module, and an inkjet ink are provided. ..
  • total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition.
  • solid content is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.
  • substitution and non-substitution includes those having no substituent as well as those having a substituent.
  • alkyl group includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam.
  • particle beams such as an electron beam and an ion beam.
  • the light used for exposure generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation can be mentioned.
  • EUV light extreme ultraviolet rays
  • active rays such as electron beams, or radiation
  • Acryloyl "represents both acryloyl and / or methacryloyl.
  • Me in the chemical formula is a methyl group
  • Et is an ethyl group
  • Pr is a propyl group
  • Bu is a butyl group
  • Ac is an acetyl group
  • Bn is a benzyl group
  • Ph is a phenyl group. Shown.
  • the term "process” is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
  • % by mass and % by weight are synonymous, and “parts by mass” and “parts by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the transmittance in the present disclosure is the transmittance at 25 ° C. unless otherwise specified.
  • the weight average molecular weight and the number average molecular weight of the resin are defined as polystyrene-equivalent values measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the near-infrared absorbing composition according to the present disclosure (hereinafter, also simply referred to as “composition”) has an SP value other than the near-infrared absorbing pigment, the resin having a basic group, and the resin having the basic group. 19.7 MPa 1/2 to 21.2 MPa 1/2 and a binder resin having an acid value of 70 mgKOH / g to 105 mgKOH / g (hereinafter, also referred to as “specific binder resin”).
  • a dispersant which is a resin having a basic group, and a binder resin, specifically, for example, the curable composition described in Patent Document 1, over time.
  • the viscosity of the product may increase and the storage stability may decrease. The reason for this is presumed as follows.
  • the basic group of the dispersant has an adsorption performance for the near-infrared absorbing pigment and enhances the dispersibility of the near-infrared absorbing pigment.
  • the dispersant may be adsorbed on the basic group of the dispersant and the dispersant may be peeled off from the near-infrared absorbing pigment.
  • the dispersion performance of the near-infrared absorbing pigment by the resin having a basic group becomes difficult to be exhibited, and the near-infrared absorbing pigment aggregates with time, thereby lowering the storage stability. Therefore, as a result of examining the problem of enhancing storage stability, it was found that the above problem can be solved by using a binder resin having a specific SP value and a specific acid value.
  • the near-infrared absorbing composition according to the present disclosure is a composition containing a near-infrared absorbing pigment and a resin having a basic group, and has an SP value of 19.7 MPa 1/2 to 21.2 MPa 1/2 and an acid.
  • a specific binder resin having a value of 70 mgKOH / g to 105 mgKOH / g is applied.
  • the film is formed by the near-infrared absorbing composition according to the present disclosure, it is possible to maintain a high dispersion of the near-infrared absorbing pigment even in the film. As a result, when a part of the formed film is removed by development or the like, it is presumed that the generation of residue due to the aggregation of the near-infrared absorbing pigment is reduced.
  • the composition according to the present disclosure is a binder having an SP value of 19.7 MPa 1/2 to 21.2 MPa 1/2 and an acid value of 70 mgKOH / g to 105 mgKOH / g, other than the resin having a basic group described later.
  • the specific binder resin is a component that contributes to film-forming property, and by containing the specific binder resin, a film is formed by the composition according to the present disclosure.
  • the SP value (unit: MPa 1/2 ) of the specific binder resin in the present disclosure is a solubility parameter obtained by the Okitsu method.
  • the Okitsu method is one of the well-known methods for calculating the SP value. For example, Vol. 29, No. 6 (1993) The method described in detail on pages 249 to 259, and the SP value of the specific binder resin in the present disclosure is also calculated by this method.
  • the acid value of the specific binder resin in the present disclosure represents the mass of potassium hydroxide required to neutralize the acid group per 1 g of the specific binder resin.
  • the acid value is calculated by the formula (I) with the inflection point of the titration pH curve as the titration end point.
  • Formula (I): A: Acid value (mgKOH / g) 56.11 ⁇ Vs ⁇ 0.5 ⁇ f / w
  • A represents the acid value (mgKOH / g)
  • Vs represents the amount (mL) of the 0.1 mol / L sodium hydroxide aqueous solution required for titration
  • f is 0.1 mol / L water. It represents the titer of the aqueous sodium oxide solution
  • w represents the measurement sample mass (g) (in terms of solid content).
  • the SP value in the specific binder resin from the viewpoint of enhancing the storage stability, 20.0MPa 1/2 ⁇ 21.0MPa 1/2 is preferred.
  • the acid value of the specific binder resin is preferably 72 mgKOH / g to 102 mgKOH, more preferably 90 mgKOH / g to 100 mgKOH, from the viewpoint of enhancing storage stability.
  • the structure of the specific binder resin is not particularly limited as long as it satisfies the above SP value and acid value.
  • Specific binder resins include acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, and polyolefin. Examples thereof include resins, cyclic olefin resins, polyester resins, styrene resins, siloxane resins, and urethane resins. Of these, an acrylic resin is preferable from the viewpoint of easily controlling the SP value and acid value and from the viewpoint of improving the alkali developability of the formed film.
  • the specific binder resin has a structural unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring from the viewpoint of controlling the SP value and the acid value (particularly the SP value) within the above ranges. , It is preferable that the resin is contained in an amount of 50 mol% to 90 mol% with respect to all the constituent units of the specific binder resin.
  • the content of the structural unit having at least one ring structure selected from the group consisting of the aromatic ring and the aliphatic ring shall be 55 mol% to 90 mol% with respect to all the structural units of the specific binder resin. Is preferable, and 60 mol% to 88 mol% is more preferable.
  • the specific binder resin contains a structural unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring
  • the aliphatic ring is preferably a bicyclo ring or a tricyclo ring, and is aromatic.
  • the ring is preferably a benzene ring, a naphthalene ring, or a nitrogen-containing heteroaromatic ring.
  • bicyclo ring examples include bicyclo [2,2,1] heptane, and a ring into which a substituent such as an alkyl group is introduced (for example, an isobornyl ring).
  • tricyclo ring examples include adamantane (also referred to as tricyclo [3.3.1.1 3,7 ] decane) and a ring into which a substituent such as an alkyl group is introduced.
  • nitrogen-containing heteroaromatic ring examples include a carbazole ring and a ring into which a substituent such as an alkyl group is introduced. Further, a substituent such as an alkyl group may be introduced into the benzene ring and the naphthalene ring.
  • the structural unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring is preferably a structural unit represented by the following formula (a).
  • R 1 represents a hydrogen atom or a methyl group
  • X 1 is selected from the group consisting of an aromatic ring and an aliphatic ring. Represents a group containing at least one ring structure.
  • X 1 represents a isobornyl group, adamantane group, a benzyl group, a naphthyl group, or a carbazole group.
  • the specific binder resin contains only one structural unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring (preferably, a structural unit represented by the formula (a)). It may be used, or it may contain two or more kinds.
  • the specific binder resin contains 10 mol% to 40 mol% of the structural units having an acid group with respect to all the structural units of the specific binder resin. It is preferable that the resin is contained in.
  • the content of the structural unit having an acid group is preferably 10 mol% to 38 mol%, more preferably 12 mol% to 38 mol%, based on all the structural units of the specific binder resin.
  • Examples of the acid group include a carboxy group, a sulfonic acid group, and a phosphoric acid group.
  • carboxy is used from the viewpoint of achieving both the stability of the composition according to the present disclosure with time and the alkali developability of the film to be formed. Groups are preferred.
  • the structural unit having an acid group is preferably a structural unit represented by the following formula (b).
  • R 2 represents a hydrogen atom or a methyl group
  • L 2 represents a divalent linking group having 2 to 10 carbon atoms in a single bond
  • X 2 represents an acid group
  • L 2 is preferably a divalent linking group having 2 to 10 carbon atoms containing an alkylene group and an ester bond, and 2 to 10 carbon atoms consisting of the alkylene group and an ester bond. More preferably, it is a valence linking group.
  • X 2 is preferably a carboxy group.
  • the specific binder resin may contain one type of structural unit having an acid group (preferably a structural unit represented by the formula (b)) alone, or may contain two or more types.
  • the specific binder resin may contain other structural units in addition to the structural unit having at least one ring structure and the structural unit having an acid group selected from the group consisting of an aromatic ring and an aliphatic ring. ..
  • the other structural unit is not particularly limited as long as the SP value and acid value can be controlled within the above ranges, and a structural unit formed of the (meth) acrylate compound is preferably mentioned. It is preferably a (meth) acrylic acid alkyl ester compound, and more preferably 2-hydroxyethyl (meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate and the like.
  • the other structural unit is preferably a structural unit represented by the following formula (c).
  • R 3 represents a hydrogen atom or a methyl group
  • X 3 represents an alkyl group
  • X 3 is preferably a substituted or unsubstituted alkyl group of 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkyl group of 1 to 8 carbon atoms.
  • substituent introduced into the alkyl group represented by X 3 include a hydroxy group and an allyl group.
  • the specific binder resin may contain other structural units (preferably the structural units represented by the formula (c)) of one type alone, or may contain two or more types.
  • the weight average molecular weight (Mw) of the specific binder resin is preferably 20,000 or less, more preferably 15,000 or less, further preferably 12,000 or less, and particularly preferably 10,000 or less.
  • the lower limit of the weight average molecular weight (Mw) of the specific binder resin is preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more.
  • Specific examples of the specific binder resin include, but are not limited to, the following resins 1 to 6.
  • the numerical value added to each structural unit of the main chain is the molar ratio.
  • composition according to the present disclosure may contain one type of specific binder resin alone, or may contain two or more types.
  • the content of the specific binder resin in the composition according to the present disclosure may be appropriately determined according to the purpose of use, use and the like of the composition according to the present disclosure.
  • the specific binder resin is, for example, 1 to 30 times (preferably 1.5 to 27 times, more preferably 2 to 25 times) the resin having a basic group described later on a mass basis. Can be used.
  • the composition according to the present disclosure may contain other binder resins other than the specific binder resin as long as the above-mentioned effects such as excellent storage stability are not impaired.
  • the other binder resin is a resin in which either the SP value or the acid value does not satisfy the above range, and has no basic group in the molecule, and is a "resin having a basic group". Not applicable resin.
  • the content of the other binder resin with respect to the total binder resin contained in the composition according to the present disclosure is preferably 10% by mass or less, and more preferably 5% by mass or less. It is preferably 0% by mass, and particularly preferably 0% by mass.
  • the composition according to the present disclosure contains a near-infrared absorbing pigment.
  • near infrared rays refers to infrared rays having a wavelength of 700 nm to 2,500 nm
  • near infrared absorbing pigments are pigments having a maximum absorption wavelength in the wavelength range of 750 nm to 2,500 nm.
  • the near-infrared absorbing pigment is preferably a pigment having a maximum absorption wavelength in the wavelength range of 750 nm to 1800 nm.
  • the ratio A 1 / A 2 between the absorbance A 2 in the absorbance A 1 and the maximum absorption wavelength at a wavelength 500nm may be preferably 0.08 or less, 0.04 or less More preferred.
  • the pigment means a dye that is insoluble in a solvent.
  • insoluble in a solvent means that the solubility of the target substance in 100 mg of the solvent at 25 ° C. is 0.1 g or less.
  • examples of the solvent include propylene glycol monomethyl ether acetate and water, and any solvent having the above-mentioned solubility is a pigment.
  • Near-infrared absorbing pigments include pyrolopyrrole compounds, squarylium compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonor compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, Examples thereof include azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, metal oxides, and metal boroides.
  • a pyrrolopyrrole compound or a squarylium compound is particularly preferable from the viewpoint of durability.
  • the pyrrolopyrrole compound is preferably a compound represented by the formula (PP).
  • R 1a and R 1b each independently represent an alkyl group, an aryl group, or a heteroaryl group
  • R 2 and R 3 each independently represent a hydrogen atom or a substituent
  • R. 2 and R 3 may be bonded to each other to form a ring
  • R 4 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4A R 4B, or a metal atom
  • R 4 may be covalently or coordinated with at least one selected from R 1a , R 1b , and R 3 , where R 4A and R 4B each independently represent a substituent.
  • R 1a and R 1b are each independently preferably an aryl group or a heteroaryl group, and more preferably an aryl group. Further, the alkyl group, aryl group, and heteroaryl group represented by R 1a and R 1b may have a substituent or may be unsubstituted. Examples of the substituent include a substituent T described later.
  • Rt 1 and Rt 2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. Rt 1 and Rt 2 may be combined to form a ring.
  • R 2 and R 3 each independently represent a hydrogen atom or substituent.
  • substituent include the above-mentioned Substituent T.
  • At least one of R 2 and R 3 is preferably an electron-attracting group, and is preferably a cyano group, a carboxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, or an alkyl. It is more preferably a sulfonyl group or an arylsulfonyl group, and even more preferably a cyano group.
  • R 2 preferably represents an electron-attracting group (preferably a cyano group) and R 3 preferably represents a heteroaryl group.
  • the heteroaryl group is preferably a 5-membered ring or a 6-membered ring.
  • the heteroaryl group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 8, and more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2.
  • hetero atom examples include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the heteroaryl group preferably has one or more nitrogen atoms.
  • Two R 2 together in the formula (PP) may be the same or may be different.
  • two R 3 together in the formula (PP) may be the same or may be different.
  • R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or a group represented by -BR 4A R 4B, and is preferably a hydrogen atom, an alkyl group, an aryl group, or a group.
  • -BR 4A A group represented by R 4B is more preferable, and a group represented by -BR 4A R 4B is further preferable.
  • R 4A and R 4B are preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and particularly preferably an aryl group. These groups may further have a substituent.
  • Two R 4 together in the formula (PP) may be the same or may be different.
  • R 4A and R 4B may be combined with each other to form a ring.
  • the pyrrolopyrrole compound may be a compound represented by the formula (PP-1).
  • R 1a , R 2 , R 3 , and R 4 are all synonymous with R 1a , R 2 , R 3 , and R 4 in formula (PP) , and R 1b.
  • L is a group represented by the following formula (L1) or the following formula (L2).
  • R 1a in the formula (PP-1), R 1b , R 2, R 3, and R 4 are both, R 1a in the formula (PP), R 1b, R 2, R 3, and the R 4 It has the same meaning, and the preferred embodiment is also the same.
  • X 1 and X 2 are each independently a single bond, -O -, - S -, - NR 1A -, - CO -, - COO -, - OCOO -, - SO 2 NR 1A -, - CONR 1A -, - OCONR 1A -, or -NR 1A CONR 1A - represents, R 1A each independently represent a hydrogen atom, an alkyl group, or an aryl group, a 1 represents a single bond, It represents an aliphatic ring structure, an aromatic ring structure, or a heterocyclic structure, where * represents a connection position with R 1b , where when A 1 is a single bond , both X 1 and X 2 are single bonds. It will never be.
  • X 3 and X 4 are independently single-bonded, -O-, -S-, -NR 2A- , -CO-, -COO-, -OCOO-, -SO 2 NR 2A. -, -CONR 2A- , -OCONR 2A- , or -NR 2A CONR 2A- , R 2A represents a hydrogen atom or an alkyl group, L 2 represents a single bond, -O-, -S-, -NR.
  • R 2B independently represents a hydrogen atom or an alkyl group
  • a 2 and A 3 each independently represent an aliphatic ring structure. Represents an aromatic ring structure or a heterocyclic structure.
  • pyrrolopyrrole compound examples include the following compounds.
  • Me represents a methyl group and Ph represents a phenyl group.
  • Examples of the pyrrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP2009-263614 and the compounds described in paragraphs 0037-0052 of JP2011-68831. The content is incorporated herein by reference.
  • the squarylium compound is preferably a compound represented by the following formula (SQ).
  • a 1 and A 2 each independently represent an aryl group, a heteroaryl group, or a group represented by formula (A-1);
  • Z 1 represents a non-metal atomic group forming a nitrogen-containing heterocycle
  • R 2 represents an alkyl group, an alkenyl group or an aralkyl group
  • d represents 0 or 1.
  • the wavy line represents the connecting hand.
  • the squarylium compound is preferably a compound represented by the following formula (SQ-1).
  • rings A and B each independently represent an aromatic ring
  • X A and X B each independently represents a substituent
  • a G A and G B are each independently a substituent Represented
  • kA represents an integer from 0 to n A
  • kB represents an integer from 0 to n B
  • n A and n B represent the largest integer substitutable to ring A or ring B, respectively
  • X A and G a, X B and G B, X a and X B may form a ring, if G a and G B are present in plural, taken together, they are bonded together to form a ring structure You may.
  • the substituent represented by G A and G B include aforementioned substituent T.
  • a group having active hydrogen is preferable, and -OH, -SH, -COOH, -SO 3 H, -NR X1 R X2 , -NHCOR X1 , -CONR X1 R. X2 , -NHCONR X1 R X2 , -NHCOOR X1 , -NHSO 2 R X1 , -B (OH) 2 and -PO (OH) 2 are more preferred, and -OH, -SH and -NR X1 R X2 are even more preferred.
  • RX1 and RX2 each independently represent a hydrogen atom or a substituent.
  • X A and the alkyl group as the substituent R X1 and R X2 in X B an aryl group, or, include heteroaryl groups, alkyl groups are preferred.
  • Ring A and ring B each independently represent an aromatic ring.
  • the aromatic ring may be a monocyclic ring or a condensed ring.
  • Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a pentalene ring, an inden ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthalene ring, and a chrysene ring.
  • Triphenylene ring Fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring, indole ring, benzofuran ring, Benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, aclysine ring, phenanthrene ring, thianthrene ring, chromene ring, xanthene.
  • Examples thereof include a ring, a phenoxatiin ring, a phenothiazine ring, and a phenazine ring, and a benzene ring or a naphthalene ring is preferable.
  • the aromatic ring may be unsubstituted or may have a substituent. Examples of the substituent include the above-mentioned Substituent T.
  • X A and G A, X B and G B, X A and X B may be bonded to each other to form a ring, if G A and G B are present in plural, the rings bonded to each other It may be formed.
  • the ring a 5-membered ring or a 6-membered ring is preferable.
  • the ring may be a monocyclic ring or a condensed ring.
  • X A and G A, X B and G B, X A and X B, if G A s or G B are bonded to each other to form a ring, may be they are attached directly to form a ring, alkylene Rings may be formed by bonding via a divalent linking group consisting of a group, -CO-, -O-, -NH-, -BR- and a combination thereof.
  • R represents a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned Substituent T, and an alkyl group or an aryl group is preferable.
  • kA represents an integer from 0 to n A
  • kB represents an integer from 0 to n B
  • n A represents the largest integer substitutable for ring A
  • n B is the largest substitutable for ring B.
  • kA and kB 0 to 4 is preferable, 0 to 2 is more preferable, and 0 to 1 is particularly preferable.
  • the squarylium compound is preferably a compound represented by the following formula (SQ-2).
  • Rs 119 and Rs 120 each independently represent a substituent
  • a 1 and A 2 each independently represent an oxygen atom or NRs 125
  • Rs 121 to Rs 125 each independently represent a hydrogen atom.
  • the two Rs 122 may be the same or different. Or, two Rs 122 may be bonded to each other to form a ring, Ar 100 represents an aryl group or a heteroaryl group, and ns100 represents an integer of 0 to 2.
  • the squarylium compound is preferably a compound represented by the following formula (SQ-3).
  • X 1 , X 2 , Y 1 , and Y 2 are each independently bonded to an alkylene group, an alkynylene group, a cycloalkylene group, an arylene group, a heteroarylene group, or two or more of them.
  • R 7 and R 8 each independently represent a substituent
  • n1 and n2 each independently represent an integer of 0 to 5.
  • X 1 , X 2 , Y 1 and Y 2 represent an alkylene group and A 1 and A 2 represent -N ( RN2 )-
  • Z 1 and Z 2 is -O.
  • the squarylium compound is preferably a compound represented by the following formula (SQ-4).
  • Q 1 , Q 2, Q 3, and Q 4 each independently represents a carbon atom or a nitrogen atom. If Q 1 , Q 2 , Q 3 , and Q 4 are nitrogen atoms, then X 1 , X 4 , X 5 , and X 8 are absent.
  • R 1 to R 5 independently represent a hydrogen atom, an alkyl group, a sulfo group, -SO 3- M + , or a halogen atom.
  • M + represents an inorganic or organic cation.
  • Each of X 1 to X 8 independently contains a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent.
  • X 1 to X 8 may be combined with each other to form a ring.
  • R 6 to R 12 are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, or a substituent. Represents a pyridinyl group which may have.
  • R 2 and R 3 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , and R 11 and R 12 , respectively, may be coupled to each other to form a ring.
  • squarylium compound examples include the following compounds [SQ-1 to SQ-61].
  • examples of the squarylium compound include the compounds described in paragraphs 0044 to 0049 of JP2011-208101A, the compounds described in paragraphs 0060 to 0061 of Patent No. 6065169, and paragraphs of International Publication No. 2016/181987.
  • composition according to the present disclosure may contain one kind of near-infrared absorbing pigment alone, or may contain two or more kinds.
  • the content of the near-infrared absorbing pigment in the composition according to the present disclosure may be appropriately determined according to the purpose of use, use and the like of the composition according to the present disclosure.
  • the content of the near-infrared absorbing pigment is preferably 1% by mass or more and 80% by mass or less with respect to the total solid content of the composition, for example, from the viewpoint of exhibiting the functions required for the near-infrared absorbing pigment. More preferably, it is 5% by mass or more and 50% by mass or less.
  • the composition according to the present disclosure contains a resin having a basic group.
  • the basic group is a functional group exhibiting properties as a base, preferably a group containing a nitrogen atom, and more specifically, a primary amino group or a salt thereof, a secondary amino. More preferably, it is a group or a salt thereof, a tertiary amino group or a salt thereof, a quaternary ammonium base or the like.
  • the basic group in the resin having a basic group may be neutralized with the acid group of the specific binder resin to form a salt.
  • the composition according to the present disclosure is a composition containing a near-infrared absorbing pigment, a specific binder resin, and a resin having a salt neutralized with an acid group of the specific binder resin as a basic group. May be good.
  • the resin having a basic group is preferably at least one selected from the group consisting of, for example, a resin having a tertiary amino group in the side chain and a resin having a nitrogen atom in the main chain.
  • the resin having the tertiary amino group in the side chain is preferably a resin having a quaternary ammonium base in the side chain. That is, the resin having a basic group is preferably a resin having a tertiary amino group and a quaternary ammonium base in the side chain.
  • the resin having a tertiary amino group in the side chain is preferably a resin having a structural unit having a tertiary amino group, and a structural unit having a tertiary amino group and a structural unit having a quaternary ammonium base. It is more preferable that the resin has and. Further, the resin having a tertiary amino group in the side chain may further have other structural units in addition to the structural unit having a tertiary amino group and the structural unit having a quaternary ammonium base. .. It is also preferable that the resin having a tertiary amino group in the side chain has a block structure.
  • the amine value is 10 mgKOH / g to 250 mgKOH / g
  • the quaternary ammonium salt value is 10 mgKOH / g to 90 mgKOH / g.
  • Those having an amine value of 50 mgKOH / g to 200 mgKOH / g and a quaternary ammonium salt value of 10 mgKOH / g to 50 mgKOH / g are more preferable.
  • the above amine value is obtained by converting the amine value obtained by the potentiometric titration method into the equivalent of potassium hydroxide using a 0.1 N hydrochloric acid aqueous solution.
  • the quaternary ammonium salt value is obtained by titrating with a 0.1 N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and converting the amine value to the equivalent of potassium hydroxide.
  • the weight average molecular weight (Mw) of the resin having a tertiary amino group in the side chain is preferably 3,000 to 300,000, more preferably 5,000 to 30,000.
  • Resins having a tertiary amino group in the side chain include an ethylenically unsaturated compound having a tertiary amino group, an ethylenically unsaturated compound having a quaternary ammonium base, and other ethylenically unsaturated compounds, if necessary. It is obtained by copolymerizing with a saturated compound.
  • the polymer is reacted with a halogenated hydrocarbon compound such as benzyl chloride to partially react with a tertiary amino.
  • the group may be modified to a quaternary ammonium base to introduce a quaternary ammonium group.
  • Examples of the ethylenically unsaturated compound having a tertiary amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and dimethylaminopropyl (meth). ) Acrylamide and the like.
  • Examples of the ethylenically unsaturated compound having a quaternary ammonium base include (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, and (meth) acryloyloxy.
  • Ethyl (4-benzoylbenzyl) dimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride and the like can be mentioned.
  • Examples of the ethylenically unsaturated compound having a tertiary amino group and the ethylenically unsaturated compound having a quaternary ammonium base include those described in Paragraphs 0150 to 0170 of International Publication No. 2018/230486. The content is incorporated herein by reference.
  • Examples of other ethylenically unsaturated compounds include alkyl (meth) acrylates, preferably alkyl (meth) acrylates having an alkyl group having 1 to 10 carbon atoms, and alkyl (meth) acrylate having an alkyl group having 1 to 5 carbon atoms. ) Acrylate is more preferred.
  • other ethylenically unsaturated compounds include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. Examples thereof include (meth) acrylate and tert-butyl (meth) acrylate.
  • resin having a tertiary amino group in the side chain include the following compounds.
  • the numerical value added to each structural unit of the main chain is the molar ratio.
  • the resin containing a nitrogen atom in the main chain preferably contains a poly (lower alkyleneimine) -based constituent unit.
  • the lower alkyleneimine in the present disclosure represents an alkyleneimine having 1 to 5 carbon atoms.
  • the oligoimine-based resin is a poly (lower alkyleneimine) -based constituent unit from the viewpoint of improving the dispersibility of the near-infrared absorbing pigment, and has a side chain X containing a functional group of pKa14 or less bonded to a nitrogen atom.
  • a resin having a unit and a structural unit having a side chain Y containing an oligomer chain or a polymer chain having 40 to 10,000 atoms is preferable.
  • the oligoimine-based resin is at least one selected from the group consisting of a primary amino group or a salt thereof, a secondary amino group or a salt thereof, a tertiary amino group or a salt thereof, and a quaternary ammonium base. Is preferably included.
  • the oligoimine-based resin is preferably a resin having a structural unit represented by the formula (OI-1) and a structural unit represented by the formula (OI-2).
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and a independently represents an integer of 1 to 5, respectively.
  • * represents a connecting portion between structural units
  • X represents a side chain containing a functional group of pKa14 or less
  • Y represents a side chain containing an oligomer chain or a polymer chain having 40 to 10,000 atoms.
  • Examples of the functional group having a pKa14 or less contained in the side chain represented by X include the following.
  • the term "pKa” in the present disclosure is defined in the Chemical Handbook (II) (Revised 4th Edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
  • the structure of the "functional group having a pKa of 14 or less” is not particularly limited, and examples thereof include known functional groups having a pKa of 14 or less, but a functional group having a pKa of 12 or less is more preferable, and a pKa is 11 or less.
  • the following functional groups are more preferred.
  • a carboxylic acid group (about pKa3 to 5), a sulfonic acid group (about pKa-3 to -2), -COCH 2 CO- (about pKa8 to 10), -COCH 2 CN (pKa8 to 11).
  • R F is .PKa9 ⁇ about 11 represents a perfluoroalkyl group
  • a sulfonamido group PKa9 ⁇ 11
  • a carboxylic acid group, a sulfonic acid group, or -COCH 2 CO- is preferable.
  • the oligoimine-based resin has a structural unit represented by the formula (OI-1) and a structural unit represented by the formula (OI-2), and further has a structural unit represented by the formula (OI-3). Is preferable.
  • Y' represents a side chain containing an oligomer chain or polymer chain having an anionic group and having 40 to 10,000 atoms.
  • the structural unit represented by the formula (OI-3) is an oligomer having a group having a group that reacts with an amine to form a salt in a resin having a structural unit having a primary or secondary amino group in the main chain portion. It can be formed by adding a polymer and reacting.
  • R 1 and R 2 are preferably hydrogen atoms, and a is 2. preferable.
  • the oligoimine-based resin may contain poly (lower alkyleneimine) as a constituent unit in addition to the constituent units represented by the formulas (OI-1), formula (OI-2), and formula (OI-3). .. Similar to the above, the lower alkyleneimine represents an alkyleneimine having 1 to 5 carbon atoms. In addition, one or more of the side chains represented by X, Y, or Y'may be further bonded to the nitrogen atom in poly (lower alkyleneimine).
  • the resin (oligoimine-based resin) containing a nitrogen atom in the main chain include the following three compounds.
  • the numerical value added to each structural unit of the main chain is the molar ratio
  • the numerical value added to the side chain is the number of repeating units.
  • the resin having a basic group may be used alone or in combination of two or more.
  • the content of the resin having a basic group in the composition according to the present disclosure may be appropriately set according to the type and content of the near-infrared absorbing pigment.
  • the content of the resin having a basic group is 15% by mass to 90% by mass with respect to the total amount of the near-infrared absorbing pigment (preferably the total amount of the near-infrared absorbing pigment and the pigment other than the near-infrared absorbing pigment). It is preferably 25% by mass to 70% by mass, more preferably 30% by mass to 50% by mass.
  • the composition according to the present disclosure may contain tin (Sn) used in the synthesis of the resin having a basic group, depending on the type of the resin having a basic group used. Therefore, the content of tin (Sn) in the composition according to the present disclosure is preferably, for example, 1 ppm to 15 ppm with respect to the total solid content of the composition. In the present disclosure, “ppm”, “ppb” and “ppt” described later are all based on mass. Examples of the resin having a basic group used to satisfy the above-mentioned tin content include a resin containing a nitrogen atom in the main chain.
  • the tin content in the composition according to the present disclosure is measured by the following method.
  • the tin content is measured by preparing a calibration curve by gas chromatography according to a known method.
  • the composition according to the present disclosure is preferably a composition from which a film can be obtained, and preferably a curable composition from which a cured film can be finally obtained by curing. Further, since the composition according to the present disclosure contains a specific binder resin having a specific acid value, for example, a curable composition capable of forming a pattern of a cured film by pattern exposure and developing and removing an unexposed portion. It is preferably a thing. That is, the composition according to the present disclosure is preferably a negative type curable composition.
  • composition according to the present disclosure is a negative type curable composition
  • a polymerization initiator and a polymerizable compound are further added.
  • the including aspect is preferable.
  • the composition according to the present disclosure contains a dispersant other than the resin having the above-mentioned basic group and a pigment other than the near-infrared absorbing pigment as long as the effect of the composition according to the present disclosure is not impaired. You may.
  • the composition according to the present disclosure is preferably a so-called curable composition containing a near-infrared absorbing pigment, a specific binder resin, and a resin having a basic group, as well as a polymerizable compound and a polymerization initiator. .. Since the above-mentioned curable composition contains the composition according to the present disclosure, it is possible to maintain a high dispersion of the near-infrared absorbing pigment even in the film formed from the curable composition.
  • the content of the near-infrared absorbing pigment in the curable composition in the present disclosure is preferably 1% by mass to 30% by mass, and 5% by mass to 30% by mass, based on the total solid content of the curable composition. Is more preferable, and 5% by mass to 20% by mass is further preferable. When the content of the near-infrared absorbing pigment is within the above range, the function of the near-infrared absorbing pigment is sufficiently exhibited.
  • the content of the specific binder resin in the curable composition in the present disclosure is preferably 10% by mass to 50% by mass, preferably 10% by mass to 40% by mass, based on the total solid content of the curable composition. It is more preferable, and it is further preferable that it is 15% by mass to 35% by mass. When the content of the specific binder resin is within the above range, excellent film forming property can be obtained.
  • the content of the resin having a basic group in the curable composition in the present disclosure is preferably 0.5% by mass to 20% by mass, and 1% by mass, based on the total solid content of the curable composition. It is more preferably about 20% by mass, and even more preferably 5% by mass to 15% by mass. When the content of the resin having a basic group is within the above range, the storage stability is enhanced.
  • the curable composition in the present disclosure preferably contains a polymerizable compound.
  • the polymerizable compound is more preferably an ethylenically unsaturated compound, and particularly preferably a compound having a terminal ethylenically unsaturated group.
  • known compounds can be used without particular limitation.
  • the polymerizable compound has a chemical form such as, for example, a monomer, a prepolymer, that is, a dimer, a trimer, and an oligomer, or a mixture thereof, and a copolymer thereof.
  • Examples of the polymerizable compound include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides thereof, and preferred examples thereof. Esters of unsaturated carboxylic acid and aliphatic polyhydric alcohol compound, and amides of unsaturated carboxylic acid and aliphatic polyvalent amine compound are used. Examples of polymerizable compounds include addition reactions of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxy groups, amino groups, and mercapto groups with monofunctional or polyfunctional isocyanates or epoxys.
  • unsaturated carboxylic acids eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters of unsaturated carboxylic acids having nucleophilic substituents such as hydroxy group, amino group and mercapto group, or dehydration condensation reaction products of amides and monofunctional or polyfunctional carboxylic acids.
  • polymerizable compounds include esters of unsaturated carboxylic acids having polyelectron substituents such as isocyanate groups and epoxy groups, or amides and monofunctional or polyfunctional alcohols, amines and thiols.
  • substitution reactants are also suitable.
  • the polymerizable compound there is a group of compounds in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, styrene, vinyl ether or the like.
  • the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol as acrylic acid esters.
  • the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethyl propantri as methacrylic acid esters.
  • a urethane-based addition polymerizable compound produced by using an addition reaction of an isocyanate group and a hydroxy group is also suitable, and specific examples thereof include, for example, Japanese Patent Application Laid-Open No. 48-41708.
  • Two or more of the polyisocyanate compounds having two or more isocyanate groups in one molecule described therein are added with a vinyl monomer containing a hydroxy group represented by the following general formula (I). Examples thereof include vinyl urethane compounds containing a polymerizable vinyl group.
  • CH 2 C (R) COOCH 2 CH (R') OH (I) (However, R and R'indicate H or CH 3. )
  • urethane acrylates as described in JP-A No. 51-37193, Tokusho 2-32933, Tokuhei 2-16765, Tokukou Sho 58-49860, Tokukou Sho 56-17654, Tokukou Urethane compounds having an ethylene oxide-based skeleton described in Kosho 62-39417 and Tokusho 62-39418 are also suitable. Further, by using the addition polymerizable compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, A composition having a very high photosensitive speed can be obtained.
  • examples of the polymerizable compound include the compounds described in paragraphs 0178 to 0190 of JP-A-2007-277514. Further, as the polymerizable compound, the epoxy compound described in JP-A-2015-187211 may be used.
  • the polymerizable compound may be used alone or in combination of two or more.
  • the content of the polymerizable compound in the curable composition in the present disclosure is preferably 1% by mass to 90% by mass, and 5% by mass to 80% by mass, based on the total solid content of the curable composition. Is more preferable, and 10% by mass to 70% by mass is further preferable. When the content of the polymerizable compound is within the above range, the curable composition is excellent in curability.
  • the curable composition in the present disclosure preferably contains a polymerization initiator.
  • the polymerization initiator is particularly preferably a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
  • the photopolymerization initiator may be a compound that produces an active radical by causing some action with the photoexcited sensitizer. Above all, the photopolymerization initiator is particularly preferably a photoradical polymerization initiator.
  • the photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, and the like.
  • halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
  • acylphosphine compounds examples include hexaarylbiimidazole, oxime compounds, organic peroxides, and the like.
  • oxime compounds examples include thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds and ⁇ -aminoketone compounds.
  • the photopolymerization initiator is a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole.
  • Dimer, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxaziazole compounds and 3-aryl substituted coumarin compounds are preferred, oxime compounds, ⁇ -hydroxyketone compounds, ⁇ - A compound selected from an aminoketone compound and an acylphosphine compound is more preferable, and an oxime compound is further preferable.
  • the descriptions in paragraphs 0065 to 0111 of JP-A-2014-130173 and paragraphs 0274 to 0306 of JP-A-2013-29760 can be referred to, and these contents are incorporated in the present disclosure.
  • ⁇ -hydroxyketone compounds include DAROCUR 1173, IRGACURE 500, and IGM Resins B. manufactured by BASF. V. Examples include Omnirad 184 (formerly IRGACURE 184), Omnirad 2959 (formerly IRGACURE 2959), and Omnirad 127 (formerly IRGACURE-127). As a commercial product of the ⁇ -aminoketone compound, IGM Resins B.I. V. Examples thereof include Omnirad 907 (former IRGACURE-907), Omnirad 369 (former IRGACURE 369), Omnirad 379 (former IRGACURE 379), and Omnirad 379 (former IRGACURE-379EG).
  • IGM Resins B.I. V. Examples include Omnirad 819 (formerly IRGACURE 819) manufactured by BASF and Omnirad TPO H (formerly IRGACURE TPO) manufactured by BASF.
  • Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, and the compounds described in JP-A-2006-342166.
  • 2-acetoxyimino-1-phenylpropane-1-one 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxy Examples thereof include carbonyloxyimino-1-phenylpropane-1-one.
  • IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE03, and IRGACURE OXE04 manufactured by BASF are also preferably used.
  • oxime compounds include TRONLY TR-PBG-304, TRONLY TR-PBG-309, and TRONLY TR-PBG-manufactured by Changshu Powerful Electronics New Materials Co., Ltd. 305, ADEKA Arkuru's NCI-930 and ADEKA PUTMER N-1919 (corresponding to Photopolymerization Initiator 2 of JP2012-14052A) manufactured by ADEKA Corporation.
  • 2009-221114 which contains a triazine skeleton and an oxime skeleton in the same molecule, and has an absorption maximum at 405 nm and good sensitivity to a g-ray light source.
  • the compound described in 1 and the like may be used.
  • an oxime compound having a fluorene ring can also be used.
  • Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466, the contents of which are incorporated in the present disclosure.
  • an oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a benzofuran skeleton include compounds OE-01 to OE-75 described in International Publication No. 2015/036910.
  • an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
  • Specific examples of this oxime compound include the compounds described in International Publication No. 2013/083505.
  • an oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471.
  • an oxime compound having a nitro group can be used as the photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466, and Patent No. 4223071. Examples thereof include the compounds described in paragraphs 0007 to 0025 of the publication, ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation) and the like.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm. Further, the oxime compound is preferably a compound having a large absorbance at wavelengths of 365 nm and 405 nm.
  • the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, from the viewpoint of sensitivity. It is particularly preferably 000.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • a bifunctional or trifunctional or higher functional photopolymerization initiator may be used as the photopolymerization initiator.
  • Specific examples of such a photopolymerization initiator include paragraphs 0417 to 0412 of JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015/004565, and JP-A-2016-532675.
  • Dimers of oxime compounds described in paragraphs 0039 to 0055 of WO 2017/033680, compounds (E) and compounds (G) described in JP2013-522445, WO 2016 Examples thereof include Cmpd1 to 7 described in No. 034963.
  • the polymerization initiator may be used alone or in combination of two or more.
  • the content of the polymerization initiator in the curable composition in the present disclosure is preferably 0.1% by mass to 50% by mass, more preferably 0% by mass, based on the total solid content of the curable composition. It is 5% by mass to 30% by mass, particularly preferably 1% by mass to 20% by mass. When the content of the polymerization initiator is in the above range, good sensitivity and pattern forming property can be obtained.
  • the curable composition in the present disclosure may contain other components other than the components described above.
  • examples of other components include pigment derivatives, polymerization inhibitors, solvents, sensitizers, co-sensitizers, and other additives.
  • the curable composition in the present disclosure preferably contains a pigment derivative.
  • the pigment derivative include compounds in which at least one group selected from the group consisting of an acid group, a basic group, and a hydrogen-bonding group is bonded to the pigment skeleton.
  • the acid group include a sulfo group, a carboxy group, a phosphoric acid group, a boronic acid group, a sulfonimide group, a sulfonamide group and salts thereof, and a desalted structure of these salts.
  • alkali metal ions Li + , Na + , K +, etc.
  • alkaline earth metal ions Ca 2+ , Mg 2+, etc.
  • ammonium ions imidazolium ions, pyridinium ions, etc.
  • examples of the desalting structure of the salt include groups in which atoms or atomic groups forming a salt are eliminated from the salt.
  • desalting structure of salt of carboxy group a carboxylate group - is (-COO).
  • the basic group include an amino group, a pyridinyl group, and salts thereof, and a desalted structure of these salts.
  • Examples of the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion.
  • examples of the desalting structure of the salt include groups in which atoms or atomic groups forming a salt are eliminated from the salt.
  • a hydrogen-bonding group is a group that interacts with a hydrogen atom.
  • Specific examples of the hydrogen-bonding group include an amide group, a hydroxy group, -NHCONHR, -NHCOOR, and -OCONHR.
  • R is preferably an alkyl group and an aryl group.
  • the pigment derivative is a sulfo group, a carboxy group, a phosphoric acid group, a boronic acid group, a sulfonimide group, a sulfonamide group, an amino group, a pyridinyl group, salts thereof, or at least one group selected from these desalted structures. It is preferable to have a sulfo group, a carboxy group, and an amino group. When the pigment derivative has such a group, the dispersibility of the near-infrared absorbing pigment can be further improved.
  • Examples of the pigment derivative include a compound represented by the formula (B1).
  • P represents a dye skeleton
  • L represents a single bond or a linking group
  • X represents an acid group, a basic group, or a hydrogen bonding group
  • m represents an integer of 1 or more.
  • n represents an integer of 1 or more, and when m is 2 or more, the plurality of Ls and Xs may be different from each other, and when n is 2 or more, the plurality of Xs may be different from each other.
  • the pigment skeleton represented by P is a squarylium pigment skeleton, a pyrolopyrrolop pigment skeleton, a diketopyrrolopyrrole pigment skeleton, a quinacridone pigment skeleton, an anthraquinone pigment skeleton, a dianthraquinone pigment skeleton, a benzoisoindole pigment skeleton, and a thiazine indigo pigment.
  • At least one selected from the skeleton is preferable, and a squarylium pigment skeleton or a pyrolopyrrolop pigment skeleton is particularly preferable from the viewpoint of compatibility with the above-mentioned near-infrared absorber.
  • the linking group represented by L includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms.
  • a group consisting of is preferable, and it may be unsubstituted or further having a substituent. Examples of the substituent include the above-mentioned Substituent T.
  • Examples of the acid group, the basic group, and the hydrogen-bonding group represented by X include the above-mentioned groups.
  • the amount of the pigment derivative dissolved in 100 g of propylene glycol methyl ether acetate at 25 ° C. is preferably 0.01 mg to 10 g.
  • the upper limit is preferably 7.5 g or less, and more preferably 5 g or less.
  • the lower limit is preferably 0.05 mg or more, and more preferably 0.1 mg or more. According to this aspect, the dispersibility of the near-infrared absorbing pigment in the composition according to the present disclosure can be further improved.
  • the molecular weight of the pigment derivative is preferably 160 to 4500.
  • the upper limit of the molecular weight of the pigment derivative is preferably 4000 or less, and more preferably 3500 or less.
  • the lower limit of the molecular weight of the pigment derivative is preferably 200 or more, more preferably 250 or more.
  • the pigment derivative is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 nm to 1,200 nm, preferably a compound having a maximum absorption wavelength in the wavelength range of 700 nm to 1,100 nm, and has a wavelength of 700 nm to 1,
  • a compound having a maximum absorption wavelength in the range of 000 nm is preferable.
  • a pigment derivative having a maximum absorption wavelength in the above wavelength range can easily have the spread of the ⁇ plane close to that of the near-infrared absorbing pigment, improve the adsorptivity to the near-infrared absorbing pigment, and easily obtain more excellent dispersibility.
  • the pigment derivative is preferably a compound containing an aromatic ring, and more preferably a compound containing a structure in which two or more aromatic rings are condensed. Further, the pigment derivative is preferably a compound having a ⁇ -conjugated plane, and more preferably a compound having a ⁇ -conjugated plane having the same structure as the ⁇ -conjugated plane contained in the near-infrared absorbing pigment.
  • the number of ⁇ electrons contained in the ⁇ -conjugated plane of the pigment derivative is preferably 8 to 100.
  • the upper limit is preferably 90 or less, and more preferably 80 or less.
  • the lower limit is preferably 10 or more, and more preferably 12 or more.
  • the pigment derivative is a compound having a ⁇ -conjugated plane containing a partial structure represented by the following formula (SQ-a) or a ⁇ -conjugated plane containing a partial structure represented by the following formula (CR-a). It is also preferable that there is.
  • the wavy line represents a bond.
  • the pigment derivative is at least one selected from the compound represented by the following formula (Syn1) and the compound represented by the following formula (Syn2).
  • Rsy 1 and Rsy 2 each independently represent an organic group
  • L 1 represents a single bond or a p1 + 1 valent group
  • a 1 represents a sulfo group, a carboxy group, a phosphate group, a boronic acid group, and the like. It represents a sulfonimide group, a sulfonamide group, an amino group, a pyridinyl group, a salt thereof or a group selected from the desalted structure thereof
  • p1 and q1 each independently represent an integer of 1 or more. If p1 is 2 or more, a plurality of A 1 may be the same or different. If q1 is 2 or more, a plurality of L 1 and A 1 may be the same or different.
  • Rsy 3 and Rsy 4 each independently represent an organic group
  • L 2 represents a single bond or a p2 + 1 valent group
  • a 2 represents a sulfo group, a carboxy group, a phosphoric acid group, a boronic acid group, It represents a sulfonimide group, a sulfonamide group, an amino group, a pyridinyl group, a salt thereof or a group selected from the desalted structure thereof
  • p2 and q2 each independently represent an integer of 1 or more. If p2 is 2 or more, plural A 2 may be the same or different. If q2 is 2 or more, the plurality of L 2 and A 2 may be the same or may be different.
  • Examples of the organic group represented by Rsy 1 and Rsy 2 of the formula (Syn1) and the organic group represented by Rsy 3 and Rsy 4 of the formula (Syn2) include an aryl group, a heteroaryl group, and the following formula (R1). The group represented by is mentioned.
  • R 1 to R 3 independently represent a hydrogen atom or a substituent
  • As 3 represents a heteroaryl group
  • nr1 represents an integer of 0 or more
  • R 1 and R 2 are bonded to each other.
  • R 1 and As 3 may be bonded to each other to form a ring
  • R 2 and R 3 may be bonded to each other to form a ring
  • n r 1 is 2.
  • the plurality of R 2 and R 3 may be the same or different
  • * represents a bond.
  • the aryl group represented by Rsy 1 to Rsy 4 preferably has 6 to 48 carbon atoms, more preferably 6 to 22 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
  • the number of carbon atoms constituting the ring of the heteroaryl group represented by Rsy 1 to Rsy 4 is preferably 1 to 30, and more preferably 1 to 12.
  • Examples of the type of hetero atom constituting the ring of the heteroaryl group include a nitrogen atom, an oxygen atom and a sulfur atom.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2.
  • the heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 8, and even more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4.
  • the aryl group and heteroaryl group represented by Rsy 1 to Rsy 4 may have a substituent. Examples of the substituent include the above-mentioned Substituent T and a group represented by the following formula (RSQ).
  • Rsq 1 represents an organic group.
  • the organic group represented by Rsq 1 includes an aryl group, a heteroaryl group, a group represented by the formula (R1), a group represented by the formula (1) and a group represented by the formula (10), which will be described later. Examples thereof include a group represented by the formula (20), a group represented by the formula (30), and a group represented by the formula (40).
  • R 1 to R 3 in the formula (R1) independently represent a hydrogen atom or a substituent.
  • substituents include the above-mentioned Substituent T.
  • the substituent represented by R 1 to R 3 is preferably an alkyl group.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • R 1 to R 3 are preferably hydrogen atoms.
  • As 3 in the formula (R1) represents a heteroaryl group. Examples of the heteroaryl group represented by As 3 include the same heteroaryl groups represented by Rsy 1 to Rsy 4 , and preferred embodiments are also the same.
  • R 1 and R 2 may be coupled to each other to form a ring
  • R 1 and As 3 may be coupled to each other to form a ring
  • R 2 and R 3 may be coupled to each other to form a ring.
  • a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, -CH-, and a combination thereof is preferable.
  • N r1 in the formula (R1) represents an integer of 0 or more.
  • n r1 is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
  • the plurality of R 2 and R 3 may be the same or different.
  • the organic groups represented by Rsy 1 and Rsy 2 of the formula (Syn1) and the organic groups represented by Rsy 3 and Rsy 4 of the formula (Syn2) are the groups represented by the following formula (1). Is preferable.
  • ring Z 1 represents an aromatic heterocycle or a fused ring containing an aromatic heterocycle, which may have one or more substituents
  • ring Z 2 is one or more. which may have a substituent, a hydrocarbon ring or heterocyclic ring 4-9 membered, wherein ring Z 1 and the ring Z 2 has plural substituents, the plural substituents may be the same It may be different, and * represents a bond.
  • ring Z 1 represents an aromatic heterocycle or a fused ring containing an aromatic heterocycle, which may have one or more substituents.
  • the aromatic heterocycle include an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrazole ring, a furan ring, a thiophene ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a pyridazine ring, a pyrimidine ring and the like.
  • an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, and a pyrazole ring are preferable.
