WO2024070694A1 - Composition, film, optical filter, solid-state imaging element, image display device, infrared sensor, camera module, and compound - Google Patents

Composition, film, optical filter, solid-state imaging element, image display device, infrared sensor, camera module, and compound Download PDF

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WO2024070694A1
WO2024070694A1 PCT/JP2023/033368 JP2023033368W WO2024070694A1 WO 2024070694 A1 WO2024070694 A1 WO 2024070694A1 JP 2023033368 W JP2023033368 W JP 2023033368W WO 2024070694 A1 WO2024070694 A1 WO 2024070694A1
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group
formula
rpm
compound
ring
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PCT/JP2023/033368
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French (fr)
Japanese (ja)
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彰宏 原
季彦 松村
恭平 荒山
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富士フイルム株式会社
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/44Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14Styryl dyes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006Preparation of organic pigments
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/22Absorbing filters

Definitions

  • the present invention relates to a polymethine compound and a composition containing the same.
  • the present invention also relates to a film, an optical filter, a solid-state imaging device, an image display device, an infrared sensor, and a camera module that use a composition containing a polymethine compound.
  • Video cameras, digital still cameras, mobile phones with cameras, and other devices use solid-state color image sensors such as CCDs (charge-coupled devices) and CMOS (complementary metal-oxide semiconductors). These solid-state image sensors use silicon photodiodes that are sensitive to infrared light in their light receiving section. For this reason, infrared-cut filters are sometimes used to correct visibility.
  • CCDs charge-coupled devices
  • CMOS complementary metal-oxide semiconductors
  • Infrared cut filters are manufactured using a composition that contains an infrared absorbing agent.
  • Polymethine compounds are known examples of infrared absorbing agents.
  • Patent Document 1 describes the production of infrared cut filters and the like using a composition containing a specific polymethine compound.
  • polymethine compounds tend to have low light resistance and heat resistance. For this reason, there is room for further improvement in the light resistance of films obtained using compositions containing these compounds.
  • an object of the present invention is to provide a composition capable of forming a film having excellent light resistance and heat resistance.
  • the present invention is to provide a film, an optical filter, a solid-state imaging device, an image display device, an infrared sensor, a camera module, and a compound.
  • the present invention provides the following:
  • a composition comprising a compound represented by formula (1) and a curable compound; (PM) (Z) m ...
  • PM represents an anion represented by formula (PM1): Z represents a divalent or higher cation; m is a number greater than 0 and represents the number required to neutralize the charge of PM;
  • Rpm 1 to Rpm 5 each independently represent a hydrogen atom or a substituent; n represents an integer of 1 or more; any two of Rpm 2 to Rpm 4 may be bonded to form a ring, Rpm 1 and T 1 may be bonded to form a ring, and Rpm 5 and T 2 may be bonded to form a ring;
  • T 1 is a group represented by formula (T 1A ), formula (T 1B ) or formula (T 1C );
  • T2 is a group represented by formula ( T2A ), formula ( T2B ) or formula ( T2C ), At least one of Rpm 1 to Rpm 5 , T 1 and T 2
  • PM in the formula (1) is an anion represented by formula (PM2), formula (PM3) or formula (PM4);
  • Rpm 11 to Rpm 15 each independently represent a hydrogen atom or a substituent;
  • Rpm 12 and Rpm 14 may be bonded to form a ring;
  • Rpm 11 and T 1 may be bonded to form a ring, and Rpm 15 and T 2 may be bonded to form a ring;
  • T 1 is a group represented by the above formula (T 1A ), formula (T 1B ) or formula (T 1C );
  • T2 is a group represented by the above formula ( T2A ), formula ( T2B ) or formula ( T2C ), At least one of Rpm 11 to Rpm 15 , T 1 and T 2 contains an anionic group;
  • composition according to any one of ⁇ 1> to ⁇ 3>, further comprising an infrared absorbing agent other than the compound represented by formula (1) ⁇ 5> A film obtained by using the composition according to any one of ⁇ 1> to ⁇ 4>.
  • PM represents an anion represented by formula (PM1): Z represents a divalent or higher cation; m is a number greater than 0 and represents the number required to neutralize the charge of PM;
  • Rpm 1 to Rpm 5 each independently represent a hydrogen atom or a substituent; n represents an integer of 1 or more; any two of Rpm 2 to Rpm 4 may be bonded to form a ring, Rpm 1 and T 1 may be bonded to form a ring, and Rpm 5 and T 2 may be bonded to form a ring;
  • T 1 is a group represented by formula (T 1A ), formula (T 1B ) or formula (T 1C );
  • T2 is a group represented by formula ( T2A ), formula ( T2B ) or formula ( T2C ), At least one of Rpm 1 to Rpm 5 , T 1 and T 2 contains an anionic group;
  • X 1 to X 6 each independently represent an oxygen atom, a sulfur atom,
  • the present invention can provide a composition capable of forming a film having excellent light resistance and heat resistance.
  • the present invention can also provide a film, an optical filter, a solid-state imaging device, an image display device, an infrared sensor, a camera module, and a compound.
  • FIG. 1 is a schematic diagram illustrating an embodiment of an infrared sensor.
  • alkyl group encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
  • Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, active rays or radiation such as electron beams.
  • (meth)acrylate refers to both or either of acrylate and methacrylate
  • (meth)acrylic refers to both or either of acrylic and methacrylic
  • (meth)acryloyl refers to both or either of acryloyl and methacryloyl.
  • the weight average molecular weight and the number average molecular weight are defined as values calculated in terms of polystyrene as measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • Me in the chemical formulae represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • infrared rays refer to light (electromagnetic waves) with a wavelength of 700 to 2500 nm.
  • the total solids content refers to the total mass of all components of the composition excluding the solvent.
  • the term "process” refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved.
  • composition of the present invention is characterized by containing a compound represented by formula (1) and a curable compound.
  • the compound represented by formula (1) contained in the composition of the present invention has excellent heat resistance and light resistance, and the composition of the present invention containing such a compound can form a film having excellent light resistance and heat resistance.
  • the composition of the present invention can be used as a composition for an optical filter.
  • Types of optical filters include infrared cut filters and infrared transmission filters. Since the compound represented by formula (1) has excellent visible light transmittance and infrared shielding properties, the composition of the present invention is particularly preferably used as a composition for an infrared cut filter.
  • composition of the present invention contains a compound represented by formula (1).
  • the compound represented by formula (1) is also a compound of the present invention.
  • the compound represented by formula (1) is also referred to as a specific compound.
  • PM represents an anion represented by formula (PM1): Z represents a divalent or higher cation; m is a number greater than 0 and represents the number required to neutralize the charge of PM.
  • the divalent or higher cation represented by Z in formula (1) may be an organic cation or an inorganic cation.
  • an inorganic cation the dispersibility in a hydrophilic solvent is excellent.
  • the dispersibility in a hydrophobic solvent is excellent.
  • Z is preferably a divalent, trivalent or tetravalent cation, and more preferably a divalent or trivalent cation.
  • the types of divalent or higher cations represented by Z include (1) divalent or higher metal cations, and (2) divalent or higher cations having two or more cations in one molecule, such as pyridinium cations, ammonium cations, imidazolium cations, oxazolium cations, thiazolium cations, pyrrolidinium cations, piperidinium cations, and phosphonium cations.
  • the divalent or higher metal cation is preferably a cation of an element selected from the group consisting of periodic elements, 4th period elements, 5th period elements, 6th period elements, 7th period elements, and rare earth elements, and more preferably a cation of an element selected from the group consisting of periodic elements, 4th period elements, 5th period elements, and rare earth elements.
  • magnesium cation, aluminum cation, calcium cation, scandium cation, titanium cation, vanadium cation, chromium cation, manganese cation, iron cation, cobalt cation, nickel cation, copper cation, zinc cation, gallium cation, strontium cation, yttrium cation, zirconium cation, ruthenium cation, rhodium cation, palladium cation, indium cation, tin cation, barium cation, hafnium cation, tantalum cation, rhenium cation, iridium cation, platinum cation, or a cation of a rare earth element is preferable, and magnesium cation, aluminum cation, calcium cation, scandium cation, titanium cation, vanadium cation, chromium cation, manganese cation, iron cation,
  • magnesium cation aluminum cation, calcium cation, scandium cation, titanium cation, vanadium cation, chromium cation, manganese cation, iron cation, cobalt cation, nickel cation, copper cation, zinc cation, gallium cation, strontium cation, barium cation, hafnium cation, radium cation, lanthanum cation, cerium cation, praseodymium cation, neodymium cation, samarium cation, europium cation, gadolinium cation, terbium cation, thulium cation, ytterbium cation, or lutetium cation.
  • cations other than metal cations include cations having the structures shown below: In the following structural formulas, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.
  • m is a number greater than 0 and represents a number necessary to neutralize the charge of the PM of formula (1). That is, in formula (1), m is a number that satisfies the following relationship.