  • the fused ring containing an aromatic heterocycle include an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrrol ring, a furan ring, a thiophene ring, a pyrazole ring, an isooxazole ring, an isothiazole ring, a pyridazine ring, and a pyrimidine.
  • One or more rings selected from the rings (two or more rings may be of the same type or different types), a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, A fused ring with a ring selected from a phenanthrene ring, a triphenylene ring, a tetraphen ring, and a pyrene ring (preferably a benzene ring and a naphthalene ring); an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrrol ring, and a furan ring.
  • Thiophen ring pyrazole ring, isooxazole ring, isothiazole ring, pyridazine ring, pyrimidine ring, two or more rings (in the case of two or more, the same type of ring may be used, and different types of rings may be used. (May be present), such as a fused ring.
  • the number of condensed rings is preferably 2 to 6 and more preferably 2 to 4 because more excellent spectral characteristics can be easily obtained.
  • ring Z 2 represents a 4- to 9-membered hydrocarbon ring or heterocycle which may have one or more substituents.
  • the hydrocarbon ring and the heterocycle represented by ring Z 2 are preferably a 5- to 7-membered ring, and more preferably a 5- or 6-membered ring.
  • hydrocarbon ring examples include a cyclobutene ring, a cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a cyclohexadiene ring, a cycloheptene ring, a cycloheptene ring, a cycloheptene ring, a cyclooctene ring, a cyclooctadiene ring, and a cyclooctane.
  • Cycloalkene rings such as triene ring, cyclononene ring, cyclononadien ring, cyclononatorien ring, cyclononatetraene ring can be mentioned, cyclopentene ring, cyclohexene ring, cycloheptene ring and cyclooctene ring are preferable, and cyclopentene ring and cyclohexene ring are more preferable.
  • the heterocycle represented by ring Z 2 is preferably a nitrogen-containing heterocycle.
  • substituents that the ring Z 1 and the ring Z 2 may have include the above-mentioned substituent T. Further, the substituent that the ring Z 1 may have is preferably an electron-attracting group.
  • Substituents with a positive Hammett substituent constant ⁇ value act as electron-attracting groups.
  • the substituent constants obtained by Hammett's law include ⁇ p value and ⁇ m value. These values can be found in many common books.
  • a substituent having a Hammett substituent constant ⁇ value of 0.1 or more can be exemplified as an electron-attracting group.
  • the ⁇ value is preferably 0.15 or more, more preferably 0.2 or more, and even more preferably 0.3 or more.
  • the upper limit is not particularly limited, but is preferably 1.0 or less.
  • Specific examples of the electron-attracting group include a halogen atom, an alkyl group in which at least a part of a hydrogen atom is replaced with a halogen atom, an aryl group in which at least a part of a hydrogen atom is replaced with a halogen atom, and a nitro group.
  • R z is an alkyl group in which at least a part of a hydrogen atom may be replaced with a fluorine atom, an aryl group in which at least a part of a hydrogen atom may be replaced with a fluorine atom, an amino group, a halogen atom, or a cyano group.
  • the cyanomethyl group includes a monocyanomethyl group (-CH 2 CN), a dicyanomethyl group (-CH (CN) 2 ), and a tricyanomethyl group (-C (CN) 3 ).
  • the alkyl group in which at least a part of the hydrogen atom may be replaced with a fluorine atom preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and further preferably 1 to 4 carbon atoms.
  • the aryl group in which at least a part of the hydrogen atom may be replaced with a fluorine atom preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. In these alkyl groups and aryl groups, all of the hydrogen atoms may be replaced with fluorine atoms, only some of them may be replaced with fluorine atoms, or they may not be replaced with fluorine atoms.
  • the group represented by the formula (1) is preferably a group represented by the formula (1-1) or the formula (1-2).
  • ring Z 1a represents a polycyclic aromatic ring having a 5- or 6-membered nitrogen-containing heterocycle which may have one or more substituents
  • ring Z 2a represents a 4- to 9-membered hydrocarbon ring or heterocycle which may have one or more substituents.
  • the plurality of substituents may be the same or different.
  • R 5 and R 7 each independently represent a hydrogen atom or a substituent.
  • the polycyclic aromatic ring represented by the ring Z 1a includes an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, and a pyrazole ring.
  • Examples thereof include a fused ring containing a 5- or 6-membered nitrogen-containing heterocycle selected from an isooxazole ring, an isothiazole ring, a pyridazine ring, and a pyrimidine ring, and one or more rings (2) selected from the above-mentioned nitrogen-containing heterocycles.
  • the number of rings contained in the polycyclic aromatic ring is preferably 2 to 6 and more preferably 2 to 4 because more excellent spectral characteristics can be easily obtained.
  • examples of the 4- to 9-membered hydrocarbon ring and the heterocycle represented by the ring Z 2a include those described in the section of the ring Z 2 of the formula (1).
  • the substituents that the rings Z 1a and Z 2a may have, and the substituents represented by R 5 and R 7 include the above-mentioned substituent T.
  • the substituent that the ring Z1a may have is preferably an electron-attracting group.
  • the electron-attracting group include an electron-attracting group as a substituent that the ring Z 1 may have.
  • ring Z 1b represents a polycyclic aromatic ring having a 5- or 6-membered nitrogen-containing heterocycle which may have one or more substituents
  • ring Z. 2b represents a 4- to 9-membered nitrogen-containing heterocycle which may have one or more substituents, and when rings Z 1b and Z 2b have a plurality of substituents, a plurality of substituents. May be the same or different.
  • the polycyclic aromatic ring represented by the ring Z 1b includes an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, and a pyrazole ring.
  • Examples thereof include a fused ring containing a 5- or 6-membered nitrogen-containing heterocycle selected from an isooxazole ring, an isothiazole ring, a pyridazine ring, and a pyrimidine ring, and one or more rings (2) selected from the above-mentioned nitrogen-containing heterocycles.
  • the number of rings contained in the polycyclic aromatic ring is preferably 2 to 6 and more preferably 2 to 4 because more excellent spectral characteristics can be easily obtained.
  • the nitrogen-containing heterocycle represented by ring Z 2b is preferably a 5- to 7-membered ring, and more preferably a 5- or 6-membered ring.
  • examples of the substituent that the ring Z 1b and the ring Z 2b may have include the above-mentioned substituent T. Further, it is also preferable that the substituent that the ring Z 1b may have is an electron-attracting group. Examples of the electron-attracting group include an electron-attracting group as a substituent that the ring Z 1 may have.
  • the organic group represented by Rsy 1 and Rsy 2 of the formula (Syn1) and the organic group represented by Rsy 3 and Rsy 4 of the formula (Syn2) shall be the group represented by the following formula (10). Is also preferable.
  • R 11 to R 14 each independently represent a hydrogen atom or a substituent, and two adjacent groups of R 11 to R 14 may be bonded to each other to form a ring.
  • R 20 represents an aryl group or a heteroaryl group
  • R 21 represents a substituent
  • X 10 represents -CO- or -SO 2- .
  • examples of the substituent represented by R 11 to R 14 include the above-mentioned substituent T.
  • R 20 represents an aryl group or a heteroaryl group, and is preferably an aryl group.
  • the aryl group preferably has 6 to 48 carbon atoms, more preferably 6 to 22 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
  • the number of carbon atoms constituting the ring of the heteroaryl group is preferably 1 to 30, more preferably 1 to 12.
  • Examples of the type of hetero atom constituting the ring of the heteroaryl group include a nitrogen atom, an oxygen atom and a sulfur atom.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2.
  • the heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 8, and even more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4.
  • Aryl groups and heteroaryl groups may have substituents. Examples of the substituent include the above-mentioned Substituent T.
  • the aryl group and the heteroaryl group preferably have no substituent.
  • R 21 represents a substituent.
  • substituent represented by R 21 include the above-mentioned Substituent T, and an alkyl group, an aryl group, a heteroaryl group, -OCORt 1 , or -NHCORt 1 is preferable.
  • Rt 1 is preferably an alkyl group, an aryl group or a heteroaryl group, and more preferably an alkyl group.
  • the organic group represented by Rsy 1 and Rsy 2 of the formula (Syn1) and the organic group represented by Rsy 3 and Rsy 4 of the formula (Syn2) shall be the group represented by the following formula (20). Is also preferable.
  • R 20 and R 21 each independently represent a hydrogen atom or a substituent
  • R 20 and R 21 may be bonded to each other to form a ring
  • X 20 is an oxygen atom and sulfur.
  • atom, -NR 22 - it represents a selenium atom, or a tellurium atom
  • R 22 represents a hydrogen atom or a substituent
  • n r2 is 0 to an integer of 5
  • n r2 is 2 or more
  • the plurality of R 20 may be the same or different
  • two of the plurality of R 20 may also be R 20 are bonded to each other to form a ring
  • * represents a bond.
  • examples of the substituent represented by R 20 and R 21 include the above-mentioned substituent T.
  • R 20 is preferably an alkyl group, an alkyl halide group (preferably an alkyl fluoride group), an aryl group, or a halogen atom, more preferably an alkyl group or an alkyl halide group, and an alkyl halide. It is more preferably a group.
  • R 21 is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • X 20 represents an oxygen atom, a sulfur atom, -NR 22 - are preferred, -NR 22 - is more preferable.
  • R 22 represents a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned Substituent T, and an alkyl group is preferable.
  • R 22 and R 20 may combine with each other to form a ring. Examples of the ring formed by combining R 22 and R 20 include a 4- to 9-membered hydrocarbon ring or a heterocycle, and a 5- to 7-membered hydrocarbon ring or heterocycle is preferable, and a 5- to 6-membered hydrocarbon ring or heterocycle is preferable.
  • the hydrocarbon ring or heterocycle is more preferable, a 5- to 6-membered hydrocarbon ring is further preferable, and a 6-membered hydrocarbon ring is particularly preferable.
  • n r2 represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and preferably an integer of 1 to 2. More preferred. If n r2 is 2 or more, the plurality of R 20 may be the same or different, may be two R 20 are bonded to each other among the plurality of R 20 form a ring .. Ring R 20 together are formed by bonding may be a hydrocarbon ring may be a heterocyclic ring. Further, the ring formed by bonding these groups to each other may be a monocyclic ring or a condensed ring.
  • the organic group represented by Rsy 1 and Rsy 2 of the formula (Syn1) and the organic group represented by Rsy 3 and Rsy 4 of the formula (Syn2) include the group represented by the following formula (30) or the formula. It is also preferable that it is a group represented by (40).
  • R 35 to R 38 each independently represent a hydrogen atom or a substituent, and R 35 and R 36 , R 36 and R 37 , and R 37 and R 38 combine with each other to form a ring. * May represent a bond.
  • R 39 to R 45 each independently represent a hydrogen atom or a substituent, and R 39 and R 45 , R 40 and R 41 , R 40 and R 42 , R 42 and R 43 , and R 43 .
  • R 44 , R 44 and R 45 may be bonded to each other to form a ring, and * represents a bond.
  • Examples of the substituent represented by R 35 to R 38 of the formula (30) and the substituent represented by R 39 to R 45 of the formula (40) include the above-mentioned substituent T, which is an alkyl group. Alternatively, an aryl group is preferable, and an alkyl group is more preferable.
  • R 35 and R 36 , R 36 and R 37 , and R 37 and R 38 may be coupled to each other to form a ring.
  • R 39 and R 45 , R 40 and R 41 , R 40 and R 42 , R 42 and R 43 , R 43 and R 44 , and R 44 and R 45 are coupled to each other and ring. May be formed.
  • the ring formed by bonding these groups to each other include a hydrocarbon ring and a heterocycle, and a hydrocarbon ring is preferable.
  • the ring formed by bonding these groups to each other may be a monocyclic ring or a condensed ring, but a condensed ring is preferable.
  • R 35 and R 36 are bonded to form a ring.
  • R 40 and R 41 and R 44 and R 45 are bonded to each other to form a ring.
  • the group represented by the formula (30) is preferably a group represented by the following formula (30a). Further, the group represented by the formula (40) is preferably a group represented by the following formula (40a).
  • R 35 , R 36 , and R 101 to R 106 each independently represent a hydrogen atom or a substituent, and * represents a bond.
  • R 39 , R 42 , R 43 , and R 201 to R 212 each independently represent a hydrogen atom or a substituent, and * represents a bond.
  • Substituents represented by R 35 , R 36 , R 101 to R 106 and substituents represented by R 39 , R 39 , R 42 , R 43 , and R 201 to R 212 have the above-mentioned substituent T.
  • the alkyl group or the aryl group is preferable, and the alkyl group is more preferable.
  • the p1 + 1 valent group represented by L 1 of the formula (Syn1) and the p2 + 1 valent group represented by L 2 of the formula (Syn2) include a hydrocarbon group, a heterocyclic group, -O-, and -S. -, -CO-, -COO-, -OCO-, -SO 2- , -NR L- , -NR L CO-, -CONR L- , -NR L SO 2- , -SO 2 NR L- , and A group consisting of a combination of these can be mentioned.
  • RL represents a hydrogen atom, an alkyl group, or an aryl group.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • Examples of the hydrocarbon group include an alkylene group, an arylene group, or a group obtained by removing one or more hydrogen atoms from these groups.
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms.
  • the alkylene group may be linear, branched or cyclic.
  • the cyclic alkylene group may be either monocyclic or polycyclic.
  • the arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • the heterocyclic group is preferably a single ring or a condensed ring having 2 to 4 condensation numbers.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3.
  • the hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
  • the hydrocarbon group and the heterocyclic group may have a substituent. Examples of the substituent include the above-mentioned Substituent T.
  • the alkyl group represented by RL preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 8 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the alkyl group represented by RL may further have a substituent. Examples of the substituent include the above-mentioned Substituent T.
  • the number of carbon atoms of the aryl group represented by RL is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
  • the aryl group represented by RL may further have a substituent. Examples of the substituent include the above-mentioned Substituent T.
  • L 1 in the formula (Syn 1) is preferably a p1 + 1 valent group.
  • L 2 in the formula (Syn 2) is a group having a p2 + 1 valence.
  • the compound represented by formula (SYN1) includes a group represented by the mother nucleus and A 1 is preferably that are separated more than 1 atom by p1 + 1 valent group represented by L 1, 3 atom It is more preferable that they are separated by the above.
  • the mother nucleus and the group represented by A 2 are separated by one or more atoms by a p2 + 1 valent group represented by L 2. It is more preferable that they are separated by an atom or more. With this structure, it is easy to obtain better dispersibility of the near-infrared absorbing pigment.
  • pigment derivative examples include compounds having the following structures [BP-1 to BP-4, B-1 to B-17].
  • Japanese Patent Application Laid-Open No. 56-118462 Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 1-2170777, Japanese Patent Application Laid-Open No. 3-9961, Japanese Patent Application Laid-Open No. 3-26767, Japanese Patent Application Laid-Open No. 3-153780.
  • Japanese Patent Application Laid-Open No. 3-455662 Japanese Patent Application Laid-Open No. 4-285669, Japanese Patent Application Laid-Open No. 6-145546, Japanese Patent Application Laid-Open No. 6-21208, Japanese Patent Application Laid-Open No.
  • JP-A-10-195326 paragraphs 0083 to 098 of International Publication No. 2011/024896, paragraphs 0063 to 0094 of International Publication No. 2012/102399, and the like.
  • pigment derivatives JP-A-2015-172732 (metal salt of a quinophthalone compound having a sulfo group), JP-A-2014-199308, JP-A-2014-85562, JP-A-2014-35351,
  • the compounds described in JP-A-2008-81565 can also be used, and their contents are incorporated in the present specification.
  • one pigment derivative may be used alone, or two or more pigment derivatives may be used in combination.
  • the content of the pigment derivative in the curable composition in the present disclosure is preferably 1% by mass to 30% by mass, more preferably 5% by mass to 30% by mass, based on the total amount of all pigments including the near-infrared absorbing pigment. It is more preferably 10% by mass to 30% by mass.
  • the curable composition in the present disclosure preferably contains a polymerization inhibitor from the viewpoint of storage stability.
  • the polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used.
  • examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, quaternary-thiobis (3-methyl-6-t-butylphenol), and the like.
  • the polymerization inhibitor may be used alone or in combination of two or more.
  • the content of the polymerization inhibitor in the curable composition in the present disclosure is preferably 0.1 ppm to 1,000 ppm with respect to the total solid content of the curable composition from the viewpoint of storage stability, and is 1 ppm. It is more preferably about 500 ppm, and particularly preferably 1 ppm to 100 ppm.
  • the curable composition in the present disclosure preferably contains a solvent.
  • the solvent include esters such as ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and the like.
  • Ethyl lactate methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate and ethyl 3-oxypropionate.
  • 3-Oxypropionic acid alkyl esters such as (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and methyl 2-oxypropionate.
  • 2-Oxypropionate alkyl esters such as ethyl 2-oxypropionate, and propyl 2-oxypropionate (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2, -Methyl ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy- 2-Methyl propionate), as well as methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc .;
  • Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol.
  • methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
  • the solvent may be used alone or in combination of two or more.
  • an organic solvent having a low metal content it is preferable to use an organic solvent having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 ppb or less. If necessary, a ppt-level organic solvent may be used, and such an organic solvent is provided by, for example, Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).
  • Examples of the method for removing impurities such as metals from the organic solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the organic solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.
  • the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.
  • one type of solvent may be used alone, or two or more types may be used in combination.
  • the solid content of the curable composition in the present disclosure varies depending on the coating method and the presence or absence of a solvent, but is preferably 1% by mass to 100% by mass, preferably 5% by mass to 50% by mass, for example. More preferably, 10% by mass to 30% by mass is more preferable. That is, in the curable composition in the present disclosure, a solvent may be used so that the solid content is within the above range.
  • the curable composition in the present disclosure may contain a sensitizer for the purpose of improving the generation efficiency of polymerization initiator species such as radicals and cations of the polymerization initiator and lengthening the photosensitive wavelength.
  • a sensitizer for the purpose of improving the generation efficiency of polymerization initiator species such as radicals and cations of the polymerization initiator and lengthening the photosensitive wavelength.
  • the sensitizer those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable.
  • Examples of the sensitizer include those belonging to the compounds listed below and having an absorption wavelength in the wavelength region of a wavelength of 300 nm to 450 nm.
  • Examples of preferable sensitizers include those belonging to the following compounds and having an absorption wavelength in the wavelength region of 330 nm to 450 nm.
  • Examples of sensitizers include polynuclear aromatics (eg, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (eg, fluoressein, eosin, erythrosin, rhodamine B, etc.).
  • Rose Bengal thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanins (eg thiacarbocyanin, oxacarbocyanin), merocyanins (eg merocyanin, carbomerocyanin), phthalocyanins, thiadins (eg thionin) , Methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acryflabin), anthraquinones (eg, anthraquinone), squaryliums (eg, squarylium), acridine oranges, coumarins (eg, 7-diethylamino-).
  • cyanins eg thiacarbocyanin, oxacarbocyanin
  • merocyanins eg merocyan
  • sensitizers include European Patent Nos. 568,993, US Pat. Nos. 4,508,811, 5,227,227, Japanese Patent Application Laid-Open No. 2001-125255, and Japanese Patent Office No. 4,508,811. Examples thereof include the compounds described in Kaihei 11-271969.
  • the sensitizer may be used alone or in combination of two or more.
  • the content of the sensitizer is 0. It is preferably 1% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass.
  • the curable composition in the present disclosure may contain a cosensitizer.
  • the co-sensitizer has an action of further improving the sensitivity of the sensitizing dye or the initiator to active radiation, or suppressing the polymerization inhibition of the polymerizable compound by oxygen.
  • co-sensitizer examples include the compounds described in paragraphs 0233 to 0241 of JP-A-2007-277514.
  • the cosensitizer may be used alone or in combination of two or more.
  • the content of the co-sensitizer is the total solid content of the curable composition from the viewpoint of improving the curing rate by balancing the polymerization growth rate and the chain transfer.
  • the range of 0.1% by mass to 30% by mass is preferable, the range of 0.5% by mass to 25% by mass is more preferable, and the range of 1% by mass to 20% by mass is further preferable.
  • the curable composition in the present disclosure contains various additives such as a surfactant, a colorant other than a near-infrared absorbing pigment, an adhesion accelerator, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent, if necessary. can do.
  • Examples of other components include the compounds described in paragraphs 0238 to 0249 of JP-A-2007-277514.
  • the curable composition in the present disclosure can be prepared by mixing each of the above-mentioned components. Further, it is preferable to filter with a filter for the purpose of removing foreign substances and reducing defects.
  • the filter can be used without particular limitation as long as it has been conventionally used for filtration purposes and the like.
  • fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultra-high).
  • PTFE polytetrafluoroethylene
  • nylon eg, nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultra-high).
  • PP polypropylene
  • polypropylene including high-density polypropylene
  • nylon is preferable.
  • the pore size of the filter is preferably 0.01 ⁇ m to 7.0 ⁇ m, more preferably 0.01 ⁇ m to 3.0 ⁇ m, and even more preferably 0.05 ⁇ m to 0.5 ⁇ m.
  • the filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like.
  • SBP type series (SBP008, etc.) and TPR type series (TPR002) manufactured by Roki Techno Co., Ltd. , TPR005, etc.), SHPX type series (SHPX003, etc.) filter cartridges can be used.
  • filters different filters may be combined. At that time, the filtration with the first filter may be performed only once or twice or more. Further, first filters having different pore diameters within the above-mentioned range may be combined.
  • the nominal value of the filter manufacturer can be referred to.
  • a commercially available filter for example, it can be selected from various filters provided by Nippon Paul Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Entegris Japan Co., Ltd., Kits Micro Filter Co., Ltd., and the like. ..
  • the curable composition in the present disclosure can be in a liquid state, for example, a film can be easily produced by applying the curable composition in the present disclosure to a substrate or the like and drying it.
  • the viscosity of the curable composition in the present disclosure at 23 ° C. is preferably 1 mPa ⁇ s to 100 mPa ⁇ s from the viewpoint of coatability when a film is formed by coating.
  • the lower limit is more preferably 2 mPa ⁇ s or more, and further preferably 3 mPa ⁇ s or more.
  • the upper limit is more preferably 50 mPa ⁇ s or less, further preferably 30 mPa ⁇ s or less, and particularly preferably 15 mPa ⁇ s or less.
  • the viscosity in the present disclosure shall be measured at 23 ° C. using a viscometer (trade name: VISCOMETER TV-22) manufactured by Toki Sangyo Co., Ltd.
  • the use of the curable composition in the present disclosure is not particularly limited.
  • it can be preferably used for forming an infrared cut filter or the like.
  • it is preferably used as an infrared cut filter on the light receiving side of the solid-state image sensor (for example, for an infrared cut filter for a wafer level lens), an infrared cut filter on the back surface side of the solid-state image sensor (opposite the light receiving side), and the like.
  • it can.
  • it can be preferably used as an infrared cut filter on the light receiving side of the solid-state image sensor.
  • an infrared transmission filter capable of transmitting infrared rays having a specific wavelength or higher can be formed.
  • an infrared transmission filter that shields light from a wavelength of 400 nm to 850 nm and can transmit a part of infrared rays having a wavelength of 850 nm or more.
  • the curable composition in the present disclosure is preferably stored in a storage container.
  • a storage container a multi-layer bottle in which the inner wall of the container is composed of 6 types and 6 layers of resin or a bottle in which 6 types of resin is composed of 7 layers may be used for the purpose of preventing impurities from being mixed into the raw materials and compositions.
  • these containers include the containers described in Japanese Patent Application Laid-Open No. 2015-123351.
  • the film according to the present disclosure is a film made of the curable composition according to the present disclosure or obtained by curing the curable composition according to the present disclosure. If the curable composition in the present disclosure contains a solvent, it may be dried.
  • the film according to the present disclosure can be preferably used as an infrared cut filter. It can also be used as a heat ray shielding filter and an infrared ray transmitting filter.
  • the film according to the present disclosure may be used by being laminated on a support, or may be peeled off from the support and used.
  • the film according to the present disclosure may have a pattern or may be a film having no pattern (flat film).
  • the drying in the present disclosure, it is sufficient to remove at least a part of the solvent, it is not necessary to completely remove the solvent, and the amount of the solvent removed can be set as desired. Further, the above-mentioned curing may be performed as long as the hardness of the film is improved, but curing by polymerization is preferable.
  • the thickness of the film according to the present disclosure can be appropriately adjusted according to the purpose.
  • the thickness of the film is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more.
  • the film according to the present disclosure preferably has a maximum absorption wavelength in the wavelength range of 650 nm to 1,500 nm, more preferably has a maximum absorption wavelength in the wavelength range of 680 nm to 1,300 nm, and has a wavelength range of 700 nm to 850 nm. It is more preferable to have a maximum absorption wavelength.
  • the film according to the present disclosure preferably satisfies at least one of the following (1) to (4), and the above (1) to (4). It is more preferable that all the conditions are satisfied.
  • the transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 80% or more, further preferably 85% or more, and particularly preferably 90% or more.
  • the transmittance at a wavelength of 500 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.
  • the transmittance at a wavelength of 600 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.
  • the transmittance at a wavelength of 650 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.
  • the film according to the present disclosure can also be used in combination with a color filter containing a chromatic colorant.
  • the color filter can be produced by using a coloring composition containing a chromatic colorant.
  • the chromatic colorant include conventionally known chromatic colorants.
  • the coloring composition may further contain a resin, a polymerizable compound, a polymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber and the like.
  • the above-mentioned components may be appropriately used.
  • the color filter is arranged on the optical path of the film according to the present disclosure.
  • the film and the color filter according to the present disclosure can be laminated and used as a laminated body.
  • the film and the color filter according to the present disclosure may or may not be adjacent to each other in the thickness direction.
  • the film according to the present disclosure may be formed on a support different from the support on which the color filter is formed.
  • Other members for example, a microlens, a flattening layer, etc. constituting the solid-state image sensor may be interposed between the film and the color filter according to the disclosure.
  • the infrared cut filter means a filter that transmits light having a wavelength in the visible region (visible light) and blocks at least a part of light having a wavelength in the near infrared region (infrared light).
  • the infrared cut filter may transmit all the light having a wavelength in the visible region, and among the light having a wavelength in the visible region, the light having a specific wavelength region is passed through and the light having a specific wavelength region is blocked. It may be a thing.
  • the color filter means a filter that passes light in a specific wavelength region and blocks light in a specific wavelength region among light having a wavelength in the visible region.
  • the infrared transmission filter means a filter that blocks visible light and transmits at least a part of infrared rays.
  • the film according to the present disclosure can be used for solid-state imaging devices such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor), and various devices such as infrared sensors and image display devices.
  • CCD charge-coupled device
  • CMOS complementary metal oxide semiconductor
  • ⁇ Membrane manufacturing method> Next, a method for producing a film according to the present disclosure will be described.
  • the film according to the present disclosure can be produced through a step of applying the composition according to the present disclosure.
  • the composition is applied on a support.
  • the support include a substrate made of a material such as silicon, non-alkali glass, soda glass, Pyrex (registered trademark) glass, and quartz glass.
  • An organic film, an inorganic film, or the like may be formed on these substrates.
  • the material of the organic film include the above-mentioned resin.
  • a substrate made of the above-mentioned resin can also be used.
  • the support may be formed with a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like.
  • the support may be formed with a black matrix that isolates each pixel.
  • the support may be provided with an undercoat layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the support such as a substrate.
  • an undercoat layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the support such as a substrate.
  • a known method can be used as a method for applying the composition.
  • a dropping method drop casting
  • a slit coating method for example, a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395).
  • Methods described in the publication Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc.
  • Various printing methods; transfer method using a mold or the like; nano-imprint method and the like can be mentioned.
  • the method of application to inkjet is not particularly limited, and is, for example, the method shown in "Expandable and usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). (Page 133), and the methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned.
  • the composition layer formed by applying the composition may be dried (prebaked). Prebaking may not be required if the pattern is formed by a low temperature process.
  • the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower.
  • the lower limit is, for example, preferably 50 ° C. or higher, and more preferably 80 ° C. or higher.
  • the prebaking time is preferably 10 seconds to 3,000 seconds, more preferably 40 seconds to 2,500 seconds, and even more preferably 80 seconds to 220 seconds. Drying can be performed on a hot plate, an oven, or the like.
  • the film manufacturing method according to the present disclosure may further include a step of forming a pattern.
  • the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method.
  • the film according to the present disclosure is used as a flat film, it is not necessary to perform the step of forming the pattern.
  • the process of forming the pattern will be described in detail.
  • the pattern forming method in the photolithography method includes a step of exposing the composition layer formed by applying the composition according to the present disclosure in a pattern (exposure step) and developing and removing the composition layer of the unexposed portion. It is preferable to include a step of forming a pattern (development step). If necessary, a step of baking the developed pattern (post-baking step) may be provided. Hereinafter, each step will be described.
  • the composition layer is exposed in a pattern.
  • the composition layer can be pattern-exposed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure device such as a stepper.
  • the exposed portion can be cured.
  • the radiation (light) that can be used for exposure ultraviolet rays such as g-ray and i-line are preferable, and i-ray is more preferable.
  • Irradiation dose (exposure dose) for example, preferably 0.03J / cm 2 ⁇ 2.5J / cm 2, more preferably 0.05J / cm 2 ⁇ 1.0J / cm 2, 0.08J / cm 2 ⁇ 0.5 J / cm 2 is particularly preferable.
  • the oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere where the oxygen concentration is 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free). ), Or in a high oxygen atmosphere where the oxygen concentration exceeds 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume).
  • the exposure intensity is can be set appropriately, preferably 1,000W / m 2 ⁇ 100,000W / m 2 ( e.g., 5,000W / m 2, 15,000W / m 2, 35,000W / It can be selected from the range of m 2).
  • Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10,000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20,000W / m 2.
  • the composition layer in the unexposed portion of the composition layer after exposure is developed and removed to form a pattern.
  • the development and removal of the composition layer in the unexposed portion can be performed using a developing solution.
  • the composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains on the support.
  • the developing solution an alkaline developing solution that does not damage the underlying solid-state image sensor or circuit is desirable.
  • the temperature of the developing solution is preferably, for example, 20 ° C to 30 ° C.
  • the development time is preferably 20 seconds to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.
  • alkaline agent used in the developing solution examples include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide.
  • Organic alkalinity such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrol, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene.
  • Examples thereof include compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate.
  • an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used.
  • the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 1% by mass.
  • the surfactant include conventionally known surfactants used in developing solutions, and nonionic surfactants are preferable.
  • the developer may be once produced as a concentrated solution and diluted to a concentration required for use from the viewpoint of convenience of transfer and storage.
  • the dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 times to 100 times.
  • a developer composed of such an alkaline aqueous solution it is preferable to wash (rinse) it with pure water after development.
  • post-baking is a post-development heat treatment to complete the curing of the film.
  • the post-baking temperature is preferably, for example, 100 ° C. to 240 ° C. From the viewpoint of film curing, 200 ° C. to 230 ° C. is more preferable.
  • the post-bake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower. Preferably, 100 ° C. or lower is more preferable, and 90 ° C.
  • Post-baking should be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the above conditions are met. Can be done. Further, when the pattern is formed by the low temperature process, post-baking may not be performed, and a step of re-exposure (post-exposure step) may be added.
  • a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the above conditions are met. Can be done. Further, when the pattern is formed by the low temperature process, post-baking may not be performed, and a step of re-exposure (post-exposure step) may be added.
  • the composition layer formed by applying the composition on a support or the like is cured to form a cured product layer, and then a photoresist layer patterned on the cured product layer is formed. Then, using the patterned photoresist layer as a mask, the cured product layer can be dry-etched with an etching gas.
  • the description in paragraphs 0010 to 0067 of JP2013-64993A can be referred to, and this content is incorporated in the present specification.
  • the optical filter according to the present disclosure has a film according to the present disclosure.
  • the optical filter according to the present disclosure can be preferably used as an infrared cut filter or an infrared transmission filter, and can be more preferably used as an infrared cut filter.
  • a preferred embodiment of the optical filter according to the present disclosure is also an embodiment having a film according to the present disclosure and pixels selected from the group consisting of red, green, blue, magenta, yellow, cyan, black and colorless.
  • the infrared cut filter according to the present disclosure has a film according to the present disclosure.
  • the infrared cut filter according to the present disclosure may be a filter that cuts only infrared rays having a wavelength of a part of the infrared region, or a filter that cuts the entire infrared region.
  • Examples of the filter that cuts only infrared rays having a wavelength of a part of the infrared region include a near-infrared ray cut filter.
  • Examples of near-infrared rays include infrared rays having a wavelength of 750 nm to 2,500 nm.
  • the infrared cut filter according to the present disclosure is preferably a filter that cuts infrared rays in the wavelength range of 750 nm to 1,000 nm, and more preferably a filter that cuts infrared rays in the wavelength range of 750 nm to 1,200 nm. It is preferable that the filter cuts infrared rays having a wavelength of 750 nm to 1,500 nm.
  • the infrared cut filter according to the present disclosure may further have a copper-containing layer, a dielectric multilayer film, an ultraviolet absorbing layer, and the like.
  • the infrared cut filter according to the present disclosure further has at least a copper-containing layer or a dielectric multilayer film, it is easy to obtain an infrared cut filter having a wide viewing angle and excellent infrared shielding property. Further, the infrared cut filter according to the present disclosure can be made into an infrared cut filter having excellent ultraviolet shielding property by further having an ultraviolet absorbing layer.
  • the ultraviolet absorbing layer for example, the absorbing layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/09960 can be referred to, and the contents thereof are incorporated in the present specification.
  • the description in paragraphs 0255 to 0259 of JP2014-413118A can be referred to, and the contents thereof are incorporated in the present specification.
  • a glass base material made of copper-containing glass (copper-containing glass base material) or a layer containing a copper complex (copper complex-containing layer) can also be used.
  • the copper-containing glass base material include copper-containing phosphate glass and copper-containing fluoride glass.
  • commercially available copper-containing glass products include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (manufactured by Schott AG), CD5000 (manufactured by HOYA Corporation), and the like.
  • the infrared cut filter according to the present disclosure can be used in various devices such as a solid-state image sensor such as a CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor), an infrared sensor, and an image display device.
  • a solid-state image sensor such as a CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor)
  • CMOS complementary metal oxide semiconductor
  • the infrared cut filter according to the present disclosure is selected from at least a group consisting of film pixels (patterns) obtained by using the composition according to the present disclosure, red, green, blue, magenta, yellow, cyan, black and colorless.
  • a mode having one type of pixel (pattern) is also a preferred mode.
  • the method for producing the optical filter according to the present disclosure is not particularly limited, but a step of applying the composition according to the present disclosure on a support to form a composition layer and exposing the composition layer in a pattern. It is preferable that the method includes a step of forming a pattern by developing and removing an unexposed portion and a step of forming a pattern in this order.
  • a step of applying the composition according to the present disclosure on a support to form a composition layer and curing to form a layer, and a step of forming a layer on the layer, and a photo This method includes a step of forming a resist layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the layer using the resist pattern as an etching mask. It is also preferable.
  • each step in the method for manufacturing an optical filter according to the present disclosure each step in the method for manufacturing a film according to the present disclosure can be referred to.
  • the solid-state image sensor according to the present disclosure has a film according to the present disclosure.
  • the configuration of the solid-state image sensor is not particularly limited as long as it has a film according to the present disclosure and functions as a solid-state image sensor. For example, the following configuration can be mentioned.
  • a transfer electrode made of a plurality of photodiodes and polysilicon or the like constituting the light receiving area of the solid-state image sensor is provided, and light shielding made of tungsten or the like having only the light receiving portion of the photodiode opened on the photodiode and the transfer electrode.
  • a configuration having a film, a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and a photodiode light-receiving portion, and a film according to the present disclosure on the device protective film. Is.
  • a structure having a light collecting means for example, a microlens or the like; the same applies hereinafter
  • the color filter used in the solid-state image sensor may have a structure in which a film forming each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
  • the partition wall preferably has a lower refractive index than each pixel. Examples of the solid-state image sensor having such a structure include the devices described in JP-A-2012-227478 and JP-A-2014-179757.
  • the image display device has a film according to the present disclosure.
  • the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device.
  • organic EL organic electroluminescence
  • the image display device for example, “Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., 1990)", “Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd., 1989)” ) ”And so on.
  • the liquid crystal display device is described in, for example, “Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994)".
  • the liquid crystal display device applicable to the present disclosure is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".
  • the image display device may have a white organic EL element.
  • the white organic EL element preferably has a tandem structure.
  • Japanese Patent Application Laid-Open No. 2003-45676 supervised by Akiyoshi Mikami, "Forefront of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, It is described on pages 326 to 328, 2008 and the like.
  • the spectrum of white light emitted by the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm), and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable.
  • the infrared sensor according to the present disclosure has a film according to the present disclosure.
  • the configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor.
  • an embodiment of the infrared sensor according to the present disclosure will be described with reference to the drawings.
  • reference numeral 110 is a solid-state image sensor.
  • the image pickup region provided on the solid-state image sensor 110 includes an infrared cut filter 111 and an infrared transmission filter 114. Further, a color filter 112 is laminated on the infrared cut filter 111.
  • a microlens 115 is arranged on the incident light h ⁇ side of the color filter 112 and the infrared transmission filter 114.
  • the flattening layer 116 is formed so as to cover the microlens 115.
  • the infrared cut filter 111 can be formed by using the composition according to the present disclosure.
  • the spectral characteristics of the infrared cut filter 111 are selected according to the emission wavelength of the infrared light emitting diode (infrared LED) used.
  • the color filter 112 is a color filter on which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used.
  • a color filter in which red (R), green (G), and blue (B) pixels are formed is used.
  • R red
  • G green
  • B blue
  • the description in paragraphs 0214 to 0263 of JP2014-43556A can be referred to, and this content is incorporated in the present specification.
  • the characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used.
  • the infrared transmittance filter 114 preferably has a maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 nm to 650 nm of 30% or less. It is more preferably% or less, further preferably 10% or less, and particularly preferably 0.1% or less. It is preferable that the transmittance satisfies the above conditions in the entire range of the wavelength range of 400 nm to 650 nm.
  • the infrared transmittance filter 114 preferably has a minimum value of the light transmittance in the film thickness direction in the wavelength range of 800 nm or more (preferably 800 nm to 1,300 nm) of 70% or more, preferably 80% or more. More preferably, it is more preferably 90% or more.
  • the above-mentioned transmittance preferably satisfies the above condition in a part of the wavelength range of 800 nm or more, and more preferably the above-mentioned condition at a wavelength corresponding to the emission wavelength of the infrared LED.
  • the film thickness of the infrared transmission filter 114 is preferably 100 ⁇ m or less, more preferably 15 ⁇ m or less, further preferably 5 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
  • the lower limit is preferably 0.1 ⁇ m.
  • the film thickness is measured by using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC) on the dried substrate having the film.
  • the spectral characteristics of the film are values obtained by measuring the transmittance in the wavelength range of 300 nm to 1,300 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).
  • the infrared transmittance filter 114 has a maximum value of the light transmittance in the film thickness direction in the wavelength range of 450 nm to 650 nm of 20% or less, and the film.
  • the transmittance of light having a wavelength of 835 nm in the thickness direction of the film is 20% or less, and the minimum value of the transmittance of light in the thickness direction of the film in the wavelength range of 1,000 nm to 1,300 nm is 70% or more. Is preferable.
  • an infrared cut filter (another infrared cut filter) different from the infrared cut filter 111 may be further arranged on the flattening layer 116.
  • examples of other infrared cut filters include those having a copper-containing layer or at least a dielectric multilayer film. These details include those mentioned above.
  • a dual bandpass filter may be used as another infrared cut filter.
  • the absorption wavelengths of the infrared transmission filter and the infrared cut filter used in the present disclosure are appropriately combined and used according to the light source used and the like.
  • the camera module according to the present disclosure includes a solid-state image sensor and an optical filter according to the present disclosure. Further, it is preferable that the camera module according to the present disclosure further includes a lens and a circuit for processing an image pickup obtained from the solid-state image sensor.
  • the solid-state image sensor used in the camera module according to the present disclosure may be the solid-state image sensor according to the present disclosure or a known solid-state image sensor.
  • the lens used in the camera module according to the present disclosure and the circuit for processing the image pickup obtained from the solid-state image sensor known ones can be used.
  • the camera modules described in JP-A-2016-6476 or JP-A-2014-197190 can be referred to, and the contents thereof are incorporated in the present specification.
  • the inkjet ink according to the present disclosure includes the curable composition in the present disclosure. Further, the curable composition in the present disclosure can also be used for paints, security inks and the like. Further, the curable composition in the present disclosure can also be used as a heat shield material, a heat storage material, or a photothermal conversion material.
  • % and “parts” mean “mass%” and “parts by mass”, respectively, unless otherwise specified.
  • the molecular weight is the weight average molecular weight (Mw), and the ratio of the constituent units is the molar percentage, except for those specified specifically.
  • the weight average molecular weight (Mw) is a value measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
  • the raw materials used for each curable composition are as follows.
  • Pigments PP1 to PP4 and SQ1 to SQ3 Compounds with the following structures SQ-1, SQ-14, SQ-13, SQ-15, SQ-17, SQ-33, SQ-24, SQ-25, SQ-27, SQ -30, SQ-21, SQ-37, SQ-43, SQ-52, SQ-56, and SQ-60: Compounds listed as specific examples of the above-mentioned squarylium compounds [SQ-1, SQ-14, SQ-13, SQ-15, SQ-17, SQ-33, SQ-24, SQ-25, SQ-27, SQ-30, SQ-21, SQ-37, SQ-43, SQ-52, SQ- 56 and SQ-60]
  • -Pigment derivative- Pigment derivatives 1 to 7 Compounds having the following structures B-1, B-2, B-3, B-6, B-14, and B-17: Compounds listed as specific examples of the pigment derivatives described above [B] -1, B-2, B-3, B-6, B-14, and B-17]
  • -Binder resin- Resins 1 to 6 (specific binder resin): Resins 1 to 6 described in Specific Examples of Specific Binder Resin.
  • Resins 7 to 12 comparative binder resin: Resins having the following structure (numerical values added to each structural unit of the main chain are molar ratios)
  • Photopolymerization Initiator A compound having the following structure (I-1) (IRGACURE OXE-01, manufactured by BASF).
  • Polymerization Initiator 2 A compound having the following structure (I-2)
  • UV1 UV1
  • the curable composition was applied onto a silicon wafer using a spin coater (manufactured by Mikasa Sports Co., Ltd.) so that the film thickness after post-baking was 1.0 ⁇ m to form a coating film. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) , exposure was performed at an exposure amount of 1000 mJ / cm 2 through a mask having a Bayer pattern of 1 ⁇ m square. Then, paddle development was carried out at 23 ° C.
  • TMAH tetramethylammonium hydroxide
  • the average value of the number of residues having a diameter of 5 nm to 200 nm was more than 0 and less than 1 at 10 points in the unexposed portion.
  • 3 At 10 locations in the unexposed portion, the average value of the number of residues having a diameter of 5 nm to 200 nm was more than 1 and 5 or less.
  • 2 The average number of residues having a diameter of 5 nm to 200 nm was more than 5 at 10 unexposed portions.
  • 1 At 10 locations of the unexposed portion, a residue having a diameter of 200 nm or more was present, or the unexposed portion was hardly dissolved.
  • the curable compositions of Examples 1 to 68 which are the compositions according to the present disclosure, are excellent in storage stability as compared with the compositions of Comparative Examples 1 to 6. Furthermore, it can be seen that the development residue is also reduced.
  • the ultraviolet absorber, the surfactant, and the polymerization inhibitor were removed in Example 1, the same result as in Example 1 was obtained. Even if only the monomer 1 was replaced with 6.4 parts of the polymerizable compound in Example 1, the same result as in Example 1 was obtained. Even if the polymerization initiator is replaced with a mixture of the polymerization initiator 1 and the polymerization initiator 2 (0.5 parts each) from the polymerization initiator 1 (1 part) in Example 1, the same result as in Example 1 is obtained. Met.
  • Example 1 When the solvent B was replaced with cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.) from the solvent 1 in Example 1, the same result as in Example 1 was obtained. When the amount of the solvent B was changed to 31.7 parts or 51.7 parts in Example 1, the same result as in Example 1 was obtained.
  • Example 101 to Example 168 Using the compositions of Examples 1 to 68, 2 ⁇ m square patterns (infrared cut filters) were formed by the following methods.
  • Patterns were prepared by the following methods using the curable compositions of Examples 1 to 68.
  • the curable composition was applied onto a silicon wafer by a spin coating method so that the film thickness after film formation was 1.0 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes.
  • an i-line stepper exposure apparatus FPA-3000i5 + manufactured by Canon Inc.
  • exposure was performed at 1,000 mJ / cm 2 through a mask with a 2 ⁇ m square dot pattern.
  • paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and further washed with pure water.
  • a 2 ⁇ m square pattern (infrared cut filter) was formed by heating at 200 ° C. for 5 minutes using a hot plate.
  • the Red composition was applied onto the pattern of the infrared cut filter by a spin coating method so that the film thickness after film formation was 1.0 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at 1,000 mJ / cm 2 through a mask with a 2 ⁇ m square dot pattern. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and further washed with pure water.
  • TMAH tetramethylammonium hydroxide
  • the Red composition was then patterned on the pattern of the infrared cut filter by heating at 200 ° C. for 5 minutes using a hot plate.
  • the Green composition and the Blue composition were sequentially patterned to form red, green, and blue coloring patterns (Bayer patterns).
  • the Bayer pattern is one red element, two green elements, and one blue element, as disclosed in US Pat. No. 3,971,065. ) This is a pattern in which a 2 ⁇ 2 array of color filter elements having elements is repeated. In this embodiment, one red element, one green element, and one blue element are used.
  • a Bayer pattern was formed by repeating a 2 ⁇ 2 array of an element and a filter element having one infrared transmissive filter element.
  • composition for forming an infrared transmission filter (the following composition 100 or composition 101) was applied onto the patterned film by a spin coating method so that the film thickness after film formation was 2.0 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at 1,000 mJ / cm 2 through a 2 ⁇ m square Bayer pattern mask. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH).
  • TMAH tetramethylammonium hydroxide
  • the infrared transmission filter was patterned in the missing portion of the Bayer pattern of the infrared cut filter in which the coloring pattern was not formed.
  • the obtained solid-state image sensor was irradiated with infrared rays by an infrared light emitting diode (infrared LED) in a low illuminance environment (0.001 lux), and an image was captured to evaluate the image performance.
  • infrared LED infrared light emitting diode
  • the Red composition, Green composition, Blue composition, and composition for forming an infrared transmission filter used for the above patterning are as follows.
  • Red pigment dispersion 51.7 parts by mass Resin 4 (40% by mass PGMEA solution): 0.6 parts by mass Polymerizable compound 12: 0.6 parts by mass Photopolymerization initiator 1: 0.3 parts by mass Surfactant 2 : 4.2 parts by mass PGMEA: 42.6 parts by mass
  • Green pigment dispersion 73.7 parts by mass Resin 4 (40% by mass PGMEA solution): 0.3 parts by mass Polymerizable compound 11: 1.2 parts by mass Photopolymerization initiator 1: 0.6 parts by mass Surface active agent 2 : 4.2 parts by mass UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.): 0.5 parts by mass PGMEA: 19.5 parts by mass
  • Blue pigment dispersion 44.9 parts by mass Resin 4 (40% by mass PGMEA solution): 2.1 parts by mass Polymerizable compound 11: 1.5 parts by mass Polymerizable compound 12: 0.7 parts by mass Photoinitiator 1 : 0.8 parts by mass Surfactant 2: 4.2 parts by mass PGMEA: 45.8 parts by mass
  • composition for forming an infrared transmission filter The components having the following composition were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare a composition for forming an infrared transmission filter.
  • Pigment dispersion 21 1,000 parts by mass Polymerizable compound (dipentaerythritol hexaacrylate): 50 parts by mass Resin 4:17 parts by mass Photopolymerization initiator (1- [4- (phenylthio) phenyl] -1, 2-Octandion-2- (O-benzoyloxime)): 10 parts by mass PGMEA: 179 parts by mass Alkali-soluble polymer F-1: 17 parts by mass (solid content concentration 35 parts by mass)
  • This polymer had a polystyrene-equivalent weight average molecular weight of 9,700, a number average molecular weight of 5,700, and a Mw / Mn of 1.70.
  • the raw materials used for the Red composition, the Green composition, the Blue composition, and the composition for forming an infrared transmission filter are as follows.
  • a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform dispersion treatment at a flow rate of 500 g / min under a pressure of 2,000 kg / cm 3. This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion.
  • -Green pigment dispersion C. I. Pigment Green 36 at 6.4 parts by mass
  • C.I. I. A mixed solution consisting of 5.3 parts by mass of Pigment Yellow 150, 5.2 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA is used in a bead mill (zirconia beads 0.3 mm diameter). To prepare a pigment dispersion liquid by mixing and dispersing for 3 hours.
  • a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform dispersion treatment at a flow rate of 500 g / min under a pressure of 2,000 kg / cm 3. This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion.
  • Pigment dispersion 1-1 The mixed solution having the following composition is mixed and dispersed in a bead mill (high pressure disperser with decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.)) for 3 hours using zirconia beads having a diameter of 0.3 mm.