  • m ⁇ (valence of cation represented by Z in formula (1)) valence of anion represented by PM in formula (1)
  • m is 1/2.
  • m is expressed as the number of moles of cation represented by Z relative to 1 mole of anion represented by PM. Therefore, in the above case, m is expressed as a fraction, but it means that the compound represented by formula (1) has 1 mole of anion represented by Z relative to 2 moles of anion represented by PM.
  • Rpm 1 to Rpm 5 each independently represent a hydrogen atom or a substituent; n represents an integer of 1 or more; any two of Rpm 2 to Rpm 4 may be bonded to form a ring, Rpm 1 and T 1 may be bonded to form a ring, and Rpm 5 and T 2 may be bonded to form a ring; T 1 is a group represented by formula (T 1A ), formula (T 1B ) or formula (T 1C ); T2 is a group represented by formula ( T2A ), formula ( T2B ) or formula ( T2C ), At least one of Rpm 1 to Rpm 5 , T 1 and T 2 contains an anionic group.
  • Examples of the substituents represented by Rpm 1 to Rpm 5 include the groups exemplified as the substituent T described below, and anionic groups.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 5.
  • the alkyl group may be linear, branched, or cyclic.
  • the number of carbon atoms in the alkenyl group is preferably from 2 to 20, more preferably from 2 to 15, still more preferably from 2 to 10, and particularly preferably from 2 to 5.
  • the alkenyl group may be either linear or branched.
  • the aryl group preferably has 6 to 20 carbon atoms, and more preferably has 6 to 12 carbon atoms.
  • the heterocyclic group is preferably a monocyclic or fused ring heterocyclic group having 2 to 8 fused rings, more preferably a monocyclic or fused ring heterocyclic group having 2 to 4 fused rings.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3.
  • Examples of the heteroatoms constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom, and the nitrogen atom is preferred.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 1 to 20, more preferably 1 to 18, and more preferably 1 to 12.
  • the heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
  • the alkyl group, alkenyl group, aryl group and heterocyclic group may have a substituent. Examples of the substituent include the groups exemplified as the substituent T described later.
  • the anionic group includes a group represented by the formula (AN-1) and a group represented by the formula (AN-2).
  • L AN1 represents a single bond or a p+1-valent linking group.
  • An1 represents -SO3- , -COO- , -PO3H- , -CON - SO2Ran1 , -SO2N - SO2Ran1 or -SO2N - CORan1 , where Ran1 represents an alkyl group or an aryl group, and p represents an integer of 1 to 4.
  • L AN2 and L AN4 each independently represent a single bond or a divalent linking group.
  • L AN3 represents -CON - SO 2 -, -SO 2 N - SO 2 - or -SO 2 N - CO-;
  • R AN1 and R AN2 each independently represent an alkylene group or an arylene group;
  • An 2 represents -SO 3 - , -COO - or -PO 3 H - .
  • Examples of the p+1-valent linking group represented by L AN1 in formula (AN-1) include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, -O-, -CO-, -NH-, -COO-, -OCO-, -CONH-, -NHCO-, -SO 2 -, -SO 2 NH-, -NHSO 2 -, -S-, and groups consisting of a combination of two or more of these groups.
  • the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 5.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic.
  • the aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, and more preferably has 6 to 12 carbon atoms.
  • the heterocyclic group is preferably a monocyclic or fused ring heterocyclic group having 2 to 8 fused rings, more preferably a monocyclic or fused ring heterocyclic group having 2 to 4 fused rings.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. Examples of the heteroatoms constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom, and the nitrogen atom is preferred.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 1 to 20, more preferably 1 to 18, and more preferably 1 to 12.
  • the heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
  • the aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group may have a substituent. Examples of the substituent include the
  • An 1 represents -SO 3 - , -COO - , -PO 3 H - , -CON - SO 2 R an1 , -SO 2 N - SO 2 R an1 or -SO 2 N - COR an1 , where R an1 represents an alkyl group or an aryl group.
  • An 1 is preferably -SO 3 - , -COO - , -CON - SO 2 R an1 , -SO 2 N - SO 2 R an1 or -SO 2 N - COR an1 , and more preferably -SO 3 - , -COO - or -SO 2 N - SO 2 R an1 .
  • the number of carbon atoms in the alkyl group represented by R an1 is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5.
  • the alkyl group may be linear, branched, or cyclic.
  • the alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, and an aryloxy group.
  • the alkyl group may have a plurality of substituents.