  • a pigment dispersion liquid 1-1 To prepare a pigment dispersion liquid 1-1.
  • Pigment dispersion 1-2 The mixed solution having the following composition is mixed and dispersed in a bead mill (high pressure disperser with decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.)) for 3 hours using zirconia beads having a diameter of 0.3 mm.
  • the pigment dispersion liquid 1-2 was prepared.
  • Polymerizable compound 11 KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
  • Polymerizable compound 12 The following structure
  • Polymerizable compound 13 The following structure (a mixture of the left compound and the right compound having a molar ratio of 7: 3)
  • Photopolymerization initiator 1 IRGACURE OXE01 (1- [4- (phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime), manufactured by BASF) -Photopolymerization initiator 2: A compound having the following structure
  • -Surfactant 2 The same as the above-mentioned surfactant 1.
  • -Silane coupling agent A compound having the following structure.
  • Et represents an ethyl group.
  • Examples 201 to 268 The following compositions were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare the pattern-forming composition of Example 201.
  • Curable composition of Example 1 22.67 parts by mass Pigment dispersion 2-1: 51.23 parts by mass Evaluation of development residue using the pattern-forming composition of Example 201 in the same manner as in Example 1. The same effect as in Example 1 was obtained. Further, the cured film obtained by using the pattern-forming composition of Example 201 blocks light having a wavelength in the visible region and transmits at least a part of light having a wavelength in the near infrared region (near infrared ray).
  • Example 201 The pattern-forming compositions of Examples 202 to 268 using the curable compositions of Examples 2 to 68 instead of the curable composition of Example 1 were evaluated in the same manner as in Example 201. , The same effect as that of Example 201 was obtained.
  • Example 301 to 368 The following compositions were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare the pattern-forming composition of Example 301.
  • Curable composition of Example 1 36.99 parts by mass Pigment dispersion 1-1: 46.5 parts by mass Pigment dispersion 1-2: 37.1 parts by mass Using the pattern-forming composition of Example 301 When the development residue was evaluated in the same manner as in Example 1, the same effect as in Example 1 was obtained.
  • the cured film obtained by using the pattern-forming composition of Example 301 blocks light having a wavelength in the visible region and transmits at least a part of light having a wavelength in the near infrared region (near infrared ray). I was able to.
  • the pattern-forming compositions of Examples 302 to 368 using the curable compositions of Examples 2 to 68 instead of the curable composition of Example 1 were evaluated in the same manner as in Example 301. , The same effect as that of Example 301 was obtained.
  • Example 400 In the above Examples 1 to 68, Examples 101 to 168, Examples 201 to 268, and Examples 301 to 368, when the silicon wafer is changed to a glass substrate and evaluated in the same manner, the same as in the above example. The effect was obtained.
  • 110 Solid-state image sensor
  • 111 Infrared cut filter
  • 112 Color filter
  • 114 Infrared transmission filter
  • 115 Microlens
  • 116 Flattening layer

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Abstract

Provided are: a near-infrared absorption composition having excellent storage stability; a film using the near-infrared absorption composition; and an application thereof. The near-infrared absorption composition includes: a near-infrared absorption pigment; a basic group-containing resin; and a binder resin which has an SP value of 19.7 MPa1/2 to 21.2 MPa1/2 and an acid value of 70 mgKOH/g to 105 mgKOH/g, and which is a resin other than the basic group-containing resin.

Description

近赤外吸収組成物、膜、光学フィルタ及びその製造方法、固体撮像素子、赤外線センサ、カメラモジュール、並びに、インクジェットインクNear-infrared absorption composition, film, optical filter and its manufacturing method, solid-state image sensor, infrared sensor, camera module, and inkjet ink
　本開示は、近赤外吸収組成物、膜、光学フィルタ及びその製造方法、固体撮像素子、赤外線センサ、カメラモジュール、並びに、インクジェットインクに関する。 The present disclosure relates to a near-infrared absorbing composition, a film, an optical filter and a method for manufacturing the same, a solid-state image sensor, an infrared sensor, a camera module, and an inkjet ink.
　光学フィルタの一例として、近赤外線吸収顔料を含む、赤外線カットフィルタ、赤外線透過フィルタ等が知られている。
　上記のような光学フィルタを得るための硬化性組成物としては、例えば、特許文献１にて、近赤外線吸収色素と、不飽和二重結合を有する基を有する重合性モノマーとを含む硬化性組成物であって、上記近赤外線吸収色素は、単環又は縮合環の芳香族環を含むπ共役平面を有する化合物であり、上記硬化性組成物の全固形分中における上記近赤外線吸収色素の含有量が１０質量％以上であり、上記重合性モノマーの全質量中における、酸基及び水酸基から選ばれる少なくとも一種の基と不飽和二重結合を有する基とを有する重合性モノマーの含有量が５０質量％以下である、硬化性組成物が開示されている。 As an example of the optical filter, an infrared cut filter, an infrared transmission filter and the like containing a near-infrared absorbing pigment are known.
As a curable composition for obtaining an optical filter as described above, for example, in Patent Document 1, a curable composition containing a near-infrared absorbing dye and a polymerizable monomer having a group having an unsaturated double bond. The near-infrared absorbing dye is a compound having a π-conjugated plane containing an aromatic ring of a monocycle or a condensed ring, and contains the near-infrared absorbing dye in the total solid content of the curable composition. The content of the polymerizable monomer having an amount of 10% by mass or more and having at least one group selected from an acid group and a hydroxyl group and a group having an unsaturated double bond in the total mass of the above-mentioned polymerizable monomer is 50. Curable compositions that are no more than% by weight are disclosed.
国際公開第２０１８／１４２７９９号International Publication No. 2018/142799
　本開示の一実施形態が解決しようとする課題は、保存安定性に優れる近赤外吸収組成物を提供することである。
　また、本開示の別の一実施形態が解決しようとする課題は、上記近赤外吸収組成物を用いた膜、光学フィルタ及びその製造方法、固体撮像素子、赤外線センサ、カメラモジュール、並びにインクジェットインクを提供することである。 An object to be solved by one embodiment of the present disclosure is to provide a near-infrared absorption composition having excellent storage stability.
Further, the problem to be solved by another embodiment of the present disclosure is a film using the near infrared absorption composition, an optical filter and a method for manufacturing the same, a solid-state image sensor, an infrared sensor, a camera module, and an inkjet ink. Is to provide.
　上記課題を解決するための手段には、以下の態様が含まれる。 The means for solving the above problems include the following aspects.
＜１＞　近赤外線吸収顔料と、
　塩基性基を有する樹脂と、
　上記塩基性基を有する樹脂以外の、ＳＰ値が１９．７ＭＰａ１／２～２１．２ＭＰａ１／２で且つ酸価が７０ｍｇＫＯＨ／ｇ～１０５ｍｇＫＯＨ／ｇであるバインダー樹脂と、
　を含む近赤外吸収組成物。 <1> Near-infrared absorbing pigment and
Resins with basic groups and
Binder resins having an SP value of 19.7 MPa 1/2 to 21.2 MPa 1/2 and an acid value of 70 mgKOH / g to 105 mgKOH / g, other than the resin having a basic group,
Near-infrared absorption composition containing.
＜２＞　上記バインダー樹脂が、芳香族環及び脂肪族環よりなる群から選択される少なくとも１種の環構造を有する構成単位を、上記バインダー樹脂の全構成単位に対して５０モル％～９０モル％で含む樹脂である、＜１＞に記載の近赤外吸収組成物。
＜３＞　上記脂肪族環がビシクロ環又はトリシクロ環である、＜２＞に記載の近赤外吸収組成物。
＜４＞　上記芳香族環がベンゼン環、ナフタレン環、又は含窒素複素芳香環である、＜２＞又は＜３＞に記載の近赤外吸収組成物。 <2> The binder resin contains at least one structural unit having a ring structure selected from the group consisting of an aromatic ring and an aliphatic ring, in an amount of 50 mol% to 90 mol with respect to all the structural units of the binder resin. The near-infrared absorption composition according to <1>, which is a resin contained in%.
<3> The near-infrared absorption composition according to <2>, wherein the aliphatic ring is a bicyclo ring or a tricyclo ring.
<4> The near-infrared absorption composition according to <2> or <3>, wherein the aromatic ring is a benzene ring, a naphthalene ring, or a nitrogen-containing heteroaromatic ring.
＜５＞　上記バインダー樹脂が、酸基を有する構成単位を、上記バインダー樹脂の全構成単位に対して１０モル％～４０モル％で含む樹脂である、＜１＞～＜４＞のいずれか１つに記載の近赤外吸収組成物。
＜６＞　上記バインダー樹脂の重量平均分子量が２０，０００以下である、＜１＞～＜５＞のいずれか１つに記載の近赤外吸収組成物。 <5> Any one of <1> to <4>, wherein the binder resin contains a structural unit having an acid group in an amount of 10 mol% to 40 mol% with respect to all the structural units of the binder resin. The near-infrared absorption composition according to 1.
<6> The near-infrared absorption composition according to any one of <1> to <5>, wherein the binder resin has a weight average molecular weight of 20,000 or less.
＜７＞　上記塩基性基を有する樹脂が、第３級アミノ基を側鎖に有する樹脂、及び、主鎖に窒素原子を含む樹脂よりなる群から選択される少なくとも１種である、＜１＞～＜６＞のいずれか１つに記載の近赤外吸収組成物。
＜８＞　上記第３級アミノ基を側鎖に有する樹脂が、更に第４級アンモニウム塩基を側鎖に有する樹脂である、＜７＞に記載の近赤外吸収組成物。 <7> The resin having the basic group is at least one selected from the group consisting of a resin having a tertiary amino group in the side chain and a resin having a nitrogen atom in the main chain. <1> The near-infrared absorption composition according to any one of <6>.
<8> The near-infrared absorption composition according to <7>, wherein the resin having a tertiary amino group in the side chain is a resin having a quaternary ammonium base in the side chain.
＜９＞　上記近赤外線吸収顔料が、ピロロピロール化合物又はスクアリリウム化合物である、＜１＞～＜８＞のいずれか１つに記載の近赤外吸収組成物。
＜１０＞　スズの含有量が、近赤外吸収組成物の全固形分に対して、１ｐｐｍ～１５ｐｐｍである、＜１＞～＜９＞のいずれか１つに記載の近赤外吸収組成物。 <9> The near-infrared absorbing composition according to any one of <1> to <8>, wherein the near-infrared absorbing pigment is a pyrrolopyrrole compound or a squarylium compound.
<10> The near-infrared absorption composition according to any one of <1> to <9>, wherein the tin content is 1 ppm to 15 ppm with respect to the total solid content of the near-infrared absorption composition. ..
＜１１＞　更に、重合性化合物及び重合開始剤を含む、＜１＞～＜１０＞のいずれか１つに記載の近赤外吸収組成物。
＜１２＞　＜１＞～＜１１＞のいずれか１つに記載の近赤外吸収組成物からなる又は上記近赤外吸収組成物を硬化してなる膜。
＜１３＞　＜１２＞に記載の膜を有する光学フィルタ。
＜１４＞　赤外線カットフィルタ又は赤外線透過フィルタである、＜１３＞に記載の光学フィルタ。
＜１５＞　＜１２＞に記載の膜を有する固体撮像素子。
＜１６＞　＜１２＞に記載の膜を有する赤外線センサ。
＜１７＞　＜１１＞に記載の近赤外吸収組成物を支持体上に適用して組成物層を形成する工程と、
　上記組成物層をパターン状に露光する工程と、
　未露光部を現像除去してパターンを形成する工程と、を含む
　光学フィルタの製造方法。
＜１８＞　＜１１＞に記載の近赤外吸収組成物を支持体上に適用して組成物層を形成し、硬化して層を形成する工程と、
　上記層上にフォトレジスト層を形成する工程と、
　露光及び現像することにより上記フォトレジスト層をパターニングしてレジストパターンを得る工程と、
　上記レジストパターンをエッチングマスクとして上記層をドライエッチングする工程と、を含む
　光学フィルタの製造方法。
＜１９＞　固体撮像素子と、＜１３＞又は＜１４＞に記載の光学フィルタとを有するカメラモジュール。
＜２０＞　＜１１＞に記載の近赤外吸収組成物を含むインクジェットインク。 <11> The near-infrared absorption composition according to any one of <1> to <10>, further comprising a polymerizable compound and a polymerization initiator.
<12> A film comprising the near-infrared absorption composition according to any one of <1> to <11> or obtained by curing the near-infrared absorption composition.
<13> An optical filter having the film according to <12>.
<14> The optical filter according to <13>, which is an infrared cut filter or an infrared transmission filter.
<15> A solid-state image sensor having the film according to <12>.
<16> An infrared sensor having the film according to <12>.
<17> A step of applying the near-infrared absorption composition according to <11> onto a support to form a composition layer, and
The step of exposing the composition layer in a pattern and
A method for manufacturing an optical filter, which includes a step of developing and removing an unexposed portion to form a pattern.
<18> A step of applying the near-infrared absorption composition according to <11> onto a support to form a composition layer, and then curing to form a layer.
The step of forming a photoresist layer on the above layer and
A step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and
A method for manufacturing an optical filter, which comprises a step of dry etching the layer using the resist pattern as an etching mask.
<19> A camera module having a solid-state image sensor and the optical filter according to <13> or <14>.
<20> An inkjet ink containing the near-infrared absorbing composition according to <11>.
　本開示の一実施形態によれば、保存安定性に優れる近赤外吸収組成物が提供される。
　更に、本開示の別の一実施形態によれば、上記近赤外吸収組成物を用いた膜、光学フィルタ及びその製造方法、固体撮像素子、赤外線センサ、カメラモジュール、並びにインクジェットインクが提供される。 According to one embodiment of the present disclosure, a near-infrared absorption composition having excellent storage stability is provided.
Further, according to another embodiment of the present disclosure, a film using the near infrared absorption composition, an optical filter and a method for manufacturing the same, a solid-state image sensor, an infrared sensor, a camera module, and an inkjet ink are provided. ..
本開示に係る赤外線センサの一実施形態を示す概略図である。It is the schematic which shows one Embodiment of the infrared sensor which concerns on this disclosure.
　以下において、本開示の内容について詳細に説明する。
　本明細書において「全固形分」とは、組成物の全組成から溶剤を除いた成分の総質量をいう。また、「固形分」とは、上述のように、溶剤を除いた成分であり、例えば、２５℃において固体であっても、液体であってもよい。
　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、置換基を有さないものと共に置換基を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、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も含む。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線又は放射線が挙げられる。
　本明細書において、「（メタ）アクリレート」は、アクリレート及びメタクリレートの双方、又は、いずれかを表し、「（メタ）アクリル」は、アクリル及びメタクリルの双方、又は、いずれかを表し、「（メタ）アクリロイル」は、アクリロイル及びメタクリロイルの双方、又は、いずれかを表す。
　本明細書において、化学式中のＭｅはメチル基を、Ｅｔはエチル基を、Ｐｒはプロピル基を、Ｂｕはブチル基を、Ａｃはアセチル基を、Ｂｎはベンジル基を、Ｐｈはフェニル基をそれぞれ示す。
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
　また、本開示において、「質量％」と「重量％」とは同義であり、「質量部」と「重量部」とは同義である。
　更に、本開示において、２以上の好ましい態様の組み合わせは、より好ましい態様である。
　また、本開示における透過率は、特に断りのない限り、２５℃における透過率である。 The contents of the present disclosure will be described in detail below.
As used herein, the term "total solid content" refers to the total mass of the components excluding the solvent from the total composition of the composition. Further, the "solid content" is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.
In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam. Further, as the light used for exposure, generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation can be mentioned.
In the present specification, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either, and "(meth) acrylate". ) Acryloyl "represents both acryloyl and / or methacryloyl.
In the present specification, Me in the chemical formula is a methyl group, Et is an ethyl group, Pr is a propyl group, Bu is a butyl group, Ac is an acetyl group, Bn is a benzyl group, and Ph is a phenyl group. Shown.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
Further, in the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
Further, the transmittance in the present disclosure is the transmittance at 25 ° C. unless otherwise specified.
　本明細書において、樹脂の重量平均分子量及び数平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定したポリスチレン換算値として定義される。
　本開示において、樹脂における「構成単位」の含有量をモル比で規定する場合、「構成単位」は「モノマー単位」と同義であるものとする。但し、本開示における「モノマー単位」は、高分子反応等により重合後に修飾されていてもよい。 In the present specification, the weight average molecular weight and the number average molecular weight of the resin are defined as polystyrene-equivalent values measured by gel permeation chromatography (GPC).
In the present disclosure, when the content of the "constituent unit" in the resin is defined by the molar ratio, the "constituent unit" is synonymous with the "monomer unit". However, the "monomer unit" in the present disclosure may be modified after polymerization by a polymer reaction or the like.
＜近赤外吸収組成物＞
　本開示に係る近赤外吸収組成物（以下、単に「組成物」ともいう）は、近赤外線吸収顔料と、塩基性基を有する樹脂と、上記塩基性基を有する樹脂以外の、ＳＰ値が１９．７ＭＰａ１／２～２１．２ＭＰａ１／２で且つ酸価が７０ｍｇＫＯＨ／ｇ～１０５ｍｇＫＯＨ／ｇであるバインダー樹脂（以下、「特定バインダー樹脂」ともいう）と、を含む。 <Near infrared absorption composition>
The near-infrared absorbing composition according to the present disclosure (hereinafter, also simply referred to as “composition”) has an SP value other than the near-infrared absorbing pigment, the resin having a basic group, and the resin having the basic group. 19.7 MPa 1/2 to 21.2 MPa 1/2 and a binder resin having an acid value of 70 mgKOH / g to 105 mgKOH / g (hereinafter, also referred to as “specific binder resin”).
　近赤外線吸収顔料、塩基性基を有する樹脂である分散剤、及びバインダー樹脂を含む近赤外吸収組成物、具体的には、例えば、特許文献１に記載の硬化性組成物においては、経時での粘度上昇が見られ、保存安定性が低下する場合がある。
　この理由は以下のように推測される。
　分散剤が有する塩基性基は、近赤外線吸収顔料に対する吸着性能を有しており、近赤外線吸収顔料の分散性を高めている。しかしながら、組成物中に併存するバインダー樹脂によっては、分散剤の塩基性基に吸着し、分散剤を近赤外線吸収顔料から引き剥がしてしまう。その結果、塩基性基を有する樹脂による近赤外線吸収顔料の分散性能が発現し難くなり、経時にて近赤外線吸収顔料が凝集することで、保存安定性を低下させていたと考えられる。
　そこで、保存安定性を高める課題について検討を行ったところ、特定のＳＰ値と特定の酸価とを有するバインダー樹脂を用いることで、上記課題を解決しうることを見出した。 In a near-infrared absorbing composition containing a near-infrared absorbing pigment, a dispersant which is a resin having a basic group, and a binder resin, specifically, for example, the curable composition described in Patent Document 1, over time. The viscosity of the product may increase and the storage stability may decrease.
The reason for this is presumed as follows.
The basic group of the dispersant has an adsorption performance for the near-infrared absorbing pigment and enhances the dispersibility of the near-infrared absorbing pigment. However, depending on the binder resin coexisting in the composition, the dispersant may be adsorbed on the basic group of the dispersant and the dispersant may be peeled off from the near-infrared absorbing pigment. As a result, it is considered that the dispersion performance of the near-infrared absorbing pigment by the resin having a basic group becomes difficult to be exhibited, and the near-infrared absorbing pigment aggregates with time, thereby lowering the storage stability.
Therefore, as a result of examining the problem of enhancing storage stability, it was found that the above problem can be solved by using a binder resin having a specific SP value and a specific acid value.
　即ち、本開示に係る近赤外吸収組成物は、近赤外線吸収顔料及び塩基性基を有する樹脂を含む組成物に、ＳＰ値が１９．７ＭＰａ１／２～２１．２ＭＰａ１／２で且つ酸価が７０ｍｇＫＯＨ／ｇ～１０５ｍｇＫＯＨ／ｇである特定バインダー樹脂を適用する。
　このような組成とすることで、塩基性基を有する樹脂による近赤外線吸収顔料の分散性能が阻害されず、近赤外線吸収顔料の分散が保たれ、その結果、保存安定性に優れる近赤外吸収組成物が得られると推測される。
　また、本開示に係る近赤外吸収組成物により膜が形成された場合、膜中においても、近赤外線吸収顔料の分散が高い状態を保つことができる。その結果、形成された膜の一部を現像等により除去する際には、近赤外線吸収顔料の凝集に由来する残渣の発生が低減すると推測される。 That is, the near-infrared absorbing composition according to the present disclosure is a composition containing a near-infrared absorbing pigment and a resin having a basic group, and has an SP value of 19.7 MPa 1/2 to 21.2 MPa 1/2 and an acid. A specific binder resin having a value of 70 mgKOH / g to 105 mgKOH / g is applied.
With such a composition, the dispersion performance of the near-infrared absorbing pigment by the resin having a basic group is not impaired, the dispersion of the near-infrared absorbing pigment is maintained, and as a result, the near-infrared absorption excellent in storage stability is maintained. It is presumed that the composition will be obtained.
Further, when the film is formed by the near-infrared absorbing composition according to the present disclosure, it is possible to maintain a high dispersion of the near-infrared absorbing pigment even in the film. As a result, when a part of the formed film is removed by development or the like, it is presumed that the generation of residue due to the aggregation of the near-infrared absorbing pigment is reduced.
　以下、本開示に係る組成物に含まれる各成分の詳細を説明する。 Hereinafter, details of each component contained in the composition according to the present disclosure will be described.
＜特定バインダー樹脂＞
　本開示に係る組成物は、後述する塩基性基を有する樹脂以外の、ＳＰ値が１９．７ＭＰａ１／２～２１．２ＭＰａ１／２で且つ酸価が７０ｍｇＫＯＨ／ｇ～１０５ｍｇＫＯＨ／ｇであるバインダー樹脂を含む。
　即ち、本開示における特定バインダー樹脂は、分子内に塩基性基を有さず、「塩基性基を有する樹脂」には該当しない樹脂である。
　特定バインダー樹脂は、膜形成性に寄与する成分であり、特定バインダー樹脂を含むことで、本開示に係る組成物により膜が形成される。 <Specific binder resin>
The composition according to the present disclosure is a binder having an SP value of 19.7 MPa 1/2 to 21.2 MPa 1/2 and an acid value of 70 mgKOH / g to 105 mgKOH / g, other than the resin having a basic group described later. Contains resin.
That is, the specific binder resin in the present disclosure is a resin that does not have a basic group in the molecule and does not fall under the category of "resin having a basic group".
The specific binder resin is a component that contributes to film-forming property, and by containing the specific binder resin, a film is formed by the composition according to the present disclosure.
　ここで、本開示における特定バインダー樹脂のＳＰ値（単位：ＭＰａ１／２）は、沖津法によって求められる溶解度パラメータである。沖津法は、従来周知のＳＰ値の算出方法の一つであり、例えば、日本接着学会誌Ｖｏｌ．２９、Ｎｏ．６（１９９３年）２４９～２５９頁に詳述されている方法であって、本開示における特定バインダー樹脂のＳＰ値もこの方法により算出される。 Here, the SP value (unit: MPa 1/2 ) of the specific binder resin in the present disclosure is a solubility parameter obtained by the Okitsu method. The Okitsu method is one of the well-known methods for calculating the SP value. For example, Vol. 29, No. 6 (1993) The method described in detail on pages 249 to 259, and the SP value of the specific binder resin in the present disclosure is also calculated by this method.
　また、本開示における特定バインダー樹脂の酸価は、特定バインダー樹脂１ｇあたりの酸基を中和するのに要する水酸化カリウムの質量を表したものである。特定バインダー樹脂の酸価は次のようにして測定する。
　すなわち、測定サンプルを、テトラヒドロフラン／水＝９／１（質量比）混合溶媒に溶解し、電位差滴定装置（商品名：ＡＴ－５１０、京都電子工業（株）製）を用いて、得られた溶液を、２５℃にて、０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液で中和滴定する。
　滴定ｐＨ曲線の変曲点を滴定終点として、式（Ｉ）により酸価を算出する。
　式（Ｉ）　：　Ａ：酸価（ｍｇＫＯＨ／ｇ）＝５６．１１×Ｖｓ×０．５×ｆ／ｗ
　式（Ｉ）中、Ａは酸価（ｍｇＫＯＨ／ｇ）を表し、Ｖｓは滴定に要した０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液の使用量（ｍＬ）を表し、ｆは０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液の力価を表し、ｗは測定サンプル質量（ｇ）（固形分換算）を表す。 The acid value of the specific binder resin in the present disclosure represents the mass of potassium hydroxide required to neutralize the acid group per 1 g of the specific binder resin. The acid value of the specific binder resin is measured as follows.
That is, the solution obtained by dissolving the measurement sample in a mixed solvent of tetrahydrofuran / water = 9/1 (mass ratio) and using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Denshi Kogyo Co., Ltd.). Is neutralized and titrated with a 0.1 mol / L aqueous sodium hydroxide solution at 25 ° C.
The acid value is calculated by the formula (I) with the inflection point of the titration pH curve as the titration end point.
Formula (I): A: Acid value (mgKOH / g) = 56.11 × Vs × 0.5 × f / w
In formula (I), A represents the acid value (mgKOH / g), Vs represents the amount (mL) of the 0.1 mol / L sodium hydroxide aqueous solution required for titration, and f is 0.1 mol / L water. It represents the titer of the aqueous sodium oxide solution, and w represents the measurement sample mass (g) (in terms of solid content).
　特定バインダー樹脂におけるＳＰ値としては、保存安定性を高める観点から、２０．０ＭＰａ１／２～２１．０ＭＰａ１／２が好ましい。
　特定バインダー樹脂における酸価としては、保存安定性を高める観点から、７２ｍｇＫＯＨ／ｇ～１０２ｍｇＫＯＨが好ましく、９０ｍｇＫＯＨ／ｇ～１００ｍｇＫＯＨがより好ましい。 The SP value in the specific binder resin, from the viewpoint of enhancing the storage stability, 20.0MPa 1/2 ~ 21.0MPa 1/2 is preferred.
The acid value of the specific binder resin is preferably 72 mgKOH / g to 102 mgKOH, more preferably 90 mgKOH / g to 100 mgKOH, from the viewpoint of enhancing storage stability.
　特定バインダー樹脂は、上記のＳＰ値及び酸価を満たしていれば、構造については特に制限はない。
　特定バインダー樹脂は、アクリル樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂、シロキサン樹脂、ウレタン樹脂等が挙げられる。
　中でも、ＳＰ値及び酸価を制御し易い観点、及び、形成される膜のアルカリ現像性が良好となる観点から、アクリル樹脂が好ましい。 The structure of the specific binder resin is not particularly limited as long as it satisfies the above SP value and acid value.
Specific binder resins include acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, and polyolefin. Examples thereof include resins, cyclic olefin resins, polyester resins, styrene resins, siloxane resins, and urethane resins.
Of these, an acrylic resin is preferable from the viewpoint of easily controlling the SP value and acid value and from the viewpoint of improving the alkali developability of the formed film.
　特定バインダー樹脂は、ＳＰ値及び酸価（特にＳＰ値）を上記の範囲に制御する観点から、芳香族環及び脂肪族環よりなる群から選択される少なくとも１種の環構造を有する構成単位を、特定バインダー樹脂の全構成単位に対して５０モル％～９０モル％で含む樹脂であることが好ましい。
　芳香族環及び脂肪族環よりなる群から選択される少なくとも１種の環構造を有する構成単位の含有量は、特定バインダー樹脂の全構成単位に対して、５５モル％～９０モル％であることが好ましく、６０モル％～８８モル％であることがより好ましい。 The specific binder resin has a structural unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring from the viewpoint of controlling the SP value and the acid value (particularly the SP value) within the above ranges. , It is preferable that the resin is contained in an amount of 50 mol% to 90 mol% with respect to all the constituent units of the specific binder resin.
The content of the structural unit having at least one ring structure selected from the group consisting of the aromatic ring and the aliphatic ring shall be 55 mol% to 90 mol% with respect to all the structural units of the specific binder resin. Is preferable, and 60 mol% to 88 mol% is more preferable.
　特定バインダー樹脂が、芳香族環及び脂肪族環よりなる群から選択される少なくとも１種の環構造を有する構成単位を含む場合、脂肪族環がビシクロ環又はトリシクロ環であることが好ましく、芳香族環がベンゼン環、ナフタレン環、又は含窒素複素芳香環であることが好ましい。 When the specific binder resin contains a structural unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring, the aliphatic ring is preferably a bicyclo ring or a tricyclo ring, and is aromatic. The ring is preferably a benzene ring, a naphthalene ring, or a nitrogen-containing heteroaromatic ring.
　上記ビシクロ環としては、例えば、ビシクロ〔２，２，１〕ヘプタン、及びこれにアルキル基等の置換基が導入された環（例えば、イソボルニル環等）等が挙げられる。
　上記トリシクロ環としては、アダマンタン（トリシクロ［３．３．１．１３，７］デカンともいう）、及びこれにアルキル基等の置換基が導入された環等が挙げられる。 Examples of the bicyclo ring include bicyclo [2,2,1] heptane, and a ring into which a substituent such as an alkyl group is introduced (for example, an isobornyl ring).
Examples of the tricyclo ring include adamantane ( also referred to as tricyclo [3.3.1.1 3,7 ] decane) and a ring into which a substituent such as an alkyl group is introduced.
　上記含窒素複素芳香環としては、カルバゾール環、これにアルキル基等の置換基が導入された環等が挙げられる。
　また、ベンゼン環及びナフタレン環はアルキル基等の置換基が導入されていてもよい。 Examples of the nitrogen-containing heteroaromatic ring include a carbazole ring and a ring into which a substituent such as an alkyl group is introduced.
Further, a substituent such as an alkyl group may be introduced into the benzene ring and the naphthalene ring.
　芳香族環及び脂肪族環よりなる群から選択される少なくとも１種の環構造を有する構成単位は、下記式（ａ）で表される構成単位であることが好ましい。 The structural unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring is preferably a structural unit represented by the following formula (a).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（ａ）中、Ｒ１は水素原子又はメチル基を表し、Ｌ１は単結合又は－Ｃ（＝Ｏ）Ｏ－を表し、Ｘ１は芳香族環及び脂肪族環よりなる群から選択される少なくとも１種の環構造を含む基を表す。 In formula (a), R 1 represents a hydrogen atom or a methyl group, L 1 represents a single bond or -C (= O) O-, and X 1 is selected from the group consisting of an aromatic ring and an aliphatic ring. Represents a group containing at least one ring structure.
　式（ａ）中、Ｘ１は、イソボルニル基、アダマンタン基、ベンジル基、ナフチル基、又はカルバゾール基が好ましい。 Wherein (a), X 1 represents a isobornyl group, adamantane group, a benzyl group, a naphthyl group, or a carbazole group.
　特定バインダー樹脂は、芳香族環及び脂肪族環よりなる群から選択される少なくとも１種の環構造を有する構成単位（好ましくは、式（ａ）で表される構成単位）を１種単独で含んでいてもよいし、２種以上を含んでいてもよい。 The specific binder resin contains only one structural unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring (preferably, a structural unit represented by the formula (a)). It may be used, or it may contain two or more kinds.
　特定バインダー樹脂は、ＳＰ値及び酸価（特に酸価）を上記の範囲に制御する観点から、酸基を有する構成単位を、特定バインダー樹脂の全構成単位に対して１０モル％～４０モル％で含む樹脂であることが好ましい。
　酸基を有する構成単位の含有量は、特定バインダー樹脂の全構成単位に対して、１０モル％～３８モル％であることが好ましく、１２モル％～３８モル％であることがより好ましい。 From the viewpoint of controlling the SP value and the acid value (particularly the acid value) in the above range, the specific binder resin contains 10 mol% to 40 mol% of the structural units having an acid group with respect to all the structural units of the specific binder resin. It is preferable that the resin is contained in.
The content of the structural unit having an acid group is preferably 10 mol% to 38 mol%, more preferably 12 mol% to 38 mol%, based on all the structural units of the specific binder resin.
　上記酸基としては、カルボキシ基、スルホン酸基、リン酸基が挙げられるが、中でも、本開示に係る組成物の経時安定性と形成される膜のアルカリ現像性との両立の観点から、カルボキシ基が好ましい。 Examples of the acid group include a carboxy group, a sulfonic acid group, and a phosphoric acid group. Among them, carboxy is used from the viewpoint of achieving both the stability of the composition according to the present disclosure with time and the alkali developability of the film to be formed. Groups are preferred.
　酸基を有する構成単位は、下記式（ｂ）で表される構成単位であることが好ましい。 The structural unit having an acid group is preferably a structural unit represented by the following formula (b).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　式（ｂ）中、Ｒ２は水素原子又はメチル基を表し、Ｌ２は単結合炭素数２～１０の２価の連結基を表し、Ｘ２は酸基を表す。 In formula (b), R 2 represents a hydrogen atom or a methyl group, L 2 represents a divalent linking group having 2 to 10 carbon atoms in a single bond, and X 2 represents an acid group.
　式（ｂ）中、Ｌ２は、アルキレン基とエステル結合とを含む炭素数２～１０の２価の連結基であることが好ましく、アルキレン基とエステル結合とからなる炭素数２～１０の２価の連結基であることがより好ましい。
　式（ｂ）中、Ｘ２は、カルボキシ基が好ましい。 In the formula (b), L 2 is preferably a divalent linking group having 2 to 10 carbon atoms containing an alkylene group and an ester bond, and 2 to 10 carbon atoms consisting of the alkylene group and an ester bond. More preferably, it is a valence linking group.
In formula (b), X 2 is preferably a carboxy group.
　特定バインダー樹脂は、酸基を有する構成単位（好ましくは、式（ｂ）で表される構成単位）を１種単独で含んでいてもよいし、２種以上を含んでいてもよい。 The specific binder resin may contain one type of structural unit having an acid group (preferably a structural unit represented by the formula (b)) alone, or may contain two or more types.
　特定バインダー樹脂は、芳香族環及び脂肪族環よりなる群から選択される少なくとも１種の環構造を有する構成単位及び酸基を有する構成単位の他に、その他の構成単位を含んでいてもよい。
　その他の構成単位としては、ＳＰ値及び酸価を上記の範囲に制御しうるものであれば特に制限はなく、（メタ）アクリレート化合物により形成される構成単位が好ましく挙げられる。
　（メタ）アクリル酸アルキルエステル化合物であることが好ましく、２－ヒドロキシエチル（メタ）アクリレート、イソブチル（メタ）アクリレート、メチル（メタ）アクリレート等がより好ましく挙げられる。 The specific binder resin may contain other structural units in addition to the structural unit having at least one ring structure and the structural unit having an acid group selected from the group consisting of an aromatic ring and an aliphatic ring. ..
The other structural unit is not particularly limited as long as the SP value and acid value can be controlled within the above ranges, and a structural unit formed of the (meth) acrylate compound is preferably mentioned.
It is preferably a (meth) acrylic acid alkyl ester compound, and more preferably 2-hydroxyethyl (meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate and the like.
　その他の構成単位は、下記式（ｃ）で表される構成単位であることが好ましい。 The other structural unit is preferably a structural unit represented by the following formula (c).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（ｃ）中、Ｒ３は水素原子又はメチル基を表し、Ｌ３は－Ｃ（＝Ｏ）Ｏ－を表し、Ｘ３はアルキル基を表す。 In formula (c), R 3 represents a hydrogen atom or a methyl group, L 3 represents -C (= O) O-, and X 3 represents an alkyl group.
　式（ｃ）中、Ｘ３は、炭素数１～１０である置換又は無置換のアルキル基が好ましく、炭素数１～８である置換又は無置換のアルキル基がより好ましい。
　なお、Ｘ３で表されるアルキル基に導入される置換基としては、ヒドロキシ基、アリル基等が挙げられる。 Wherein (c), X 3 is preferably a substituted or unsubstituted alkyl group of 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkyl group of 1 to 8 carbon atoms.
Examples of the substituent introduced into the alkyl group represented by X 3 include a hydroxy group and an allyl group.
　特定バインダー樹脂は、その他の構成単位（好ましくは、式（ｃ）で表される構成単位）を１種単独で含んでいてもよいし、２種以上を含んでいてもよい。 The specific binder resin may contain other structural units (preferably the structural units represented by the formula (c)) of one type alone, or may contain two or more types.
　特定バインダー樹脂の重量平均分子量（Ｍｗ）は、２０，０００以下が好ましく、１５，０００以下がより好ましく、１２，０００以下が更に好ましく、１０，０００以下が特に好ましい。
　特定バインダー樹脂の重量平均分子量（Ｍｗ）の下限としては、２，０００以上が好ましく、３，０００以上がより好ましく、４，０００以上が更に好ましい。 The weight average molecular weight (Mw) of the specific binder resin is preferably 20,000 or less, more preferably 15,000 or less, further preferably 12,000 or less, and particularly preferably 10,000 or less.
The lower limit of the weight average molecular weight (Mw) of the specific binder resin is preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more.
　特定バインダー樹脂の具体例としては、以下に示す樹脂１～６が挙げられるが、これらに限定されるものではない。
　なお、樹脂１～６において、主鎖の各構成単位に付記した数値はモル比である。 Specific examples of the specific binder resin include, but are not limited to, the following resins 1 to 6.
In the resins 1 to 6, the numerical value added to each structural unit of the main chain is the molar ratio.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　本開示に係る組成物は、特定バインダー樹脂を１種単独で含んでいてもよいし、２種以上を含んでいてもよい。 The composition according to the present disclosure may contain one type of specific binder resin alone, or may contain two or more types.
　本開示に係る組成物における特定バインダー樹脂の含有量は、本開示に係る組成物の使用目的、用途等に応じて、適宜、決定されればよい。
　特定バインダー樹脂は、例えば、後述する塩基性基を有する樹脂に対して、質量基準にて、１倍～３０倍（好ましくは１．５倍～２７倍、より好ましくは２倍～２５倍）にて用いることができる。 The content of the specific binder resin in the composition according to the present disclosure may be appropriately determined according to the purpose of use, use and the like of the composition according to the present disclosure.
The specific binder resin is, for example, 1 to 30 times (preferably 1.5 to 27 times, more preferably 2 to 25 times) the resin having a basic group described later on a mass basis. Can be used.
［その他のバインダー樹脂］
　本開示に係る組成物は、既述の保存安定性に優れるといった効果を損なわない範囲において、特定バインダー樹脂以外のその他のバインダー樹脂を含んでいてもよい。
　その他のバインダー樹脂は、ＳＰ値及び酸価のいずれか一方が上記の範囲を満たさない樹脂であって、且つ、分子内に塩基性基を有さず、「塩基性基を有する樹脂」には該当しない樹脂である。
　その他のバインダー樹脂を用いる場合、本開示に係る組成物に含まれる総バインダー樹脂に対する、その他のバインダー樹脂の含有量は、１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、０質量％であることが特に好ましい。 [Other binder resins]
The composition according to the present disclosure may contain other binder resins other than the specific binder resin as long as the above-mentioned effects such as excellent storage stability are not impaired.
The other binder resin is a resin in which either the SP value or the acid value does not satisfy the above range, and has no basic group in the molecule, and is a "resin having a basic group". Not applicable resin.
When other binder resins are used, the content of the other binder resin with respect to the total binder resin contained in the composition according to the present disclosure is preferably 10% by mass or less, and more preferably 5% by mass or less. It is preferably 0% by mass, and particularly preferably 0% by mass.
＜近赤外線吸収顔料＞
　本開示に係る組成物は、近赤外線吸収顔料を含む。
　本開示において、「近赤外線」は、波長７００ｎｍ～２，５００ｎｍの赤外線を指し、「近赤外線吸収顔料」は、波長７５０ｎｍ～２，５００ｎｍの範囲に極大吸収波長を有する顔料である。
　近赤外線吸収顔料は、波長７５０ｎｍ～１，８００ｎｍの範囲に極大吸収波長を有する顔料であることが好ましい。また、近赤外線吸収顔料は、波長５００ｎｍにおける吸光度Ａ１と極大吸収波長における吸光度Ａ２との比率Ａ１／Ａ２が、０．０８以下であることが好ましく、０．０４以下であることがより好ましい。
　なお、本開示において、顔料とは、溶剤に不溶の色素を意味する。ここで、溶剤に不溶とは、２５℃における対象物質の溶剤１００ｍｇに対する溶解度が０．１ｇ以下であることを指す。ここで溶剤としては、プロピレングリコールモノメチルエーテルアセテ－ト又は水が挙げられ、いずれの溶剤であっても上記の溶解度であるものが顔料である。 <Near infrared absorbing pigment>
The composition according to the present disclosure contains a near-infrared absorbing pigment.
In the present disclosure, "near infrared rays" refers to infrared rays having a wavelength of 700 nm to 2,500 nm, and "near infrared absorbing pigments" are pigments having a maximum absorption wavelength in the wavelength range of 750 nm to 2,500 nm.
The near-infrared absorbing pigment is preferably a pigment having a maximum absorption wavelength in the wavelength range of 750 nm to 1800 nm. Also, near infrared absorbing pigments, the ratio A 1 / A 2 between the absorbance A 2 in the absorbance A 1 and the maximum absorption wavelength at a wavelength 500nm may be preferably 0.08 or less, 0.04 or less More preferred.
In the present disclosure, the pigment means a dye that is insoluble in a solvent. Here, insoluble in a solvent means that the solubility of the target substance in 100 mg of the solvent at 25 ° C. is 0.1 g or less. Here, examples of the solvent include propylene glycol monomethyl ether acetate and water, and any solvent having the above-mentioned solubility is a pigment.
　近赤外線吸収顔料としては、ピロロピロール化合物、スクアリリウム化合物、シアニン化合物、フタロシアニン化合物、ナフタロシアニン化合物、クアテリレン化合物、メロシアニン化合物、クロコニウム化合物、オキソノール化合物、イミニウム化合物、ジチオール化合物、トリアリールメタン化合物、ピロメテン化合物、アゾメチン化合物、アントラキノン化合物、ジベンゾフラノン化合物、金属酸化物、金属ホウ化物等が挙げられる。
　中でも、近赤外線吸収顔料としては、耐久性の観点から、ピロロピロール化合物又はスクアリリウム化合物が特に好ましい。 Near-infrared absorbing pigments include pyrolopyrrole compounds, squarylium compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonor compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, Examples thereof include azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, metal oxides, and metal boroides.
Among them, as the near-infrared absorbing pigment, a pyrrolopyrrole compound or a squarylium compound is particularly preferable from the viewpoint of durability.
［ピロロピロール化合物］
　ピロロピロール化合物としては、式（ＰＰ）で表される化合物であることが好ましい。 [Pyrrolopyrrole compound]
The pyrrolopyrrole compound is preferably a compound represented by the formula (PP).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式（ＰＰ）中、Ｒ１ａ及びＲ１ｂは、各々独立に、アルキル基、アリール基、又はヘテロアリール基を表し、Ｒ２及びＲ３は、各々独立に、水素原子又は置換基を表し、Ｒ２及びＲ３は、互いに結合して環を形成してもよく、Ｒ４は、各々独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、－ＢＲ４ＡＲ４Ｂ、又は金属原子を表し、Ｒ４は、Ｒ１ａ、Ｒ１ｂ、及びＲ３から選ばれる少なくとも一つと共有結合若しくは配位結合していてもよく、Ｒ４Ａ及びＲ４Ｂは、各々独立に、置換基を表す。 In formula (PP), R 1a and R 1b each independently represent an alkyl group, an aryl group, or a heteroaryl group, and R 2 and R 3 each independently represent a hydrogen atom or a substituent, R. 2 and R 3 may be bonded to each other to form a ring, R 4 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4A R 4B, or a metal atom , R 4 may be covalently or coordinated with at least one selected from R 1a , R 1b , and R 3 , where R 4A and R 4B each independently represent a substituent.
　式（ＰＰ）の詳細については、特開２００９－２６３６１４号公報の段落番号００１７～００４７、特開２０１１－６８７３１号公報の段落番号００１１～００３６、国際公開第２０１５／１６６８７３号の段落番号００１０～００２４の記載を参酌でき、これらの内容は本明細書に組み込まれる。 For details of the formula (PP), paragraph numbers 0017 to 0047 of JP2009-263614, paragraphs 0011 to 0036 of JP2011-68831, and paragraphs 0010 to 0024 of International Publication No. 2015/166783. The description of the above can be taken into consideration, and these contents are incorporated in the present specification.
　式（ＰＰ）において、Ｒ１ａ及びＲ１ｂは、各々独立に、アリール基又はヘテロアリール基が好ましく、アリール基がより好ましい。また、Ｒ１ａ及びＲ１ｂで表されるアルキル基、アリール基、及びヘテロアリール基は、置換基を有していてもよく、無置換であってもよい。
　置換基としては、後述する置換基Ｔが挙げられる。 In the formula (PP), R 1a and R 1b are each independently preferably an aryl group or a heteroaryl group, and more preferably an aryl group. Further, the alkyl group, aryl group, and heteroaryl group represented by R 1a and R 1b may have a substituent or may be unsubstituted.
Examples of the substituent include a substituent T described later.
－置換基Ｔ－
　置換基Ｔとしては、ハロゲン原子、シアノ基、ニトロ基、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、－ＯＲｔ１、－ＣＯＲｔ１、－ＣＯＯＲｔ１、－ＯＣＯＲｔ１、－ＮＲｔ１Ｒｔ２、－ＮＨＣＯＲｔ１、－ＣＯＮＲｔ１Ｒｔ２、－ＮＨＣＯＮＲｔ１Ｒｔ２、－ＮＨＣＯＯＲｔ１、－ＳＲｔ１、－ＳＯ２Ｒｔ１、－ＳＯ２ＯＲｔ１、－ＮＨＳＯ２Ｒｔ１又は－ＳＯ２ＮＲｔ１Ｒｔ２が挙げられる。Ｒｔ１及びＲｔ２は、各々独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、又はヘテロアリール基を表す。Ｒｔ１とＲｔ２が結合して環を形成してもよい。 -Substituent T-
As the substituent T, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, -ORt 1 , -CORt 1 , -COORt 1 , -OCORt 1 , -NRt 1 Rt 2 , -NHCORt 1 , -CONRT 1 Rt 2 , -NHCONRT 1 Rt 2 , -NHCOORt 1 , -SRt 1 , -SO 2 Rt 1 , -SO 2 ORt 1 , -NHSO 2 Rt 1 or -SO 2 NRt 1 Rt 2 can be mentioned. Rt 1 and Rt 2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. Rt 1 and Rt 2 may be combined to form a ring.
　式（ＰＰ）において、Ｒ２及びＲ３は、各々独立に水素原子又は置換基を表す。置換基としては、既述の置換基Ｔが挙げられる。Ｒ２及びＲ３の少なくとも一方は電子求引性基であることが好ましく、シアノ基、カルボキシ基、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、カルバモイル基、アルキルカルボニル基、アリールカルボニル基、アルキルスルホニル基、又はアリールスルホニル基であることがより好ましく、シアノ基であることが更に好ましい。 In formula (PP), R 2 and R 3 each independently represent a hydrogen atom or substituent. Examples of the substituent include the above-mentioned Substituent T. At least one of R 2 and R 3 is preferably an electron-attracting group, and is preferably a cyano group, a carboxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, or an alkyl. It is more preferably a sulfonyl group or an arylsulfonyl group, and even more preferably a cyano group.
　式（ＰＰ）において、Ｒ２は電子求引性基（好ましくはシアノ基）を表し、Ｒ３はヘテロアリール基を表すことが好ましい。ヘテロアリール基は、５員環又は６員環が好ましい。また、ヘテロアリール基は、単環又は縮合環が好ましく、単環又は縮合数が２～８の縮合環が好ましく、単環又は縮合数が２～４の縮合環がより好ましい。ヘテロアリール基を構成するヘテロ原子の数は、１～３が好ましく、１～２がより好ましい。ヘテロ原子としては、例えば、窒素原子、酸素原子、硫黄原子が例示される。ヘテロアリール基は、窒素原子を１個以上有することが好ましい。式（ＰＰ）における２個のＲ２同士は同一であってもよく、異なっていてもよい。また、式（ＰＰ）における２個のＲ３同士は同一であってもよく、異なっていてもよい。 In formula (PP), R 2 preferably represents an electron-attracting group (preferably a cyano group) and R 3 preferably represents a heteroaryl group. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 8, and more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroaryl group preferably has one or more nitrogen atoms. Two R 2 together in the formula (PP) may be the same or may be different. Also, two R 3 together in the formula (PP) may be the same or may be different.
　式（ＰＰ）において、Ｒ４は、水素原子、アルキル基、アリール基、ヘテロアリール基、又は－ＢＲ４ＡＲ４Ｂで表される基であることが好ましく、水素原子、アルキル基、アリール基、又は－ＢＲ４ＡＲ４Ｂで表される基であることがより好ましく、－ＢＲ４ＡＲ４Ｂで表される基であることが更に好ましい。Ｒ４Ａ及びＲ４Ｂは、ハロゲン原子、アルキル基、アルコキシ基、アリール基、又は、ヘテロアリール基が好ましく、アルキル基、アリール基、又は、ヘテロアリール基がより好ましく、アリール基が特に好ましい。これらの基は更に置換基を有していてもよい。式（ＰＰ）における２個のＲ４同士は同一であってもよく、異なっていてもよい。Ｒ４Ａ及びＲ４Ｂは互いに結合して環を形成していてもよい。 In formula (PP), R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or a group represented by -BR 4A R 4B, and is preferably a hydrogen atom, an alkyl group, an aryl group, or a group. -BR 4A A group represented by R 4B is more preferable, and a group represented by -BR 4A R 4B is further preferable. R 4A and R 4B are preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and particularly preferably an aryl group. These groups may further have a substituent. Two R 4 together in the formula (PP) may be the same or may be different. R 4A and R 4B may be combined with each other to form a ring.
　ピロロピロール化合物としては、式（ＰＰ－１）で表される化合物であってもよい。 The pyrrolopyrrole compound may be a compound represented by the formula (PP-1).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式（ＰＰ－１）中、Ｒ１ａ、Ｒ２、Ｒ３、及びＲ４は、いずれも、式（ＰＰ）中のＲ１ａ、Ｒ２、Ｒ３、及びＲ４と同義であり、Ｒ１ｂは、アルキレン基、アリーレン基、又はヘテロアリーレン基を表し、Ｌは、下記式（Ｌ１）又は下記式（Ｌ２）で表される基である。 In formula (PP-1), R 1a , R 2 , R 3 , and R 4 are all synonymous with R 1a , R 2 , R 3 , and R 4 in formula (PP) , and R 1b. Represents an alkylene group, an arylene group, or a heteroarylene group, and L is a group represented by the following formula (L1) or the following formula (L2).
　式（ＰＰ－１）中のＲ１ａ、Ｒ１ｂ、Ｒ２、Ｒ３、及びＲ４は、いずれも、式（ＰＰ）中のＲ１ａ、Ｒ１ｂ、Ｒ２、Ｒ３、及びＲ４と同義であり、好ましい態様も同様である。 R 1a in the formula (PP-1), R 1b , R 2, R 3, and R 4 are both, R 1a in the formula (PP), R 1b, R 2, R 3, and the R 4 It has the same meaning, and the preferred embodiment is also the same.
　＊－Ｘ１－Ａ１―Ｘ２－＊　　式（Ｌ１）
　上記式（Ｌ１）中、Ｘ１及びＸ２は、各々独立に、単結合、－Ｏ－、－Ｓ－，－ＮＲ１Ａ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯＯ－、－ＳＯ２ＮＲ１Ａ－、－ＣＯＮＲ１Ａ－、－ＯＣＯＮＲ１Ａ－、又は－ＮＲ１ＡＣＯＮＲ１Ａ－を表し、Ｒ１Ａは、各々独立に、水素原子、アルキル基、又はアリール基を表し、Ａ１は、単結合、脂肪族環構造、芳香族環構造、又は複素環構造を表し、＊は、Ｒ１ｂとの連結位置を表し、ただし、Ａ１が単結合のとき、Ｘ１及びＸ２の両方が単結合となることはない。 * -X 1- A 1- X 2- * Equation (L1)
In the formula (L1), X 1 and X 2 are each independently a single bond, -O -, - S -, - NR 1A -, - CO -, - COO -, - OCOO -, - SO 2 NR 1A -, - CONR 1A -, - OCONR 1A -, or -NR 1A CONR 1A - represents, R 1A each independently represent a hydrogen atom, an alkyl group, or an aryl group, a 1 represents a single bond, It represents an aliphatic ring structure, an aromatic ring structure, or a heterocyclic structure, where * represents a connection position with R 1b , where when A 1 is a single bond , both X 1 and X 2 are single bonds. It will never be.
　＊－Ｘ３―Ａ２―Ｌ２―Ａ３―Ｘ４－＊　　式（Ｌ２）
　上記式（Ｌ２）中、Ｘ３及びＸ４は各々独立に、単結合、－Ｏ－、－Ｓ－、－ＮＲ２Ａ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯＯ－、－ＳＯ２ＮＲ２Ａ－、－ＣＯＮＲ２Ａ－、－ＯＣＯＮＲ２Ａ－、又は－ＮＲ２ＡＣＯＮＲ２Ａ－を表し、Ｒ２Ａは水素原子又はアルキル基を表し、Ｌ２は、単結合、－Ｏ－、－Ｓ－、－ＮＲ２Ｂ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯＯ－、－ＳＯ２ＮＲ２Ｂ－、－ＣＯＮＲ２Ｂ－、－ＯＣＯＮＲ２Ｂ－、－ＮＲ２ＢＣＯＮＲ２Ｂ－、炭素数１～６のアルキレン基、アルケニル基、アルキニル基、芳香族環構造、又はこれらを組み合わせた基を表し、Ｒ２Ｂは、各々独立に、水素原子又はアルキル基を表し、Ａ２及びＡ３は、各々独立に、脂肪族環構造、芳香族環構造、又は複素環構造を表す。 * -X 3 -A 2 -L 2 -A 3 -X 4 - * the formula (L2)
In the above formula (L2), X 3 and X 4 are independently single-bonded, -O-, -S-, -NR 2A- , -CO-, -COO-, -OCOO-, -SO 2 NR 2A. -, -CONR 2A- , -OCONR 2A- , or -NR 2A CONR 2A- , R 2A represents a hydrogen atom or an alkyl group, L 2 represents a single bond, -O-, -S-, -NR. 2B -, - CO -, - COO -, - OCOO -, - SO 2 NR 2B -, - CONR 2B -, - OCONR 2B -, - NR 2B CONR 2B -, an alkylene group, an alkenyl group having 1 to 6 carbon atoms , An alkynyl group, an aromatic ring structure, or a group combining these, R 2B independently represents a hydrogen atom or an alkyl group, and A 2 and A 3 each independently represent an aliphatic ring structure. Represents an aromatic ring structure or a heterocyclic structure.
　ピロロピロール化合物の具体例としては、下記化合物が挙げられる。
　以下の構造式中、Ｍｅはメチル基を表し、Ｐｈはフェニル基を表す。
　また、ピロロピロール化合物としては、特開２００９－２６３６１４号公報の段落番号００１６～００５８に記載の化合物、特開２０１１－６８７３１号公報の段落番号００３７～００５２に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。 Specific examples of the pyrrolopyrrole compound include the following compounds.
In the following structural formula, Me represents a methyl group and Ph represents a phenyl group.
Examples of the pyrrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP2009-263614 and the compounds described in paragraphs 0037-0052 of JP2011-68831. The content is incorporated herein by reference.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
［スクアリリウム化合物］
　スクアリリウム化合物としては、下記式（ＳＱ）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000008
 [Squarylium compound]
The squarylium compound is preferably a compound represented by the following formula (SQ).
Figure JPOXMLDOC01-appb-C000008
　式（ＳＱ）中、Ａ１及びＡ２は、各々独立に、アリール基、ヘテロアリール基、又は式（Ａ－１）で表される基を表す； In formula (SQ), A 1 and A 2 each independently represent an aryl group, a heteroaryl group, or a group represented by formula (A-1);
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（Ａ－１）中、Ｚ１は、含窒素複素環を形成する非金属原子団を表し、Ｒ２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（ＳＱ）の詳細については、特開２０１１－２０８１０１号公報の段落番号００２０～００４９、特許第６０６５１６９号公報の段落番号００４３～００６２、国際公開第２０１６／１８１９８７号の段落番号００２４～００４０の記載を参酌でき、これらの内容は本明細書に組み込まれる。 In formula (A-1), Z 1 represents a non-metal atomic group forming a nitrogen-containing heterocycle, R 2 represents an alkyl group, an alkenyl group or an aralkyl group, and d represents 0 or 1. The wavy line represents the connecting hand. For details of the formula (SQ), paragraph numbers 0020 to 0049 of Japanese Patent Application Laid-Open No. 2011-208101, paragraph numbers 0043 to 0062 of Japanese Patent No. 6065169, and paragraph numbers 0024 to 0040 of International Publication No. 2016/181987. These contents are incorporated herein by reference.
　なお、式（ＳＱ）においてカチオンは、以下のように非局在化して存在している。 In the formula (SQ), the cation is delocalized and exists as follows.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　スクアリリウム化合物は、下記式（ＳＱ－１）で表される化合物であることが好ましい。 The squarylium compound is preferably a compound represented by the following formula (SQ-1).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　式（ＳＱ－１）中、環Ａ及び環Ｂは、各々独立に芳香族環を表し、ＸＡ及びＸＢは各々独立に置換基を表し、ＧＡ及びＧＢは各々独立に置換基を表し、ｋＡは０～ｎＡの整数を表し、ｋＢは０～ｎＢの整数を表し、ｎＡ及びｎＢはそれぞれ環Ａ又は環Ｂに置換可能な最大の整数を表し、ＸＡとＧＡ、ＸＢとＧＢ、ＸＡとＸＢは、互いに結合して環を形成してもよく、ＧＡ及びＧＢがそれぞれ複数存在する場合は、互いに結合して環構造を形成していてもよい。 Wherein (SQ-1), rings A and B each independently represent an aromatic ring, X A and X B each independently represents a substituent, a G A and G B are each independently a substituent Represented, kA represents an integer from 0 to n A , kB represents an integer from 0 to n B , n A and n B represent the largest integer substitutable to ring A or ring B, respectively, and X A and G. a, X B and G B, X a and X B may form a ring, if G a and G B are present in plural, taken together, they are bonded together to form a ring structure You may.
　ＧＡ及びＧＢで表される置換基としては、既述の置換基Ｔが挙げられる。 The substituent represented by G A and G B, include aforementioned substituent T.
　ＸＡ及びＸＢで表される置換基としては、活性水素を有する基が好ましく、－ＯＨ、－ＳＨ、－ＣＯＯＨ、－ＳＯ３Ｈ、－ＮＲＸ１ＲＸ２、－ＮＨＣＯＲＸ１、－ＣＯＮＲＸ１ＲＸ２、－ＮＨＣＯＮＲＸ１ＲＸ２、－ＮＨＣＯＯＲＸ１、－ＮＨＳＯ２ＲＸ１、－Ｂ（ＯＨ）２及び－ＰＯ（ＯＨ）２がより好ましく、－ＯＨ、－ＳＨ及び－ＮＲＸ１ＲＸ２が更に好ましい。ＲＸ１及びＲＸ２は、各々独立に水素原子又は置換基を表す。ＸＡ及びＸＢにおける置換基ＲＸ１及びＲＸ２としてはアルキル基、アリール基、又は、ヘテロアリール基が挙げられ、アルキル基が好ましい。 As the substituent represented by X A and X B , a group having active hydrogen is preferable, and -OH, -SH, -COOH, -SO 3 H, -NR X1 R X2 , -NHCOR X1 , -CONR X1 R. X2 , -NHCONR X1 R X2 , -NHCOOR X1 , -NHSO 2 R X1 , -B (OH) 2 and -PO (OH) 2 are more preferred, and -OH, -SH and -NR X1 R X2 are even more preferred. RX1 and RX2 each independently represent a hydrogen atom or a substituent. X A and the alkyl group as the substituent R X1 and R X2 in X B, an aryl group, or, include heteroaryl groups, alkyl groups are preferred.
　環Ａ及び環Ｂは、各々独立に、芳香族環を表す。芳香族環は単環であってもよく、縮合環であってもよい。芳香族環の具体例としては、ベンゼン環、ナフタレン環、ペンタレン環、インデン環、アズレン環、ヘプタレン環、インダセン環、ペリレン環、ペンタセン環、アセナフテン環、フェナントレン環、アントラセン環、ナフタセン環、クリセン環、トリフェニレン環、フルオレン環、ビフェニル環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、インドリジン環、インドール環、ベンゾフラン環、ベンゾチオフェン環、イソベンゾフラン環、キノリジン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キノキサゾリン環、イソキノリン環、カルバゾール環、フェナントリジン環、アクリジン環、フェナントロリン環、チアントレン環、クロメン環、キサンテン環、フェノキサチイン環、フェノチアジン環、及び、フェナジン環が挙げられ、ベンゼン環又はナフタレン環が好ましい。芳香族環は、無置換であってもよく、置換基を有していてもよい。置換基としては、既述の置換基Ｔが挙げられる。 Ring A and ring B each independently represent an aromatic ring. The aromatic ring may be a monocyclic ring or a condensed ring. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a pentalene ring, an inden ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthalene ring, and a chrysene ring. , Triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring, indole ring, benzofuran ring, Benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, aclysine ring, phenanthrene ring, thianthrene ring, chromene ring, xanthene. Examples thereof include a ring, a phenoxatiin ring, a phenothiazine ring, and a phenazine ring, and a benzene ring or a naphthalene ring is preferable. The aromatic ring may be unsubstituted or may have a substituent. Examples of the substituent include the above-mentioned Substituent T.
　ＸＡとＧＡ、ＸＢとＧＢ、ＸＡとＸＢは、互いに結合して環を形成してもよく、ＧＡ及びＧＢがそれぞれ複数存在する場合は、互いに結合して環を形成していてもよい。環としては、５員環又は６員環が好ましい。環は単環であってもよく、縮合環であってもよい。ＸＡとＧＡ、ＸＢとＧＢ、ＸＡとＸＢ、ＧＡ同士又はＧＢ同士が結合して環を形成する場合、これらが直接結合して環を形成してもよく、アルキレン基、－ＣＯ－、－Ｏ－、－ＮＨ－、－ＢＲ－及びそれらの組み合わせからなる２価の連結基を介して結合して環を形成してもよい。Ｒは、水素原子又は置換基を表す。置換基としては、既述の置換基Ｔが挙げられ、アルキル基又はアリール基が好ましい。 X A and G A, X B and G B, X A and X B may be bonded to each other to form a ring, if G A and G B are present in plural, the rings bonded to each other It may be formed. As the ring, a 5-membered ring or a 6-membered ring is preferable. The ring may be a monocyclic ring or a condensed ring. X A and G A, X B and G B, X A and X B, if G A s or G B are bonded to each other to form a ring, may be they are attached directly to form a ring, alkylene Rings may be formed by bonding via a divalent linking group consisting of a group, -CO-, -O-, -NH-, -BR- and a combination thereof. R represents a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned Substituent T, and an alkyl group or an aryl group is preferable.
　ｋＡは０～ｎＡの整数を表し、ｋＢは０～ｎＢの整数を表し、ｎＡは、環Ａに置換可能な最大の整数を表し、ｎＢは、環Ｂに置換可能な最大の整数を表す。ｋＡ及びｋＢは、各々独立に０～４が好ましく、０～２がより好ましく、０～１が特に好ましい。 kA represents an integer from 0 to n A , kB represents an integer from 0 to n B , n A represents the largest integer substitutable for ring A, and n B is the largest substitutable for ring B. Represents an integer. As for kA and kB, 0 to 4 is preferable, 0 to 2 is more preferable, and 0 to 1 is particularly preferable.
　スクアリリウム化合物は、下記式（ＳＱ－２）で表される化合物であることが好ましい。 The squarylium compound is preferably a compound represented by the following formula (SQ-2).
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　式（ＳＱ－２）中、Ｒｓ１１９及びＲｓ１２０は各々独立に置換基を表し、Ａ１及びＡ２は各々独立に酸素原子又はＮＲｓ１２５を表し、Ｒｓ１２１～Ｒｓ１２５は各々独立に水素原子又は置換基を表し、Ｘ３０及びＸ３１は、各々独立に、炭素原子、ホウ素原子、又はＣ（＝Ｏ）を表し、Ｘ３０が炭素原子の場合にはｎｓ３２は２であり、Ｘ３０がホウ素原子の場合にはｎｓ３２は１であり、Ｘ３０がＣ（＝Ｏ）の場合にはｎｓ３２は０であり、Ｘ３１が炭素原子の場合にはｎｓ３３は２であり、Ｘ３１がホウ素原子の場合にはｎｓ３３は１であり、Ｘ３１がＣ（＝Ｏ）の場合にはｎｓ３３は０であり、ｎｓ３０及びｎｓ３１は各々独立に０～５の整数を表し、ｎｓ３０が２以上の場合は、複数のＲｓ１１９は同一であっても異なっていてもよく、複数のＲｓ１１９のうち２個のＲｓ１１９同士が結合して環を形成してもよく、ｎｓ３１が２以上の場合は、複数のＲｓ１２０は同一であっても異なっていてもよく、複数のＲｓ１２０のうち２個のＲｓ１２０同士が結合して環を形成してもよく、ｎｓ３２が２の場合は、２個のＲｓ１２１は同一であっても異なっていてもよく、２個のＲｓ１２１同士が結合して環を形成してもよく、ｎｓ３３が２の場合は、２個のＲｓ１２２は同一であっても異なっていてもよく、２個のＲｓ１２２同士が結合して環を形成してもよく、Ａｒ１００はアリール基又はヘテロアリール基を表し、ｎｓ１００は０～２の整数を表す。 In formula (SQ-2), Rs 119 and Rs 120 each independently represent a substituent, A 1 and A 2 each independently represent an oxygen atom or NRs 125 , and Rs 121 to Rs 125 each independently represent a hydrogen atom. Alternatively, X 30 and X 31 each independently represent a carbon atom, a boron atom, or C (= O), and when X 30 is a carbon atom, ns32 is 2 and X 30 is. when the boron atom NS32 is 1, NS32 when X 30 is C (= O) is 0, when X 31 is a carbon atom ns33 is 2, X 31 boron atoms the case is 1 NS33 is, NS33 when X 31 is C (= O) is 0, an integer of 0 to 5 each independently ns30 and NS31, if ns30 is 2 or more a plurality of Rs 119 may be the same or different and may form a ring by bonding two Rs 119 between among the plurality of Rs 119, in the case of ns31 is 2 or more, a plurality of Rs 120 may be the same or different and may be bonded two Rs 120 between among the plurality of Rs 120 to form a ring, if ns32 is 2, two Rs 121 may be the same or different, and two Rs 121 may be bonded to each other to form a ring. When ns33 is 2, the two Rs 122 may be the same or different. Or, two Rs 122 may be bonded to each other to form a ring, Ar 100 represents an aryl group or a heteroaryl group, and ns100 represents an integer of 0 to 2.
　スクアリリウム化合物は、下記式（ＳＱ－３）で表される化合物であることが好ましい。 The squarylium compound is preferably a compound represented by the following formula (SQ-3).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式（ＳＱ－３）中、Ｘ１、Ｘ２、Ｙ１、及びＹ２は、各々独立に、アルキレン基、アルキニレン基、シクロアルキレン基、アリーレン基、ヘテロアリーレン基、又はこれらを２以上結合した二価の基を表し、Ｚ１及びＺ２は、各々独立に、単結合、－Ｏ－、カルボニル基、－Ｓ－、－Ｎ（ＲＮ１）－、－Ｓ（＝Ｏ）－、又は、－Ｓ（＝Ｏ）２－を表し、Ａ１及びＡ２は、各々独立に、－Ｏ－又は－Ｎ（ＲＮ２）－を表し、ＲＮ１及びＲＮ２は、各々独立に、水素原子、アルキル基、又は、アリール基を表し、Ｒ７及びＲ８は各々独立に置換基を表し、ｎ１及びｎ２は各々独立に０～５の整数を表す。
　但し、Ｘ１、Ｘ２、Ｙ１、及びＹ２がアルキレン基を表し、Ａ１及びＡ２が－Ｎ（ＲＮ２）－を表す場合、Ｚ１及びＺ２のうち少なくとも一方が、－Ｏ－、カルボニル基、－Ｓ－、－Ｎ（ＲＮ１）－、－Ｓ（＝Ｏ）－、又は、－Ｓ（＝Ｏ）２－を表す。 In the formula (SQ-3), X 1 , X 2 , Y 1 , and Y 2 are each independently bonded to an alkylene group, an alkynylene group, a cycloalkylene group, an arylene group, a heteroarylene group, or two or more of them. Representing a divalent group, Z 1 and Z 2 are independently single-bonded, -O-, carbonyl groups, -S-, -N ( RN1 )-, -S (= O)-, or -S (= O) 2- represents, A 1 and A 2 each independently represent -O- or -N ( RN2 )-, and RN1 and RN2 each independently represent a hydrogen atom. It represents an alkyl group or an aryl group, R 7 and R 8 each independently represent a substituent, and n1 and n2 each independently represent an integer of 0 to 5.
However, when X 1 , X 2 , Y 1 and Y 2 represent an alkylene group and A 1 and A 2 represent -N ( RN2 )-, at least one of Z 1 and Z 2 is -O. Represents-, carbonyl group, -S-, -N ( RN1 )-, -S (= O)-, or -S (= O) 2-.
　スクアリリウム化合物は、下記式（ＳＱ－４）で表される化合物であることが好ましい。 The squarylium compound is preferably a compound represented by the following formula (SQ-4).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　式（ＳＱ－４）中、Ｑ１、Ｑ２、Ｑ３、及びＱ４は、各々独立に、炭素原子又は窒素原子を表す。Ｑ１、Ｑ２、Ｑ３、及びＱ４が窒素原子の場合、Ｘ１、Ｘ４、Ｘ５、及びＸ８はないものとする。Ｒ１～Ｒ５は、各々独立に、水素原子、アルキル基、スルホ基、－ＳＯ３－Ｍ＋、又はハロゲン原子を表す。Ｍ＋は無機又は有機のカチオンを表す。Ｘ１～Ｘ８は、各々独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアリール基、置換基を有してもよいアラルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、ヒドロキシル基、アミノ基、－ＮＲ６Ｒ７、スルホ基、－ＳＯ２ＮＲ８Ｒ９、－ＣＯＯＲ１０、－ＣＯＮＲ１１Ｒ１２、ニトロ基、シアノ基、又はハロゲン原子を表す。Ｘ１～Ｘ８は互いに結合して環を形成してもよい。Ｒ６～Ｒ１２は、各々独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアシル基、又は置換基を有してもよいピリジニル基を表す。Ｒ２とＲ３、Ｒ６とＲ７、Ｒ７とＲ８、Ｒ８とＲ９、Ｒ１１とＲ１２は、それぞれ、互いに結合して環を形成してもよい。 Wherein (SQ-4), Q 1 , Q 2, Q 3, and Q 4 each independently represents a carbon atom or a nitrogen atom. If Q 1 , Q 2 , Q 3 , and Q 4 are nitrogen atoms, then X 1 , X 4 , X 5 , and X 8 are absent. R 1 to R 5 independently represent a hydrogen atom, an alkyl group, a sulfo group, -SO 3- M + , or a halogen atom. M + represents an inorganic or organic cation. Each of X 1 to X 8 independently contains a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, hydroxyl group, amino group, -NR 6 R 7 , sulfo group, -SO 2 NR 8 R 9 , -COOR 10 , -CONR 11 R 12 , represents a nitro group, a cyano group, or a halogen atom. X 1 to X 8 may be combined with each other to form a ring. R 6 to R 12 are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, or a substituent. Represents a pyridinyl group which may have. R 2 and R 3 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , and R 11 and R 12 , respectively, may be coupled to each other to form a ring.
　スクアリリウム化合物の具体例としては、下記の化合物［ＳＱ－１～ＳＱ－６１］が挙げられる。
　また、スクアリリウム化合物としては、特開２０１１－２０８１０１号公報の段落番号００４４～００４９に記載の化合物、特許第６０６５１６９号公報の段落番号００６０～００６１に記載の化合物、国際公開第２０１６／１８１９８７号の段落番号００４０に記載の化合物、国際公開第２０１３／１３３０９９号に記載の化合物、国際公開第２０１４／０８８０６３号に記載の化合物、特開２０１４－１２６６４２号公報に記載の化合物、特開２０１６－１４６６１９号公報に記載の化合物、特開２０１５－１７６０４６号公報に記載の化合物、特開２０１７－２５３１１号公報に記載の化合物、国際公開第２０１６／１５４７８２号に記載の化合物、特許５８８４９５３号公報に記載の化合物、特許６０３６６８９号公報に記載の化合物、特許５８１０６０４号公報に記載の化合物、特開２０１７－０６８１２０号公報に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。 Specific examples of the squarylium compound include the following compounds [SQ-1 to SQ-61].
Examples of the squarylium compound include the compounds described in paragraphs 0044 to 0049 of JP2011-208101A, the compounds described in paragraphs 0060 to 0061 of Patent No. 6065169, and paragraphs of International Publication No. 2016/181987. The compound described in No. 0040, the compound described in International Publication No. 2013/133099, the compound described in International Publication No. 2014/088063, the compound described in JP-A-2014-126642, JP-A-2016-1466619. , The compound described in JP-A-2015-176046, the compound described in JP-A-2017-25311, the compound described in International Publication No. 2016/154782, the compound described in Japanese Patent Application Laid-Open No. 5884953, Examples thereof include the compound described in Japanese Patent Application Laid-Open No. 6036689, the compound described in Japanese Patent Application Laid-Open No. 581604, and the compound described in JP-A-2017-068120, and the contents thereof are incorporated in the present specification.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　本開示に係る組成物は、近赤外線吸収顔料を１種単独で含んでいてもよいし、２種以上を含んでいてもよい。 The composition according to the present disclosure may contain one kind of near-infrared absorbing pigment alone, or may contain two or more kinds.
　本開示に係る組成物における近赤外線吸収顔料の含有量は、本開示に係る組成物の使用目的、用途等に応じて、適宜、決定されればよい。
　近赤外線吸収顔料の含有量は、例えば、近赤外線吸収顔料に求められる機能を発現する観点から、例えば、組成物の全固形分に対し、１質量％以上８０質量％以下であることが好ましく、５質量％以上５０質量％以下であることがより好ましい。 The content of the near-infrared absorbing pigment in the composition according to the present disclosure may be appropriately determined according to the purpose of use, use and the like of the composition according to the present disclosure.
The content of the near-infrared absorbing pigment is preferably 1% by mass or more and 80% by mass or less with respect to the total solid content of the composition, for example, from the viewpoint of exhibiting the functions required for the near-infrared absorbing pigment. More preferably, it is 5% by mass or more and 50% by mass or less.
＜塩基性基を有する樹脂＞
　本開示に係る組成物は、塩基性基を有する樹脂を含む。
　ここで、塩基性基としては、塩基としての性質を示す官能基であり、窒素原子を含む基であることが好ましく、より具体的には、第１級アミノ基又はその塩、第２級アミノ基又はその塩、第３級アミノ基又はその塩、第４級アンモニウム塩基等であることがより好ましい。塩基性基を有する樹脂中の塩基性基は、特定バインダー樹脂の酸基にて中和され、塩を形成していてもよい。つまり、本開示に係る組成物は、近赤外線吸収顔料と、特定バインダー樹脂と、特定バインダー樹脂の酸基にて中和された塩を塩基性基として有する樹脂と、を含む組成物であってもよい。 <Resin having a basic group>
The composition according to the present disclosure contains a resin having a basic group.
Here, the basic group is a functional group exhibiting properties as a base, preferably a group containing a nitrogen atom, and more specifically, a primary amino group or a salt thereof, a secondary amino. More preferably, it is a group or a salt thereof, a tertiary amino group or a salt thereof, a quaternary ammonium base or the like. The basic group in the resin having a basic group may be neutralized with the acid group of the specific binder resin to form a salt. That is, the composition according to the present disclosure is a composition containing a near-infrared absorbing pigment, a specific binder resin, and a resin having a salt neutralized with an acid group of the specific binder resin as a basic group. May be good.
　塩基性基を有する樹脂としては、例えば、第３級アミノ基を側鎖に有する樹脂、及び、主鎖に窒素原子を含む樹脂よりなる群から選択される少なくとも１種であることが好ましい。
　特に、近赤外線吸収顔料の分散性向上の観点から、上記第３級アミノ基を側鎖に有する樹脂が、更に第４級アンモニウム塩基を側鎖に有する樹脂であることが好ましい。即ち、塩基性基を有する樹脂としては、第３級アミノ基と第４級アンモニウム塩基とを側鎖に有する樹脂であることが好ましい。 The resin having a basic group is preferably at least one selected from the group consisting of, for example, a resin having a tertiary amino group in the side chain and a resin having a nitrogen atom in the main chain.
In particular, from the viewpoint of improving the dispersibility of the near-infrared absorbing pigment, the resin having the tertiary amino group in the side chain is preferably a resin having a quaternary ammonium base in the side chain. That is, the resin having a basic group is preferably a resin having a tertiary amino group and a quaternary ammonium base in the side chain.
［第３級アミノ基を側鎖に有する樹脂］
　第３級アミノ基を側鎖に有する樹脂は、第３級アミノ基を有する構成単位を有する樹脂であることが好ましく、第３級アミノ基を有する構成単位と第４級アンモニウム塩基を有する構成単位とを有する樹脂であることがより好ましい。また、第３級アミノ基を側鎖に有する樹脂は、第３級アミノ基を有する構成単位及び第４級アンモニウム塩基を有する構成単位以外に、更に、その他の構成単位を有していてもよい。
　また、第３級アミノ基を側鎖に有する樹脂は、ブロック構造を有していることも好ましい。 [Resin having a tertiary amino group in the side chain]
The resin having a tertiary amino group in the side chain is preferably a resin having a structural unit having a tertiary amino group, and a structural unit having a tertiary amino group and a structural unit having a quaternary ammonium base. It is more preferable that the resin has and. Further, the resin having a tertiary amino group in the side chain may further have other structural units in addition to the structural unit having a tertiary amino group and the structural unit having a quaternary ammonium base. ..
It is also preferable that the resin having a tertiary amino group in the side chain has a block structure.
　第３級アミノ基と第４級アンモニウム塩基とを側鎖に有する樹脂の場合、アミン価が１０ｍｇＫＯＨ／ｇ～２５０ｍｇＫＯＨ／ｇ、且つ、第４級アンモニウム塩価が１０ｍｇＫＯＨ／ｇ～９０ｍｇＫＯＨ／ｇであるものが好ましく、アミン価が５０ｍｇＫＯＨ／ｇ～２００ｍｇＫＯＨ／ｇ、且つ、第４級アンモニウム塩価が１０ｍｇＫＯＨ／ｇ～５０ｍｇＫＯＨ／ｇであるものがより好ましい。 In the case of a resin having a tertiary amino group and a quaternary ammonium base in the side chain, the amine value is 10 mgKOH / g to 250 mgKOH / g, and the quaternary ammonium salt value is 10 mgKOH / g to 90 mgKOH / g. Those having an amine value of 50 mgKOH / g to 200 mgKOH / g and a quaternary ammonium salt value of 10 mgKOH / g to 50 mgKOH / g are more preferable.
　ここで、上記のアミン価は、０．１Ｎの塩酸水溶液を用い、電位差滴定法によって求められたアミン価を、水酸化カリウムの当量に換算したものである。
　また、上記の４級アンモニウム塩価は、５％クロム酸カリウム水溶液を指示薬として、０．１Ｎの硝酸銀水溶液で滴定して求められたアミン価を、水酸化カリウムの当量に換算したものである。 Here, the above amine value is obtained by converting the amine value obtained by the potentiometric titration method into the equivalent of potassium hydroxide using a 0.1 N hydrochloric acid aqueous solution.
The quaternary ammonium salt value is obtained by titrating with a 0.1 N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and converting the amine value to the equivalent of potassium hydroxide.
　第３級アミノ基を側鎖に有する樹脂の重量平均分子量（Ｍｗ）は、３，０００～３００，０００であることが好ましく、５，０００～３０，０００であることがより好ましい。 The weight average molecular weight (Mw) of the resin having a tertiary amino group in the side chain is preferably 3,000 to 300,000, more preferably 5,000 to 30,000.
　第３級アミノ基を側鎖に有する樹脂は、第３級アミノ基を有するエチレン性不飽和化合物と、必要に応じて、第４級アンモニウム塩基を有するエチレン性不飽和化合物、及びその他エチレン性不飽和化合物と、を共重合することで得られる。
　なお、予め、第３級アミンを有するエチレン性不飽和化合物を用いて重合体を合成した後、該重合体に塩化ベンジル等のハロゲン化炭化水素化合物を反応させて、部分的に第３級アミノ基を第４級アンモニウム塩基に変性して、第４級アンモニウム基を導入してもよい。 Resins having a tertiary amino group in the side chain include an ethylenically unsaturated compound having a tertiary amino group, an ethylenically unsaturated compound having a quaternary ammonium base, and other ethylenically unsaturated compounds, if necessary. It is obtained by copolymerizing with a saturated compound.
In addition, after synthesizing a polymer using an ethylenically unsaturated compound having a tertiary amine in advance, the polymer is reacted with a halogenated hydrocarbon compound such as benzyl chloride to partially react with a tertiary amino. The group may be modified to a quaternary ammonium base to introduce a quaternary ammonium group.
　第３級アミノ基を有するエチレン性不飽和化合物としては、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート、ジエチルアミノプロピル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリルアミド等が挙げられる。
　第４級アンモニウム塩基を有するエチレン性不飽和化合物としては、（メタ）アクリロイルアミノプロピルトリメチルアンモニウムクロライド、（メタ）アクリロイルオキシエチルトリメチルアンモニウムクロライド、（メタ）アクリロイルオキシエチルトリエチルアンモニウムクロライド、（メタ）アクリロイルオキシエチル（４－ベンゾイルベンジル）ジメチルアンモニウムブロマイド、（メタ）アクリロイルオキシエチルベンジルジメチルアンモニウムクロライド、（メタ）アクリロイルオキシエチルベンジルジエチルアンモニウムクロライド等が挙げられる。
　第３級アミノ基を有するエチレン性不飽和化合物及び第４級アンモニウム塩基を有するエチレン性不飽和化合物については、国際公開第２０１８／２３０４８６号の段落０１５０～０１７０に記載されたものも挙げられ、この内容は本明細書に組み込まれる。
　その他のエチレン性不飽和化合物としては、アルキル（メタ）アクリレートが挙げられ、炭素数１～１０のアルキル基を有するアルキル（メタ）アクリレートが好ましく、炭素数１～５のアルキル基を有するアルキル（メタ）アクリレートがより好ましい。具体的には、その他のエチレン性不飽和化合物としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート等が挙げられる。 Examples of the ethylenically unsaturated compound having a tertiary amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and dimethylaminopropyl (meth). ) Acrylamide and the like.
Examples of the ethylenically unsaturated compound having a quaternary ammonium base include (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, and (meth) acryloyloxy. Ethyl (4-benzoylbenzyl) dimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride and the like can be mentioned.
Examples of the ethylenically unsaturated compound having a tertiary amino group and the ethylenically unsaturated compound having a quaternary ammonium base include those described in Paragraphs 0150 to 0170 of International Publication No. 2018/230486. The content is incorporated herein by reference.
Examples of other ethylenically unsaturated compounds include alkyl (meth) acrylates, preferably alkyl (meth) acrylates having an alkyl group having 1 to 10 carbon atoms, and alkyl (meth) acrylate having an alkyl group having 1 to 5 carbon atoms. ) Acrylate is more preferred. Specifically, other ethylenically unsaturated compounds include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. Examples thereof include (meth) acrylate and tert-butyl (meth) acrylate.
　第３級アミノ基を側鎖に有する樹脂の具体例としては、下記の化合物が挙げられる。下記の化合物において、主鎖の各構成単位に付記した数値はモル比である。 Specific examples of the resin having a tertiary amino group in the side chain include the following compounds. In the following compounds, the numerical value added to each structural unit of the main chain is the molar ratio.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
［主鎖に窒素原子を含む樹脂］
　主鎖に窒素原子を含む樹脂（以下、オリゴイミン系樹脂ともいう）は、ポリ（低級アルキレンイミン）系の構成単位を含むことが好ましい。
　ここで、本開示における低級アルキレンイミンとは、炭素数１～５のアルキレンイミンを表す。
　オリゴイミン系樹脂としては、近赤外線吸収顔料の分散性向上の観点から、ポリ（低級アルキレンイミン）系の構成単位であって、窒素原子に結合したｐＫａ１４以下の官能基を含む側鎖Ｘを有する構成単位と、原子数４０～１０，０００のオリゴマー鎖又はポリマー鎖を含む側鎖Ｙを有する構成単位と、を有する樹脂であることが好ましい。
　また、オリゴイミン系樹脂としては、第１級アミノ基又はその塩、第２級アミノ基又はその塩、第３級アミノ基又はその塩、第４級アンモニウム塩基からなる群より選択される少なくとも１種を含むことが好ましい。 [Resin containing nitrogen atom in main chain]
The resin containing a nitrogen atom in the main chain (hereinafter, also referred to as oligoimine-based resin) preferably contains a poly (lower alkyleneimine) -based constituent unit.
Here, the lower alkyleneimine in the present disclosure represents an alkyleneimine having 1 to 5 carbon atoms.
The oligoimine-based resin is a poly (lower alkyleneimine) -based constituent unit from the viewpoint of improving the dispersibility of the near-infrared absorbing pigment, and has a side chain X containing a functional group of pKa14 or less bonded to a nitrogen atom. A resin having a unit and a structural unit having a side chain Y containing an oligomer chain or a polymer chain having 40 to 10,000 atoms is preferable.
The oligoimine-based resin is at least one selected from the group consisting of a primary amino group or a salt thereof, a secondary amino group or a salt thereof, a tertiary amino group or a salt thereof, and a quaternary ammonium base. Is preferably included.
　オリゴイミン系樹脂としては、式（ＯＩ－１）で表される構成単位と式（ＯＩ－２）で表される構成単位とを有する樹脂であることが好ましい。 The oligoimine-based resin is preferably a resin having a structural unit represented by the formula (OI-1) and a structural unit represented by the formula (OI-2).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　式（ＯＩ－１）及び（ＯＩ－２）中、Ｒ１及びＲ２は、各々独立に、水素原子、ハロゲン原子、又はアルキル基を表し、ａは、各々独立に、１～５の整数を表し、＊は構成単位間の連結部を表し、ＸはｐＫａ１４以下の官能基を含む側鎖を表し、Ｙは原子数４０～１０，０００のオリゴマー鎖又はポリマー鎖を含む側鎖を表す。 In formulas (OI-1) and (OI-2), R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and a independently represents an integer of 1 to 5, respectively. Represented, * represents a connecting portion between structural units, X represents a side chain containing a functional group of pKa14 or less, and Y represents a side chain containing an oligomer chain or a polymer chain having 40 to 10,000 atoms.
　Ｘで表される側鎖に含まれるｐＫａ１４以下の官能基としては、以下のものが挙げられる。
　なお、本開示における「ｐＫａ」とは、化学便覧（II）（改訂４版、１９９３年、日本化学会編、丸善株式会社）に記載されている定義のものである。
　「ｐＫａ１４以下の官能基」は、その構造は特に限定されず、公知の官能基でｐＫａが１４以下を満たすものが挙げられるが、特にｐＫａが１２以下である官能基がより好ましく、ｐＫａが１１以下である官能基が更に好ましい。具体的には、例えば、カルボン酸基（ｐＫａ３～５程度）、スルホン酸基（ｐＫａ－３～－２程度）、－ＣＯＣＨ２ＣＯ－（ｐＫａ８～１０程度）、－ＣＯＣＨ２ＣＮ（ｐＫａ８～１１程度）、－ＣＯＮＨＣＯ－、フェノール性水酸基、－ＲＦＣＨ２ＯＨ、又は－（ＲＦ）２ＣＨＯＨ（ここで、ＲＦはペルフルオロアルキル基を表す。ｐＫａ９～１１程度）、スルホンアミド基（ｐＫａ９～１１程度）等が挙げられ、特に、カルボン酸基、スルホン酸基、又は－ＣＯＣＨ２ＣＯ－が好ましい。 Examples of the functional group having a pKa14 or less contained in the side chain represented by X include the following.
The term "pKa" in the present disclosure is defined in the Chemical Handbook (II) (Revised 4th Edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
The structure of the "functional group having a pKa of 14 or less" is not particularly limited, and examples thereof include known functional groups having a pKa of 14 or less, but a functional group having a pKa of 12 or less is more preferable, and a pKa is 11 or less. The following functional groups are more preferred. Specifically, for example, a carboxylic acid group (about pKa3 to 5), a sulfonic acid group (about pKa-3 to -2), -COCH 2 CO- (about pKa8 to 10), -COCH 2 CN (pKa8 to 11). degree), - CONHCO-, phenolic hydroxyl, -R F CH 2 OH, or - (R F) 2 CHOH (wherein, R F is .PKa9 ~ about 11 represents a perfluoroalkyl group), a sulfonamido group (PKa9 ~ 11) and the like, and in particular, a carboxylic acid group, a sulfonic acid group, or -COCH 2 CO- is preferable.
　オリゴイミン系樹脂は、式（ＯＩ－１）で表される構成単位及び式（ＯＩ－２）で表される構成単位の他に、更に、式（ＯＩ－３）で表される構成単位を有することが好ましい。 The oligoimine-based resin has a structural unit represented by the formula (OI-1) and a structural unit represented by the formula (OI-2), and further has a structural unit represented by the formula (OI-3). Is preferable.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式（ＯＩ－３）中、＊、Ｒ１、Ｒ２、及びａは一般式（ＯＩ－１）と同義である。Ｙ’はアニオン基を有する原子数４０～１０，０００のオリゴマー鎖又はポリマー鎖を含む側鎖を表す。 In the formula (OI-3), *, R 1 , R 2 , and a are synonymous with the general formula (OI-1). Y'represents a side chain containing an oligomer chain or polymer chain having an anionic group and having 40 to 10,000 atoms.
　ここで、式（ＯＩ－３）で表される構成単位は、主鎖部に一級又は二級アミノ基を有する構成単位を有する樹脂に、アミンと反応して塩を形成する基を有するオリゴマー又はポリマーを添加して反応させることで形成することが可能である。 Here, the structural unit represented by the formula (OI-3) is an oligomer having a group having a group that reacts with an amine to form a salt in a resin having a structural unit having a primary or secondary amino group in the main chain portion. It can be formed by adding a polymer and reacting.
　式（ＯＩ－１）、式（ＯＩ－２）、及び式（ＯＩ－３）において、原料入手の観点から、Ｒ１及びＲ２は水素原子であることが好ましく、ａは２であることが好ましい。 In the formula (OI-1), the formula (OI-2), and the formula (OI-3), R 1 and R 2 are preferably hydrogen atoms, and a is 2. preferable.
　オリゴイミン系樹脂は、式（ＯＩ－１）、式（ＯＩ－２）、及び式（ＯＩ－３）で表される構成単位以外に、ポリ（低級アルキレンイミン）を構成単位として含んでいてもよい。前述と同様に、低級アルキレンイミンとは、炭素数１～５のアルキレンイミンを表す。
　なお、ポリ（低級アルキレンイミン）における窒素原子には、更に、前記Ｘ、Ｙ、又はＹ’で表される側鎖のうち１種以上が結合していてもよい。 The oligoimine-based resin may contain poly (lower alkyleneimine) as a constituent unit in addition to the constituent units represented by the formulas (OI-1), formula (OI-2), and formula (OI-3). .. Similar to the above, the lower alkyleneimine represents an alkyleneimine having 1 to 5 carbon atoms.
In addition, one or more of the side chains represented by X, Y, or Y'may be further bonded to the nitrogen atom in poly (lower alkyleneimine).
　オリゴイミン系樹脂については、特開２０１２－２５５１２８号公報の段落０１０２～０１６６の記載を参酌でき、この内容は本明細書に組み込まれる。 Regarding the oligoimine-based resin, the description in paragraphs 0102 to 0166 of JP2012-255128A can be referred to, and this content is incorporated in the present specification.
　主鎖に窒素原子を含む樹脂（オリゴイミン系樹脂）の具体例としては、下記の３つの化合物が挙げられる。下記化合物において、主鎖の各構成単位に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。 Specific examples of the resin (oligoimine-based resin) containing a nitrogen atom in the main chain include the following three compounds. In the following compounds, the numerical value added to each structural unit of the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　本開示において、塩基性基を有する樹脂は、１種単独で使用してもよいし、２種以上を併用してもよい。 In the present disclosure, the resin having a basic group may be used alone or in combination of two or more.
　本開示に係る組成物における塩基性基を有する樹脂の含有量は、近赤外線吸収顔料の種類及び含有量に応じて適宜設定すればよい。
　例えば、塩基性基を有する樹脂の含有量は、近赤外線吸収顔料の総量（好ましくは、近赤外線吸収顔料と近赤外線吸収顔料以外の顔料との総量）に対して、１５質量％～９０質量％であることが好ましく、２５質量％～７０質量％であることがより好ましく、３０質量％～５０質量％であることが更に好ましい。 The content of the resin having a basic group in the composition according to the present disclosure may be appropriately set according to the type and content of the near-infrared absorbing pigment.
For example, the content of the resin having a basic group is 15% by mass to 90% by mass with respect to the total amount of the near-infrared absorbing pigment (preferably the total amount of the near-infrared absorbing pigment and the pigment other than the near-infrared absorbing pigment). It is preferably 25% by mass to 70% by mass, more preferably 30% by mass to 50% by mass.
（スズの含有量）
　本開示に係る組成物は、使用する塩基性基を有する樹脂の種類によっては、塩基性基を有する樹脂の合成時に使用されるスズ（Ｓｎ）が含まれることがある。
　そこで、本開示に係る組成物におけるスズ（Ｓｎ）の含有量は、例えば、組成物の全固形分に対して、１ｐｐｍ～１５ｐｐｍが好ましい。
　本開示において、「ｐｐｍ」、後述する「ｐｐｂ」及び「ｐｐｔ」は、いずれも、質量基準である。
　上記のスズの含有量を満たすために用いられる塩基性基を有する樹脂としては、例えば、主鎖に窒素原子を含む樹脂が挙げられる。 (Tin content)
The composition according to the present disclosure may contain tin (Sn) used in the synthesis of the resin having a basic group, depending on the type of the resin having a basic group used.
Therefore, the content of tin (Sn) in the composition according to the present disclosure is preferably, for example, 1 ppm to 15 ppm with respect to the total solid content of the composition.
In the present disclosure, "ppm", "ppb" and "ppt" described later are all based on mass.
Examples of the resin having a basic group used to satisfy the above-mentioned tin content include a resin containing a nitrogen atom in the main chain.
　本開示に係る組成物におけるスズの含有量は、以下の方法にて測定される。
　スズの含有量は、公知の方法に従い、ガスクロマトグラフィーにて検量線を作成の上、測定する。 The tin content in the composition according to the present disclosure is measured by the following method.
The tin content is measured by preparing a calibration curve by gas chromatography according to a known method.
［その他の成分］
　本開示に係る組成物は、膜が得られる組成物であることが好ましく、最終的に硬化することにより硬化膜が得られる硬化性組成物であることが好ましい。
　また、本開示に係る組成物は、特定の酸価を有する特定バインダー樹脂を含むことから、例えば、パターン露光により硬化膜のパターンを形成し、未露光部を現像除去することができる硬化性組成物であることが好ましい。すなわち、本開示に係る組成物はネガ型の硬化性組成物であることが好ましい。
　本開示に係る組成物がネガ型の硬化性組成物の場合、既述の、近赤外線吸収顔料、特定バインダー樹脂、及び塩基性基を有する樹脂以外に、更に、重合開始剤及び重合性化合物を含む態様が好ましい。
　また、本開示に係る組成物は、本開示に係る組成物の効果を損なわない範囲において、既述の塩基性基を有する樹脂以外の分散剤、及び、近赤外線吸収顔料以外の顔料を含んでいてもよい。 [Other ingredients]
The composition according to the present disclosure is preferably a composition from which a film can be obtained, and preferably a curable composition from which a cured film can be finally obtained by curing.
Further, since the composition according to the present disclosure contains a specific binder resin having a specific acid value, for example, a curable composition capable of forming a pattern of a cured film by pattern exposure and developing and removing an unexposed portion. It is preferably a thing. That is, the composition according to the present disclosure is preferably a negative type curable composition.
When the composition according to the present disclosure is a negative type curable composition, in addition to the above-mentioned near-infrared absorbing pigment, specific binder resin, and resin having a basic group, a polymerization initiator and a polymerizable compound are further added. The including aspect is preferable.
In addition, the composition according to the present disclosure contains a dispersant other than the resin having the above-mentioned basic group and a pigment other than the near-infrared absorbing pigment as long as the effect of the composition according to the present disclosure is not impaired. You may.
［硬化性組成物］
　本開示に係る組成物は、近赤外線吸収顔料、特定バインダー樹脂、及び塩基性基を有する樹脂に加え、更に、重合性化合物及び重合開始剤を含む、所謂、硬化性組成物であることが好ましい。
　上記の硬化性組成物は本開示に係る組成物を含むことから、硬化性組成物から形成された膜中においても、近赤外線吸収顔料の分散が高い状態を保つことができる。その結果、上記の硬化性組成物によれば、形成された膜の一部を現像除去する際に、近赤外線吸収顔料の凝集に由来する残渣が生じにくく、現像残渣が低減される。
　以下、本開示に係る組成物がネガ型の硬化性組成物である場合について詳細に記載する。 [Curable composition]
The composition according to the present disclosure is preferably a so-called curable composition containing a near-infrared absorbing pigment, a specific binder resin, and a resin having a basic group, as well as a polymerizable compound and a polymerization initiator. ..