  • the alkyl group represented by R an1 is preferably an alkyl group having a halogen atom as a substituent, and more preferably an alkyl group having a fluorine atom as a substituent.
  • the number of carbon atoms of the aryl group represented by R an1 is preferably 6 to 20, and more preferably 6 to 12.
  • the aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group. The number of substituents may be multiple.
  • the aryl group represented by R an1 is preferably an aryl group having a halogen atom as a substituent, and more preferably an aryl group having a fluorine atom as a substituent.
  • L AN2 and L AN4 in formula (AN-2) each independently represent a single bond or a divalent linking group.
  • the divalent linking group represented by L AN2 and L AN4 include an alkylene group, an arylene group, a heterocyclic group, -O-, -CO-, -NH-, -COO-, -OCO-, -CONH-, -NHCO-, -SO 2 -, -SO 2 NH-, -NHSO 2 -, -S-, and groups formed by combining two or more of these groups.
  • the number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 5.
  • the alkylene group may be linear, branched, or cyclic.
  • the arylene group preferably has 6 to 20 carbon atoms, and more preferably has 6 to 12 carbon atoms.
  • the heterocyclic group is preferably a monocyclic or fused ring heterocyclic group having 2 to 8 fused rings, more preferably a monocyclic or fused ring heterocyclic group having 2 to 4 fused rings.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. Examples of the heteroatoms constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom, and the nitrogen atom is preferred.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 1 to 20, more preferably 1 to 18, and more preferably 1 to 12.
  • the heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
  • the alkylene group, the arylene group and the heterocyclic group may have a substituent. Examples of the substituent include the substituent T described below.
  • L AN3 in the formula (AN-2) represents -CON - SO 2 -, -SO 2 N - SO 2 - or -SO 2 N - CO-, and is preferably -SO 2 N - SO 2 -.
  • R AN1 and R AN2 each independently represent an alkylene group or an arylene group.
  • the number of carbon atoms in the alkylene group represented by R AN1 and R AN2 is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5.
  • the alkylene group may be linear, branched, or cyclic.
  • the alkylene group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, and an aryloxy group. There may be multiple substituents.
  • the alkylene group represented by R AN2 is preferably an alkylene group having a halogen atom as a substituent, and more preferably an alkylene group having a fluorine atom as a substituent.
  • the number of carbon atoms in the arylene group represented by R AN1 and R AN2 is preferably 6 to 20, and more preferably 6 to 12.
  • the arylene group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group. The number of substituents may be multiple.
  • the arylene group represented by R AN2 is preferably an arylene group having a halogen atom as a substituent, and more preferably an arylene group having a fluorine atom as a substituent.
  • An 2 in formula (AN-2) represents -SO 3 - , -COO - or -PO 3 H - , preferably -SO 3 - or -COO - , and more preferably -SO 3 - .
  • any two of Rpm 2 to Rpm 4 may be bonded to form a ring, Rpm 1 and T 1 may be bonded to form a ring, and Rpm 5 and T 2 may be bonded to form a ring.
  • the ring formed is preferably a 5-membered or 6-membered ring.
  • the ring formed may have a substituent. Examples of the substituent include the groups listed as the substituent T described below and anionic groups. Examples of the anionic group include the groups represented by the above formula (AN-1) and formula (AN-2).
  • n represents an integer of 1 or more, and is preferably an integer of 1 to 3.
  • T1 is a group represented by formula ( T1A ), formula ( T1B ) or formula ( T1C ), and T2 is a group represented by formula ( T2A ), formula ( T2B ) or formula ( T2C ).
  • X 1 to X 6 each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR X1 -, where R X1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • Examples of the halogen atom represented by R X1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the number of carbon atoms in the alkyl group represented by R X1 is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 5.
  • the alkyl group may be linear, branched, or cyclic.
  • the aryl group represented by R 3 X1 preferably has 6 to 20 carbon atoms, and more preferably has 6 to 12 carbon atoms.
  • the heterocyclic group represented by R X1 is preferably a monocyclic or fused ring heterocyclic group having 2 to 8 fused rings, more preferably a monocyclic or fused ring heterocyclic group having 2 to 4 fused rings.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3.
  • Examples of the heteroatoms constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom, and are preferably a nitrogen atom.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 1 to 20, more preferably 1 to 18, and more preferably 1 to 12.
  • the heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
  • the alkyl group, aryl group and heterocyclic group represented by R X1 may have a substituent. Examples of the substituent include the groups exemplified as the substituent T described below.