Since the above-mentioned curable composition contains the composition according to the present disclosure, it is possible to maintain a high dispersion of the near-infrared absorbing pigment even in the film formed from the curable composition. As a result, according to the above-mentioned curable composition, when a part of the formed film is developed and removed, a residue due to aggregation of the near-infrared absorbing pigment is less likely to be generated, and the development residue is reduced.
Hereinafter, the case where the composition according to the present disclosure is a negative type curable composition will be described in detail.
　本開示における硬化性組成物での近赤外線吸収顔料の含有量は、硬化性組成物の全固形分に対して、１質量％～３０質量％であることが好ましく、５質量％～３０質量％であることがより好ましく、５質量％～２０質量％であることが更に好ましい。
　近赤外線吸収顔料の含有量が上記範囲内であると、近赤外線吸収顔料による機能が十分に発現する。 The content of the near-infrared absorbing pigment in the curable composition in the present disclosure is preferably 1% by mass to 30% by mass, and 5% by mass to 30% by mass, based on the total solid content of the curable composition. Is more preferable, and 5% by mass to 20% by mass is further preferable.
When the content of the near-infrared absorbing pigment is within the above range, the function of the near-infrared absorbing pigment is sufficiently exhibited.
　本開示における硬化性組成物での特定バインダー樹脂の含有量は、硬化性組成物の全固形分に対して、１０質量％～５０質量％であることが好ましく、１０質量％～４０質量％であることがより好ましく、１５質量％～３５質量％であることが更に好ましい。
　特定バインダー樹脂の含有量が上記範囲内であると、優れた膜形成性が得られる。 The content of the specific binder resin in the curable composition in the present disclosure is preferably 10% by mass to 50% by mass, preferably 10% by mass to 40% by mass, based on the total solid content of the curable composition. It is more preferable, and it is further preferable that it is 15% by mass to 35% by mass.
When the content of the specific binder resin is within the above range, excellent film forming property can be obtained.
　本開示における硬化性組成物での塩基性基を有する樹脂の含有量は、硬化性組成物の全固形分に対して、０．５質量％～２０質量％であることが好ましく、１質量％～２０質量％であることがより好ましく、５質量％～１５質量％であることが更に好ましい。
　塩基性基を有する樹脂の含有量が上記範囲内であると、保存安定性が高まる。 The content of the resin having a basic group in the curable composition in the present disclosure is preferably 0.5% by mass to 20% by mass, and 1% by mass, based on the total solid content of the curable composition. It is more preferably about 20% by mass, and even more preferably 5% by mass to 15% by mass.
When the content of the resin having a basic group is within the above range, the storage stability is enhanced.
［重合性化合物］
　本開示における硬化性組成物は、重合性化合物を含むことが好ましい。
　重合性化合物としては、エチレン性不飽和化合物であることがより好ましく、末端エチレン性不飽和基を有する化合物であることが特に好ましい。
　このような化合物群としては、公知のものを特に限定なく用いることができる。
　重合性化合物は、例えば、モノマー、プレポリマー、即ち、２量体、３量体、及びオリゴマー、又はそれらの混合物、並びに、それらの共重合体などの化学的形態をもつ。 [Polymerizable compound]
The curable composition in the present disclosure preferably contains a polymerizable compound.
The polymerizable compound is more preferably an ethylenically unsaturated compound, and particularly preferably a compound having a terminal ethylenically unsaturated group.
As such a group of compounds, known compounds can be used without particular limitation.
The polymerizable compound has a chemical form such as, for example, a monomer, a prepolymer, that is, a dimer, a trimer, and an oligomer, or a mixture thereof, and a copolymer thereof.
　重合性化合物の例としては、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など）、そのエステル類、及びそのアミド類が挙げられ、好ましくは、不飽和カルボン酸と脂肪族多価アルコール化合物とのエステル類、不飽和カルボン酸と脂肪族多価アミン化合物とのアミド類が用いられる。
　重合性化合物の例としては、ヒドロキシ基、アミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸のエステル類或いはアミド類と単官能若しくは多官能イソシアネート類或いはエポキシ類との付加反応物、及び、ヒドロキシ基、アミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸のエステル類或いはアミド類と単官能若しくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。
　また、重合性化合物の例としては、イソシアネート基、エポキシ基等の親電子性置換基を有する不飽和カルボン酸のエステル類或いはアミド類と単官能若しくは多官能の、アルコール類、アミン類、チオール類との付加反応物、更に、ハロゲン原子、トシルオキシ基等の脱離性置換基を有する不飽和カルボン酸のエステル類或いはアミド類と単官能若しくは多官能の、アルコール類、アミン類、チオール類との置換反応物も好適である。
　また、重合性化合物の更に別の例としては、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン、ビニルエーテル等に置き換えた化合物群が挙げられる。 Examples of the polymerizable compound include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides thereof, and preferred examples thereof. Esters of unsaturated carboxylic acid and aliphatic polyhydric alcohol compound, and amides of unsaturated carboxylic acid and aliphatic polyvalent amine compound are used.
Examples of polymerizable compounds include addition reactions of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxy groups, amino groups, and mercapto groups with monofunctional or polyfunctional isocyanates or epoxys. Also suitable are esters of unsaturated carboxylic acids having nucleophilic substituents such as hydroxy group, amino group and mercapto group, or dehydration condensation reaction products of amides and monofunctional or polyfunctional carboxylic acids. used.
Examples of polymerizable compounds include esters of unsaturated carboxylic acids having polyelectron substituents such as isocyanate groups and epoxy groups, or amides and monofunctional or polyfunctional alcohols, amines and thiols. Addition reactants with, further, esters or amides of unsaturated carboxylic acids having a releasable substituent such as a halogen atom or a tosyloxy group, and monofunctional or polyfunctional alcohols, amines, thiols. Substitution reactants are also suitable.
Further, as another example of the polymerizable compound, there is a group of compounds in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, styrene, vinyl ether or the like.
　脂肪族多価アルコール化合物と不飽和カルボン酸とのエステルのモノマーの具体例としては、アクリル酸エステルとして、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、１，３－ブタンジオールジアクリレート、テトラメチレングリコールジアクリレート、プロピレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリメチロールエタントリアクリレート、ヘキサンジオールジアクリレート、１，４－シクロヘキサンジオールジアクリレート、テトラエチレングリコールジアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールジアクリレート、ジペンタエリスリトールヘキサアクリレート、ソルビトールトリアクリレート、ソルビトールテトラアクリレート、ソルビトールペンタアクリレート、ソルビトールヘキサアクリレート、トリ（アクリロイルオキシエチル）イソシアヌレート、ポリエステルアクリレートオリゴマー、イソシアヌル酸ＥＯ変性トリアクリレート等がある。 Specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol as acrylic acid esters. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropanetri (acryloyloxypropyl) ether, trimethylol ethanetriacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, There are tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO modified triacrylate and the like.
　脂肪族多価アルコール化合物と不飽和カルボン酸とのエステルのモノマーの具体例としては、メタクリル酸エステルとしては、テトラメチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリメタクリレート、トリメチロールエタントリメタクリレート、エチレングリコールジメタクリレート、１，３－ブタンジオールジメタクリレート、ヘキサンジオールジメタクリレート、ペンタエリスリトールジメタクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールジメタクリレート、ジペンタエリスリトールヘキサメタクリレート、ソルビトールトリメタクリレート、ソルビトールテトラメタクリレート、ビス〔ｐ－（３－メタクリルオキシ－２－ヒドロキシプロポキシ）フェニル〕ジメチルメタン、ビス－〔ｐ－（メタクリルオキシエトキシ）フェニル〕ジメチルメタン等がある。 Specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethyl propantri as methacrylic acid esters. Methacrylate, Trimethylol Etantrimethacrylate, Ethylene Glycol Dimethacrylate, 1,3-Butanediol Dimethacrylate, Hexadiol Dimethacrylate, Pentaerythritol Dimethacrylate, Pentaerythritol Trimethacrylate, Pentaerythritol Tetramethacrylate, Dipentaerythritol Dimethacrylate, Dipenta There are erythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (methacrylicoxyethoxy) phenyl] dimethylmethane and the like.
　また、重合性化合物としては、イソシアネート基とヒドロキシ基の付加反応を用いて製造されるウレタン系付加重合性化合物も好適であり、そのような具体例としては、例えば、特公昭４８－４１７０８号公報中に記載されている１分子に２個以上のイソシアネート基を有するポリイソシアネート化合物に、下記一般式（Ｉ）で示されるヒドロキシ基を含有するビニルモノマーを付加させた１分子中に２個以上の重合性ビニル基を含有するビニルウレタン化合物等が挙げられる。 Further, as the polymerizable compound, a urethane-based addition polymerizable compound produced by using an addition reaction of an isocyanate group and a hydroxy group is also suitable, and specific examples thereof include, for example, Japanese Patent Application Laid-Open No. 48-41708. Two or more of the polyisocyanate compounds having two or more isocyanate groups in one molecule described therein are added with a vinyl monomer containing a hydroxy group represented by the following general formula (I). Examples thereof include vinyl urethane compounds containing a polymerizable vinyl group.
　ＣＨ２＝Ｃ（Ｒ）ＣＯＯＣＨ２ＣＨ（Ｒ’）ＯＨ　　（Ｉ）
（ただし、Ｒ及びＲ’は、Ｈ又はＣＨ３を示す。） CH 2 = C (R) COOCH 2 CH (R') OH (I)
(However, R and R'indicate H or CH 3. )
　また、特開昭５１－３７１９３号、特公平２－３２２９３号、特公平２－１６７６５号に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号、特公昭５６－１７６５４号、特公昭６２－３９４１７号、特公昭６２－３９４１８号記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。更に、特開昭６３－２７７６５３号、特開昭６３－２６０９０９号、特開平１－１０５２３８号に記載される、分子内にアミノ構造やスルフィド構造を有する付加重合性化合物類を用いることによっては、非常に感光スピードに優れた組成物を得ることができる。 In addition, urethane acrylates as described in JP-A No. 51-37193, Tokusho 2-32933, Tokuhei 2-16765, Tokukou Sho 58-49860, Tokukou Sho 56-17654, Tokukou Urethane compounds having an ethylene oxide-based skeleton described in Kosho 62-39417 and Tokusho 62-39418 are also suitable. Further, by using the addition polymerizable compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, A composition having a very high photosensitive speed can be obtained.
　その他、重合性化合物としては、例えば、特開２００７－２７７５１４号公報の段落０１７８～０１９０に記載の化合物が挙げられる。
　また、重合性化合物としては、特開２０１５－１８７２１１号公報に記載のエポキシ化合物を用いてもよい In addition, examples of the polymerizable compound include the compounds described in paragraphs 0178 to 0190 of JP-A-2007-277514.
Further, as the polymerizable compound, the epoxy compound described in JP-A-2015-187211 may be used.
　本開示における硬化性組成物では、重合性化合物は、１種単独で使用してもよいし、２種以上を併用してもよい。 In the curable composition in the present disclosure, the polymerizable compound may be used alone or in combination of two or more.
　本開示における硬化性組成物での重合性化合物の含有量としては、硬化性組成物の全固形分に対して、１質量％～９０質量％であることが好ましく、５質量％～８０質量％であることがより好ましく、１０質量％～７０質量％であることが更に好ましい。重合性化合物の含有量が上記範囲内であると、硬化性組成物の硬化性に優れる。 The content of the polymerizable compound in the curable composition in the present disclosure is preferably 1% by mass to 90% by mass, and 5% by mass to 80% by mass, based on the total solid content of the curable composition. Is more preferable, and 10% by mass to 70% by mass is further preferable. When the content of the polymerizable compound is within the above range, the curable composition is excellent in curability.
［重合開始剤］
　本開示における硬化性組成物は、重合開始剤を含むことが好ましい。
　重合開始剤としては、特に、光重合開始剤であることが好ましい。
　光重合開始剤としては、重合性化合物の重合を開始する能力を有する限り、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する化合物が好ましい。また、光重合開始剤は、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する化合物であってもよい。中でも、光重合開始剤は光ラジカル重合開始剤であることが特に好ましい。 [Polymerization initiator]
The curable composition in the present disclosure preferably contains a polymerization initiator.
The polymerization initiator is particularly preferably a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, the photopolymerization initiator may be a compound that produces an active radical by causing some action with the photoexcited sensitizer. Above all, the photopolymerization initiator is particularly preferably a photoradical polymerization initiator.
　光重合開始剤としては、例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物など）、アシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、α－ヒドロキシケトン化合物、α－アミノケトン化合物などが挙げられる。光重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン－ベンゼン－鉄錯体、ハロメチルオキサジアゾール化合物及び３－アリール置換クマリン化合物が好ましく、オキシム化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、及び、アシルホスフィン化合物から選ばれる化合物がより好ましく、オキシム化合物が更に好ましい。光重合開始剤については、特開２０１４－１３０１７３号公報の段落００６５～０１１１、特開２０１３－２９７６０号公報の段落０２７４～０３０６の記載を参酌でき、これらの内容は本開示に組み込まれる。 Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, and the like. Examples thereof include thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds and α-aminoketone compounds. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole. Dimer, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxaziazole compounds and 3-aryl substituted coumarin compounds are preferred, oxime compounds, α-hydroxyketone compounds, α- A compound selected from an aminoketone compound and an acylphosphine compound is more preferable, and an oxime compound is further preferable. Regarding the photopolymerization initiator, the descriptions in paragraphs 0065 to 0111 of JP-A-2014-130173 and paragraphs 0274 to 0306 of JP-A-2013-29760 can be referred to, and these contents are incorporated in the present disclosure.
　α－ヒドロキシケトン化合物の市販品としては、ＢＡＳＦ社製の、ＤＡＲＯＣＵＲ　１１７３、ＩＲＧＡＣＵＲＥ　５００、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社の、Ｏｍｎｉｒａｄ　１８４（旧ＩＲＧＡＣＵＲＥ　１８４）、Ｏｍｎｉｒａｄ　２９５９（旧ＩＲＧＡＣＵＲＥ　２９５９）、Ｏｍｎｉｒａｄ　１２７（旧ＩＲＧＡＣＵＲＥ－１２７）などが挙げられる。
　α－アミノケトン化合物の市販品としては、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社の、Ｏｍｎｉｒａｄ　９０７（旧ＩＲＧＡＣＵＲＥ－９０７）、Ｏｍｎｉｒａｄ　３６９（旧ＩＲＧＡＣＵＲＥ　３６９）、Ｏｍｎｉｒａｄ　３７９（旧ＩＲＧＡＣＵＲＥ　３７９）、及び、Ｏｍｎｉｒａｄ　３７９（旧ＩＲＧＡＣＵＲＥ－３７９ＥＧ）などが挙げられる。
　アシルホスフィン化合物の市販品としては、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社の、Ｏｍｎｉｒａｄ　８１９（旧ＩＲＧＡＣＵＲＥ　８１９）、ＢＡＳＦ社製の、Ｏｍｎｉｒａｄ　ＴＰＯ　Ｈ（旧ＩＲＧＡＣＵＲＥ　ＴＰＯ）などが挙げられる。 Commercially available α-hydroxyketone compounds include DAROCUR 1173, IRGACURE 500, and IGM Resins B. manufactured by BASF. V. Examples include Omnirad 184 (formerly IRGACURE 184), Omnirad 2959 (formerly IRGACURE 2959), and Omnirad 127 (formerly IRGACURE-127).
As a commercial product of the α-aminoketone compound, IGM Resins B.I. V. Examples thereof include Omnirad 907 (former IRGACURE-907), Omnirad 369 (former IRGACURE 369), Omnirad 379 (former IRGACURE 379), and Omnirad 379 (former IRGACURE-379EG).
As a commercially available product of the acylphosphine compound, IGM Resins B.I. V. Examples include Omnirad 819 (formerly IRGACURE 819) manufactured by BASF and Omnirad TPO H (formerly IRGACURE TPO) manufactured by BASF.
　オキシム化合物としては、例えば、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１６５３－１６６０）に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１５６－１６２）に記載の化合物、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年、ｐｐ．２０２－２３２）に記載の化合物、特開２０００－６６３８５号公報に記載の化合物、特開２０００－８００６８号公報に記載の化合物、特表２００４－５３４７９７号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、特開２０１７－１９７６６号公報に記載の化合物、特許第６０６５５９６号公報に記載の化合物、国際公開第２０１５／１５２１５３号に記載の化合物、国際公開第２０１７／０５１６８０号に記載の化合物などがあげられる。オキシム化合物の具体例としては、例えば、３－ベンゾイルオキシイミノブタン－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－ベンゾイルオキシイミノ－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－オンなどが挙げられる。
　オキシム化合物の市販品としては、ＢＡＳＦ社製の、ＩＲＧＡＣＵＲＥ　ＯＸＥ０１、ＩＲＧＡＣＵＲＥ　ＯＸＥ０２、ＩＲＧＡＣＵＲＥ　ＯＸＥ０３、ＩＲＧＡＣＵＲＥ　ＯＸＥ０４も好適に用いられる。
　また、オキシム化合物の市販品としては、常州強力電子新材料有限公司（ＣＨＡＮＧＺＨＯＵ　ＴＲＯＮＬＹ　ＮＥＷ　ＥＬＥＣＴＲＯＮＩＣ　ＭＡＴＥＲＩＡＬＳ　ＣＯ．，ＬＴＤ）製の、ＴＲＯＮＬＹ　ＴＲ－ＰＢＧ－３０４、ＴＲＯＮＬＹ　ＴＲ－ＰＢＧ－３０９、ＴＲＯＮＬＹ　ＴＲ－ＰＢＧ－３０５、（株）ＡＤＥＫＡ製の、アデカアークルズＮＣＩ－９３０、アデカオプトマーＮ－１９１９（特開２０１２－１４０５２号公報の光重合開始剤２に該当）が挙げられる。 Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, and the compounds described in JP-A-2006-342166. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Phototherapy Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-66385, the compound described in JP-A-2000-66385. Compounds described in JP-A-2000-80068, compounds described in JP-A-2004-534977, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-197666, Patent No. Examples thereof include the compound described in Japanese Patent Application Laid-Open No. 6065596, the compound described in International Publication No. 2015/152153, and the compound described in International Publication No. 2017/051680. Specific examples of the oxime compound include, for example, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminovtan-2-one, and 2-acetoxyimiminopentane-3-3. On, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxy Examples thereof include carbonyloxyimino-1-phenylpropane-1-one.
As commercially available products of the oxime compound, IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE03, and IRGACURE OXE04 manufactured by BASF are also preferably used.
Commercially available oxime compounds include TRONLY TR-PBG-304, TRONLY TR-PBG-309, and TRONLY TR-PBG-manufactured by Changshu Powerful Electronics New Materials Co., Ltd. 305, ADEKA Arkuru's NCI-930 and ADEKA PUTMER N-1919 (corresponding to Photopolymerization Initiator 2 of JP2012-14052A) manufactured by ADEKA Corporation.
　また、上記以外のオキシム化合物として、カルバゾール環の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号明細書に記載の化合物、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第２００９－２９２０３９号明細書に記載の化合物、国際公開第２００９／１３１１８９号明細書に記載のケトオキシム化合物、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第７５５６９１０号明細書に記載の化合物、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号公報に記載の化合物などを用いてもよい。 Further, as an oxime compound other than the above, the compound described in JP-A-2009-5199004, in which an oxime is linked to the N-position of the carbazole ring, and a US Pat. No. 6,626,957 in which a heterosubstituted group is introduced at the benzophenone moiety are described. , Compounds described in JP-A-2010-15025 and US Patent Publication No. 2009-292039, and ketooxime compounds described in International Publication No. 2009/131189, in which a nitro group is introduced into a dye moiety. Japanese Patent Application Laid-Open No. 2009-221114, which contains a triazine skeleton and an oxime skeleton in the same molecule, and has an absorption maximum at 405 nm and good sensitivity to a g-ray light source. The compound described in 1 and the like may be used.
　光重合開始剤としては、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開２０１４－１３７４６６号公報に記載の化合物が挙げられ、この内容は本開示に組み込まれる。 As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466, the contents of which are incorporated in the present disclosure.
　光重合開始剤としては、ベンゾフラン骨格を有するオキシム化合物を用いることもできる。ベンゾフラン骨格を有するオキシム化合物の具体例としては、国際公開第２０１５／０３６９１０号に記載の化合物ＯＥ－０１～ＯＥ－７５が挙げられる。 As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples of the oxime compound having a benzofuran skeleton include compounds OE-01 to OE-75 described in International Publication No. 2015/036910.
　光重合開始剤としては、カルバゾール環の少なくとも１つのベンゼン環がナフタレン環となった骨格を有するオキシム化合物を用いることもできる。このオキシム化合物の具体例としては、国際公開第２０１３／０８３５０５号に記載の化合物が挙げられる。 As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of this oxime compound include the compounds described in International Publication No. 2013/083505.
　光重合開始剤としては、フッ素原子を有するオキシム化合物を用いることもできる。フッ素原子を有するオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載の化合物、特表２０１４－５００８５２号公報に記載の化合物２４、３６～４０、特開２０１３－１６４４７１号公報に記載の化合物（Ｃ－３）などが挙げられ、この内容は本開示に組み込まれる。 As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like, the contents of which are incorporated in the present disclosure.
　光重合開始剤としては、ニトロ基を有するオキシム化合物を用いることができる。ニトロ基を有するオキシム化合物は、二量体とすることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開２０１３－１１４２４９号公報の段落００３１～００４７、特開２０１４－１３７４６６号公報の段落０００８～００１２、００７０～００７９に記載の化合物、特許第４２２３０７１号公報の段落０００７～００２５に記載の化合物、アデカアークルズＮＣＩ－８３１（（株）ＡＤＥＫＡ製）などが挙げられる。 As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466, and Patent No. 4223071. Examples thereof include the compounds described in paragraphs 0007 to 0025 of the publication, ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation) and the like.
　本開示において好ましく使用されるオキシム化合物の具体例を以下に示すが、本開示はこれらに限定されるものではない。 Specific examples of the oxime compound preferably used in the present disclosure are shown below, but the present disclosure is not limited thereto.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　オキシム化合物は、３５０ｎｍ～５００ｎｍの波長領域に極大吸収波長を有する化合物が好ましく、３６０ｎｍ～４８０ｎｍの波長領域に極大吸収波長を有する化合物がより好ましい。また、オキシム化合物は、波長３６５ｎｍ及び４０５ｎｍの吸光度が大きい化合物が好ましい。 The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm. Further, the oxime compound is preferably a compound having a large absorbance at wavelengths of 365 nm and 405 nm.
　オキシム化合物の波長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であることが特に好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）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 molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, from the viewpoint of sensitivity. It is particularly preferably 000. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
　光重合開始剤としては、２官能或いは３官能以上の光重合開始剤を用いてもよい。そのような光重合開始剤の具体例としては、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号公報の段落０４１７～０４１２、国際公開第２０１７／０３３６８０号の段落００３９～００５５に記載されているオキシム化合物の２量体、特表２０１３－５２２４４５号公報に記載されている化合物（Ｅ）及び化合物（Ｇ）、国際公開第２０１６／０３４９６３号に記載されているＣｍｐｄ１～７などが挙げられる。 As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photopolymerization initiator may be used. Specific examples of such a photopolymerization initiator include paragraphs 0417 to 0412 of JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015/004565, and JP-A-2016-532675. Dimers of oxime compounds described in paragraphs 0039 to 0055 of WO 2017/033680, compounds (E) and compounds (G) described in JP2013-522445, WO 2016 Examples thereof include Cmpd1 to 7 described in No. 034963.
　本開示における硬化性組成物では、重合開始剤は、１種単独で使用してもよいし、２種以上を併用してもよい。 In the curable composition in the present disclosure, the polymerization initiator may be used alone or in combination of two or more.
　本開示における硬化性組成物での重合開始剤の含有量としては、硬化性組成物の全固形分に対して、０．１質量％～５０質量％であることが好ましく、より好ましくは０．５質量％～３０質量％、特に好ましくは１質量％～２０質量％である。
　重合開始剤の含有量が上記の範囲であることで、良好な感度とパターン形成性が得られる。 The content of the polymerization initiator in the curable composition in the present disclosure is preferably 0.1% by mass to 50% by mass, more preferably 0% by mass, based on the total solid content of the curable composition. It is 5% by mass to 30% by mass, particularly preferably 1% by mass to 20% by mass.
When the content of the polymerization initiator is in the above range, good sensitivity and pattern forming property can be obtained.
［その他の成分］
　本開示における硬化性組成物は、既述の成分以外の、その他の成分を含んでいてもよい。
　その他の成分としては、顔料誘導体、重合禁止剤、溶剤、増感剤、共増感剤、その他の添加剤等が挙げられる。 [Other ingredients]
The curable composition in the present disclosure may contain other components other than the components described above.
Examples of other components include pigment derivatives, polymerization inhibitors, solvents, sensitizers, co-sensitizers, and other additives.
（顔料誘導体）
　本開示における硬化性組成物は、顔料誘導体を含むことが好ましい。
　顔料誘導体としては、色素骨格に、酸基、塩基性基、及び水素結合性基よりなる群から選ばれる少なくとも１種の基が結合した化合物が挙げられる。
　酸基としては、スルホ基、カルボキシ基、リン酸基、ボロン酸基、スルホンイミド基、スルホンアミド基及びこれらの塩、並びにこれらの塩の脱塩構造が挙げられる。塩を構成する原子又は原子団としては、アルカリ金属イオン（Ｌｉ＋、Ｎａ＋、Ｋ＋など）、アルカリ土類金属イオン（Ｃａ２＋、Ｍｇ２＋など）、アンモニウムイオン、イミダゾリウムイオン、ピリジニウムイオン、ホスホニウムイオンなどが挙げられる。また、上記塩の脱塩構造としては上記の塩から塩を形成する原子又は原子団が脱離した基が挙げられる。例えば、カルボキシ基の塩の脱塩構造は、カルボキシラート基（－ＣＯＯ－）である。
　塩基性基としては、アミノ基、ピリジニル基、及びこれらの塩、並びにこれらの塩の脱塩構造が挙げられる。塩を構成する原子又は原子団としては、水酸化物イオン、ハロゲンイオン、カルボン酸イオン、スルホン酸イオン、フェノキシドイオンなどが挙げられる。また、上記塩の脱塩構造としては上記の塩から塩を形成する原子又は原子団が脱離した基が挙げられる。
　水素結合性基とは、水素原子を介して相互作用する基のことである。水素結合性基の具体例としては、アミド基、ヒドロキシ基、－ＮＨＣＯＮＨＲ、－ＮＨＣＯＯＲ、－ＯＣＯＮＨＲなどが挙げられる。ここで、Ｒは、アルキル基及びアリール基であることが好ましい。 (Pigment derivative)
The curable composition in the present disclosure preferably contains a pigment derivative.
Examples of the pigment derivative include compounds in which at least one group selected from the group consisting of an acid group, a basic group, and a hydrogen-bonding group is bonded to the pigment skeleton.
Examples of the acid group include a sulfo group, a carboxy group, a phosphoric acid group, a boronic acid group, a sulfonimide group, a sulfonamide group and salts thereof, and a desalted structure of these salts. As the atoms or atomic groups constituting the salt, alkali metal ions (Li + , Na + , K +, etc.), alkaline earth metal ions (Ca 2+ , Mg 2+, etc.), ammonium ions, imidazolium ions, pyridinium ions, etc. Examples include phosphonium ions. In addition, examples of the desalting structure of the salt include groups in which atoms or atomic groups forming a salt are eliminated from the salt. For example, desalting structure of salt of carboxy group, a carboxylate group - is (-COO).
Examples of the basic group include an amino group, a pyridinyl group, and salts thereof, and a desalted structure of these salts. Examples of the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion. In addition, examples of the desalting structure of the salt include groups in which atoms or atomic groups forming a salt are eliminated from the salt.
A hydrogen-bonding group is a group that interacts with a hydrogen atom. Specific examples of the hydrogen-bonding group include an amide group, a hydroxy group, -NHCONHR, -NHCOOR, and -OCONHR. Here, R is preferably an alkyl group and an aryl group.
　顔料誘導体は、スルホ基、カルボキシ基、リン酸基、ボロン酸基、スルホンイミド基、スルホンアミド基、アミノ基、ピリジニル基、これらの塩、又はこれらの脱塩構造から選ばれる少なくとも１種の基を有することが好ましく、スルホ基、カルボキシ基、アミノ基を有することがより好ましい。顔料誘導体がこのような基を有することで、近赤外線吸収顔料の分散性をより向上させることができる。 The pigment derivative is a sulfo group, a carboxy group, a phosphoric acid group, a boronic acid group, a sulfonimide group, a sulfonamide group, an amino group, a pyridinyl group, salts thereof, or at least one group selected from these desalted structures. It is preferable to have a sulfo group, a carboxy group, and an amino group. When the pigment derivative has such a group, the dispersibility of the near-infrared absorbing pigment can be further improved.
　顔料誘導体としては、式（Ｂ１）で表される化合物が挙げられる。 Examples of the pigment derivative include a compound represented by the formula (B1).
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　式（Ｂ１）中、Ｐは色素骨格を表し、Ｌは単結合又は連結基を表し、Ｘは、酸基、塩基性基、又は水素結合性基を表し、ｍは１以上の整数を表し、ｎは１以上の整数を表し、ｍが２以上の場合は複数のＬ及びＸは互いに異なっていてもよく、ｎが２以上の場合は複数のＸは互いに異なっていてもよい。 In formula (B1), P represents a dye skeleton, L represents a single bond or a linking group, X represents an acid group, a basic group, or a hydrogen bonding group, and m represents an integer of 1 or more. n represents an integer of 1 or more, and when m is 2 or more, the plurality of Ls and Xs may be different from each other, and when n is 2 or more, the plurality of Xs may be different from each other.
　上記Ｐで表される色素骨格としては、スクアリリウム色素構造、ピロロピロール色素骨格、ジケトピロロピロール色素骨格、キナクリドン色素骨格、アントラキノン色素骨格、ジアントラキノン色素骨格、ベンゾイソインドール色素骨格、チアジンインジゴ色素骨格、アゾ色素骨格、キノフタロン色素骨格、フタロシアニン色素骨格、ナフタロシアニン色素骨格、ジオキサジン色素骨格、ペリレン色素骨格、ペリノン色素骨格、ベンゾイミダゾロン色素骨格、ベンゾチアゾール色素骨格、ベンゾイミダゾール色素骨格及びベンゾオキサゾール色素骨格から選ばれる少なくとも１種が好ましく、既述の近赤外線吸収剤との親和性の観点から、スクアリリウム色素骨格又はピロロピロール色素骨格が特に好ましい。 The pigment skeleton represented by P is a squarylium pigment skeleton, a pyrolopyrrolop pigment skeleton, a diketopyrrolopyrrole pigment skeleton, a quinacridone pigment skeleton, an anthraquinone pigment skeleton, a dianthraquinone pigment skeleton, a benzoisoindole pigment skeleton, and a thiazine indigo pigment. Skeleton, azo pigment skeleton, quinophthalocyanine pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, dioxazine pigment skeleton, perylene pigment skeleton, perinone pigment skeleton, benzoimidazolone pigment skeleton, benzothiazole pigment skeleton, benzoimidazole pigment skeleton and benzoxazole pigment At least one selected from the skeleton is preferable, and a squarylium pigment skeleton or a pyrolopyrrolop pigment skeleton is particularly preferable from the viewpoint of compatibility with the above-mentioned near-infrared absorber.
　Ｌで表される連結基としては、１～１００個の炭素原子、０～１０個の窒素原子、０～５０個の酸素原子、１～２００個の水素原子、及び０～２０個の硫黄原子から成り立つ基が好ましく、無置換であってもよく、置換基を更に有していてもよい。
　置換基としては、既述の置換基Ｔが挙げられる。 The linking group represented by L includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. A group consisting of is preferable, and it may be unsubstituted or further having a substituent.
Examples of the substituent include the above-mentioned Substituent T.
　Ｘで表される、酸基、塩基性基、及び水素結合性基としては、それぞれ、上述した基が挙げられる。 Examples of the acid group, the basic group, and the hydrogen-bonding group represented by X include the above-mentioned groups.
　顔料誘導体は２５℃のプロピレングリコールメチルエーテルアセテート１００ｇへの溶解量が０．０１ｍｇ～１０ｇであることが好ましい。上限は、７．５ｇ以下であることが好ましく、５ｇ以下であることがより好ましい。下限は、０．０５ｍｇ以上であることが好ましく、０．１ｍｇ以上であることがより好ましい。この態様によれば、本開示に係る組成物中における近赤外線吸収顔料の分散性をより向上させることができる。 The amount of the pigment derivative dissolved in 100 g of propylene glycol methyl ether acetate at 25 ° C. is preferably 0.01 mg to 10 g. The upper limit is preferably 7.5 g or less, and more preferably 5 g or less. The lower limit is preferably 0.05 mg or more, and more preferably 0.1 mg or more. According to this aspect, the dispersibility of the near-infrared absorbing pigment in the composition according to the present disclosure can be further improved.
　顔料誘導体の分子量は１６０～４５００であることが好ましい。顔料誘導体の分子量の上限は４０００以下であることが好ましく、３５００以下であることがより好ましい。顔料誘導体の分子量の下限は２００以上であることが好ましく、２５０以上であることがより好ましい。顔料誘導体の分子量が上記範囲であれば、近赤外線吸収顔料の分散性の向上効果が期待できる。 The molecular weight of the pigment derivative is preferably 160 to 4500. The upper limit of the molecular weight of the pigment derivative is preferably 4000 or less, and more preferably 3500 or less. The lower limit of the molecular weight of the pigment derivative is preferably 200 or more, more preferably 250 or more. When the molecular weight of the pigment derivative is within the above range, the effect of improving the dispersibility of the near-infrared absorbing pigment can be expected.
　顔料誘導体は、波長７００ｎｍ～１，２００ｎｍの範囲に極大吸収波長を化合物であることが好ましく、波長７００ｎｍ～１，１００ｎｍの範囲に極大吸収波長を有する化合物であることが好ましく、波長７００ｎｍ～１，０００ｎｍの範囲に極大吸収波長を有する化合物であることが好ましい。上記波長の範囲に極大吸収波長を有する顔料誘導体は、π平面の広がりが近赤外線吸収顔料と近づけやすくでき、近赤外線吸収顔料への吸着性が向上し、より優れた分散性が得られやすい。 The pigment derivative is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 nm to 1,200 nm, preferably a compound having a maximum absorption wavelength in the wavelength range of 700 nm to 1,100 nm, and has a wavelength of 700 nm to 1, A compound having a maximum absorption wavelength in the range of 000 nm is preferable. A pigment derivative having a maximum absorption wavelength in the above wavelength range can easily have the spread of the π plane close to that of the near-infrared absorbing pigment, improve the adsorptivity to the near-infrared absorbing pigment, and easily obtain more excellent dispersibility.
　また、顔料誘導体は、芳香族環を含む化合物であることも好ましく、２以上の芳香族環が縮合した構造を含む化合物であることもより好ましい。
　更に、顔料誘導体はπ共役平面を有する化合物であることも好ましく、近赤外線吸収顔料に含まれるπ共役平面と同一の構造のπ共役平面を有する化合物であることもより好ましい。ここで、顔料誘導体のπ共役平面に含まれるπ電子の数は８個～１００個であることが好ましい。上限は、９０個以下であることが好ましく、８０個以下であることがより好ましい。下限は１０個以上であることが好ましく、１２個以上であることがより好ましい。 Further, the pigment derivative is preferably a compound containing an aromatic ring, and more preferably a compound containing a structure in which two or more aromatic rings are condensed.
Further, the pigment derivative is preferably a compound having a π-conjugated plane, and more preferably a compound having a π-conjugated plane having the same structure as the π-conjugated plane contained in the near-infrared absorbing pigment. Here, the number of π electrons contained in the π-conjugated plane of the pigment derivative is preferably 8 to 100. The upper limit is preferably 90 or less, and more preferably 80 or less. The lower limit is preferably 10 or more, and more preferably 12 or more.
　顔料誘導体は、下記式（ＳＱ－ａ）で表される部分構造を含むπ共役平面を有するか、又は、下記式（ＣＲ－ａ）で表される部分構造を含むπ共役平面を有する化合物であることも好ましい。下記式（ＳＱ－ａ）及び（ＣＲ－ａ）中、波線は結合手を表す。 The pigment derivative is a compound having a π-conjugated plane containing a partial structure represented by the following formula (SQ-a) or a π-conjugated plane containing a partial structure represented by the following formula (CR-a). It is also preferable that there is. In the following equations (SQ-a) and (CR-a), the wavy line represents a bond.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　顔料誘導体は、下記式（Ｓｙｎ１）で表される化合物及び下記式（Ｓｙｎ２）で表わされる化合物から選ばれる少なくとも１種であることも好ましい。 It is also preferable that the pigment derivative is at least one selected from the compound represented by the following formula (Syn1) and the compound represented by the following formula (Syn2).
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　式（Ｓｙｎ１）中、Ｒｓｙ１及びＲｓｙ２は各々独立に有機基を表し、Ｌ１は単結合又はｐ１＋１価の基を表し、Ａ１はスルホ基、カルボキシ基、リン酸基、ボロン酸基、スルホンイミド基、スルホンアミド基、アミノ基、ピリジニル基、これらの塩又はこれらの脱塩構造から選ばれる基を表し、ｐ１及びｑ１は各々独立に１以上の整数を表す。ｐ１が２以上の場合、複数のＡ１は同一であってもよく、異なっていてもよい。ｑ１が２以上の場合、複数のＬ１及びＡ１は同一であってもよく、異なっていてもよい。 In the formula (Syn1), Rsy 1 and Rsy 2 each independently represent an organic group, L 1 represents a single bond or a p1 + 1 valent group, and A 1 represents a sulfo group, a carboxy group, a phosphate group, a boronic acid group, and the like. It represents a sulfonimide group, a sulfonamide group, an amino group, a pyridinyl group, a salt thereof or a group selected from the desalted structure thereof, and p1 and q1 each independently represent an integer of 1 or more. If p1 is 2 or more, a plurality of A 1 may be the same or different. If q1 is 2 or more, a plurality of L 1 and A 1 may be the same or different.
　式（Ｓｙｎ２）中、Ｒｓｙ３及びＲｓｙ４は各々独立に有機基を表し、Ｌ２は単結合又はｐ２＋１価の基を表し、Ａ２はスルホ基、カルボキシ基、リン酸基、ボロン酸基、スルホンイミド基、スルホンアミド基、アミノ基、ピリジニル基、これらの塩又はこれらの脱塩構造から選ばれる基を表し、ｐ２及びｑ２は各々独立に１以上の整数を表す。ｐ２が２以上の場合、複数のＡ２は同一であってもよく、異なっていてもよい。ｑ２が２以上の場合、複数のＬ２及びＡ２は同一であってもよく、異なっていてもよい。 In the formula (Syn2), Rsy 3 and Rsy 4 each independently represent an organic group, L 2 represents a single bond or a p2 + 1 valent group, and A 2 represents a sulfo group, a carboxy group, a phosphoric acid group, a boronic acid group, It represents a sulfonimide group, a sulfonamide group, an amino group, a pyridinyl group, a salt thereof or a group selected from the desalted structure thereof, and p2 and q2 each independently represent an integer of 1 or more. If p2 is 2 or more, plural A 2 may be the same or different. If q2 is 2 or more, the plurality of L 2 and A 2 may be the same or may be different.
　式（Ｓｙｎ１）のＲｓｙ１及びＲｓｙ２で表される有機基、並びに、式（Ｓｙｎ２）のＲｓｙ３及びＲｓｙ４で表される有機基としては、アリール基、ヘテロアリール基、下記式（Ｒ１）で表される基が挙げられる。 Examples of the organic group represented by Rsy 1 and Rsy 2 of the formula (Syn1) and the organic group represented by Rsy 3 and Rsy 4 of the formula (Syn2) include an aryl group, a heteroaryl group, and the following formula (R1). The group represented by is mentioned.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　式（Ｒ１）中、Ｒ１～Ｒ３は、各々独立に水素原子又は置換基を表し、Ａｓ３はヘテロアリール基を表し、ｎｒ１は０以上の整数を表し、Ｒ１とＲ２は互いに結合して環を形成してもよく、Ｒ１とＡｓ３は互いに結合して環を形成してもよく、Ｒ２とＲ３は互いに結合して環を形成してもよく、ｎｒ１が２以上の場合、複数のＲ２及びＲ３はそれぞれ同一であってもよく、異なっていてもよく、＊は結合手を表す。 In the formula (R1), R 1 to R 3 independently represent a hydrogen atom or a substituent, As 3 represents a heteroaryl group, nr1 represents an integer of 0 or more, and R 1 and R 2 are bonded to each other. R 1 and As 3 may be bonded to each other to form a ring, R 2 and R 3 may be bonded to each other to form a ring, and n r 1 is 2. In the above case, the plurality of R 2 and R 3 may be the same or different, and * represents a bond.
　Ｒｓｙ１～Ｒｓｙ４で表されるアリール基の炭素数は、６～４８が好ましく、６～２２がより好ましく、６～１２が特に好ましい。
　Ｒｓｙ１～Ｒｓｙ４で表されるヘテロアリール基の環を構成する炭素原子の数は、１～３０が好ましく、１～１２がより好ましい。ヘテロアリール基の環を構成するヘテロ原子の種類としては、窒素原子、酸素原子及び硫黄原子が挙げられる。ヘテロアリール基を構成するヘテロ原子の数としては、１～３が好ましく、１～２がより好ましい。ヘテロアリール基は、単環又は縮合環が好ましく、単環又は縮合数が２～８の縮合環がより好ましく、単環又は縮合数が２～４の縮合環が更に好ましい。
　Ｒｓｙ１～Ｒｓｙ４で表されるアリール基及びヘテロアリール基は、置換基を有していてもよい。置換基としては、既述の置換基Ｔ、下記式（Ｒ－ＳＱ）で表される基などが挙げられる。 The aryl group represented by Rsy 1 to Rsy 4 preferably has 6 to 48 carbon atoms, more preferably 6 to 22 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
The number of carbon atoms constituting the ring of the heteroaryl group represented by Rsy 1 to Rsy 4 is preferably 1 to 30, and more preferably 1 to 12. Examples of the type of hetero atom constituting the ring of the heteroaryl group include a nitrogen atom, an oxygen atom and a sulfur atom. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 8, and even more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4.
The aryl group and heteroaryl group represented by Rsy 1 to Rsy 4 may have a substituent. Examples of the substituent include the above-mentioned Substituent T and a group represented by the following formula (RSQ).
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　式（Ｒ－ＳＱ）中、Ｒｓｑ１は有機基を表す。Ｒｓｑ１で表される有機基は、アリール基、ヘテロアリール基、式（Ｒ１）で表される基、後述する、式（１）で表される基、式（１０）で表される基、式（２０）で表される基、式（３０）で表される基、式（４０）で表される基が挙げられる。 In formula (RSQ), Rsq 1 represents an organic group. The organic group represented by Rsq 1 includes an aryl group, a heteroaryl group, a group represented by the formula (R1), a group represented by the formula (1) and a group represented by the formula (10), which will be described later. Examples thereof include a group represented by the formula (20), a group represented by the formula (30), and a group represented by the formula (40).
　式（Ｒ１）におけるＲ１～Ｒ３は各々独立に水素原子又は置換基を表す。置換基としては、既述の置換基Ｔが挙げられる。Ｒ１～Ｒ３で表される置換基はアルキル基であることが好ましい。アルキル基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～８が更に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよく、直鎖又は分岐が好ましい。Ｒ１～Ｒ３は水素原子であることが好ましい。
　式（Ｒ１）におけるＡｓ３はヘテロアリール基を表す。Ａｓ３で表されるヘテロアリール基は、Ｒｓｙ１～Ｒｓｙ４で表されるヘテロアリール基と同様のものが挙げられ、好ましい態様も同様である。 R 1 to R 3 in the formula (R1) independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned Substituent T. The substituent represented by R 1 to R 3 is preferably an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. R 1 to R 3 are preferably hydrogen atoms.
As 3 in the formula (R1) represents a heteroaryl group. Examples of the heteroaryl group represented by As 3 include the same heteroaryl groups represented by Rsy 1 to Rsy 4 , and preferred embodiments are also the same.
　式（Ｒ１）において、Ｒ１とＲ２は、互いに結合して環を形成してもよく、Ｒ１とＡｓ３は、互いに結合して環を形成してもよく、Ｒ２とＲ３は、互いに結合して環を形成してもよい。上記の環を形成する場合の連結基としては、－ＣＯ－、－Ｏ－、－ＮＨ－、－ＣＨ－、及びそれらの組み合わせからなる群より選ばれる２価の連結基が好ましい。 In formula (R1), R 1 and R 2 may be coupled to each other to form a ring, R 1 and As 3 may be coupled to each other to form a ring, and R 2 and R 3 may be coupled to each other to form a ring. , May be combined with each other to form a ring. As the linking group for forming the above ring, a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, -CH-, and a combination thereof is preferable.
　式（Ｒ１）におけるｎｒ１は、０以上の整数を表す。ｎｒ１は０～２の整数が好ましく、０又は１がより好ましく、０が更に好ましい。式（Ｒ１）において、ｎｒ１が２以上の場合、複数のＲ２及びＲ３はそれぞれ同一であってもよく、異なっていてもよい。 N r1 in the formula (R1) represents an integer of 0 or more. n r1 is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. In the formula (R1), when n r1 is 2 or more, the plurality of R 2 and R 3 may be the same or different.
　式（Ｓｙｎ１）のＲｓｙ１及びＲｓｙ２で表される有機基、並びに、式（Ｓｙｎ２）のＲｓｙ３及びＲｓｙ４で表される有機基としては、下記式（１）で表される基であることが好ましい。 The organic groups represented by Rsy 1 and Rsy 2 of the formula (Syn1) and the organic groups represented by Rsy 3 and Rsy 4 of the formula (Syn2) are the groups represented by the following formula (1). Is preferable.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　式（１）中、環Ｚ１は１つ又は複数の置換基を有していてもよい、芳香族複素環又は芳香族複素環を含む縮合環を表し、環Ｚ２は１つ又は複数の置換基を有していてもよい、４～９員の炭化水素環又は複素環を表し、環Ｚ１及び環Ｚ２が複数の置換基を有する場合、複数の置換基は同一であっても異なっていてもよく、＊は結合手を表す。 In formula (1), ring Z 1 represents an aromatic heterocycle or a fused ring containing an aromatic heterocycle, which may have one or more substituents, and ring Z 2 is one or more. which may have a substituent, a hydrocarbon ring or heterocyclic ring 4-9 membered, wherein ring Z 1 and the ring Z 2 has plural substituents, the plural substituents may be the same It may be different, and * represents a bond.
　式（１）において、環Ｚ１は１つ又は複数の置換基を有していてもよい、芳香族複素環又は芳香族複素環を含む縮合環を表す。芳香族複素環としては、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピロール環、フラン環、チオフェン環、ピラゾール環、イソオキサゾール環、イソチアゾール環、ピリダジン環、ピリミジン環などが挙げられ、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピロール環が好ましい。芳香族複素環を含む縮合環としては、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピロール環、フラン環、チオフェン環、ピラゾール環、イソオキサゾール環、イソチアゾール環、ピリダジン環、ピリミジン環から選ばれる１個以上の環（２個以上の場合は同じ種類の環であってもよく、異なる種類の環であってもよい）と、ベンゼン環、ナフタレン環、アントラセン環、テトラセン環、フェナントレン環、トリフェニレン環、テトラフェン環、ピレン環から選ばれる環（好ましくはベンゼン環、ナフタレン環）との縮合環；イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピロール環、フラン環、チオフェン環、ピラゾール環、イソオキサゾール環、イソチアゾール環、ピリダジン環、ピリミジン環から選ばれる２個以上の環（２個以上の場合は同じ種類の環であってもよく、異なる種類の環であってもよい）の縮合環などが挙げられる。縮合環の縮合数は、より優れた分光特性が得られやすいという理由から２～６が好ましく、２～４がより好ましい。 In formula (1), ring Z 1 represents an aromatic heterocycle or a fused ring containing an aromatic heterocycle, which may have one or more substituents. Examples of the aromatic heterocycle include an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrazole ring, a furan ring, a thiophene ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a pyridazine ring, a pyrimidine ring and the like. Therefore, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, and a pyrazole ring are preferable. Examples of the fused ring containing an aromatic heterocycle include an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrrol ring, a furan ring, a thiophene ring, a pyrazole ring, an isooxazole ring, an isothiazole ring, a pyridazine ring, and a pyrimidine. One or more rings selected from the rings (two or more rings may be of the same type or different types), a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, A fused ring with a ring selected from a phenanthrene ring, a triphenylene ring, a tetraphen ring, and a pyrene ring (preferably a benzene ring and a naphthalene ring); an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrrol ring, and a furan ring. , Thiophen ring, pyrazole ring, isooxazole ring, isothiazole ring, pyridazine ring, pyrimidine ring, two or more rings (in the case of two or more, the same type of ring may be used, and different types of rings may be used. (May be present), such as a fused ring. The number of condensed rings is preferably 2 to 6 and more preferably 2 to 4 because more excellent spectral characteristics can be easily obtained.