  • X 1 to X 6 are each preferably independently an oxygen atom or a sulfur atom, more preferably an oxygen atom. According to this embodiment, the heat resistance and light resistance can be further improved.
  • Examples of the anionic group represented by R 1 to R 16 and R 31 to R 46 include the groups represented by the above-mentioned formula (AN-1) and formula (AN-2).
  • Examples of the halogen atom represented by R 1 to R 16 and R 31 to R 46 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the number of carbon atoms in the alkyl group represented by R 1 to R 16 , R 31 to R 46 , R L1 and R L2 is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 5.
  • the alkyl group may be linear, branched or cyclic.
  • the number of carbon atoms in the alkenyl group represented by R 1 to R 16 , R 31 to R 46 , R L1 and R L2 is preferably 2 to 20, more preferably 2 to 15, still more preferably 2 to 10, and particularly preferably 2 to 5.
  • the alkenyl group may be either linear or branched.
  • the aryl group represented by R 1 to R 16 , R 31 to R 46 , R L1 and R L2 preferably has 6 to 20 carbon atoms, and more preferably has 6 to 12 carbon atoms.
  • the heterocyclic group represented by R 1 to R 16 , R 31 to R 46 , R L1 and R L2 is preferably a monocyclic or fused ring heterocyclic group having 2 to 8 fused rings, more preferably a monocyclic or fused ring heterocyclic group having 2 to 4 fused rings.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3.
  • heteroatom constituting the ring of the heterocyclic group examples include a nitrogen atom, an oxygen atom and a sulfur atom, and the nitrogen atom is preferable.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 1 to 20, more preferably 1 to 18, and more preferably 1 to 12.
  • the heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
  • the alkyl group, alkenyl group, aryl group and heterocyclic group may have a substituent. Examples of the substituent include the groups exemplified as the substituent T described later.
  • Any two adjacent groups among R 1 to R 16 and R 31 to R 46 may be bonded to each other to form a ring.
  • the ring formed is preferably a 5-membered or 6-membered ring.
  • the ring formed may have a substituent.
  • substituents include the groups listed as the substituent T described below and anionic groups.
  • anionic group include the groups represented by the formula (AN-1) and the groups represented by the formula (AN-2) described above.
  • At least one of Rpm 1 to Rpm 5 , T 1 and T 2 contains an anionic group. It is preferable that at least one of T 1 and T 2 contains an anionic group, and it is more preferable that each of T 1 and T 2 contains an anionic group.
  • T1 contains an anionic group
  • T1 is a group represented by formula ( T1A ) in which at least one of R1 to R6 is a group containing an anionic group
  • T1 is a group represented by formula ( T1B ) in which at least one of R7 to R12 is a group containing an anionic group
  • T1 is a group represented by formula ( T1C ) in which at least one of R13 to R16 is a group containing an anionic group.
  • T2 contains an anionic group
  • T2 is a group represented by formula ( T2A ) in which at least one of R31 to R36 is a group containing an anionic group
  • T2 is a group represented by formula ( T2B ) in which at least one of R37 to R42 is a group containing an anionic group
  • T2 is a group represented by formula ( T2C ) in which at least one of R43 to R46 is a group containing an anionic group.
  • the total number of anions contained in Rpm 1 to Rpm 5 , T 1 and T 2 is preferably 2-20, more preferably 2-15, and even more preferably 2-10.
  • the anion represented by formula (PM1) is preferably a 1-19 valent anion, more preferably a 1-14 valent anion, and even more preferably a 1-9 valent anion.
  • PM in formula (1) is preferably an anion represented by formula (PM2), formula (PM3) or formula (PM4), and more preferably an anion represented by formula (PM2) or formula (PM3).
  • Rpm 11 to Rpm 15 each independently represent a hydrogen atom or a substituent; Rpm 12 and Rpm 14 may be bonded to form a ring; Rpm 11 and T 1 may be bonded to form a ring, and Rpm 15 and T 2 may be bonded to form a ring; T 1 is a group represented by the above formula (T 1A ), formula (T 1B ) or formula (T 1C ); T2 is a group represented by the above formula ( T2A ), formula ( T2B ) or formula ( T2C ), At least one of Rpm 11 to Rpm 15 , T 1 and T 2 contains an anionic group; In formula (PM3), Rpm 21 to Rpm 27 each independently represent a hydrogen atom or a substituent; Rpm 23 and Rpm 25 may be bonded to form a ring; Rpm 21 and T1 may be bonded to form a ring, Rpm 27 and T2 may be bonded to form a ring, T 1 is a group represented by
  • Examples of the substituents represented by Rpm 11 to Rpm 15 in formula (PM2), the substituents represented by Rpm 21 to Rpm 27 in formula (PM3), and the substituents represented by Rpm 31 to Rpm 39 in formula (PM4) include the groups exemplified as the substituent T described later, and anionic groups.
  • the substituent other than the anionic group is preferably the group given as the preferred examples of the substituent other than the anionic group represented by Rpm 1 to Rpm 5 in the above formula (PM1).
  • anionic group examples include the group represented by the above formula (AN-1) and the group represented by the formula (AN-2).
  • Rpm 12 and Rpm 14 may be bonded to form a ring
  • Rpm 11 and T 1 may be bonded to form a ring
  • Rpm 15 and T 2 may be bonded to form a ring
  • Rpm 23 and Rpm 25 may be bonded to form a ring
  • Rpm 21 and T1 may be bonded to form a ring
  • Rpm 27 and T2 may be bonded to form a ring
  • Rpm 34 and Rpm 36 may be bonded to form a ring
  • Rpm 31 and T1 may be bonded to form a ring
  • Rpm 39 and T2 may be bonded to form a ring.
  • the ring formed by bonding the above groups together is preferably a 5-membered or 6-membered ring.
  • the ring formed may have a substituent.
  • substituents include the groups listed as the substituent T described below and anionic groups.
  • anionic group include the group represented by the above formula (AN-1) and the group represented by the formula (AN-2).
  • At least one of Rpm 11 to Rpm 15 , T 1 and T 2 contains an anionic group. It is preferable that at least one of T 1 and T 2 contains an anionic group, and it is more preferable that each of T 1 and T 2 contains an anionic group.
  • the total number of anions contained in Rpm 11 to Rpm 15 , T 1 and T 2 is preferably 2-20, more preferably 2-15, and even more preferably 2-10.
  • the anion represented by formula (PM2) is preferably a 1- to 19-valent anion, more preferably a 1- to 14-valent anion, and even more preferably a 1- to 9-valent anion.
  • Rpm 21 to Rpm 27 , T 1 and T 2 contains an anionic group. It is preferable that at least one of T 1 and T 2 contains an anionic group, and it is more preferable that each of T 1 and T 2 contains an anionic group.
  • the total number of anions contained in Rpm 21 to Rpm 27 , T 1 and T 2 is preferably 2-20, more preferably 2-15, and even more preferably 2-10.
  • the anion represented by formula (PM3) is preferably a 1- to 19-valent anion, more preferably a 1- to 14-valent anion, and even more preferably a 1- to 9-valent anion.
  • At least one of Rpm 31 to Rpm 39 , T 1 and T 2 contains an anionic group. It is preferable that at least one of T 1 and T 2 contains an anionic group, and it is more preferable that each of T 1 and T 2 contains an anionic group.
  • the total number of anions contained in Rpm 31 to Rpm 39 , T 1 and T 2 is preferably 2-20, more preferably 2-15, and even more preferably 2-10.
  • the anion represented by formula (PM4) is preferably a 1- to 19-valent anion, more preferably a 1- to 14-valent anion, and even more preferably a 1- to 9-valent anion.
  • substituent T examples include the following groups: a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms), a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms), an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), a heterocyclic oxy group (preferably a heterocyclic oxy group (preferably a heterocyclic oxy
  • an aryloxycarbonyl group preferably an aryloxycarbonyl group having 7 to 30 carbon atoms
  • a heterocyclic oxycarbonyl group preferably a heterocyclic oxycarbonyl group having 2 to 30 carbon atoms
  • an acyloxy group preferably an acyloxy group having 2 to 30 carbon atoms
  • an acylamino group preferably an acylamino group having 2 to 30 carbon atoms
  • an aminocarbonylamino group preferably an aminocarbonylamino group having 2 to 30 carbon atoms
  • an alkoxycarbonylamino group preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms
  • an aryloxycarbonylamino group preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms
  • a sulfamoyl group preferably a sulfamoyl group having 0 to 30 carbon atoms
  • Specific examples - Specific examples of the specific compound include compounds having the structures shown below. Resonance structures of these compounds are also specific examples of the specific compound.
  • Me is a methyl group
  • Ph is a phenyl group.
  • the number of moles of cations is expressed as a value relative to 1 mole of dye anion, taking into account the respective charges of the dye anion and the cation. For example, A-1 indicates that there is 1 mole of cations for 2 moles of dye anion, and A-3 indicates that there are 3 moles of cations for 2 moles of dye anion.