　式（１）において、環Ｚ２は１つ又は複数の置換基を有していてもよい、４～９員の炭化水素環又は複素環を表す。環Ｚ２で表される炭化水素環及び複素環は、５～７員環であることが好ましく、５又は６員環であることがより好ましい。炭化水素環の具体例としては、シクロブテン環、シクロペンテン環、シクロペンタジエン環、シクロヘキセン環、シクロヘキサジエン環、シクロヘプテン環、シクロヘプタジエン環、シクロヘプタトリエン環、シクロオクテン環、シクロオクタジエン環、シクロオクタトリエン環、シクロノネン環、シクロノナジエン環、シクロノナトリエン環、シクロノナテトラエン環等のシクロアルケン環が挙げられ、シクロペンテン環、シクロヘキセン環、シクロヘプテン環及びシクロオクテン環が好ましく、シクロペンテン環及びシクロヘキセン環がより好ましい。環Ｚ２で表される複素環は、含窒素複素環であることが好ましい。 In formula (1), ring Z 2 represents a 4- to 9-membered hydrocarbon ring or heterocycle which may have one or more substituents. The hydrocarbon ring and the heterocycle represented by ring Z 2 are preferably a 5- to 7-membered ring, and more preferably a 5- or 6-membered ring. Specific examples of the hydrocarbon ring include a cyclobutene ring, a cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a cyclohexadiene ring, a cycloheptene ring, a cycloheptene ring, a cycloheptene ring, a cyclooctene ring, a cyclooctadiene ring, and a cyclooctane. Cycloalkene rings such as triene ring, cyclononene ring, cyclononadien ring, cyclononatorien ring, cyclononatetraene ring can be mentioned, cyclopentene ring, cyclohexene ring, cycloheptene ring and cyclooctene ring are preferable, and cyclopentene ring and cyclohexene ring are more preferable. preferable. The heterocycle represented by ring Z 2 is preferably a nitrogen-containing heterocycle.
　環Ｚ１及び環Ｚ２が有してもよい置換基としては、既述の置換基Ｔが挙げられる。
　また、環Ｚ１が有してもよい置換基は、電子求引性基であることも好ましい。ハメットの置換基定数σ値（シグマ値）が正の置換基は、電子求引性基として作用する。ここで、ハメット則で求められた置換基定数にはσｐ値とσｍ値がある。これらの値は多くの一般的な成書に見出すことができる。本開示においては、ハメットの置換基定数σ値が０．１以上の置換基を電子求引性基として例示することができる。σ値は、０．１５以上が好ましく、０．２以上がより好ましく、０．３以上が更に好ましい。上限は特に制限はないが、好ましくは１．０以下である。電子求引性基の具体例としては、ハロゲン原子、水素原子の少なくとも一部がハロゲン原子で置き換えられているアルキル基、水素原子の少なくとも一部がハロゲン原子で置き換えられているアリール基、ニトロ基、シアノ基、シアノメチル基、－ＣＨ＝Ｃ（ＣＮ）２、－Ｃ（ＣＮ）＝Ｃ（ＣＮ）２、－Ｐ（ＣＮ）２、－Ｎ＝ＮＣＮ、－ＣＯＲｚ、－ＣＯＯＲｚ、－ＯＣＯＲｚ、－ＮＨＣＯＲｚ、－ＣＯＮＨＲｚ、－ＳＯＲｚ、－ＳＯ２Ｒｚ、－ＳＯ２ＯＲｚ、－ＮＨＳＯ２Ｒｚ、又はＳＯ２ＮＨＲｚが挙げられる。Ｒｚは、水素原子の少なくとも一部がフッ素原子で置き換えられていてもよいアルキル基、水素原子の少なくとも一部がフッ素原子で置き換えられていてもよいアリール基、アミノ基、ハロゲン原子、シアノ基、又はシアノメチル基を表す。ここで、シアノメチル基には、モノシアノメチル基（－ＣＨ２ＣＮ）、ジシアノメチル基（－ＣＨ（ＣＮ）２）、及びトリシアノメチル基（－Ｃ（ＣＮ）３）が含まれる。水素原子の少なくとも一部がフッ素原子で置き換えられていてもよいアルキル基は、炭素数が１～６が好ましく、炭素数１～５がより好ましく、炭素数１～４が更に好ましい。水素原子の少なくとも一部がフッ素原子で置き換えられていてもよいアリール基は、炭素数６～１４が好ましく、炭素数６～１０がより好ましい。これらのアルキル基とアリール基は、水素原子の全部がフッ素原子で置き換えられていてもよく、一部のみがフッ素原子で置き換えられていてもよく、フッ素原子で置き換えられていなくてもよい。 Examples of the substituent that the ring Z 1 and the ring Z 2 may have include the above-mentioned substituent T.
Further, the substituent that the ring Z 1 may have is preferably an electron-attracting group. Substituents with a positive Hammett substituent constant σ value (sigma value) act as electron-attracting groups. Here, the substituent constants obtained by Hammett's law include σp value and σm value. These values can be found in many common books. In the present disclosure, a substituent having a Hammett substituent constant σ value of 0.1 or more can be exemplified as an electron-attracting group. The σ value is preferably 0.15 or more, more preferably 0.2 or more, and even more preferably 0.3 or more. The upper limit is not particularly limited, but is preferably 1.0 or less. Specific examples of the electron-attracting group include a halogen atom, an alkyl group in which at least a part of a hydrogen atom is replaced with a halogen atom, an aryl group in which at least a part of a hydrogen atom is replaced with a halogen atom, and a nitro group. , Cyano group, cyanomethyl group, -CH = C (CN) 2 , -C (CN) = C (CN) 2 , -P (CN) 2 , -N = NCN, -COR z , -COOR z , -OCOR Examples thereof include z, -NHCOR z , -CONHR z , -SOR z , -SO 2 R z , -SO 2 OR z , -NHSO 2 R z , or SO 2 NHR z . R z is an alkyl group in which at least a part of a hydrogen atom may be replaced with a fluorine atom, an aryl group in which at least a part of a hydrogen atom may be replaced with a fluorine atom, an amino group, a halogen atom, or a cyano group. , Or represents a cyanomethyl group. Here, the cyanomethyl group includes a monocyanomethyl group (-CH 2 CN), a dicyanomethyl group (-CH (CN) 2 ), and a tricyanomethyl group (-C (CN) 3 ). The alkyl group in which at least a part of the hydrogen atom may be replaced with a fluorine atom preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and further preferably 1 to 4 carbon atoms. The aryl group in which at least a part of the hydrogen atom may be replaced with a fluorine atom preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. In these alkyl groups and aryl groups, all of the hydrogen atoms may be replaced with fluorine atoms, only some of them may be replaced with fluorine atoms, or they may not be replaced with fluorine atoms.
　式（１）で表される基は、式（１－１）又は式（１－２）で表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000032
 The group represented by the formula (1) is preferably a group represented by the formula (1-1) or the formula (1-2).
Figure JPOXMLDOC01-appb-C000032
　式（１－１）中、環Ｚ１ａは１つ又は複数の置換基を有していてもよい、５又は６員環の含窒素複素環を有する多環芳香族環を表し、環Ｚ２ａは、１つ又は複数の置換基を有していてもよい、４～９員の炭化水素環又は複素環を表す。環Ｚ１ａ及び環Ｚ２ａが複数の置換基を有する場合、複数の置換基は同一であっても異なっていてもよい。Ｒ５及びＲ７は各々独立に、水素原子又は置換基を表す。 In formula (1-1), ring Z 1a represents a polycyclic aromatic ring having a 5- or 6-membered nitrogen-containing heterocycle which may have one or more substituents, and ring Z 2a. Represents a 4- to 9-membered hydrocarbon ring or heterocycle which may have one or more substituents. When the ring Z 1a and the ring Z 2a have a plurality of substituents, the plurality of substituents may be the same or different. R 5 and R 7 each independently represent a hydrogen atom or a substituent.
　式（１－１）において、環Ｚ１ａで表される多環芳香族環としては、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピロール環、フラン環、チオフェン環、ピラゾール環、イソオキサゾール環、イソチアゾール環、ピリダジン環、ピリミジン環から選ばれる５又は６員環の含窒素複素環を含む縮合環が挙げられ、前述の含窒素複素環から選ばれる１個以上の環（２個以上の場合は同じ種類の含窒素複素環であってもよく、異なる種類の含窒素複素環であってもよい）と、ベンゼン環又はナフタレン環との縮合環；前述の含窒素複素環から選ばれる２個以上の環（同じ種類の含窒素複素環であってもよく、異なる種類の含窒素複素環であってもよい）の縮合環などが挙げられる。多環芳香族環に含まれる環の数（縮合環の縮合数）は、より優れた分光特性が得られやすいという理由から２～６が好ましく、２～４がより好ましい。 In the formula (1-1), the polycyclic aromatic ring represented by the ring Z 1a includes an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, and a pyrazole ring. Examples thereof include a fused ring containing a 5- or 6-membered nitrogen-containing heterocycle selected from an isooxazole ring, an isothiazole ring, a pyridazine ring, and a pyrimidine ring, and one or more rings (2) selected from the above-mentioned nitrogen-containing heterocycles. In the case of two or more, it may be the same type of nitrogen-containing heterocycle or a different type of nitrogen-containing heterocycle) and a fused ring with a benzene ring or a naphthalene ring; from the above-mentioned nitrogen-containing heterocycle. Examples thereof include fused rings of two or more selected rings (which may be the same type of nitrogen-containing heterocycle or different types of nitrogen-containing heterocycles). The number of rings contained in the polycyclic aromatic ring (the number of condensed rings condensed) is preferably 2 to 6 and more preferably 2 to 4 because more excellent spectral characteristics can be easily obtained.
　式（１－１）において、環Ｚ２ａで表される４～９員の炭化水素環及び複素環としては、式（１）の環Ｚ２の項で説明したものが挙げられる。 In the formula (1-1), examples of the 4- to 9-membered hydrocarbon ring and the heterocycle represented by the ring Z 2a include those described in the section of the ring Z 2 of the formula (1).
　式（１－１）において、環Ｚ１ａ及び環Ｚ２ａが有してもよい置換基、並びにＲ５及びＲ７で表される置換基としては、既述の置換基Ｔが挙げられる。また、環Ｚ１ａが有してもよい置換基は、電子求引性基であることも好ましい。電子求引性基としては上述の環Ｚ１が有してもよい置換基としての電子求引性基が挙げられる。 In the formula (1-1), the substituents that the rings Z 1a and Z 2a may have, and the substituents represented by R 5 and R 7 include the above-mentioned substituent T. Further, the substituent that the ring Z1a may have is preferably an electron-attracting group. Examples of the electron-attracting group include an electron-attracting group as a substituent that the ring Z 1 may have.
　式（１－２）中、環Ｚ１ｂは、１つ又は複数の置換基を有していてもよい、５又は６員環の含窒素複素環を有する多環芳香族環を表し、環Ｚ２ｂは、１つ又は複数の置換基を有していてもよい、４～９員の含窒素複素環を表し、環Ｚ１ｂ及び環Ｚ２ｂが複数の置換基を有する場合、複数の置換基は同一であっても異なっていてもよい。 In formula (1-2), ring Z 1b represents a polycyclic aromatic ring having a 5- or 6-membered nitrogen-containing heterocycle which may have one or more substituents, and ring Z. 2b represents a 4- to 9-membered nitrogen-containing heterocycle which may have one or more substituents, and when rings Z 1b and Z 2b have a plurality of substituents, a plurality of substituents. May be the same or different.
　式（１－２）において、環Ｚ１ｂで表される多環芳香族環としては、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピロール環、フラン環、チオフェン環、ピラゾール環、イソオキサゾール環、イソチアゾール環、ピリダジン環、ピリミジン環から選ばれる５又は６員環の含窒素複素環を含む縮合環が挙げられ、前述の含窒素複素環から選ばれる１個以上の環（２個以上の場合は同じ種類の含窒素複素環であってもよく、異なる種類の含窒素複素環であってもよい）と、ベンゼン環又はナフタレン環との縮合環；前述の含窒素複素環から選ばれる２個以上の環（同じ種類の含窒素複素環であってもよく、異なる種類の含窒素複素環であってもよい）の縮合環などが挙げられる。多環芳香族環に含まれる環の数（縮合環の縮合数）は、より優れた分光特性が得られやすいという理由から２～６が好ましく、２～４がより好ましい。 In the formula (1-2), the polycyclic aromatic ring represented by the ring Z 1b includes an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, and a pyrazole ring. Examples thereof include a fused ring containing a 5- or 6-membered nitrogen-containing heterocycle selected from an isooxazole ring, an isothiazole ring, a pyridazine ring, and a pyrimidine ring, and one or more rings (2) selected from the above-mentioned nitrogen-containing heterocycles. In the case of two or more, it may be the same type of nitrogen-containing heterocycle or a different type of nitrogen-containing heterocycle) and a fused ring with a benzene ring or a naphthalene ring; from the above-mentioned nitrogen-containing heterocycle. Examples thereof include fused rings of two or more selected rings (which may be the same type of nitrogen-containing heterocycle or different types of nitrogen-containing heterocycles). The number of rings contained in the polycyclic aromatic ring (the number of condensed rings condensed) is preferably 2 to 6 and more preferably 2 to 4 because more excellent spectral characteristics can be easily obtained.
　式（１－２）において、環Ｚ２ｂで表される含窒素複素環は、５～７員環であることが好ましく、５又は６員環であることがより好ましい。 In the formula (1-2), the nitrogen-containing heterocycle represented by ring Z 2b is preferably a 5- to 7-membered ring, and more preferably a 5- or 6-membered ring.
　式（１－２）において、環Ｚ１ｂ及び環Ｚ２ｂが有してもよい置換基としては、既述の置換基Ｔが挙げられる。また、環Ｚ１ｂが有してもよい置換基は電子求引性基であることも好ましい。電子求引性基としては上述の環Ｚ１が有してもよい置換基としての電子求引性基が挙げられる。 In the formula (1-2), examples of the substituent that the ring Z 1b and the ring Z 2b may have include the above-mentioned substituent T. Further, it is also preferable that the substituent that the ring Z 1b may have is an electron-attracting group. Examples of the electron-attracting group include an electron-attracting group as a substituent that the ring Z 1 may have.
　式（Ｓｙｎ１）のＲｓｙ１及びＲｓｙ２で表される有機基、並びに、式（Ｓｙｎ２）のＲｓｙ３及びＲｓｙ４で表される有機基としては、下記式（１０）で表わされる基であることも好ましい。 The organic group represented by Rsy 1 and Rsy 2 of the formula (Syn1) and the organic group represented by Rsy 3 and Rsy 4 of the formula (Syn2) shall be the group represented by the following formula (10). Is also preferable.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　式（１０）中、Ｒ１１～Ｒ１４は各々独立に水素原子又は置換基を表し、Ｒ１１～Ｒ１４のうち隣接する二つの基同士は互いに結合して環を形成していてもよく、Ｒ２０はアリール基又はヘテロアリール基を表し、Ｒ２１は置換基を表し、Ｘ１０は－ＣＯ－又は－ＳＯ２－を表す。 In formula (10), R 11 to R 14 each independently represent a hydrogen atom or a substituent, and two adjacent groups of R 11 to R 14 may be bonded to each other to form a ring. R 20 represents an aryl group or a heteroaryl group, R 21 represents a substituent, and X 10 represents -CO- or -SO 2- .
　式（１０）において、Ｒ１１～Ｒ１４で表される置換基としては、既述の置換基Ｔが挙げられる。 In the formula (10), examples of the substituent represented by R 11 to R 14 include the above-mentioned substituent T.
　式（１０）において、Ｒ２０はアリール基又はヘテロアリール基を表し、アリール基であることが好ましい。アリール基の炭素数は、６～４８が好ましく、６～２２がより好ましく、６～１２が特に好ましい。ヘテロアリール基の環を構成する炭素原子の数は、１～３０が好ましく、１～１２がより好ましい。ヘテロアリール基の環を構成するヘテロ原子の種類としては、窒素原子、酸素原子及び硫黄原子が挙げられる。ヘテロアリール基を構成するヘテロ原子の数としては、１～３が好ましく、１～２がより好ましい。ヘテロアリール基は、単環又は縮合環が好ましく、単環又は縮合数が２～８の縮合環がより好ましく、単環又は縮合数が２～４の縮合環が更に好ましい。アリール基及びヘテロアリール基は、置換基を有していてもよい。置換基としては、既述の置換基Ｔが挙げられる。アリール基及びヘテロアリール基は、置換基を有さないものであることが好ましい。 In the formula (10), R 20 represents an aryl group or a heteroaryl group, and is preferably an aryl group. The aryl group preferably has 6 to 48 carbon atoms, more preferably 6 to 22 carbon atoms, and particularly preferably 6 to 12 carbon atoms. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 1 to 30, more preferably 1 to 12. Examples of the type of hetero atom constituting the ring of the heteroaryl group include a nitrogen atom, an oxygen atom and a sulfur atom. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 8, and even more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4. Aryl groups and heteroaryl groups may have substituents. Examples of the substituent include the above-mentioned Substituent T. The aryl group and the heteroaryl group preferably have no substituent.
　式（１０）において、Ｒ２１は置換基を表す。Ｒ２１で表される置換基としては、既述の置換基Ｔが挙げられ、アルキル基、アリール基、ヘテロアリール基、－ＯＣＯＲｔ１、又は－ＮＨＣＯＲｔ１が好ましい。Ｒｔ１は、アルキル基、アリール基又はヘテロアリール基であることが好ましく、アルキル基であることがより好ましい。 In formula (10), R 21 represents a substituent. Examples of the substituent represented by R 21 include the above-mentioned Substituent T, and an alkyl group, an aryl group, a heteroaryl group, -OCORt 1 , or -NHCORt 1 is preferable. Rt 1 is preferably an alkyl group, an aryl group or a heteroaryl group, and more preferably an alkyl group.
　式（Ｓｙｎ１）のＲｓｙ１及びＲｓｙ２で表される有機基、並びに、式（Ｓｙｎ２）のＲｓｙ３及びＲｓｙ４で表される有機基としては、下記式（２０）で表わされる基であることも好ましい。 The organic group represented by Rsy 1 and Rsy 2 of the formula (Syn1) and the organic group represented by Rsy 3 and Rsy 4 of the formula (Syn2) shall be the group represented by the following formula (20). Is also preferable.
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　式（２０）中、Ｒ２０及びＲ２１は各々独立に水素原子又は置換基を表し、Ｒ２０とＲ２１は、互いに結合して環を形成してもよく、Ｘ２０は、酸素原子、硫黄原子、－ＮＲ２２－、セレン原子、又はテルル原子を表し、Ｒ２２は水素原子又は置換基を表し、Ｘ２０がＮＲ２２である場合、Ｒ２２とＲ２０は互いに結合して環を形成してもよく、ｎｒ２は、０～５の整数を表し、ｎｒ２が２以上の場合、複数のＲ２０は同一であってもよく、異なっていてもよく、複数のＲ２０のうち２個のＲ２０同士が結合して環を形成してもよく、＊は結合手を表す。 In formula (20), R 20 and R 21 each independently represent a hydrogen atom or a substituent, R 20 and R 21 may be bonded to each other to form a ring, and X 20 is an oxygen atom and sulfur. atom, -NR 22 -, it represents a selenium atom, or a tellurium atom, R 22 represents a hydrogen atom or a substituent, and when X 20 is NR 22, R 22 and R 20 are combined with each other to form a ring and may be, n r2 is 0 to an integer of 5, when n r2 is 2 or more, the plurality of R 20 may be the same or different, two of the plurality of R 20 may also be R 20 are bonded to each other to form a ring, * represents a bond.
　式（２０）において、Ｒ２０及びＲ２１で表される置換基としては既述の置換基Ｔが挙げられる。
　Ｒ２０は、アルキル基、ハロゲン化アルキル基（好ましくはフッ化アルキル基）、アリール基、又はハロゲン原子であることが好ましく、アルキル基、又はハロゲン化アルキル基であることがより好ましく、ハロゲン化アルキル基であることが更に好ましい。
　Ｒ２１は、水素原子又はアルキル基であることが好ましく、水素原子であることがより好ましい。 In the formula (20), examples of the substituent represented by R 20 and R 21 include the above-mentioned substituent T.
R 20 is preferably an alkyl group, an alkyl halide group (preferably an alkyl fluoride group), an aryl group, or a halogen atom, more preferably an alkyl group or an alkyl halide group, and an alkyl halide. It is more preferably a group.
R 21 is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
　式（２０）において、Ｘ２０は、酸素原子、硫黄原子、－ＮＲ２２－が好ましく、－ＮＲ２２－であることがより好ましい。Ｒ２２は水素原子又は置換基を表す。置換基としては、既述の置換基Ｔが挙げられ、アルキル基が好ましい。Ｘ２０がＮＲ２２である場合、Ｒ２２とＲ２０は互いに結合して環を形成してもよい。Ｒ２２とＲ２０とが結合して形成される環としては、４～９員の炭化水素環又は複素環が挙げられ、５～７員の炭化水素環又は複素環が好ましく、５～６員の炭化水素環又は複素環がより好ましく、５～６員の炭化水素環が更に好ましく、６員の炭化水素環が特に好ましい。 In the formula (20), X 20 represents an oxygen atom, a sulfur atom, -NR 22 - are preferred, -NR 22 - is more preferable. R 22 represents a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned Substituent T, and an alkyl group is preferable. When X 20 is NR 22 , R 22 and R 20 may combine with each other to form a ring. Examples of the ring formed by combining R 22 and R 20 include a 4- to 9-membered hydrocarbon ring or a heterocycle, and a 5- to 7-membered hydrocarbon ring or heterocycle is preferable, and a 5- to 6-membered hydrocarbon ring or heterocycle is preferable. The hydrocarbon ring or heterocycle is more preferable, a 5- to 6-membered hydrocarbon ring is further preferable, and a 6-membered hydrocarbon ring is particularly preferable.
　式（２０）において、ｎｒ２は、０～５の整数を表し、０～３の整数であることが好ましく、０～２の整数であることがより好ましく、１～２の整数であることが更に好ましい。ｎｒ２が２以上の場合は、複数のＲ２０は同一であってもよく、異なっていてもよく、複数のＲ２０のうち２個のＲ２０同士が結合して環を形成してもよい。Ｒ２０同士が結合して形成される環は、炭化水素環であってもよく、複素環であってもよい。また、これらの基同士が結合して形成される環は単環であってもよく、縮合環であってもよい。 In the formula (20), n r2 represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and preferably an integer of 1 to 2. More preferred. If n r2 is 2 or more, the plurality of R 20 may be the same or different, may be two R 20 are bonded to each other among the plurality of R 20 form a ring .. Ring R 20 together are formed by bonding may be a hydrocarbon ring may be a heterocyclic ring. Further, the ring formed by bonding these groups to each other may be a monocyclic ring or a condensed ring.
　式（Ｓｙｎ１）のＲｓｙ１及びＲｓｙ２で表される有機基、並びに、式（Ｓｙｎ２）のＲｓｙ３及びＲｓｙ４で表される有機基としては、下記式（３０）で表される基又は式（４０）で表わされる基であることも好ましい。 The organic group represented by Rsy 1 and Rsy 2 of the formula (Syn1) and the organic group represented by Rsy 3 and Rsy 4 of the formula (Syn2) include the group represented by the following formula (30) or the formula. It is also preferable that it is a group represented by (40).
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　式（３０）中、Ｒ３５～Ｒ３８は各々独立に水素原子又は置換基を表し、Ｒ３５とＲ３６、Ｒ３６とＲ３７、Ｒ３７とＲ３８は、互いに結合して環を形成してもよく、＊は結合手を表す。
　式（４０）中、Ｒ３９～Ｒ４５は各々独立に水素原子又は置換基を表し、Ｒ３９とＲ４５、Ｒ４０とＲ４１、Ｒ４０とＲ４２、Ｒ４２とＲ４３、Ｒ４３とＲ４４、Ｒ４４とＲ４５は、互いに結合して環を形成してもよく、＊は結合手を表す。 In formula (30), R 35 to R 38 each independently represent a hydrogen atom or a substituent, and R 35 and R 36 , R 36 and R 37 , and R 37 and R 38 combine with each other to form a ring. * May represent a bond.
In formula (40), R 39 to R 45 each independently represent a hydrogen atom or a substituent, and R 39 and R 45 , R 40 and R 41 , R 40 and R 42 , R 42 and R 43 , and R 43 . R 44 , R 44 and R 45 may be bonded to each other to form a ring, and * represents a bond.
　式（３０）のＲ３５～Ｒ３８で表される置換基、及び、式（４０）のＲ３９～Ｒ４５で表される置換基としては、既述の置換基Ｔが挙げられ、アルキル基又はアリール基が好ましく、アルキル基がより好ましい。 Examples of the substituent represented by R 35 to R 38 of the formula (30) and the substituent represented by R 39 to R 45 of the formula (40) include the above-mentioned substituent T, which is an alkyl group. Alternatively, an aryl group is preferable, and an alkyl group is more preferable.
　式（３０）において、Ｒ３５とＲ３６、Ｒ３６とＲ３７、Ｒ３７とＲ３８は、互いに結合して環を形成してもよい。また、式（４０）において、Ｒ３９とＲ４５、Ｒ４０とＲ４１、Ｒ４０とＲ４２、Ｒ４２とＲ４３、Ｒ４３とＲ４４、Ｒ４４とＲ４５は、互いに結合して環を形成してもよい。これらの基同士が結合して形成される環は、炭化水素環及び複素環が挙げられ、炭化水素環が好ましい。また、これらの基同士が結合して形成される環は単環であってもよく、縮合環であってもよいが縮合環であることが好ましい。 In formula (30), R 35 and R 36 , R 36 and R 37 , and R 37 and R 38 may be coupled to each other to form a ring. Further, in the equation (40), R 39 and R 45 , R 40 and R 41 , R 40 and R 42 , R 42 and R 43 , R 43 and R 44 , and R 44 and R 45 are coupled to each other and ring. May be formed. Examples of the ring formed by bonding these groups to each other include a hydrocarbon ring and a heterocycle, and a hydrocarbon ring is preferable. Further, the ring formed by bonding these groups to each other may be a monocyclic ring or a condensed ring, but a condensed ring is preferable.
　式（３０）においては、Ｒ３５とＲ３６とが結合して環を形成していることが好ましい。また、式（４０）においては、Ｒ４０とＲ４１及びＲ４４とＲ４５とがそれぞれ結合して環を形成していることが好ましい。 In the formula (30), it is preferable that R 35 and R 36 are bonded to form a ring. Further, in the formula (40), it is preferable that R 40 and R 41 and R 44 and R 45 are bonded to each other to form a ring.
　式（３０）で表される基は下記式（３０ａ）で表される基であることが好ましい。また、式（４０）で表される基は下記式（４０ａ）で表される基であることが好ましい。 The group represented by the formula (30) is preferably a group represented by the following formula (30a). Further, the group represented by the formula (40) is preferably a group represented by the following formula (40a).
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
　式（３０ａ）中、Ｒ３５、Ｒ３６、Ｒ１０１～Ｒ１０６は各々独立に水素原子又は置換基を表し、＊は結合手を表す。式（４０ａ）中、Ｒ３９、Ｒ４２、Ｒ４３、Ｒ２０１～Ｒ２１２は各々独立に水素原子又は置換基を表し、＊は結合手を表す。Ｒ３５、Ｒ３６、Ｒ１０１～Ｒ１０６で表される置換基及びＲ３９、Ｒ３９、Ｒ４２、Ｒ４３、Ｒ２０１～Ｒ２１２で表される置換基は、既述の置換基Ｔが挙げられ、アルキル基又はアリール基が好ましく、アルキル基がより好ましい。 In formula (30a), R 35 , R 36 , and R 101 to R 106 each independently represent a hydrogen atom or a substituent, and * represents a bond. In formula (40a), R 39 , R 42 , R 43 , and R 201 to R 212 each independently represent a hydrogen atom or a substituent, and * represents a bond. Substituents represented by R 35 , R 36 , R 101 to R 106 and substituents represented by R 39 , R 39 , R 42 , R 43 , and R 201 to R 212 have the above-mentioned substituent T. The alkyl group or the aryl group is preferable, and the alkyl group is more preferable.
　式（Ｓｙｎ１）のＬ１で表されるｐ１＋１価の基、及び、式（Ｓｙｎ２）のＬ２で表されるｐ２＋１価の基としては、炭化水素基、複素環基、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＳＯ２－、－ＮＲＬ－、－ＮＲＬＣＯ－、－ＣＯＮＲＬ－、－ＮＲＬＳＯ２－、－ＳＯ２ＮＲＬ－、及びこれらの組み合わせからなる基が挙げられる。ＲＬは水素原子、アルキル基、又はアリール基を表す。
　炭化水素基は脂肪族炭化水素基であってもよく、芳香族炭化水素基であってもよい。炭化水素基としては、アルキレン基、アリーレン基、又はこれらの基から水素原子を１個以上除いた基が挙げられる。アルキレン基の炭素数は、１～３０が好ましく、１～１５がより好ましく、１～１０が更に好ましい。アルキレン基は、直鎖、分岐、環状のいずれであってもよい。また、環状のアルキレン基は、単環、多環のいずれであってもよい。アリーレン基の炭素数は、６～１８が好ましく、６～１４がより好ましく、６～１０が更に好ましい。
　複素環基は、単環又は縮合数が２～４の縮合環が好ましい。複素環基の環を構成するヘテロ原子の数は１～３が好ましい。複素環基の環を構成するヘテロ原子は、窒素原子、酸素原子又は硫黄原子が好ましい。複素環基の環を構成する炭素原子の数は３～３０が好ましく、３～１８がより好ましく、３～１２がより好ましい。炭化水素基及び複素環基は置換基を有していてもよい。置換基としては、既述の置換基Ｔが挙げられる。 The p1 + 1 valent group represented by L 1 of the formula (Syn1) and the p2 + 1 valent group represented by L 2 of the formula (Syn2) include a hydrocarbon group, a heterocyclic group, -O-, and -S. -, -CO-, -COO-, -OCO-, -SO 2- , -NR L- , -NR L CO-, -CONR L- , -NR L SO 2- , -SO 2 NR L- , and A group consisting of a combination of these can be mentioned. RL represents a hydrogen atom, an alkyl group, or an aryl group.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Examples of the hydrocarbon group include an alkylene group, an arylene group, or a group obtained by removing one or more hydrogen atoms from these groups. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms. The alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be either monocyclic or polycyclic. The arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms.
The heterocyclic group is preferably a single ring or a condensed ring having 2 to 4 condensation numbers. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. The hydrocarbon group and the heterocyclic group may have a substituent. Examples of the substituent include the above-mentioned Substituent T.
　また、ＲＬで表されるアルキル基の炭素数は１～２０が好ましく、１～１５がより好ましく、１～８が更に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよく、直鎖又は分岐が好ましく、直鎖がより好ましい。ＲＬで表されるアルキル基は更に置換基を有していてもよい。置換基としては既述の置換基Ｔが挙げられる。ＲＬで表されるアリール基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１２が更に好ましい。ＲＬで表されるアリール基は更に置換基を有していてもよい。置換基としては既述の置換基Ｔが挙げられる。 The alkyl group represented by RL preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear. The alkyl group represented by RL may further have a substituent. Examples of the substituent include the above-mentioned Substituent T. The number of carbon atoms of the aryl group represented by RL is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group represented by RL may further have a substituent. Examples of the substituent include the above-mentioned Substituent T.
　式（Ｓｙｎ１）のＬ１はｐ１＋１価の基であることが好ましい。また、式（Ｓｙｎ２）のＬ２はｐ２＋１価の基であることが好ましい。また、式（Ｓｙｎ１）で表される化合物は、母核とＡ１で表される基とが、Ｌ１で表されるｐ１＋１価の基によって１原子以上隔てられていることが好ましく、３原子以上隔てられていることがより好ましい。また、式（Ｓｙｎ２）で表される化合物は、母核と、Ａ２で表される基とが、Ｌ２で表されるｐ２＋１価の基によって１原子以上隔てられていることが好ましく、３原子以上隔てられていることがより好ましい。この構造であれば、近赤外線吸収顔料のより優れた分散性が得られやすい。 L 1 in the formula (Syn 1) is preferably a p1 + 1 valent group. Further, it is preferable that L 2 in the formula (Syn 2) is a group having a p2 + 1 valence. The compound represented by formula (SYN1) includes a group represented by the mother nucleus and A 1 is preferably that are separated more than 1 atom by p1 + 1 valent group represented by L 1, 3 atom It is more preferable that they are separated by the above. Further, in the compound represented by the formula (Syn2), it is preferable that the mother nucleus and the group represented by A 2 are separated by one or more atoms by a p2 + 1 valent group represented by L 2. It is more preferable that they are separated by an atom or more. With this structure, it is easy to obtain better dispersibility of the near-infrared absorbing pigment.
　顔料誘導体の具体例としては、下記構造の化合物［ＢＰ－１～ＢＰ－４、Ｂ－１～Ｂ－１７］が挙げられる。
　また、特開昭５６－１１８４６２号公報、特開昭６３－２６４６７４号公報、特開平１－２１７０７７号公報、特開平３－９９６１号公報、特開平３－２６７６７号公報、特開平３－１５３７８０号公報、特開平３－４５６６２号公報、特開平４－２８５６６９号公報、特開平６－１４５５４６号公報、特開平６－２１２０８８号公報、特開平６－２４０１５８号公報、特開平１０－３００６３号公報、特開平１０－１９５３２６号公報、国際公開第２０１１／０２４８９６号の段落００８６～００９８、国際公開第２０１２／１０２３９９号の段落００６３～００９４等に記載の化合物が挙げられる。
　更に、顔料誘導体としては、特開２０１５－１７２７３２号公報（スルホ基を有するキノフタロン化合物の金属塩）、特開２０１４－１９９３０８号公報、特開２０１４－８５５６２号公報、特開２０１４－３５３５１号公報、又は、特開２００８－８１５６５号公報に記載の化合物を用いることもでき、これらの内容は本明細書に組み込まれる。 Specific examples of the pigment derivative include compounds having the following structures [BP-1 to BP-4, B-1 to B-17].
In addition, Japanese Patent Application Laid-Open No. 56-118462, Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 1-2170777, Japanese Patent Application Laid-Open No. 3-9961, Japanese Patent Application Laid-Open No. 3-26767, Japanese Patent Application Laid-Open No. 3-153780. Japanese Patent Application Laid-Open No. 3-455662, Japanese Patent Application Laid-Open No. 4-285669, Japanese Patent Application Laid-Open No. 6-145546, Japanese Patent Application Laid-Open No. 6-21208, Japanese Patent Application Laid-Open No. 6-241588, Japanese Patent Application Laid-Open No. 10-30063, Examples thereof include the compounds described in JP-A-10-195326, paragraphs 0083 to 098 of International Publication No. 2011/024896, paragraphs 0063 to 0094 of International Publication No. 2012/102399, and the like.
Further, as pigment derivatives, JP-A-2015-172732 (metal salt of a quinophthalone compound having a sulfo group), JP-A-2014-199308, JP-A-2014-85562, JP-A-2014-35351, Alternatively, the compounds described in JP-A-2008-81565 can also be used, and their contents are incorporated in the present specification.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　本開示における硬化性組成物では、顔料誘導体は、１種単独で使用してもよいし、２種以上を併用してもよい。 In the curable composition in the present disclosure, one pigment derivative may be used alone, or two or more pigment derivatives may be used in combination.
　本開示における硬化性組成物での顔料誘導体の含有量は、近赤外線吸収顔料を含む全ての顔料の総量に対し、１質量％～３０質量％が好ましく、５質量％～３０質量％がより好ましく、１０質量％～３０質量％が更に好ましい。 The content of the pigment derivative in the curable composition in the present disclosure is preferably 1% by mass to 30% by mass, more preferably 5% by mass to 30% by mass, based on the total amount of all pigments including the near-infrared absorbing pigment. It is more preferably 10% by mass to 30% by mass.
（重合禁止剤）
　本開示における硬化性組成物は、保存安定性の観点から、重合禁止剤を含むことが好ましい。
　重合禁止剤としては、特に限定されず、公知の重合禁止剤を用いることができる。
　重合禁止剤としては、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔ－ブチルカテコール、ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシアミン塩（アンモニウム塩、第一セリウム塩等）、２，２，６，６－テトラメチルピペリジン－１－オキシル等が挙げられる。なお、重合禁止剤は、酸化防止剤として機能することもある。 (Polymerization inhibitor)
The curable composition in the present disclosure preferably contains a polymerization inhibitor from the viewpoint of storage stability.
The polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used.
Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, quaternary-thiobis (3-methyl-6-t-butylphenol), and the like. 2,2'-Methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, first cerium salt, etc.), 2,2,6,6-tetramethylpiperidine-1- Oxil and the like can be mentioned. The polymerization inhibitor may also function as an antioxidant.
　本開示における硬化性組成物では、重合禁止剤は、１種単独で使用してもよいし、２種以上を併用してもよい。 In the curable composition in the present disclosure, the polymerization inhibitor may be used alone or in combination of two or more.
　本開示における硬化性組成物での重合禁止剤の含有量は、保存安定性の観点から、硬化性組成物の全固形分に対して、０．１ｐｐｍ～１，０００ｐｐｍであることが好ましく、１ｐｐｍ～５００ｐｐｍであることがより好ましく、１ｐｐｍ～１００ｐｐｍであることが特に好ましい。 The content of the polymerization inhibitor in the curable composition in the present disclosure is preferably 0.1 ppm to 1,000 ppm with respect to the total solid content of the curable composition from the viewpoint of storage stability, and is 1 ppm. It is more preferably about 500 ppm, and particularly preferably 1 ppm to 100 ppm.
（溶剤）
　本開示における硬化性組成物は、溶剤を含んでいることが好ましい。
　溶剤としては、エステル類、例えば、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、アルキルエステル類、乳酸メチル、乳酸エチル、オキシ酢酸メチル、オキシ酢酸エチル、オキシ酢酸ブチル、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル、並びに、３－オキシプロピオン酸メチル及び３－オキシプロピオン酸エチルなどの３－オキシプロピオン酸アルキルエステル類（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル）、並びに、２－オキシプロピオン酸メチル、２－オキシプロピオン酸エチル、及び２－オキシプロピオン酸プロピルなどの２－オキシプロピオン酸アルキルエステル類（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル、２－オキシ－２－メチルプロピオン酸メチル、２－オキシ－２－メチルプロピオン酸エチル、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル）、並びに、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等； (solvent)
The curable composition in the present disclosure preferably contains a solvent.
Examples of the solvent include esters such as ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and the like. Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate and ethyl 3-oxypropionate. 3-Oxypropionic acid alkyl esters such as (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and methyl 2-oxypropionate. , 2-Oxypropionate alkyl esters such as ethyl 2-oxypropionate, and propyl 2-oxypropionate (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2, -Methyl ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy- 2-Methyl propionate), as well as methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc .;
　エーテル類、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、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、メチルセロソルブアセテート、エチルセロソルブアセテート、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モノブチルエーテル、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート等；
　ケトン類、例えば、メチルエチルケトン、シクロヘキサノン、２－ヘプタノン、３－ヘプタノン等；
　芳香族炭化水素類、例えば、トルエン、キシレン等が挙げられる。
　ただし、有機溶剤としての芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン等）は、環境面等の理由により低減したほうがよい場合がある（例えば、有機溶剤の全質量に対して、５０ｐｐｍ以下とすることもでき、１０ｐｐｍ以下とすることもでき、１質量ｐｐｍ以下とすることもできる。）。 Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol. Ethyl ether acetate, propylene glycol propyl ether acetate, etc .;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .;
Aromatic hydrocarbons such as toluene, xylene and the like can be mentioned.
However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may need to be reduced for environmental reasons (for example, 50 ppm or less based on the total mass of the organic solvent). It can be 10 ppm or less, or 1 mass ppm or less).
　これらのうち、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテルアセテート等が好適である。
　溶剤は、単独で用いる以外に２種以上を組み合わせて用いてもよい。 Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
The solvent may be used alone or in combination of two or more.
　本開示においては、金属含有量の少ない有機溶剤を用いることが好ましく、有機溶剤の金属含有量は、例えば、１０ｐｐｂ以下であることが好ましい。必要に応じてｐｐｔレベルの有機溶剤を用いてもよく、そのような有機溶剤は、例えば、東洋合成工業（株）が提供している（化学工業日報、２０１５年１１月１３日）。 In the present disclosure, it is preferable to use an organic solvent having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 ppb or less. If necessary, a ppt-level organic solvent may be used, and such an organic solvent is provided by, for example, Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).
　有機溶剤から金属等の不純物を除去する方法としては、例えば、蒸留（分子蒸留や薄膜蒸留等）やフィルタを用いたろ過を挙げることができる。ろ過に用いるフィルタのフィルタ孔径としては、１０μｍ以下が好ましく、５μｍ以下がより好ましく、３μｍ以下が更に好ましい。フィルタの材質は、ポリテトラフルオロエチレン、ポリエチレン又はナイロンが好ましい。 Examples of the method for removing impurities such as metals from the organic solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
　有機溶剤は、異性体（原子数が同じであるが構造が異なる化合物）が含まれていてもよい。また、異性体は、１種のみが含まれていてもよいし、複数種含まれていてもよい。 The organic solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.
　有機溶剤中の過酸化物の含有率が０．８ｍｍｏｌ／Ｌ以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。 The content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.
　本開示における硬化性組成物では、溶剤は、１種単独で使用してもよいし、２種以上を併用してもよい。 In the curable composition in the present disclosure, one type of solvent may be used alone, or two or more types may be used in combination.
　本開示における硬化性組成物の固形分量は、塗布方法及び溶剤の有無により変更されるが、例えば、１質量％～１００質量％であることが好ましく、５質量％～５０質量％であることがより好ましく、１０質量％～３０質量％がより好ましい。
　即ち、本開示における硬化性組成物では、固形分量が上記の範囲となるよう溶剤を用いればよい。 The solid content of the curable composition in the present disclosure varies depending on the coating method and the presence or absence of a solvent, but is preferably 1% by mass to 100% by mass, preferably 5% by mass to 50% by mass, for example. More preferably, 10% by mass to 30% by mass is more preferable.
That is, in the curable composition in the present disclosure, a solvent may be used so that the solid content is within the above range.
（増感剤）
　本開示における硬化性組成物は、重合開始剤のラジカル、カチオン等の重合開始種の発生効率の向上、感光波長の長波長化の目的で、増感剤を含有していてもよい。
　増感剤としては、上記した光重合開始剤に対し、電子移動機構又はエネルギー移動機構で増感させるものが好ましい。 (Sensitizer)
The curable composition in the present disclosure may contain a sensitizer for the purpose of improving the generation efficiency of polymerization initiator species such as radicals and cations of the polymerization initiator and lengthening the photosensitive wavelength.
As the sensitizer, those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable.
　増感剤としては、以下に列挙する化合物類に属しており、且つ波長３００ｎｍ～波長４５０ｎｍの波長領域に吸収波長を有するものが挙げられる。
　好ましい増感剤の例としては、以下の化合物類に属しており、かつ波長３３０ｎｍ～波長４５０ｎｍの波長領域に吸収波長を有するものを挙げることができる。
　増感剤の例としては、多核芳香族類（例えば、フェナントレン、アントラセン、ピレン、ペリレン、トリフェニレン、９，１０－ジアルコキシアントラセン）、キサンテン類（例えば、フルオレッセイン、エオシン、エリスロシン、ローダミンＢ、ローズベンガル）、チオキサントン類（イソプロピルチオキサントン、ジエチルチオキサントン、クロロチオキサントン）、シアニン類（例えばチアカルボシアニン、オキサカルボシアニン）、メロシアニン類（例えば、メロシアニン、カルボメロシアニン）、フタロシアニン類、チアジン類（例えば、チオニン、メチレンブルー、トルイジンブルー）、アクリジン類（例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン）、アントラキノン類（例えば、アントラキノン）、スクアリリウム類（例えば、スクアリリウム）、アクリジンオレンジ、クマリン類（例えば、７－ジエチルアミノ－４－メチルクマリン）、ケトクマリン、フェノチアジン類、フェナジン類、スチリルベンゼン類、アゾ化合物、ジフェニルメタン、トリフェニルメタン、ジスチリルベンゼン類、カルバゾール類、ポルフィリン、スピロ化合物、キナクリドン、インジゴ、スチリル、ピリリウム化合物、ピロメテン化合物、ピラゾロトリアゾール化合物、ベンゾチアゾール化合物、バルビツール酸誘導体、チオバルビツール酸誘導体、アセトフェノン、ベンゾフェノン、ミヒラーズケトンなどの芳香族ケトン化合物、Ｎ－アリールオキサゾリジノンなどのヘテロ環化合物などが挙げられる。増感剤の例としては、更に欧州特許第５６８，９９３号明細書、米国特許第４，５０８，８１１号明細書、同５，２２７，２２７号明細書、特開２００１－１２５２５５号公報、特開平１１－２７１９６９号公報等に記載の化合物等が挙げられる。 Examples of the sensitizer include those belonging to the compounds listed below and having an absorption wavelength in the wavelength region of a wavelength of 300 nm to 450 nm.
Examples of preferable sensitizers include those belonging to the following compounds and having an absorption wavelength in the wavelength region of 330 nm to 450 nm.
Examples of sensitizers include polynuclear aromatics (eg, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (eg, fluoressein, eosin, erythrosin, rhodamine B, etc.). Rose Bengal), thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanins (eg thiacarbocyanin, oxacarbocyanin), merocyanins (eg merocyanin, carbomerocyanin), phthalocyanins, thiadins (eg thionin) , Methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acryflabin), anthraquinones (eg, anthraquinone), squaryliums (eg, squarylium), acridine oranges, coumarins (eg, 7-diethylamino-). 4-Methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethanes, triphenylmethanes, distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridones, indigo, styryl, pyririum compounds, pyromethene Examples thereof include compounds, pyrazorotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, aromatic ketone compounds such as acetphenone, benzophenone and Michler's ketone, and heterocyclic compounds such as N-aryloxazolidinone. Examples of sensitizers include European Patent Nos. 568,993, US Pat. Nos. 4,508,811, 5,227,227, Japanese Patent Application Laid-Open No. 2001-125255, and Japanese Patent Office No. 4,508,811. Examples thereof include the compounds described in Kaihei 11-271969.
　増感剤は、１種単独で用いてもよいし、２種以上を併用してもよい。
　本開示における硬化性組成物が増感剤を含む場合、増感剤の含有量は、深部への光吸収効率と開始分解効率の観点から、硬化性組成物の全固形分に対し、０．１質量％～２０質量％であることが好ましく、０．５質量％～１５質量％がより好ましい。 The sensitizer may be used alone or in combination of two or more.
When the curable composition in the present disclosure contains a sensitizer, the content of the sensitizer is 0. It is preferably 1% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass.
（共増感剤）
　本開示における硬化性組成物は、共増感剤を含有してもよい。
　共増感剤は、増感色素や開始剤の活性放射線に対する感度を一層向上させる、或いは酸素による重合性化合物の重合阻害を抑制する等の作用を有する。 (Co-sensitizer)
The curable composition in the present disclosure may contain a cosensitizer.
The co-sensitizer has an action of further improving the sensitivity of the sensitizing dye or the initiator to active radiation, or suppressing the polymerization inhibition of the polymerizable compound by oxygen.
　その他、共増感剤としては、例えば、特開２００７－２７７５１４号公報の段落０２３３～０２４１に記載の化合物が挙げられる。 Other examples of the co-sensitizer include the compounds described in paragraphs 0233 to 0241 of JP-A-2007-277514.
　共増感剤は、１種単独で用いてもよいし、２種以上を併用してもよい。
　本開示における硬化性組成物が共増感剤を含む場合、共増感剤の含有量は、重合成長速度と連鎖移動のバランスによる硬化速度の向上の観点から、硬化性組成物の全固形分に対し、０．１質量％～３０質量％の範囲が好ましく、０．５質量％～２５質量％の範囲がより好ましく、１質量％～２０質量％の範囲が更に好ましい。 The cosensitizer may be used alone or in combination of two or more.
When the curable composition in the present disclosure contains a co-sensitizer, the content of the co-sensitizer is the total solid content of the curable composition from the viewpoint of improving the curing rate by balancing the polymerization growth rate and the chain transfer. On the other hand, the range of 0.1% by mass to 30% by mass is preferable, the range of 0.5% by mass to 25% by mass is more preferable, and the range of 1% by mass to 20% by mass is further preferable.
（その他の添加剤）
　本開示における硬化性組成物には、必要に応じて、界面活性剤、近赤外線吸収顔料以外の着色剤、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止剤などの各種添加物を含有することができる。 (Other additives)
The curable composition in the present disclosure contains various additives such as a surfactant, a colorant other than a near-infrared absorbing pigment, an adhesion accelerator, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent, if necessary. can do.
　その他成分としては、例えば、特開２００７－２７７５１４号公報の段落０２３８～０２４９に記載の化合物が挙げられる。 Examples of other components include the compounds described in paragraphs 0238 to 0249 of JP-A-2007-277514.
［硬化性組成物の調製］
　本開示における硬化性組成物は、上述した各成分を混合することによって調製することができる。また、異物の除去や欠陥の低減などの目的で、フィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているものであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素樹脂、ナイロン（例えば、ナイロン－６、ナイロン－６，６）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樹脂（高密度、超高分子量を含む）等を用いたフィルタが挙げられる。これら素材の中でもポリプロピレン（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、０．０１μｍ～７．０μｍが好ましく、０．０１μｍ～３．０μｍがより好ましく、０．０５μｍ～０．５μｍが更に好ましい。フィルタの孔径をこの範囲とすることにより、後工程において均一及び平滑な組成物の調製を阻害する、微細な異物を確実に除去することが可能となる。あるいは、ファイバ状のろ材を用いることも好ましく、ろ材としては例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられ、具体的にはロキテクノ社製のＳＢＰタイプシリーズ（ＳＢＰ００８など）、ＴＰＲタイプシリーズ（ＴＰＲ００２、ＴＰＲ００５など）、ＳＨＰＸタイプシリーズ（ＳＨＰＸ００３など）のフィルタカートリッジを用いることができる。
　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のフィルタでのろ過は、１回のみでもよいし、２回以上行ってもよい。
　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することができる。市販のフィルタとしては、例えば、日本ポール（株）（ＤＦＡ４２０１ＮＩＥＹなど）、アドバンテック東洋（株）、日本インテグリス（株）又は（株）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することができる。 [Preparation of curable composition]
The curable composition in the present disclosure can be prepared by mixing each of the above-mentioned components. Further, it is preferable to filter with a filter for the purpose of removing foreign substances and reducing defects. The filter can be used without particular limitation as long as it has been conventionally used for filtration purposes and the like. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultra-high). A filter using (including molecular weight) or the like can be mentioned. Among these materials, polypropylene (including high-density polypropylene) or nylon is preferable.
The pore size of the filter is preferably 0.01 μm to 7.0 μm, more preferably 0.01 μm to 3.0 μm, and even more preferably 0.05 μm to 0.5 μm. By setting the pore size of the filter within this range, it is possible to reliably remove fine foreign substances that hinder the preparation of a uniform and smooth composition in a subsequent step. Alternatively, it is also preferable to use a fibrous filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like. Specifically, SBP type series (SBP008, etc.) and TPR type series (TPR002) manufactured by Roki Techno Co., Ltd. , TPR005, etc.), SHPX type series (SHPX003, etc.) filter cartridges can be used.
When using filters, different filters may be combined. At that time, the filtration with the first filter may be performed only once or twice or more.
Further, first filters having different pore diameters within the above-mentioned range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Paul Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Entegris Japan Co., Ltd., Kits Micro Filter Co., Ltd., and the like. ..
［硬化性組成物の用途］
　本開示における硬化性組成物は、液状とすることができるため、例えば、本開示における硬化性組成物を基材などに付与し、乾燥させることにより膜を容易に製造できる。
　本開示における硬化性組成物の２３℃における粘度は、塗布により膜を形成する場合は、塗布性の観点から、１ｍＰａ・ｓ～１００ｍＰａ・ｓであることが好ましい。下限は、２ｍＰａ・ｓ以上がより好ましく、３ｍＰａ・ｓ以上が更に好ましい。上限は、５０ｍＰａ・ｓ以下がより好ましく、３０ｍＰａ・ｓ以下が更に好ましく、１５ｍＰａ・ｓ以下が特に好ましい。
　本開示における粘度は、東機産業（株）製の粘度計（商品名：ＶＩＳＣＯＭＥＴＥＲ　ＴＶ－２２）を使用し、２３℃において測定するものとする。 [Use of curable composition]
Since the curable composition in the present disclosure can be in a liquid state, for example, a film can be easily produced by applying the curable composition in the present disclosure to a substrate or the like and drying it.
The viscosity of the curable composition in the present disclosure at 23 ° C. is preferably 1 mPa · s to 100 mPa · s from the viewpoint of coatability when a film is formed by coating. The lower limit is more preferably 2 mPa · s or more, and further preferably 3 mPa · s or more. The upper limit is more preferably 50 mPa · s or less, further preferably 30 mPa · s or less, and particularly preferably 15 mPa · s or less.
The viscosity in the present disclosure shall be measured at 23 ° C. using a viscometer (trade name: VISCOMETER TV-22) manufactured by Toki Sangyo Co., Ltd.
　本開示における硬化性組成物の用途は、特に限定されない。例えば、赤外線カットフィルタなどの形成に好ましく用いることができる。例えば、固体撮像素子の受光側における赤外線カットフィルタ（例えば、ウエハーレベルレンズに対する赤外線カットフィルタ用など）、固体撮像素子の裏面側（受光側とは反対側）における赤外線カットフィルタなどに好ましく用いることができる。特に、固体撮像素子の受光側における赤外線カットフィルタとして好ましく用いることができる。また、本開示における硬化性組成物に対し、更に、可視光を遮光する着色剤を含有させることで、特定の波長以上の赤外線を透過可能な赤外線透過フィルタを形成することもできる。例えば、波長４００ｎｍ～８５０ｎｍまでを遮光し、波長８５０ｎｍ以上の赤外線の一部を透過可能な赤外線透過フィルタを形成することもできる。 The use of the curable composition in the present disclosure is not particularly limited. For example, it can be preferably used for forming an infrared cut filter or the like. For example, it is preferably used as an infrared cut filter on the light receiving side of the solid-state image sensor (for example, for an infrared cut filter for a wafer level lens), an infrared cut filter on the back surface side of the solid-state image sensor (opposite the light receiving side), and the like. it can. In particular, it can be preferably used as an infrared cut filter on the light receiving side of the solid-state image sensor. Further, by further adding a colorant that blocks visible light to the curable composition in the present disclosure, an infrared transmission filter capable of transmitting infrared rays having a specific wavelength or higher can be formed. For example, it is possible to form an infrared transmission filter that shields light from a wavelength of 400 nm to 850 nm and can transmit a part of infrared rays having a wavelength of 850 nm or more.
　また、本開示における硬化性組成物は、収容容器に保管されることが好ましい。
　収容容器として、原材料や組成物中への不純物の混入防止を目的に、容器内壁を６種６層の樹脂で構成する多層ボトルや６種の樹脂を７層構造にしたボトルを使用することも好ましい。これらの容器としては、例えば、特開２０１５－１２３３５１号公報に記載の容器が挙げられる。 In addition, the curable composition in the present disclosure is preferably stored in a storage container.
As a storage container, a multi-layer bottle in which the inner wall of the container is composed of 6 types and 6 layers of resin or a bottle in which 6 types of resin is composed of 7 layers may be used for the purpose of preventing impurities from being mixed into the raw materials and compositions. preferable. Examples of these containers include the containers described in Japanese Patent Application Laid-Open No. 2015-123351.
＜膜＞
　本開示に係る膜は、本開示における硬化性組成物からなる又は本開示における硬化性組成物を硬化してなる膜である。
　また、本開示における硬化性組成物が溶剤を含む場合には、乾燥を行ってもよい。
　本開示に係る膜は、赤外線カットフィルタとして好ましく用いることができる。また、熱線遮蔽フィルタ、赤外線透過フィルタとして用いることもできる。本開示に係る膜は、支持体上に積層して用いてもよく、支持体から剥離して用いてもよい。本開示に係る膜は、パターンを有していてもよく、パターンを有さない膜（平坦膜）であってもよい。
　本開示における「乾燥」は、溶剤を少なくとも一部除去すればよく、溶剤を完全に除去する必要はなく、所望に応じて、溶剤の除去量を設定することができる。
　また、上記硬化は、膜の硬さが向上していればよいが、重合による硬化が好ましい。 <Membrane>
The film according to the present disclosure is a film made of the curable composition according to the present disclosure or obtained by curing the curable composition according to the present disclosure.
If the curable composition in the present disclosure contains a solvent, it may be dried.
The film according to the present disclosure can be preferably used as an infrared cut filter. It can also be used as a heat ray shielding filter and an infrared ray transmitting filter. The film according to the present disclosure may be used by being laminated on a support, or may be peeled off from the support and used. The film according to the present disclosure may have a pattern or may be a film having no pattern (flat film).
In the "drying" in the present disclosure, it is sufficient to remove at least a part of the solvent, it is not necessary to completely remove the solvent, and the amount of the solvent removed can be set as desired.
Further, the above-mentioned curing may be performed as long as the hardness of the film is improved, but curing by polymerization is preferable.
　本開示に係る膜の厚さは、目的に応じて適宜調整できる。膜の厚さは２０μｍ以下が好ましく、１０μｍ以下がより好ましく、５μｍ以下が更に好ましい。膜の厚さの下限は０．１μｍ以上が好ましく、０．２μｍ以上がより好ましく、０．３μｍ以上が更に好ましい。 The thickness of the film according to the present disclosure can be appropriately adjusted according to the purpose. The thickness of the film is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.
　本開示に係る膜は、波長６５０ｎｍ～１，５００ｎｍの範囲に極大吸収波長を有することが好ましく、波長６８０ｎｍ～１，３００ｎｍの範囲に極大吸収波長を有することがより好ましく、波長７００ｎｍ～８５０ｎｍの範囲に極大吸収波長を有することが更に好ましい。 The film according to the present disclosure preferably has a maximum absorption wavelength in the wavelength range of 650 nm to 1,500 nm, more preferably has a maximum absorption wavelength in the wavelength range of 680 nm to 1,300 nm, and has a wavelength range of 700 nm to 850 nm. It is more preferable to have a maximum absorption wavelength.
　本開示に係る膜を赤外線カットフィルタとして用いる場合は、本開示に係る膜は以下の（１）～（４）のうちの少なくとも１つの条件を満たすことが好ましく、（１）～（４）の全ての条件を満たすことが更に好ましい。
（１）波長４００ｎｍでの透過率は７０％以上が好ましく、８０％以上がより好ましく、８５％以上が更に好ましく、９０％以上が特に好ましい。
（２）波長５００ｎｍでの透過率は７０％以上が好ましく、８０％以上がより好ましく、９０％以上が更に好ましく、９５％以上が特に好ましい。
（３）波長６００ｎｍでの透過率は７０％以上が好ましく、８０％以上がより好ましく、９０％以上が更に好ましく、９５％以上が特に好ましい。
（４）波長６５０ｎｍでの透過率は７０％以上が好ましく、８０％以上がより好ましく、９０％以上が更に好ましく、９５％以上が特に好ましい。 When the film according to the present disclosure is used as an infrared cut filter, the film according to the present disclosure preferably satisfies at least one of the following (1) to (4), and the above (1) to (4). It is more preferable that all the conditions are satisfied.
(1) The transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 80% or more, further preferably 85% or more, and particularly preferably 90% or more.
(2) The transmittance at a wavelength of 500 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.
(3) The transmittance at a wavelength of 600 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.
(4) The transmittance at a wavelength of 650 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.
　本開示に係る膜は、有彩色着色剤を含むカラーフィルタと組み合わせて用いることもできる。
　ここで、カラーフィルタは、有彩色着色剤を含む着色組成物を用いて製造できる。有彩色着色剤としては、従来公知の有彩色着色剤が挙げられる。着色組成物は、有彩色着色剤以外に、樹脂、重合性化合物、重合開始剤、界面活性剤、溶剤、重合禁止剤、紫外線吸収剤などを更に含有することができる。着色組成物に含まれる各成分としては、従来公知の各成分の他、既述の各成分を適宜用いてもよい。 The film according to the present disclosure can also be used in combination with a color filter containing a chromatic colorant.
Here, the color filter can be produced by using a coloring composition containing a chromatic colorant. Examples of the chromatic colorant include conventionally known chromatic colorants. In addition to the chromatic colorant, the coloring composition may further contain a resin, a polymerizable compound, a polymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber and the like. As each component contained in the coloring composition, in addition to the conventionally known components, the above-mentioned components may be appropriately used.
　本開示に係る膜とカラーフィルタとを組み合わせて用いる場合、本開示に係る膜の光路上にカラーフィルタが配置されていることが好ましい。例えば、本開示に係る膜とカラーフィルタとを積層して積層体として用いることができる。積層体においては、本開示に係る膜とカラーフィルタとは、両者が厚み方向で隣接していてもよく、隣接していなくてもよい。本開示に係る膜とカラーフィルタとが厚み方向で隣接していない場合は、カラーフィルタが形成された支持体とは別の支持体に、本開示に係る膜が形成されていてもよく、本開示に係る膜とカラーフィルタとの間に、固体撮像素子を構成する他の部材（例えば、マイクロレンズ、平坦化層など）が介在していてもよい。 When the film according to the present disclosure and the color filter are used in combination, it is preferable that the color filter is arranged on the optical path of the film according to the present disclosure. For example, the film and the color filter according to the present disclosure can be laminated and used as a laminated body. In the laminated body, the film and the color filter according to the present disclosure may or may not be adjacent to each other in the thickness direction. When the film according to the present disclosure and the color filter are not adjacent to each other in the thickness direction, the film according to the present disclosure may be formed on a support different from the support on which the color filter is formed. Other members (for example, a microlens, a flattening layer, etc.) constituting the solid-state image sensor may be interposed between the film and the color filter according to the disclosure.
　なお、本開示において、赤外線カットフィルタとは、可視領域の波長の光（可視光）を透過させ、近赤外領域の波長の光（赤外線）の少なくとも一部を遮光するフィルタを意味する。赤外線カットフィルタは、可視領域の波長の光をすべて透過するものであってもよく、可視領域の波長の光のうち、特定の波長領域の光を通過させ、特定の波長領域の光を遮光するものであってもよい。また、本開示において、カラーフィルタとは、可視領域の波長の光のうち、特定の波長領域の光を通過させ、特定の波長領域の光を遮光するフィルタを意味する。また、本開示において、赤外線透過フィルタとは、可視光を遮光し、赤外線の少なくとも一部を透過させるフィルタを意味する。 In the present disclosure, the infrared cut filter means a filter that transmits light having a wavelength in the visible region (visible light) and blocks at least a part of light having a wavelength in the near infrared region (infrared light). The infrared cut filter may transmit all the light having a wavelength in the visible region, and among the light having a wavelength in the visible region, the light having a specific wavelength region is passed through and the light having a specific wavelength region is blocked. It may be a thing. Further, in the present disclosure, the color filter means a filter that passes light in a specific wavelength region and blocks light in a specific wavelength region among light having a wavelength in the visible region. Further, in the present disclosure, the infrared transmission filter means a filter that blocks visible light and transmits at least a part of infrared rays.
　本開示に係る膜は、ＣＣＤ（電荷結合素子）やＣＭＯＳ（相補型金属酸化膜半導体）などの固体撮像素子や、赤外線センサ、画像表示装置などの各種装置に用いることができる。 The film according to the present disclosure can be used for solid-state imaging devices such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor), and various devices such as infrared sensors and image display devices.
＜膜の製造方法＞
　次に、本開示に係る膜の製造方法について説明する。本開示に係る膜は、本開示に係る組成物を塗布する工程を経て製造できる。 <Membrane manufacturing method>
Next, a method for producing a film according to the present disclosure will be described. The film according to the present disclosure can be produced through a step of applying the composition according to the present disclosure.
　本開示に係る膜の製造方法において、組成物は支持体上に塗布することが好ましい。支持体としては、例えば、シリコン、無アルカリガラス、ソーダガラス、パイレックス（登録商標）ガラス、石英ガラスなどの材質で構成された基板が挙げられる。これらの基板には、有機膜や無機膜などが形成されていてもよい。有機膜の材料としては、例えば上述した樹脂が挙げられる。また、支持体としては、上述した樹脂で構成された基板を用いることもできる。また、支持体には、電荷結合素子（ＣＣＤ）、相補型金属酸化膜半導体（ＣＭＯＳ）、透明導電膜などが形成されていてもよい。また、支持体には、各画素を隔離するブラックマトリクスが形成されている場合もある。また、支持体には、必要により、上部の層との密着性改良、物質の拡散防止或いは基板等の支持体表面の平坦化のために下塗り層を設けてもよい。また、支持体としてガラス基板を用いる場合においては、ガラス基板上に無機膜を形成したり、ガラス基板を脱アルカリ処理して用いることが好ましい。この態様によれば、より異物の発生が抑制された膜を製造し易い。 In the method for producing a film according to the present disclosure, it is preferable that the composition is applied on a support. Examples of the support include a substrate made of a material such as silicon, non-alkali glass, soda glass, Pyrex (registered trademark) glass, and quartz glass. An organic film, an inorganic film, or the like may be formed on these substrates. Examples of the material of the organic film include the above-mentioned resin. Further, as the support, a substrate made of the above-mentioned resin can also be used. Further, the support may be formed with a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like. Further, the support may be formed with a black matrix that isolates each pixel. Further, if necessary, the support may be provided with an undercoat layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the support such as a substrate. When a glass substrate is used as the support, it is preferable to form an inorganic film on the glass substrate or to dealkalinate the glass substrate before use. According to this aspect, it is easy to manufacture a film in which the generation of foreign substances is further suppressed.
　組成物の塗布方法としては、公知の方法を用いることができる。例えば、滴下法（ドロップキャスト）；スリットコート法；スプレー法；ロールコート法；回転塗布法（スピンコーティング）；流延塗布法；スリットアンドスピン法；プリウェット法（たとえば、特開２００９－１４５３９５号公報に記載されている方法）；インクジェット（例えばオンデマンド方式、ピエゾ方式、サーマル方式）、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷法などの各種印刷法；金型等を用いた転写法；ナノインプリント法などが挙げられる。インクジェットでの適用方法としては、特に限定されず、例えば「広がる・使えるインクジェット－特許に見る無限の可能性－、２００５年２月発行、住ベテクノリサーチ」に示された方法（特に１１５ページ～１３３ページ）や、特開２００３－２６２７１６号公報、特開２００３－１８５８３１号公報、特開２００３－２６１８２７号公報、特開２０１２－１２６８３０号公報、特開２００６－１６９３２５号公報などに記載の方法が挙げられる。 As a method for applying the composition, a known method can be used. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395). Methods described in the publication); Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Various printing methods; transfer method using a mold or the like; nano-imprint method and the like can be mentioned. The method of application to inkjet is not particularly limited, and is, for example, the method shown in "Expandable and usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). (Page 133), and the methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned.
　組成物を塗布して形成した組成物層は、乾燥（プリベーク）してもよい。低温プロセスによりパターンを形成する場合は、プリベークを行わなくてもよい。プリベークを行う場合、プリベーク温度は、１５０℃以下が好ましく、１２０℃以下がより好ましく、１１０℃以下が更に好ましい。下限は、例えば、５０℃以上とすることが好ましく、８０℃以上とすることがより好ましい。プリベーク温度を１５０℃以下で行うことにより、例えば、イメージセンサの光電変換膜を有機素材で構成した場合において、これらの特性をより効果的に維持することができる。
　プリベーク時間は、１０秒～３，０００秒が好ましく、４０秒～２，５００秒がより好ましく、８０秒～２２０秒が更に好ましい。乾燥は、ホットプレート、オーブン等で行うことができる。 The composition layer formed by applying the composition may be dried (prebaked). Prebaking may not be required if the pattern is formed by a low temperature process. When prebaking is performed, the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower. The lower limit is, for example, preferably 50 ° C. or higher, and more preferably 80 ° C. or higher. By performing the prebaking temperature at 150 ° C. or lower, for example, when the photoelectric conversion film of the image sensor is made of an organic material, these characteristics can be maintained more effectively.
The prebaking time is preferably 10 seconds to 3,000 seconds, more preferably 40 seconds to 2,500 seconds, and even more preferably 80 seconds to 220 seconds. Drying can be performed on a hot plate, an oven, or the like.
　本開示に係る膜の製造方法においては、更にパターンを形成する工程を含んでいてもよい。パターン形成方法としては、フォトリソグラフィ法を用いたパターン形成方法や、ドライエッチング法を用いたパターン形成方法が挙げられる。なお、本開示に係る膜を平坦膜として用いる場合には、パターンを形成する工程を行わなくてもよい。以下、パターンを形成する工程について詳細に説明する。 The film manufacturing method according to the present disclosure may further include a step of forming a pattern. Examples of the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method. When the film according to the present disclosure is used as a flat film, it is not necessary to perform the step of forming the pattern. Hereinafter, the process of forming the pattern will be described in detail.
－フォトリソグラフィ法でパターン形成する場合－
　フォトリソグラフィ法でのパターン形成方法は、本開示に係る組成物を塗布して形成した組成物層に対しパターン状に露光する工程（露光工程）と、未露光部の組成物層を現像除去してパターンを形成する工程（現像工程）と、を含むことが好ましい。必要に応じて、現像されたパターンをベークする工程（ポストベーク工程）を設けてもよい。以下、各工程について説明する。 -When forming a pattern by photolithography-
The pattern forming method in the photolithography method includes a step of exposing the composition layer formed by applying the composition according to the present disclosure in a pattern (exposure step) and developing and removing the composition layer of the unexposed portion. It is preferable to include a step of forming a pattern (development step). If necessary, a step of baking the developed pattern (post-baking step) may be provided. Hereinafter, each step will be described.
＜＜露光工程＞＞
　露光工程では組成物層をパターン状に露光する。例えば、組成物層に対し、ステッパー等の露光装置を用いて、所定のマスクパターンを有するマスクを介して露光することで、組成物層をパターン露光することができる。これにより、露光部分を硬化することができる。露光に際して用いることができる放射線（光）としては、ｇ線、ｉ線等の紫外線が好ましく、ｉ線がより好ましい。照射量（露光量）は、例えば、０．０３Ｊ／ｃｍ２～２．５Ｊ／ｃｍ２が好ましく、０．０５Ｊ／ｃｍ２～１．０Ｊ／ｃｍ２がより好ましく、０．０８Ｊ／ｃｍ２～０．５Ｊ／ｃｍ２が特に好ましい。露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば酸素濃度が１９体積％以下の低酸素雰囲気下（例えば、１５体積％、５体積％、実質的に無酸素）で露光してもよく、酸素濃度が２１体積％を超える高酸素雰囲気下（例えば、２２体積％、３０体積％、５０体積％）で露光してもよい。また、露光照度は適宜設定することが可能であり、好ましくは１，０００Ｗ／ｍ２～１００，０００Ｗ／ｍ２（例えば、５，０００Ｗ／ｍ２、１５，０００Ｗ／ｍ２、３５，０００Ｗ／ｍ２）の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度１０体積％で照度１０，０００Ｗ／ｍ２、酸素濃度３５体積％で照度２０，０００Ｗ／ｍ２などとすることができる。 << Exposure process >>
In the exposure step, the composition layer is exposed in a pattern. For example, the composition layer can be pattern-exposed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure device such as a stepper. As a result, the exposed portion can be cured. As the radiation (light) that can be used for exposure, ultraviolet rays such as g-ray and i-line are preferable, and i-ray is more preferable. Irradiation dose (exposure dose), for example, preferably 0.03J / cm 2 ~ 2.5J / cm 2, more preferably 0.05J / cm 2 ~ 1.0J / cm 2, 0.08J / cm 2 ~ 0.5 J / cm 2 is particularly preferable. The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere where the oxygen concentration is 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free). ), Or in a high oxygen atmosphere where the oxygen concentration exceeds 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume). The exposure intensity is can be set appropriately, preferably 1,000W / m 2 ~ 100,000W / m 2 ( e.g., 5,000W / m 2, 15,000W / m 2, 35,000W / It can be selected from the range of m 2). Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10,000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20,000W / m 2.
＜＜現像工程＞＞
　次に、露光後の組成物層における未露光部の組成物層を現像除去してパターンを形成する。未露光部の組成物層の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の組成物層が現像液に溶出し、光硬化した部分だけが支持体上に残る。現像液としては、下地の固体撮像素子や回路などにダメージを与えない、アルカリ現像液が望ましい。現像液の温度は、例えば、２０℃～３０℃が好ましい。現像時間は、２０秒～１８０秒が好ましい。また、残渣除去性を向上するため、現像液を６０秒ごとに振り切り、更に新たに現像液を供給する工程を数回繰り返してもよい。 << Development process >>
Next, the composition layer in the unexposed portion of the composition layer after exposure is developed and removed to form a pattern. The development and removal of the composition layer in the unexposed portion can be performed using a developing solution. As a result, the composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains on the support. As the developing solution, an alkaline developing solution that does not damage the underlying solid-state image sensor or circuit is desirable. The temperature of the developing solution is preferably, for example, 20 ° C to 30 ° C. The development time is preferably 20 seconds to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.
　現像液に用いるアルカリ剤としては、例えば、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、ジグリコールアミン、ジエタノールアミン、ヒドロキシアミン、エチレンジアミン、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、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセンなどの有機アルカリ性化合物や、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、メタケイ酸ナトリウムなどの無機アルカリ性化合物が挙げられる。現像液は、これらのアルカリ剤を純水で希釈したアルカリ性水溶液が好ましく使用される。アルカリ性水溶液のアルカリ剤の濃度は、０．００１質量％～１０質量％が好ましく、０．０１質量％～１質量％がより好ましい。また、現像液には、界面活性剤を用いてもよい。界面活性剤の例としては、現像液に用いる従来公知の界面活性剤が挙げられ、ノニオン系界面活性剤が好ましい。現像液は、移送や保管の便宜などの観点より、一旦濃縮液として製造し、使用時に必要な濃度に希釈してもよい。希釈倍率は特に限定されないが、例えば１．５倍～１００倍の範囲に設定することができる。なお、このようなアルカリ性水溶液からなる現像液を使用した場合には、現像後純水で洗浄（リンス）することが好ましい。 Examples of the alkaline agent used in the developing solution include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. Organic alkalinity such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrol, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene. Examples thereof include compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. As the developing solution, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 1% by mass. Moreover, you may use a surfactant as a developer. Examples of the surfactant include conventionally known surfactants used in developing solutions, and nonionic surfactants are preferable. The developer may be once produced as a concentrated solution and diluted to a concentration required for use from the viewpoint of convenience of transfer and storage. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 times to 100 times. When a developer composed of such an alkaline aqueous solution is used, it is preferable to wash (rinse) it with pure water after development.
　現像後、乾燥を施した後に加熱処理（ポストベーク）を行うこともできる。ポストベークは、膜の硬化を完全なものとするための現像後の加熱処理である。ポストベークを行う場合、ポストベーク温度は、例えば、１００℃～２４０℃が好ましい。膜硬化の観点から、２００℃～２３０℃がより好ましい。また、発光光源として有機エレクトロルミネッセンス（有機ＥＬ）素子を用いた場合や、イメージセンサの光電変換膜を有機素材で構成した場合は、ポストベーク温度は、１５０℃以下が好ましく、１２０℃以下がより好ましく、１００℃以下が更に好ましく、９０℃以下が特に好ましい。下限は、例えば、５０℃以上とすることができる。ポストベークは、現像後の膜に対して、上記条件になるようにホットプレートやコンベクションオーブン（熱風循環式乾燥機）、高周波加熱機等の加熱手段を用いて、連続式或いはバッチ式で行うことができる。また、低温プロセスによりパターンを形成する場合は、ポストベークは行わなくてもよく、再度露光する工程（後露光工程）を追加してもよい。 It is also possible to perform heat treatment (post-baking) after developing and drying. Post-baking is a post-development heat treatment to complete the curing of the film. When post-baking is performed, the post-baking temperature is preferably, for example, 100 ° C. to 240 ° C. From the viewpoint of film curing, 200 ° C. to 230 ° C. is more preferable. When an organic electroluminescence (organic EL) element is used as the light emitting light source, or when the photoelectric conversion film of the image sensor is made of an organic material, the post-bake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower. Preferably, 100 ° C. or lower is more preferable, and 90 ° C. or lower is particularly preferable. The lower limit can be, for example, 50 ° C. or higher. Post-baking should be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the above conditions are met. Can be done. Further, when the pattern is formed by the low temperature process, post-baking may not be performed, and a step of re-exposure (post-exposure step) may be added.
－ドライエッチング法でパターン形成する場合－
　ドライエッチング法でのパターン形成は、組成物を支持体上などに塗布して形成した組成物層を硬化して硬化物層を形成し、次いで、この硬化物層上にパターニングされたフォトレジスト層を形成し、次いで、パターニングされたフォトレジスト層をマスクとして硬化物層に対してエッチングガスを用いてドライエッチングするなどの方法で行うことができる。フォトレジスト層の形成においては、更にプリベーク処理を施すことが好ましい。特に、フォトレジストの形成プロセスとしては、露光後の加熱処理、現像後の加熱処理（ポストベーク処理）を実施する形態が望ましい。ドライエッチング法でのパターン形成については、特開２０１３－６４９９３号公報の段落００１０～００６７の記載を参酌でき、この内容は本明細書に組み込まれる。 -When forming a pattern by dry etching method-
In the pattern formation by the dry etching method, the composition layer formed by applying the composition on a support or the like is cured to form a cured product layer, and then a photoresist layer patterned on the cured product layer is formed. Then, using the patterned photoresist layer as a mask, the cured product layer can be dry-etched with an etching gas. In forming the photoresist layer, it is preferable to further perform a prebaking treatment. In particular, as the photoresist forming process, it is desirable to carry out a heat treatment after exposure and a heat treatment (post-baking treatment) after development. Regarding the pattern formation by the dry etching method, the description in paragraphs 0010 to 0067 of JP2013-64993A can be referred to, and this content is incorporated in the present specification.
＜光学フィルタ＞
　本開示に係る光学フィルタは、本開示に係る膜を有する。
　本開示に係る光学フィルタは、赤外線カットフィルタ又は赤外線透過フィルタとして好ましく用いることができ、赤外線カットフィルタとしてより好ましく用いることができる。
　また、本開示に係る膜と、赤、緑、青、マゼンタ、黄、シアン、黒及び無色よりなる群から選ばれる画素とを有する態様も本開示に係る光学フィルタの好ましい態様である。 <Optical filter>
The optical filter according to the present disclosure has a film according to the present disclosure.
The optical filter according to the present disclosure can be preferably used as an infrared cut filter or an infrared transmission filter, and can be more preferably used as an infrared cut filter.
A preferred embodiment of the optical filter according to the present disclosure is also an embodiment having a film according to the present disclosure and pixels selected from the group consisting of red, green, blue, magenta, yellow, cyan, black and colorless.
　本開示に係る赤外線カットフィルタは、本開示に係る膜を有する。
　なお、本開示に係る赤外線カットフィルタは、赤外線領域の一部の波長の赤外線のみをカットするフィルタであっても、赤外線領域の全体をカットするフィルタであってもよい。赤外線領域の一部の波長の赤外線のみをカットするフィルタとしては、例えば、近赤外線カットフィルタが挙げられる。なお、近赤外線としては、波長７５０ｎｍ～２，５００ｎｍの赤外線が挙げられる。
　また、本開示に係る赤外線カットフィルタは、波長７５０ｎｍ～１，０００ｎｍの範囲の赤外線をカットするフィルタであることが好ましく、波長７５０ｎｍ～１，２００ｎｍの範囲の赤外線をカットするフィルタであることがより好ましく、波長７５０ｎｍ～１，５００ｎｍの赤外線をカットするフィルタであることが更に好ましい。
　本開示に係る赤外線カットフィルタは、上記膜の他に、更に、銅を含有する層、誘電体多層膜、紫外線吸収層などを有していてもよい。本開示に係る赤外線カットフィルタが、更に、銅を含有する層、又は、誘電体多層膜を少なくとも有することで、視野角が広く、赤外線遮蔽性に優れた赤外線カットフィルタが得られ易い。また、本開示に係る赤外線カットフィルタが、更に、紫外線吸収層を有することで、紫外線遮蔽性に優れた赤外線カットフィルタとすることができる。紫外線吸収層としては、例えば、国際公開第２０１５／０９９０６０号の段落００４０～００７０及び０１１９～０１４５に記載の吸収層を参酌でき、この内容は本明細書に組み込まれる。誘電体多層膜としては、特開２０１４－４１３１８号公報の段落０２５５～０２５９の記載を参酌でき、この内容は本明細書に組み込まれる。銅を含有する層としては、銅を含有するガラスで構成されたガラス基材（銅含有ガラス基材）や、銅錯体を含む層（銅錯体含有層）を用いることもできる。銅含有ガラス基材としては、銅を含有する燐酸塩ガラス、銅を含有する弗燐酸塩ガラスなどが挙げられる。銅含有ガラスの市販品としては、ＮＦ－５０（ＡＧＣテクノグラス（株）製）、ＢＧ－６０、ＢＧ－６１（以上、ショット社製）、ＣＤ５０００（ＨＯＹＡ（株）製）等が挙げられる。 The infrared cut filter according to the present disclosure has a film according to the present disclosure.
The infrared cut filter according to the present disclosure may be a filter that cuts only infrared rays having a wavelength of a part of the infrared region, or a filter that cuts the entire infrared region. Examples of the filter that cuts only infrared rays having a wavelength of a part of the infrared region include a near-infrared ray cut filter. Examples of near-infrared rays include infrared rays having a wavelength of 750 nm to 2,500 nm.
Further, the infrared cut filter according to the present disclosure is preferably a filter that cuts infrared rays in the wavelength range of 750 nm to 1,000 nm, and more preferably a filter that cuts infrared rays in the wavelength range of 750 nm to 1,200 nm. It is preferable that the filter cuts infrared rays having a wavelength of 750 nm to 1,500 nm.
In addition to the above film, the infrared cut filter according to the present disclosure may further have a copper-containing layer, a dielectric multilayer film, an ultraviolet absorbing layer, and the like. Since the infrared cut filter according to the present disclosure further has at least a copper-containing layer or a dielectric multilayer film, it is easy to obtain an infrared cut filter having a wide viewing angle and excellent infrared shielding property. Further, the infrared cut filter according to the present disclosure can be made into an infrared cut filter having excellent ultraviolet shielding property by further having an ultraviolet absorbing layer. As the ultraviolet absorbing layer, for example, the absorbing layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/09960 can be referred to, and the contents thereof are incorporated in the present specification. As the dielectric multilayer film, the description in paragraphs 0255 to 0259 of JP2014-413118A can be referred to, and the contents thereof are incorporated in the present specification. As the copper-containing layer, a glass base material made of copper-containing glass (copper-containing glass base material) or a layer containing a copper complex (copper complex-containing layer) can also be used. Examples of the copper-containing glass base material include copper-containing phosphate glass and copper-containing fluoride glass. Examples of commercially available copper-containing glass products include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (manufactured by Schott AG), CD5000 (manufactured by HOYA Corporation), and the like.
　本開示に係る赤外線カットフィルタは、ＣＣＤ（電荷結合素子）、ＣＭＯＳ（相補型金属酸化膜半導体）などの固体撮像素子、赤外線センサ、画像表示装置などの各種装置に用いることができる。 The infrared cut filter according to the present disclosure can be used in various devices such as a solid-state image sensor such as a CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor), an infrared sensor, and an image display device.
　本開示に係る赤外線カットフィルタは、本開示に係る組成物を用いて得られる膜の画素（パターン）と、赤、緑、青、マゼンタ、黄、シアン、黒及び無色よりなる群から選ばれる少なくとも１種の画素（パターン）とを有する態様も好ましい態様である。 The infrared cut filter according to the present disclosure is selected from at least a group consisting of film pixels (patterns) obtained by using the composition according to the present disclosure, red, green, blue, magenta, yellow, cyan, black and colorless. A mode having one type of pixel (pattern) is also a preferred mode.
　本開示に係る光学フィルタの製造方法としては、特に制限はないが、本開示に係る組成物を支持体上に適用して組成物層を形成する工程と、上記組成物層をパターン状に露光する工程と、未露光部を現像除去してパターンを形成する工程と、をこの順に含む方法であることが好ましい。
　また、本開示に係る光学フィルタの製造方法としては、本開示に係る組成物を支持体上に適用して組成物層を形成し、硬化して層を形成する工程と、上記層上にフォトレジスト層を形成する工程と、露光及び現像することにより上記フォトレジスト層をパターニングしてレジストパターンを得る工程と、上記レジストパターンをエッチングマスクとして上記層をドライエッチングする工程と、を含む方法であることも好ましい。
　本開示に係る光学フィルタの製造方法における各工程としては、本開示に係る膜の製造方法における各工程を参照することができる。 The method for producing the optical filter according to the present disclosure is not particularly limited, but a step of applying the composition according to the present disclosure on a support to form a composition layer and exposing the composition layer in a pattern. It is preferable that the method includes a step of forming a pattern by developing and removing an unexposed portion and a step of forming a pattern in this order.
Further, as a method for producing an optical filter according to the present disclosure, a step of applying the composition according to the present disclosure on a support to form a composition layer and curing to form a layer, and a step of forming a layer on the layer, and a photo This method includes a step of forming a resist layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the layer using the resist pattern as an etching mask. It is also preferable.
As each step in the method for manufacturing an optical filter according to the present disclosure, each step in the method for manufacturing a film according to the present disclosure can be referred to.
＜固体撮像素子＞
　本開示に係る固体撮像素子は、本開示に係る膜を有する。固体撮像素子の構成としては、本開示に係る膜を有する構成であり、固体撮像素子として機能する構成であれば特に限定はない。例えば、以下のような構成が挙げられる。 <Solid image sensor>
The solid-state image sensor according to the present disclosure has a film according to the present disclosure. The configuration of the solid-state image sensor is not particularly limited as long as it has a film according to the present disclosure and functions as a solid-state image sensor. For example, the following configuration can be mentioned.
　支持体上に、固体撮像素子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転送電極を有し、フォトダイオード及び転送電極上にフォトダイオードの受光部のみ開口したタングステン等からなる遮光膜を有し、遮光膜上に遮光膜全面及びフォトダイオード受光部を覆うように形成された窒化シリコン等からなるデバイス保護膜を有し、デバイス保護膜上に、本開示に係る膜を有する構成である。更に、デバイス保護膜上であって、本開示に係る膜の下（支持体に近い側）に集光手段（例えば、マイクロレンズ等。以下同じ）を有する構成や、本開示に係る膜上に集光手段を有する構成等であってもよい。また、固体撮像素子に用いられるカラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各画素を形成する膜が埋め込まれた構造を有していてもよい。この場合の隔壁は各画素よりも低屈折率であることが好ましい。このような構造を有する固体撮像素子の例としては、特開２０１２－２２７４７８号公報、特開２０１４－１７９５７７号公報に記載の装置が挙げられる。 On the support, a transfer electrode made of a plurality of photodiodes and polysilicon or the like constituting the light receiving area of the solid-state image sensor is provided, and light shielding made of tungsten or the like having only the light receiving portion of the photodiode opened on the photodiode and the transfer electrode. A configuration having a film, a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and a photodiode light-receiving portion, and a film according to the present disclosure on the device protective film. Is. Further, on the device protective film, a structure having a light collecting means (for example, a microlens or the like; the same applies hereinafter) under the film according to the present disclosure (the side closer to the support), or on the film according to the present disclosure. It may be configured to have a light collecting means or the like. Further, the color filter used in the solid-state image sensor may have a structure in which a film forming each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a lower refractive index than each pixel. Examples of the solid-state image sensor having such a structure include the devices described in JP-A-2012-227478 and JP-A-2014-179757.
＜画像表示装置＞
　本開示に係る画像表示装置は、本開示に係る膜を有する。画像表示装置としては、液晶表示装置や有機エレクトロルミネッセンス（有機ＥＬ）表示装置などが挙げられる。画像表示装置の定義や詳細については、例えば「電子ディスプレイデバイス（佐々木　昭夫著、（株）工業調査会　１９９０年発行）」、「ディスプレイデバイス（伊吹　順章著、産業図書（株）平成元年発行）」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術（内田　龍男編集、（株）工業調査会　１９９４年発行）」に記載されている。本開示に適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。画像表示装置は、白色有機ＥＬ素子を有するものであってもよい。白色有機ＥＬ素子としては、タンデム構造であることが好ましい。有機ＥＬ素子のタンデム構造については、特開２００３－４５６７６号公報、三上明義監修、「有機ＥＬ技術開発の最前線－高輝度・高精度・長寿命化・ノウハウ集－」、技術情報協会、３２６～３２８ページ、２００８年などに記載されている。有機ＥＬ素子が発光する白色光のスペクトルは、青色領域（４３０ｎｍ～４８５ｎｍ）、緑色領域（５３０ｎｍ～５８０ｎｍ）及び黄色領域（５８０ｎｍ～６２０ｎｍ）に強い極大発光ピークを有するものが好ましい。これらの発光ピークに加え更に赤色領域（６５０ｎｍ～７００ｎｍ）に極大発光ピークを有するものがより好ましい。 <Image display device>
The image display device according to the present disclosure has a film according to the present disclosure. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. For the definition and details of the image display device, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., 1990)", "Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd., 1989)" ) ”And so on. The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994)". The liquid crystal display device applicable to the present disclosure is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology". The image display device may have a white organic EL element. The white organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, Japanese Patent Application Laid-Open No. 2003-45676, supervised by Akiyoshi Mikami, "Forefront of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, It is described on pages 326 to 328, 2008 and the like. The spectrum of white light emitted by the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm), and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable.
＜赤外線センサ＞
　本開示に係る赤外線センサは、本開示に係る膜を有する。赤外線センサの構成としては、赤外線センサとして機能する構成であれば特に限定はない。以下、本開示に係る赤外線センサの一実施形態について、図面を用いて説明する。 <Infrared sensor>
The infrared sensor according to the present disclosure has a film according to the present disclosure. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. Hereinafter, an embodiment of the infrared sensor according to the present disclosure will be described with reference to the drawings.
　図１において、符号１１０は、固体撮像素子である。固体撮像素子１１０上に設けられている撮像領域は、赤外線カットフィルタ１１１と、赤外線透過フィルタ１１４とを有する。また、赤外線カットフィルタ１１１上には、カラーフィルタ１１２が積層している。カラーフィルタ１１２及び赤外線透過フィルタ１１４の入射光ｈν側には、マイクロレンズ１１５が配置されている。マイクロレンズ１１５を覆うように平坦化層１１６が形成されている。 In FIG. 1, reference numeral 110 is a solid-state image sensor. The image pickup region provided on the solid-state image sensor 110 includes an infrared cut filter 111 and an infrared transmission filter 114. Further, a color filter 112 is laminated on the infrared cut filter 111. A microlens 115 is arranged on the incident light hν side of the color filter 112 and the infrared transmission filter 114. The flattening layer 116 is formed so as to cover the microlens 115.
　赤外線カットフィルタ１１１は、本開示に係る組成物を用いて形成することができる。赤外線カットフィルタ１１１の分光特性は、使用する赤外発光ダイオード（赤外ＬＥＤ）の発光波長に応じて選択される。 The infrared cut filter 111 can be formed by using the composition according to the present disclosure. The spectral characteristics of the infrared cut filter 111 are selected according to the emission wavelength of the infrared light emitting diode (infrared LED) used.
　カラーフィルタ１１２は、可視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、特に限定はなく、従来公知の画素形成用のカラーフィルタを用いることができる。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などが用いられる。例えば、特開２０１４－４３５５６号公報の段落０２１４～０２６３の記載を参酌することができ、この内容は本明細書に組み込まれる The color filter 112 is a color filter on which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the description in paragraphs 0214 to 0263 of JP2014-43556A can be referred to, and this content is incorporated in the present specification.
　赤外線透過フィルタ１１４は、使用する赤外ＬＥＤの発光波長に応じてその特性が選択される。例えば、赤外ＬＥＤの発光波長が８５０ｎｍである場合、赤外線透過フィルタ１１４は、膜の厚み方向における光透過率の、波長４００ｎｍ～６５０ｎｍの範囲における最大値が３０％以下であることが好ましく、２０％以下であることがより好ましく、１０％以下であることが更に好ましく、０．１％以下であることが特に好ましい。この透過率は、波長４００ｎｍ～６５０ｎｍの範囲の全域で上記の条件を満たすことが好ましい。 The characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used. For example, when the emission wavelength of the infrared LED is 850 nm, the infrared transmittance filter 114 preferably has a maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 nm to 650 nm of 30% or less. It is more preferably% or less, further preferably 10% or less, and particularly preferably 0.1% or less. It is preferable that the transmittance satisfies the above conditions in the entire range of the wavelength range of 400 nm to 650 nm.
　赤外線透過フィルタ１１４は、膜の厚み方向における光透過率の、波長８００ｎｍ以上（好ましくは８００ｎｍ～１，３００ｎｍ）の範囲における最小値が７０％以上であることが好ましく、８０％以上であることがより好ましく、９０％以上であることが更に好ましい。上記の透過率は、波長８００ｎｍ以上の範囲の一部で上記の条件を満たすことが好ましく、赤外ＬＥＤの発光波長に対応する波長で上記の条件を満たすことがより好ましい。 The infrared transmittance filter 114 preferably has a minimum value of the light transmittance in the film thickness direction in the wavelength range of 800 nm or more (preferably 800 nm to 1,300 nm) of 70% or more, preferably 80% or more. More preferably, it is more preferably 90% or more. The above-mentioned transmittance preferably satisfies the above condition in a part of the wavelength range of 800 nm or more, and more preferably the above-mentioned condition at a wavelength corresponding to the emission wavelength of the infrared LED.
　赤外線透過フィルタ１１４の膜厚は、１００μｍ以下が好ましく、１５μｍ以下がより好ましく、５μｍ以下が更に好ましく、１μｍ以下が特に好ましい。下限値は、０．１μｍが好ましい。膜厚が上記範囲であれば、上述した分光特性を満たす膜とすることができる。
　赤外線透過フィルタ１１４の分光特性、膜厚等の測定方法を以下に示す。
　膜厚は、膜を有する乾燥後の基板を、触針式表面形状測定器（ＵＬＶＡＣ社製ＤＥＫＴＡＫ１５０）を用いて測定する。
　膜の分光特性は、紫外可視近赤外分光光度計（（株）日立ハイテクノロジーズ製Ｕ－４１００）を用いて、波長３００ｎｍ～１，３００ｎｍの範囲において透過率を測定した値である。 The film thickness of the infrared transmission filter 114 is preferably 100 μm or less, more preferably 15 μm or less, further preferably 5 μm or less, and particularly preferably 1 μm or less. The lower limit is preferably 0.1 μm. When the film thickness is in the above range, the film can be a film satisfying the above-mentioned spectral characteristics.
The method for measuring the spectral characteristics, film thickness, etc. of the infrared transmission filter 114 is shown below.
The film thickness is measured by using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC) on the dried substrate having the film.
The spectral characteristics of the film are values obtained by measuring the transmittance in the wavelength range of 300 nm to 1,300 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).
　また、例えば、赤外ＬＥＤの発光波長が９４０ｎｍである場合、赤外線透過フィルタ１１４は、膜の厚み方向における光の透過率の、波長４５０ｎｍ～６５０ｎｍの範囲における最大値が２０％以下であり、膜の厚み方向における、波長８３５ｎｍの光の透過率が２０％以下であり、膜の厚み方向における光の透過率の、波長１，０００ｎｍ～１，３００ｎｍの範囲における最小値が７０％以上であることが好ましい。 Further, for example, when the emission wavelength of the infrared LED is 940 nm, the infrared transmittance filter 114 has a maximum value of the light transmittance in the film thickness direction in the wavelength range of 450 nm to 650 nm of 20% or less, and the film. The transmittance of light having a wavelength of 835 nm in the thickness direction of the film is 20% or less, and the minimum value of the transmittance of light in the thickness direction of the film in the wavelength range of 1,000 nm to 1,300 nm is 70% or more. Is preferable.
　図１に示す赤外線センサにおいて、平坦化層１１６上には、赤外線カットフィルタ１１１とは別の赤外線カットフィルタ（他の赤外線カットフィルタ）が更に配置されていてもよい。他の赤外線カットフィルタとしては、銅を含有する層、又は、誘電体多層膜を少なくとも有するものなどが挙げられる。これらの詳細については、上述したものが挙げられる。また、他の赤外線カットフィルタとしては、デュアルバンドパスフィルタを用いてもよい。
　また、本開示に用いられる赤外線透過フィルタ及び赤外線カットフィルタの吸収波長は、使用光源等に合わせて適宜組み合わせて用いられる。 In the infrared sensor shown in FIG. 1, an infrared cut filter (another infrared cut filter) different from the infrared cut filter 111 may be further arranged on the flattening layer 116. Examples of other infrared cut filters include those having a copper-containing layer or at least a dielectric multilayer film. These details include those mentioned above. Further, as another infrared cut filter, a dual bandpass filter may be used.
Further, the absorption wavelengths of the infrared transmission filter and the infrared cut filter used in the present disclosure are appropriately combined and used according to the light source used and the like.