  • the maximum absorption wavelength of the specific compound is preferably at least 650 nm, more preferably in the wavelength range of 650 to 1500 nm, even more preferably in the wavelength range of 700 to 1200 nm, and particularly preferably in the wavelength range of 700 to 1000 nm.
  • the specific compound is preferably used as an infrared absorber.
  • the content of the specific compound (compound represented by formula (1)) in the total solid content of the composition is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, even more preferably 3 mass% or more, and particularly preferably 5 mass% or more.
  • the upper limit of the content of the infrared absorber is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less.
  • the composition of the present invention may contain only one type of specific compound, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above range.
  • the composition of the present invention contains a curable compound.
  • the curable compound include polymerizable compounds and resins.
  • the resin may be a non-polymerizable resin (a resin having no polymerizable group) or a polymerizable resin (a resin having a polymerizable group).
  • the polymerizable group include an ethylenically unsaturated bond-containing group, a cyclic ether group, a methylol group, and an alkoxymethyl group.
  • Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a vinylphenyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a (meth)acryloylamide group, with the (meth)allyl group, the (meth)acryloyl group, and the (meth)acryloyloxy group being preferred, and the (meth)acryloyloxy group being more preferred.
  • Examples of the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred.
  • the curable compound preferably contains at least a resin.
  • a resin and a polymerizable compound preferably a polymerizable monomer that is a monomer-type polymerizable compound
  • the polymerizable compound may include a compound having an ethylenically unsaturated bond-containing group, a compound having a cyclic ether group, a compound having a methylol group, a compound having an alkoxymethyl group, etc.
  • the compound having an ethylenically unsaturated bond-containing group can be preferably used as a radical polymerizable compound.
  • the compound having a cyclic ether group can be preferably used as a cationic polymerizable compound.
  • resin-type polymerizable compounds include resins that contain repeating units with polymerizable groups.
  • the molecular weight of the monomer-type polymerizable compound is preferably less than 2000, and more preferably 1500 or less.
  • the lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, and more preferably 200 or more.
  • the weight average molecular weight (Mw) of the resin-type polymerizable compound is preferably 2000 to 2,000,000.
  • the upper limit of the weight average molecular weight is preferably 1,000,000 or less, and more preferably 500,000 or less.
  • the lower limit of the weight average molecular weight is preferably 3,000 or more, and more preferably 5,000 or more.
  • the compound having an ethylenically unsaturated bond-containing group as a polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, and more preferably a 3- to 6-functional (meth)acrylate compound.
  • Specific examples include compounds described in paragraphs 0095 to 0108 of JP 2009-288705 A, paragraph 0227 of JP 2013-029760 A, paragraphs 0254 to 0257 of JP 2008-292970 A, paragraphs 0034 to 0038 of JP 2013-253224 A, paragraph 0477 of JP 2012-208494 A, JP 2017-048367 A, Japanese Patent No. 6057891 A, Japanese Patent No. 6031807 A, and Japanese Patent No. 2017-194662 A, the contents of which are incorporated herein by reference.
  • Examples of compounds having an ethylenically unsaturated bond-containing group include dipentaerythritol tri(meth)acrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds in which the (meth)acryloyl groups of these compounds are bonded via ethylene glycol and/
  • examples of compounds having an ethylenically unsaturated bond-containing group include diglycerol EO (ethylene oxide) modified (meth)acrylate (commercially available product is M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), and light
  • trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate.
  • trifunctional (meth)acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, and M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, and TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, and PET-30 (manufactured by Nippon Kayaku Co., Ltd.).
  • the compound having an ethylenically unsaturated bond-containing group may further have an acid group such as a carboxy group, a sulfo group, or a phosphate group.
  • an acid group such as a carboxy group, a sulfo group, or a phosphate group.
  • Commercially available products of such compounds include Aronix M-305, M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
  • a compound having a caprolactone structure can also be used.
  • the description in paragraphs 0042 to 0045 of JP 2013-253224 A can be referred to, the contents of which are incorporated herein by reference.
  • Examples of compounds having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as a series from Nippon Kayaku Co., Ltd.
  • a compound having an ethylenically unsaturated bond-containing group a compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used.
  • Such a compound is preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and/or a propyleneoxy group, more preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group, and even more preferably a trifunctional to hexafunctional (meth)acrylate compound having 4 to 20 ethyleneoxy groups.