＜カメラモジュール＞
　本開示に係るカメラモジュールは、固体撮像素子と、本開示に係る光学フィルタとを有する。
　また、本開示に係るカメラモジュールは、レンズ、及び、上記固体撮像素子から得られる撮像を処理する回路を更に有することが好ましい。
　本開示に係るカメラモジュールに用いられる固体撮像素子としては、上記本開示に係る固体撮像素子であってもよいし、公知の固体撮像素子であってもよい。
　また、本開示に係るカメラモジュールに用いられるレンズ、及び、上記固体撮像素子から得られる撮像を処理する回路としては、公知のものを用いることができる。
　カメラモジュールの例としては、特開２０１６－６４７６号公報、又は、特開２０１４－１９７１９０号公報に記載のカメラモジュールを参酌でき、これらの内容は本明細書に組み込まれる。 <Camera module>
The camera module according to the present disclosure includes a solid-state image sensor and an optical filter according to the present disclosure.
Further, it is preferable that the camera module according to the present disclosure further includes a lens and a circuit for processing an image pickup obtained from the solid-state image sensor.
The solid-state image sensor used in the camera module according to the present disclosure may be the solid-state image sensor according to the present disclosure or a known solid-state image sensor.
Further, as the lens used in the camera module according to the present disclosure and the circuit for processing the image pickup obtained from the solid-state image sensor, known ones can be used.
As an example of the camera module, the camera modules described in JP-A-2016-6476 or JP-A-2014-197190 can be referred to, and the contents thereof are incorporated in the present specification.
＜インクジェットインク及びその他の用途＞
　本開示に係るインクジェットインクは、本開示における硬化性組成物を含む。
　また、本開示における硬化性組成物は、塗料、セキュリティインク等にも用いることができる。
　更に、本開示における硬化性組成物は、遮熱材料、蓄熱材料、又は、光熱変換材料として用いることもできる。 <Inkjet ink and other uses>
The inkjet ink according to the present disclosure includes the curable composition in the present disclosure.
Further, the curable composition in the present disclosure can also be used for paints, security inks and the like.
Further, the curable composition in the present disclosure can also be used as a heat shield material, a heat storage material, or a photothermal conversion material.
　以下、実施例により本開示を詳細に説明するが、本開示はこれらに限定されるものではない。
　本実施例において、「％」、「部」とは、特に断りのない限り、それぞれ「質量％」、「質量部」を意味する。なお、高分子化合物において、特別に規定したもの以外は、分子量は重量平均分子量（Ｍｗ）であり、構成単位の比率はモル百分率である。
　重量平均分子量（Ｍｗ）は、ゲル浸透クロマトグラフィー（ＧＰＣ）法によるポリスチレン換算値として測定した値である。 Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited thereto.
In this embodiment, "%" and "parts" mean "mass%" and "parts by mass", respectively, unless otherwise specified. In the polymer compound, the molecular weight is the weight average molecular weight (Mw), and the ratio of the constituent units is the molar percentage, except for those specified specifically.
The weight average molecular weight (Mw) is a value measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
［実施例１～６８、比較例１～６］
＜硬化性組成物の調製＞
　下記表１～表６に記載の原料を混合して、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）を用いてろ過して、硬化性組成物を調製した。
　なお、分散液は、以下のように調製した分散液を用いた。
　下記表１～表６の分散液の欄に記載の種類の、近赤外線吸収顔料（表中「顔料」と表記）、顔料誘導体、分散剤、及び溶剤Ａを、それぞれ下記の表１～表６の分散液の欄に記載の量で混合し、更に直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて５時間分散処理を行い、ビーズをろ過で分離して分散液を製造した。 [Examples 1 to 68, Comparative Examples 1 to 6]
<Preparation of curable composition>
The raw materials shown in Tables 1 to 6 below were mixed and filtered using a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a curable composition.
As the dispersion, the dispersion prepared as follows was used.
The types of near-infrared absorbing pigments (denoted as "pigments" in the table), pigment derivatives, dispersants, and solvent A of the types listed in the dispersion liquid column of Tables 1 to 6 below are listed in Tables 1 to 6 below, respectively. Mix in the amount described in the column of dispersion liquid, add 230 parts by mass of zirconia beads having a diameter of 0.3 mm, perform dispersion treatment for 5 hours using a paint shaker, separate the beads by filtration, and separate the dispersion liquid. Manufactured.
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000047
　各硬化性組成物に用いた原料は、以下の通りである。
－近赤外線吸収顔料（表中は「顔料」と表記）－
　顔料ＰＰ１～ＰＰ４及びＳＱ１～ＳＱ３：下記構造の化合物
　ＳＱ－１、ＳＱ－１４、ＳＱ－１３、ＳＱ－１５、ＳＱ－１７、ＳＱ－３３、ＳＱ－２４、ＳＱ－２５、ＳＱ－２７、ＳＱ－３０、ＳＱ－２１、ＳＱ－３７、ＳＱ－４３、ＳＱ－５２、ＳＱ－５６、及びＳＱ－６０：既述のスクアリリウム化合物の具体例として挙げられた化合物［ＳＱ－１、ＳＱ－１４、ＳＱ－１３、ＳＱ－１５、ＳＱ－１７、ＳＱ－３３、ＳＱ－２４、ＳＱ－２５、ＳＱ－２７、ＳＱ－３０、ＳＱ－２１、ＳＱ－３７、ＳＱ－４３、ＳＱ－５２、ＳＱ－５６、及びＳＱ－６０］ The raw materials used for each curable composition are as follows.
-Near-infrared absorbing pigment (indicated as "pigment" in the table)-
Pigments PP1 to PP4 and SQ1 to SQ3: Compounds with the following structures SQ-1, SQ-14, SQ-13, SQ-15, SQ-17, SQ-33, SQ-24, SQ-25, SQ-27, SQ -30, SQ-21, SQ-37, SQ-43, SQ-52, SQ-56, and SQ-60: Compounds listed as specific examples of the above-mentioned squarylium compounds [SQ-1, SQ-14, SQ-13, SQ-15, SQ-17, SQ-33, SQ-24, SQ-25, SQ-27, SQ-30, SQ-21, SQ-37, SQ-43, SQ-52, SQ- 56 and SQ-60]
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
－顔料誘導体－
　顔料誘導体１～７：下記構造の化合物
　Ｂ－１、Ｂ－２、Ｂ－３、Ｂ－６、Ｂ－１４、及びＢ－１７：既述の顔料誘導体の具体例として挙げられた化合物［Ｂ－１、Ｂ－２、Ｂ－３、Ｂ－６、Ｂ－１４、及びＢ－１７］ -Pigment derivative-
Pigment derivatives 1 to 7: Compounds having the following structures B-1, B-2, B-3, B-6, B-14, and B-17: Compounds listed as specific examples of the pigment derivatives described above [B] -1, B-2, B-3, B-6, B-14, and B-17]
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
－分散剤－
　分散剤１（塩基性基を有する樹脂）：下記構造の樹脂（主鎖の各構成単位に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。Ｍｗ＝２１，０００、酸価＝３６．０ｍｇＫＯＨ／ｇ、アミン価４７．０ｍｇＫＯＨ／ｇ） -Dispersant-
Dispersant 1 (resin having a basic group): Resin having the following structure (the numerical value added to each structural unit of the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Mw = 21. 000, acid value = 36.0 mgKOH / g, amine value 47.0 mgKOH / g)
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　分散剤２（塩基性基を有する樹脂）：下記構造の樹脂（主鎖の各構成単位に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。Ｍｗ＝２３，０００、酸価＝３２．３ｍｇＫＯＨ／ｇ、アミン価４５．０ｍｇＫＯＨ／ｇ）
Figure JPOXMLDOC01-appb-C000051
 Dispersant 2 (resin having a basic group): Resin having the following structure (the numerical value added to each structural unit of the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Mw = 23. 000, acid value = 32.3 mgKOH / g, amine value 45.0 mgKOH / g)
Figure JPOXMLDOC01-appb-C000051
　分散剤３（塩基性基を有する樹脂）：下記構造の樹脂（主鎖の各構成単位に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。Ｍｗ＝１０，０００、酸価＝４４．３ｍｇＫＯＨ／ｇ、アミン価４０．０ｍｇＫＯＨ／ｇ）
Figure JPOXMLDOC01-appb-C000052
 Dispersant 3 (resin having a basic group): Resin having the following structure (the numerical value added to each structural unit of the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Mw = 10 000, acid value = 44.3 mgKOH / g, amine value 40.0 mgKOH / g)
Figure JPOXMLDOC01-appb-C000052
－バインダー樹脂－
　樹脂１～６（特定バインダー樹脂）：特定バインダー樹脂の具体例に記載の樹脂１～６
　樹脂７～１２（比較用バインダー樹脂）：下記構造の樹脂（主鎖の各構成単位に付記した数値はモル比である） -Binder resin-
Resins 1 to 6 (specific binder resin): Resins 1 to 6 described in Specific Examples of Specific Binder Resin.
Resins 7 to 12 (comparative binder resin): Resins having the following structure (numerical values added to each structural unit of the main chain are molar ratios)
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
－重合性化合物－
　モノマー１：下記構造（Ｍ－１）の化合物の混合物（左側化合物を５５モル％～６３モル％含有）
　モノマー２：下記構造（Ｍ－２）の化合物
　モノマー３：下記構造（Ｍ－３）の化合物
　モノマー４：下記構造（Ｍ－４）の化合物 -Polymerizable compound-
Monomer 1: A mixture of compounds having the following structure (M-1) (containing 55 mol% to 63 mol% of the compound on the left side)
Monomer 2: Compound having the following structure (M-2) Monomer 3: Compound having the following structure (M-3) Monomer 4: Compound having the following structure (M-4)
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
－重合開始剤－
　重合開始剤１（光重合開始剤）：下記構造（Ｉ－１）の化合物（ＩＲＧＡＣＵＲＥ　ＯＸＥ－０１、ＢＡＳＦ社製）
　重合開始剤２（光重合開始剤）：下記構造（Ｉ－２）の化合物 -Polymerization initiator-
Polymerization Initiator 1 (Photopolymerization Initiator): A compound having the following structure (I-1) (IRGACURE OXE-01, manufactured by BASF).
Polymerization Initiator 2 (Photopolymerization Initiator): A compound having the following structure (I-2)
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
－紫外線吸収剤－
　紫外線吸収剤１：下記構造（ＵＶ１）の化合物 -UV absorber-
UV absorber 1: Compound with the following structure (UV1)
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
－界面活性剤－
　界面活性剤１：下記混合物（Ｍｗ＝１４，０００）の１質量％ＰＧＭＥＡ溶液。下記の式中、構成単位の割合を示す％（６２％及び３８％）はモル比である。 -Surfactant-
Surfactant 1: 1% by mass PGMEA solution of the following mixture (Mw = 14,000). In the following formula,% (62% and 38%) indicating the ratio of the constituent units is a molar ratio.
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
－重合禁止剤－
　重合禁止剤１：ｐ－メトキシフェノール（三立ケミー（株）製） -Polymerization inhibitor-
Polymerization inhibitor 1: p-methoxyphenol (manufactured by Sanritsu Chemie Co., Ltd.)
－溶剤Ａ及びＢ－
　溶剤１：プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ） -Solvents A and B-
Solvent 1: Propylene glycol monomethyl ether acetate (PGMEA)
［スズの含有量の測定］
　硬化性組成物中のスズの含有量について、既述の方法で測定した。結果を表７に示す。 [Measurement of tin content]
The tin content in the curable composition was measured by the method described above. The results are shown in Table 7.
［保存安定性の評価］
　硬化性組成物の保存安定性を以下のようにして評価した。
　製造直後の硬化性組成物の粘度（初期粘度Ａとする）を測定した。粘度を測定した硬化性組成物を４５℃の恒温槽で７２時間保管した後、再度、粘度（保管後粘度Ｂとする）を測定した。なお、粘度は、硬化性組成物の温度を２３℃に調整して測定した。
　そして、以下の計算式から増粘率を算出し、増粘率にて保存安定性を評価した。
　増粘率（％）＝［（保管後粘度Ｂ／初期粘度Ａ）－１］×１００ [Evaluation of storage stability]
The storage stability of the curable composition was evaluated as follows.
The viscosity (referred to as initial viscosity A) of the curable composition immediately after production was measured. The curable composition whose viscosity was measured was stored in a constant temperature bath at 45 ° C. for 72 hours, and then the viscosity (referred to as viscosity B after storage) was measured again. The viscosity was measured by adjusting the temperature of the curable composition to 23 ° C.
Then, the thickening rate was calculated from the following formula, and the storage stability was evaluated by the thickening rate.
Viscosity thickening rate (%) = [(Viscosity B after storage / Initial viscosity A) -1] × 100
　以下の基準で保存安定性を評価した。結果を表７に示す。
－基準－
　５：硬化性組成物の増粘率が５％以下である。
　４：硬化性組成物の増粘率が５％を超えて、７．５％以下である。
　３：硬化性組成物の増粘率が７．５％を超えて、１０％以下である。
　２：硬化性組成物の増粘率が１０％を超えて、２０％以下である。
　１：硬化性組成物の増粘率が２０％を超えている。 Storage stability was evaluated according to the following criteria. The results are shown in Table 7.
-Criteria-
5: The thickening rate of the curable composition is 5% or less.
4: The thickening rate of the curable composition exceeds 5% and is 7.5% or less.
3: The thickening rate of the curable composition exceeds 7.5% and is 10% or less.
2: The thickening rate of the curable composition exceeds 10% and is 20% or less.
1: The thickening rate of the curable composition exceeds 20%.
［硬化膜の作製及び評価］
　硬化性組成物を、ポストベーク後の膜厚が１．０μｍになるようにスピンコーター（ミカサ（株）製）を用いてシリコンウェハ上に塗布して塗膜を形成した。次いで、ホットプレートを用いて、１００℃で２分間加熱した。次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を用い、１０００ｍＪ／ｃｍ２の露光量にて、１μｍ四方のＢａｙｅｒパターンを有するマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、更に純水にて水洗した。次いで、ホットプレートを用いて、２００℃で５分間加熱（ポストベーク）することでパターンを形成した。
　パターン間（未露光部分）の任意の１０箇所について、走査型電子顕微鏡を用いて残渣を確認及び観測し、以下の基準で現像残渣を評価した。結果を表７に示す。
－基準－
　５：未露光部分の１０箇所において、残渣が確認されない。
　４：未露光部分の１０箇所において、直径５ｎｍ～２００ｎｍのサイズの残渣数の平均値が０個超え１個以下であった。
　３：未露光部分の１０箇所において、直径５ｎｍ～２００ｎｍのサイズの残渣数の平均値が１個超え５個以下であった。
　２：未露光部分の１０箇所において、直径５ｎｍ～２００ｎｍのサイズの残渣数の平均値が５個超であった。
　１：未露光部分の１０箇所において、直径２００ｎｍ以上のサイズの残渣が存在するか、又は、未露光部分がほとんど溶解していなかった。 [Preparation and evaluation of cured film]
The curable composition was applied onto a silicon wafer using a spin coater (manufactured by Mikasa Sports Co., Ltd.) so that the film thickness after post-baking was 1.0 μm to form a coating film. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) , exposure was performed at an exposure amount of 1000 mJ / cm 2 through a mask having a Bayer pattern of 1 μm square. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and further washed with pure water. Then, using a hot plate, a pattern was formed by heating (post-baking) at 200 ° C. for 5 minutes.
Residues were confirmed and observed using a scanning electron microscope at any 10 locations between patterns (unexposed areas), and the development residue was evaluated according to the following criteria. The results are shown in Table 7.
-Criteria-
5: No residue is confirmed at 10 unexposed areas.
4: The average value of the number of residues having a diameter of 5 nm to 200 nm was more than 0 and less than 1 at 10 points in the unexposed portion.
3: At 10 locations in the unexposed portion, the average value of the number of residues having a diameter of 5 nm to 200 nm was more than 1 and 5 or less.
2: The average number of residues having a diameter of 5 nm to 200 nm was more than 5 at 10 unexposed portions.
1: At 10 locations of the unexposed portion, a residue having a diameter of 200 nm or more was present, or the unexposed portion was hardly dissolved.
Figure JPOXMLDOC01-appb-T000058
Figure JPOXMLDOC01-appb-T000058
　表７に記載の結果から、本開示に係る組成物である実施例１～実施例６８の硬化性組成物は、比較例１～比較例６の組成物に比べて、保存安定性に優れ、更に、現像残渣も低減されていることがわかる。
　実施例１において、紫外線吸収剤、界面活性剤、及び重合禁止剤を除いた場合も、実施例１と同様の結果であった。
　実施例１において、重合性化合物をモノマー１のみ６．４部に置き換えても、実施例１と同様の結果であった。
　実施例１において、重合開始剤を、重合開始剤１（１部）から、重合開始剤１と重合開始剤２の混合（各０．５部）に置き換えても、実施例１と同様の結果であった。
　実施例１において、溶剤Ｂを溶剤１からシクロペンタノン（東京化成工業（株）製）に置き換えた場合も、実施例１と同様の結果であった。
　実施例１において、溶剤Ｂの量を３１．７部又は５１．７部に変更した場合も、実施例１と同様の結果であった。 From the results shown in Table 7, the curable compositions of Examples 1 to 68, which are the compositions according to the present disclosure, are excellent in storage stability as compared with the compositions of Comparative Examples 1 to 6. Furthermore, it can be seen that the development residue is also reduced.
When the ultraviolet absorber, the surfactant, and the polymerization inhibitor were removed in Example 1, the same result as in Example 1 was obtained.
Even if only the monomer 1 was replaced with 6.4 parts of the polymerizable compound in Example 1, the same result as in Example 1 was obtained.
Even if the polymerization initiator is replaced with a mixture of the polymerization initiator 1 and the polymerization initiator 2 (0.5 parts each) from the polymerization initiator 1 (1 part) in Example 1, the same result as in Example 1 is obtained. Met.
When the solvent B was replaced with cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.) from the solvent 1 in Example 1, the same result as in Example 1 was obtained.
When the amount of the solvent B was changed to 31.7 parts or 51.7 parts in Example 1, the same result as in Example 1 was obtained.
（実施例１０１～実施例１６８）
　実施例１～実施例６８の組成物をそれぞれ用い、下記手法にて２μｍ四方のパターン（赤外線カットフィルタ）をそれぞれ形成した。 (Example 101 to Example 168)
Using the compositions of Examples 1 to 68, 2 μm square patterns (infrared cut filters) were formed by the following methods.
　実施例１～６８の硬化性組成物を用いて下記方法でパターンを作製した。
　上記硬化性組成物を製膜後の膜厚が１．０μｍになるようにシリコンウェハ上にスピンコート法で塗布した。次いで、ホットプレートを用いて、１００℃で２分間加熱した。次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（キヤノン（株）製）を用い、１，０００ｍＪ／ｃｍ２で２μｍ四方のドットパターンのマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、更に純水にて水洗した。次いで、ホットプレートを用いて、２００℃で５分間加熱することで、２μｍ四方のパターン（赤外線カットフィルタ）を形成した。 Patterns were prepared by the following methods using the curable compositions of Examples 1 to 68.
The curable composition was applied onto a silicon wafer by a spin coating method so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at 1,000 mJ / cm 2 through a mask with a 2 μm square dot pattern. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and further washed with pure water. Next, a 2 μm square pattern (infrared cut filter) was formed by heating at 200 ° C. for 5 minutes using a hot plate.
　次に、赤外線カットフィルタのパターン上に、Ｒｅｄ組成物を製膜後の膜厚が１．０μｍになるようにスピンコート法で塗布した。次いで、ホットプレートを用いて、１００℃で２分間加熱した。次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（キヤノン（株）製）を用い、１，０００ｍＪ／ｃｍ２で２μｍ四方のドットパターンのマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、更に純水にて水洗した。次いで、ホットプレートを用いて、２００℃で５分間加熱することで、赤外線カットフィルタのパターン上に、Ｒｅｄ組成物をパターニングした。同様にＧｒｅｅｎ組成物、Ｂｌｕｅ組成物を順次パターニングし、赤、緑、及び青の着色パターン（Ｂａｙｅｒパターン）を形成した。
　なお、Ｂａｙｅｒパターンとは、米国特許第３，９７１，０６５号明細書に開示されているような、一個の赤色（Ｒｅｄ）素子と、二個の緑色（Ｇｒｅｅｎ）素子と、一個の青色（Ｂｌｕｅ）素子とを有する色フィルタ素子の２×２アレイを繰り返したパターンであるが、本実施例においては、一個の赤色（Ｒｅｄ）素子と、一個の緑色（Ｇｒｅｅｎ）素子と、一個の青色（Ｂｌｕｅ）素子と、一個の赤外線透過フィルタ素子を有するフィルタ素子の２×２アレイを繰り返したＢａｙｅｒパターンを形成した。 Next, the Red composition was applied onto the pattern of the infrared cut filter by a spin coating method so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at 1,000 mJ / cm 2 through a mask with a 2 μm square dot pattern. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and further washed with pure water. The Red composition was then patterned on the pattern of the infrared cut filter by heating at 200 ° C. for 5 minutes using a hot plate. Similarly, the Green composition and the Blue composition were sequentially patterned to form red, green, and blue coloring patterns (Bayer patterns).
The Bayer pattern is one red element, two green elements, and one blue element, as disclosed in US Pat. No. 3,971,065. ) This is a pattern in which a 2 × 2 array of color filter elements having elements is repeated. In this embodiment, one red element, one green element, and one blue element are used. A Bayer pattern was formed by repeating a 2 × 2 array of an element and a filter element having one infrared transmissive filter element.
　次に、上記パターン形成した膜上に、赤外線透過フィルタ形成用組成物（下記組成１００又は組成１０１）を、製膜後の膜厚が２．０μｍになるようにスピンコート法で塗布した。次いで、ホットプレートを用いて、１００℃で２分間加熱した。次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（キヤノン（株）製）を用い、１，０００ｍＪ／ｃｍ２で２μｍ四方のＢａｙｅｒパターンのマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、更に純水にて水洗した。次いで、ホットプレートを用いて、２００℃で５分間加熱することで、赤外線カットフィルタのＢａｙｅｒパターンのうち、上記着色パターンが形成されていない抜け部分に、赤外線透過フィルタのパターニングを行った。これを公知の方法に従い固体撮像素子に組み込んだ。
　得られた固体撮像素子について、低照度の環境下（０．００１ルクス（Ｌｕｘ））で赤外発光ダイオード（赤外ＬＥＤ）により赤外線を照射し、画像の取り込みを行い、画像性能を評価した。実施例１～実施例６８で得られたいずれの硬化性組成物を使用した場合でも、低照度の環境下であっても画像をはっきりと認識できた。 Next, the composition for forming an infrared transmission filter (the following composition 100 or composition 101) was applied onto the patterned film by a spin coating method so that the film thickness after film formation was 2.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at 1,000 mJ / cm 2 through a 2 μm square Bayer pattern mask. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and further washed with pure water. Next, by heating at 200 ° C. for 5 minutes using a hot plate, the infrared transmission filter was patterned in the missing portion of the Bayer pattern of the infrared cut filter in which the coloring pattern was not formed. This was incorporated into a solid-state image sensor according to a known method.
The obtained solid-state image sensor was irradiated with infrared rays by an infrared light emitting diode (infrared LED) in a low illuminance environment (0.001 lux), and an image was captured to evaluate the image performance. When any of the curable compositions obtained in Examples 1 to 68 was used, the image could be clearly recognized even in a low-light environment.
　上記パターニングに使用したＲｅｄ組成物、Ｇｒｅｅｎ組成物、Ｂｌｕｅ組成物、及び、赤外線透過フィルタ形成用組成物は、以下の通りである。 The Red composition, Green composition, Blue composition, and composition for forming an infrared transmission filter used for the above patterning are as follows.
－Ｒｅｄ組成物－
　下記成分を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、Ｒｅｄ組成物を調製した。
　Ｒｅｄ顔料分散液：５１．７質量部
　樹脂４（４０質量％ＰＧＭＥＡ溶液）：０．６質量部
　重合性化合物１２：０．６質量部
　光重合開始剤１：０．３質量部
　界面活性剤２：４．２質量部
　ＰＧＭＥＡ：４２．６質量部 -Red composition-
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a Red composition.
Red pigment dispersion: 51.7 parts by mass Resin 4 (40% by mass PGMEA solution): 0.6 parts by mass Polymerizable compound 12: 0.6 parts by mass Photopolymerization initiator 1: 0.3 parts by mass Surfactant 2 : 4.2 parts by mass PGMEA: 42.6 parts by mass
－Ｇｒｅｅｎ組成物－
　下記成分を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、Ｇｒｅｅｎ組成物を調製した。
　Ｇｒｅｅｎ顔料分散液：７３．７質量部
　樹脂４（４０質量％ＰＧＭＥＡ溶液）：０．３質量部
　重合性化合物１１：１．２質量部
　光重合開始剤１：０．６質量部
　界面活性剤２：４．２質量部
　紫外線吸収剤（ＵＶ－５０３、大東化学（株）製）：０．５質量部
　ＰＧＭＥＡ：１９．５質量部 -Green composition-
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a Green composition.
Green pigment dispersion: 73.7 parts by mass Resin 4 (40% by mass PGMEA solution): 0.3 parts by mass Polymerizable compound 11: 1.2 parts by mass Photopolymerization initiator 1: 0.6 parts by mass Surface active agent 2 : 4.2 parts by mass UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.): 0.5 parts by mass PGMEA: 19.5 parts by mass
－Ｂｌｕｅ組成物－
　下記成分を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、Ｂｌｕｅ組成物を調製した。
　Ｂｌｕｅ顔料分散液：４４．９質量部
　樹脂４（４０質量％ＰＧＭＥＡ溶液）：２．１質量部
　重合性化合物１１：１．５質量部
　重合性化合物１２：０．７質量部
　光重合開始剤１：０．８質量部
　界面活性剤２：４．２質量部
　ＰＧＭＥＡ：４５．８質量部 -Blue composition-
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a Blue composition.
Blue pigment dispersion: 44.9 parts by mass Resin 4 (40% by mass PGMEA solution): 2.1 parts by mass Polymerizable compound 11: 1.5 parts by mass Polymerizable compound 12: 0.7 parts by mass Photoinitiator 1 : 0.8 parts by mass Surfactant 2: 4.2 parts by mass PGMEA: 45.8 parts by mass
－赤外線透過フィルタ形成用組成物－
　下記組成における成分を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、赤外線透過フィルタ形成用組成物を調製した。 -Composition for forming an infrared transmission filter-
The components having the following composition were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a composition for forming an infrared transmission filter.
＜組成１００＞
　顔料分散液１－１：４６．５質量部
　顔料分散液１－２：３７．１質量部
　重合性化合物１３：１．８質量部
　樹脂４：１．１質量部
　光重合開始剤２：０．９質量部
　界面活性剤２：４．２質量部
　重合禁止剤（ｐ－メトキシフェノール）：０．００１質量部
　シランカップリング剤：０．６質量部
　ＰＧＭＥＡ：７．８質量部 <Composition 100>
Pigment dispersion 1-1: 46.5 parts by mass Pigment dispersion 1-2: 37.1 parts by mass Polymerizable compound 13: 1.8 parts by mass Resin 4: 1.1 parts by mass Photopolymerization initiator 2: 0. 9 parts by mass Surfactant 2: 4.2 parts by mass Polymerization inhibitor (p-methoxyphenol): 0.001 parts by mass silane coupling agent: 0.6 parts by mass PGMEA: 7.8 parts by mass
＜組成１０１＞
　顔料分散液２－１：１，０００質量部
　重合性化合物（ジペンタエリスリトールヘキサアクリレート）：５０質量部
　樹脂４：１７質量部
　光重合開始剤（１－［４－（フェニルチオ）フェニル］－１，２－オクタンジオン－２－（Ｏ－ベンゾイルオキシム））：１０質量部
　ＰＧＭＥＡ：１７９質量部
　アルカリ可溶性重合体Ｆ－１：１７質量部（固形分濃度３５質量部） <Composition 101>
Pigment dispersion 21: 1,000 parts by mass Polymerizable compound (dipentaerythritol hexaacrylate): 50 parts by mass Resin 4:17 parts by mass Photopolymerization initiator (1- [4- (phenylthio) phenyl] -1, 2-Octandion-2- (O-benzoyloxime)): 10 parts by mass PGMEA: 179 parts by mass Alkali-soluble polymer F-1: 17 parts by mass (solid content concentration 35 parts by mass)
＜アルカリ可溶性重合体Ｆ－１の合成例＞
　反応容器に、ベンジルメタクリレート１４部、Ｎ－フェニルマレイミド１２部、２－ヒドロキシエチルメタクリレート１５部、スチレン１０部及びメタクリル酸２０部をプロピレングリコールモノメチルエーテルアセテート２００部に溶解し、更に２，２’－アゾイソブチロニトリル３部及びα－メチルスチレンダイマー５部を投入した。反応容器内を窒素パージ後、撹拌及び窒素バブリングしながら８０℃で５時間加熱し、アルカリ可溶性重合体Ｆ－１を含む溶液（固形分濃度３５質量％）を得た。この重合体は、ポリスチレン換算の重量平均分子量が９，７００、数平均分子量が５，７００であり、Ｍｗ／Ｍｎが１．７０であった。 <Synthesis example of alkali-soluble polymer F-1>
In a reaction vessel, 14 parts of benzyl methacrylate, 12 parts of N-phenylmaleimide, 15 parts of 2-hydroxyethyl methacrylate, 10 parts of styrene and 20 parts of methacrylic acid are dissolved in 200 parts of propylene glycol monomethyl ether acetate, and further 2,2'-. 3 parts of azoisobutyronitrile and 5 parts of α-methylstyrene dimer were added. After purging the inside of the reaction vessel with nitrogen, the mixture was heated at 80 ° C. for 5 hours with stirring and nitrogen bubbling to obtain a solution containing the alkali-soluble polymer F-1 (solid content concentration: 35% by mass). This polymer had a polystyrene-equivalent weight average molecular weight of 9,700, a number average molecular weight of 5,700, and a Mw / Mn of 1.70.
＜顔料分散液２－１＞
　Ｃ．Ｉ．ピグメントブラック３２を６０部、Ｃ．Ｉ．ピグメントブルー１５：６を２０部、Ｃ．Ｉ．ピグメントイエロー１３９を２０部、日本ルーブリゾール（株）製のソルスパース７６５００を８０部（固形分濃度５０質量％）、アルカリ可溶性重合体Ｆ－１を含む溶液を１２０部（固形分濃度３５質量％）、プロピレングリコールモノメチルエーテルアセテートを７００部混合し、ペイントシェーカーを用いて８時間分散し、着色剤分散液２－１を得た。 <Pigment dispersion 2-1>
C. I. 60 copies of Pigment Black 32, C.I. I. 20 copies of Pigment Blue 15: 6, C.I. I. 20 parts of Pigment Yellow 139, 80 parts of Solsparse 76500 manufactured by Japan Lubrizol K.K. (solid content concentration 50% by mass), 120 parts of solution containing alkali-soluble polymer F-1 (solid content concentration 35% by mass) , 700 parts of propylene glycol monomethyl ether acetate was mixed and dispersed for 8 hours using a paint shaker to obtain a colorant dispersion solution 2-1.
　Ｒｅｄ組成物、Ｇｒｅｅｎ組成物、Ｂｌｕｅ組成物、及び、赤外線透過フィルタ形成用組成物に使用した原料は、以下の通りである。 The raw materials used for the Red composition, the Green composition, the Blue composition, and the composition for forming an infrared transmission filter are as follows.
・Ｒｅｄ顔料分散液
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４を９．６質量部、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９を４．３質量部、分散剤（Ｄｉｓｐｅｒｂｙｋ－１６１、ＢＹＫＣｈｅｍｉｅ社製）を６．８質量部、ＰＧＭＥＡを７９．３質量部とからなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）により３時間混合及び分散して、顔料分散液を調製した。その後更に、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２，０００ｋｇ／ｃｍ３の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行った。この分散処理を１０回繰り返し、Ｒｅｄ顔料分散液を得た。 -Red pigment dispersion C. I. Pigment Red 254 at 9.6 parts by mass, C.I. I. A mixed solution consisting of 4.3 parts by mass of Pigment Yellow 139, 6.8 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0.3 mm diameter). ) Was mixed and dispersed for 3 hours to prepare a pigment dispersion. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform dispersion treatment at a flow rate of 500 g / min under a pressure of 2,000 kg / cm 3. This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion.
・Ｇｒｅｅｎ顔料分散液
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　３６を６．４質量部、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１５０を５．３質量部、分散剤（Ｄｉｓｐｅｒｂｙｋ－１６１、ＢＹＫＣｈｅｍｉｅ社製）を５．２質量部、ＰＧＭＥＡを８３．１質量部からなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）により３時間混合及び分散して、顔料分散液を調製した。その後更に、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２，０００ｋｇ／ｃｍ３の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行った。この分散処理を１０回繰り返し、Ｇｒｅｅｎ顔料分散液を得た。 -Green pigment dispersion C. I. Pigment Green 36 at 6.4 parts by mass, C.I. I. A mixed solution consisting of 5.3 parts by mass of Pigment Yellow 150, 5.2 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA is used in a bead mill (zirconia beads 0.3 mm diameter). To prepare a pigment dispersion liquid by mixing and dispersing for 3 hours. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform dispersion treatment at a flow rate of 500 g / min under a pressure of 2,000 kg / cm 3. This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion.
・Ｂｌｕｅ顔料分散液
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６を９．７質量部、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３を２．４質量部、分散剤（Ｄｉｓｐｅｒｂｙｋ－１６１、ＢＹＫＣｈｅｍｉｅ社製）を５．５部、ＰＧＭＥＡを８２．４部からなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）により３時間混合及び分散して、顔料分散液を調製した。その後更に、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２，０００ｋｇ／ｃｍ３の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行った。この分散処理を１０回繰り返し、Ｂｌｕｅ顔料分散液を得た。 -Blue pigment dispersion C. I. Pigment Blue 15: 6 at 9.7 parts by mass, C.I. I. A mixed solution consisting of 2.4 parts by mass of Pigment Violet 23, 5.5 parts of dispersant (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts of PGMEA was prepared by a bead mill (zirconia beads 0.3 mm diameter). A pigment dispersion was prepared by time mixing and dispersion. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform dispersion treatment at a flow rate of 500 g / min under a pressure of 2,000 kg / cm 3. This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion.
・顔料分散液１－１
　下記組成の混合液を、０．３ｍｍ径のジルコニアビーズを使用して、ビーズミル（減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製））で、３時間、混合、分散して、顔料分散液１－１を調製した。
・赤色顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４）及び黄色顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９）からなる混合顔料：１１．８質量部
・樹脂（Ｄｉｓｐｅｒｂｙｋ－１１１、ＢＹＫＣｈｅｍｉｅ社製）：９．１質量部
・ＰＧＭＥＡ：７９．１質量部 ・ Pigment dispersion 1-1
The mixed solution having the following composition is mixed and dispersed in a bead mill (high pressure disperser with decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.)) for 3 hours using zirconia beads having a diameter of 0.3 mm. To prepare a pigment dispersion liquid 1-1.
-Mixed pigment consisting of red pigment (CI Pigment Red 254) and yellow pigment (CI Pigment Yellow 139): 11.8 parts by mass-Resin (Disperbyk-111, manufactured by BYK Chemie): 9.1 mass Parts ・ PGMEA: 79.1 parts by mass
・顔料分散液１－２
　下記組成の混合液を、０．３ｍｍ径のジルコニアビーズを使用して、ビーズミル（減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製））で、３時間、混合、分散して、顔料分散液１－２を調製した。
・青色顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６）及び紫色顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３）からなる混合顔料：１２．６質量部
・樹脂（Ｄｉｓｐｅｒｂｙｋ－１１１、ＢＹＫＣｈｅｍｉｅ社製）：２．０質量部
・樹脂Ａ：３．３質量部
・シクロヘキサノン：３１．２質量部
・ＰＧＭＥＡ：５０．９質量部 ・ Pigment dispersion 1-2
The mixed solution having the following composition is mixed and dispersed in a bead mill (high pressure disperser with decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.)) for 3 hours using zirconia beads having a diameter of 0.3 mm. The pigment dispersion liquid 1-2 was prepared.
-Mixed pigment consisting of blue pigment (CI Pigment Blue 15: 6) and purple pigment (CI Pigment Violet 23): 12.6 parts by mass-Resin (Disperbyk-111, manufactured by BYK Chemie): 2. 0 parts by mass ・ Resin A: 3.3 parts by mass ・ Cyclohexanone: 31.2 parts by mass ・ PGMEA: 50.9 parts by mass
　上記で使用した成分における略号の詳細を以下に示す。 Details of the abbreviations for the ingredients used above are shown below.
・樹脂Ａ：下記構造（Ｍｗ＝１４，０００、各構成単位における比はモル比である。） -Resin A: The following structure (Mw = 14,000, the ratio in each structural unit is a molar ratio)
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
・重合性化合物１１：ＫＡＹＡＲＡＤ　ＤＰＨＡ（ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートとの混合物、日本化薬（株）製）
・重合性化合物１２：下記構造 Polymerizable compound 11: KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
Polymerizable compound 12: The following structure
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
・重合性化合物１３：下記構造（左側化合物と右側化合物とのモル比が７：３の混合物） Polymerizable compound 13: The following structure (a mixture of the left compound and the right compound having a molar ratio of 7: 3)
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
・樹脂４：下記構造（酸価：７０ｍｇＫＯＨ／ｇ、Ｍｗ＝１１，０００、各構成単位における比はモル比である。） -Resin 4: The following structure (acid value: 70 mgKOH / g, Mw = 11,000, the ratio in each structural unit is a molar ratio)
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
・光重合開始剤１：ＩＲＧＡＣＵＲＥ　ＯＸＥ０１（１－［４－（フェニルチオ）フェニル］－１，２－オクタンジオン－２－（Ｏ－ベンゾイルオキシム）、ＢＡＳＦ社製）
・光重合開始剤２：下記構造の化合物 -Photopolymerization initiator 1: IRGACURE OXE01 (1- [4- (phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime), manufactured by BASF)
-Photopolymerization initiator 2: A compound having the following structure
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
・界面活性剤２：上記界面活性剤１と同じもの。 -Surfactant 2: The same as the above-mentioned surfactant 1.
・シランカップリング剤：下記構造の化合物。以下の構造式中、Ｅｔはエチル基を表す。 -Silane coupling agent: A compound having the following structure. In the following structural formula, Et represents an ethyl group.
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
（実施例２０１～２６８）
　下記組成を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、実施例２０１のパターン形成用組成物を調製した。
　実施例１の硬化性組成物：２２．６７質量部
　顔料分散液２－１：５１．２３質量部
　実施例２０１のパターン形成用組成物を用いて、実施例１と同様に、現像残渣の評価を行ったところ、実施例１と同様の効果が得られた。また、実施例２０１のパターン形成用組成物を用いて得られた硬化膜は、可視領域の波長の光を遮光し、近赤外領域の波長の光（近赤外線）の少なくとも一部を透過させることができた。
　実施例１の硬化性組成物の代わりに実施例２～実施例６８の硬化性組成物を用いた実施例２０２～２６８のパターン形成用組成物について、実施例２０１と同様に評価を行ったところ、それぞれ実施例２０１と同等の効果が得られた。 (Examples 201 to 268)
The following compositions were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare the pattern-forming composition of Example 201.
Curable composition of Example 1: 22.67 parts by mass Pigment dispersion 2-1: 51.23 parts by mass Evaluation of development residue using the pattern-forming composition of Example 201 in the same manner as in Example 1. The same effect as in Example 1 was obtained. Further, the cured film obtained by using the pattern-forming composition of Example 201 blocks light having a wavelength in the visible region and transmits at least a part of light having a wavelength in the near infrared region (near infrared ray). I was able to.
The pattern-forming compositions of Examples 202 to 268 using the curable compositions of Examples 2 to 68 instead of the curable composition of Example 1 were evaluated in the same manner as in Example 201. , The same effect as that of Example 201 was obtained.
（実施例３０１～３６８）
　下記組成を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、実施例３０１のパターン形成用組成物を調製した。
　実施例１の硬化性組成物：３６．９９質量部
　顔料分散液１－１：４６．５質量部
　顔料分散液１－２：３７．１質量部
　実施例３０１のパターン形成用組成物を用いて、実施例１と同様に、現像残渣の評価を行ったところ、実施例１と同様の効果が得られた。また、実施例３０１のパターン形成用組成物を用いて得られた硬化膜は、可視領域の波長の光を遮光し、近赤外領域の波長の光（近赤外線）の少なくとも一部を透過させることができた。
　実施例１の硬化性組成物の代わりに実施例２～実施例６８の硬化性組成物を用いた実施例３０２～３６８のパターン形成用組成物について、実施例３０１と同様に評価を行ったところ、それぞれ実施例３０１と同等の効果が得られた。 (Examples 301 to 368)
The following compositions were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare the pattern-forming composition of Example 301.
Curable composition of Example 1: 36.99 parts by mass Pigment dispersion 1-1: 46.5 parts by mass Pigment dispersion 1-2: 37.1 parts by mass Using the pattern-forming composition of Example 301 When the development residue was evaluated in the same manner as in Example 1, the same effect as in Example 1 was obtained. Further, the cured film obtained by using the pattern-forming composition of Example 301 blocks light having a wavelength in the visible region and transmits at least a part of light having a wavelength in the near infrared region (near infrared ray). I was able to.
The pattern-forming compositions of Examples 302 to 368 using the curable compositions of Examples 2 to 68 instead of the curable composition of Example 1 were evaluated in the same manner as in Example 301. , The same effect as that of Example 301 was obtained.
（実施例４００）
　上記実施例１～実施例６８、実施例１０１～１６８、実施例２０１～２６８、実施例３０１～３６８において、シリコンウェハをガラス基板に変更し、同様に評価した場合も、上記実施例と同様の効果が得られた。 (Example 400)
In the above Examples 1 to 68, Examples 101 to 168, Examples 201 to 268, and Examples 301 to 368, when the silicon wafer is changed to a glass substrate and evaluated in the same manner, the same as in the above example. The effect was obtained.
　１１０：固体撮像素子、１１１：赤外線カットフィルタ、１１２：カラーフィルタ、１１４：赤外線透過フィルタ、１１５：マイクロレンズ、１１６：平坦化層 110: Solid-state image sensor, 111: Infrared cut filter, 112: Color filter, 114: Infrared transmission filter, 115: Microlens, 116: Flattening layer

Claims (20)

  1. 　近赤外線吸収顔料と、
    　塩基性基を有する樹脂と、
    　前記塩基性基を有する樹脂以外の、ＳＰ値が１９．７ＭＰａ１／２～２１．２ＭＰａ１／２で且つ酸価が７０ｍｇＫＯＨ／ｇ～１０５ｍｇＫＯＨ／ｇであるバインダー樹脂と、
    　を含む近赤外吸収組成物。     Near-infrared absorbing pigment and
    Resins with basic groups and
    Other than the resin having a basic group, a binder resin having an SP value of 19.7 MPa 1/2 to 21.2 MPa 1/2 and an acid value of 70 mgKOH / g to 105 mgKOH / g.
    Near-infrared absorption composition containing.
  2. 　前記バインダー樹脂が、芳香族環及び脂肪族環よりなる群から選択される少なくとも１種の環構造を有する構成単位を、前記バインダー樹脂の全構成単位に対して５０モル％～９０モル％で含む樹脂である、請求項１に記載の近赤外吸収組成物。 The binder resin contains a structural unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring in an amount of 50 mol% to 90 mol% with respect to all the structural units of the binder resin. The near-infrared absorbing composition according to claim 1, which is a resin.
  3. 　前記脂肪族環がビシクロ環又はトリシクロ環である、請求項２に記載の近赤外吸収組成物。 The near-infrared absorption composition according to claim 2, wherein the aliphatic ring is a bicyclo ring or a tricyclo ring.
  4. 　前記芳香族環がベンゼン環、ナフタレン環、又は含窒素複素芳香環である、請求項２又は請求項３に記載の近赤外吸収組成物。 The near-infrared absorption composition according to claim 2 or 3, wherein the aromatic ring is a benzene ring, a naphthalene ring, or a nitrogen-containing heteroaromatic ring.
  5. 　前記バインダー樹脂が、酸基を有する構成単位を、前記バインダー樹脂の全構成単位に対して１０モル％～４０モル％で含む樹脂である、請求項１～請求項４のいずれか１項に記載の近赤外吸収組成物。 The invention according to any one of claims 1 to 4, wherein the binder resin contains a structural unit having an acid group in an amount of 10 mol% to 40 mol% with respect to all the structural units of the binder resin. Near-infrared absorption composition.
  6. 　前記バインダー樹脂の重量平均分子量が２０，０００以下である、請求項１～請求項５のいずれか１項に記載の近赤外吸収組成物。 The near-infrared absorption composition according to any one of claims 1 to 5, wherein the binder resin has a weight average molecular weight of 20,000 or less.
  7. 　前記塩基性基を有する樹脂が、第３級アミノ基を側鎖に有する樹脂、及び、主鎖に窒素原子を含む樹脂よりなる群から選択される少なくとも１種である、請求項１～請求項６のいずれか１項に記載の近赤外吸収組成物。 Claims 1 to claim that the resin having a basic group is at least one selected from the group consisting of a resin having a tertiary amino group in a side chain and a resin having a nitrogen atom in the main chain. 6. The near-infrared absorption composition according to any one of 6.
  8. 　前記第３級アミノ基を側鎖に有する樹脂が、更に第４級アンモニウム塩基を側鎖に有する樹脂である、請求項７に記載の近赤外吸収組成物。 The near-infrared absorption composition according to claim 7, wherein the resin having a tertiary amino group in the side chain is a resin having a quaternary ammonium base in the side chain.
  9. 　前記近赤外線吸収顔料が、ピロロピロール化合物又はスクアリリウム化合物である、請求項１～請求項８のいずれか１項に記載の近赤外吸収組成物。 The near-infrared absorbing composition according to any one of claims 1 to 8, wherein the near-infrared absorbing pigment is a pyrrolopyrrole compound or a squarylium compound.
  10. 　スズの含有量が、近赤外吸収組成物の全固形分に対して、１ｐｐｍ～１５ｐｐｍである、請求項１～請求項９のいずれか１項に記載の近赤外吸収組成物。 The near-infrared absorption composition according to any one of claims 1 to 9, wherein the tin content is 1 ppm to 15 ppm with respect to the total solid content of the near-infrared absorption composition.
  11. 　更に、重合性化合物及び重合開始剤を含む、請求項１～請求項１０のいずれか１項に記載の近赤外吸収組成物。 The near-infrared absorption composition according to any one of claims 1 to 10, further comprising a polymerizable compound and a polymerization initiator.
  12. 　請求項１～請求項１１のいずれか１項に記載の近赤外吸収組成物からなる又は前記近赤外吸収組成物を硬化してなる膜。 A film comprising the near-infrared absorption composition according to any one of claims 1 to 11, or obtained by curing the near-infrared absorption composition.
  13. 　請求項１２に記載の膜を有する光学フィルタ。 An optical filter having the film according to claim 12.
  14. 　赤外線カットフィルタ又は赤外線透過フィルタである、請求項１３に記載の光学フィルタ。 The optical filter according to claim 13, which is an infrared cut filter or an infrared transmission filter.
  15. 　請求項１２に記載の膜を有する固体撮像素子。 A solid-state image sensor having the film according to claim 12.
  16. 　請求項１２に記載の膜を有する赤外線センサ。 An infrared sensor having the film according to claim 12.
  17. 　請求項１１に記載の近赤外吸収組成物を支持体上に適用して組成物層を形成する工程と、
    　前記組成物層をパターン状に露光する工程と、
    　未露光部を現像除去してパターンを形成する工程と、を含む
    　光学フィルタの製造方法。     A step of applying the near-infrared absorption composition according to claim 11 onto a support to form a composition layer,
    The step of exposing the composition layer in a pattern and
    A method for manufacturing an optical filter, which includes a step of developing and removing an unexposed portion to form a pattern.
  18. 　請求項１１に記載の近赤外吸収組成物を支持体上に適用して組成物層を形成し、硬化して層を形成する工程と、
    　前記層上にフォトレジスト層を形成する工程と、
    　露光及び現像することにより前記フォトレジスト層をパターニングしてレジストパターンを得る工程と、
    　前記レジストパターンをエッチングマスクとして前記層をドライエッチングする工程と、を含む
    　光学フィルタの製造方法。     A step of applying the near-infrared absorption composition according to claim 11 onto a support to form a composition layer, and then curing to form a layer.
    A step of forming a photoresist layer on the layer and
    A step of patterning the photoresist layer by exposure and development to obtain a resist pattern,
    A method for manufacturing an optical filter, which comprises a step of dry etching the layer using the resist pattern as an etching mask.
  19. 　固体撮像素子と、請求項１３又は請求項１４に記載の光学フィルタとを有するカメラモジュール。 A camera module having a solid-state image sensor and the optical filter according to claim 13 or 14.
  20. 　請求項１１に記載の近赤外吸収組成物を含むインクジェットインク。 An inkjet ink containing the near-infrared absorbing composition according to claim 11.
PCT/JP2020/032332 2019-09-26 2020-08-27 Near-infrared absorption composition, film, optical filter and manufacturing method thereof, solid-state imaging element, infrared sensor, camera module, and inkjet ink WO2021059846A1 (en)

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