  • Examples of commercially available products include SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer, and KAYARAD TPA-330, a trifunctional (meth)acrylate having three isobutyleneoxy groups manufactured by Nippon Kayaku Co., Ltd.
  • a polymerizable compound having a fluorene skeleton can also be used.
  • Commercially available products include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).
  • a compound having an ethylenically unsaturated bond-containing group it is also preferable to use a compound that is substantially free of environmentally restricted substances such as toluene.
  • Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
  • Examples of compounds having a cyclic ether group include compounds having an epoxy group and compounds having an oxetanyl group, and compounds having an epoxy group are preferred.
  • Examples of compounds having an epoxy group include compounds having 1 to 100 epoxy groups in one molecule.
  • the upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less.
  • the lower limit of the number of epoxy groups is preferably 2 or more.
  • the compound having a cyclic ether group may be a low molecular weight compound (e.g., molecular weight less than 1000) or a high molecular weight compound (macromolecule) (e.g., molecular weight 1000 or more, in the case of a polymer, weight average molecular weight 1000 or more).
  • the weight average molecular weight of the cyclic ether group is preferably 200 to 100,000, more preferably 500 to 50,000.
  • the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.
  • the compounds described in JP 2013-011869 A, paragraphs 0034 to 0036, the compounds described in JP 2014-043556 A, paragraphs 0147 to 0156, the compounds described in JP 2014-089408 A, paragraphs 0085 to 0092, and the compounds described in JP 2017-179172 A can also be used.
  • Examples of compounds having a methylol group include compounds in which a methylol group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring.
  • Examples of compounds having an alkoxymethyl group include compounds in which an alkoxymethyl group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring.
  • Examples of compounds in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxymethylated urea, and methylolated urea.
  • Compounds described in paragraphs 0134 to 0147 of JP 2004-295116 A and paragraphs 0095 to 0126 of JP 2014-089408 A can also be used.
  • the composition of the present invention can use a resin as a curable compound. It is preferable to use a curable compound that contains at least a resin.
  • the resin is blended, for example, for dispersing pigments in the composition or for use as a binder.
  • a resin that is mainly used for dispersing pigments in the composition is also called a dispersant.
  • a resin having a polymerizable group also falls under the category of a polymerizable compound.
  • the weight average molecular weight of the resin is preferably 3,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
  • the lower limit is preferably 4,000 or more, and more preferably 5,000 or more.
  • the resins include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyurethane resins, and polyurea resins.
  • One of these resins may be used alone, or two or more may be mixed and used.
  • norbornene resin is preferred from the viewpoint of improving heat resistance.
  • Commercially available norbornene resins include, for example, the ARTON series (e.g., ARTON F4520) manufactured by JSR Corporation.
  • the resin there are resins described in paragraphs 0091 to 0099 of WO 2022/065215, blocked polyisocyanate resins described in JP 2016-222891 A, resins described in JP 2020-122052 A, resins described in JP 2020-111656 A, resins described in JP 2020-139021 A, resins having a ring structure in the main chain and a biphenyl group in the side chain described in JP 2017-138503 A, and resins described in paragraphs 0199 to 0233 of JP 2020-186373 A Resins described in the above, alkali-soluble resins described in JP 2020-186325 A, resins represented by formula 1 described in Korean Patent Publication No.
  • 10-2020-0078339 A copolymers containing epoxy groups and acid groups described in WO 2022/030445 A, resins described in paragraphs 0199 to 0233 of JP 2020-186373 A, alkali-soluble resins described in JP 2020-186325 A, resins represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339 A, and resins described in JP 2021-134350 A can also be used.
  • resins having a fluorene skeleton can also be preferably used as the resin. Examples of resins having a fluorene skeleton include resins described in U.S. Patent Application Publication No. 2017/0102610 A.
  • the resin it is preferable to use a resin having an acid group.
  • the acid group include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group. These acid groups may be of only one type, or of two or more types.
  • the resin having an acid group can also be used as a dispersant.
  • the acid value of the resin having an acid group is preferably 30 to 500 mgKOH/g.
  • the lower limit is preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more.
  • the upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, even more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.
  • the resin it is also preferable to use a resin having a polymerizable group.
  • the polymerizable group is preferably an ethylenically unsaturated bond-containing group or a cyclic ether group, and more preferably an ethylenically unsaturated bond-containing group.
  • the resin preferably contains a resin as a dispersant.
  • dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins).
  • the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups.
  • the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more when the total amount of the acid groups and the basic groups is 100 mol%.
  • the acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g.
  • the basic dispersant refers to a resin in which the amount of basic groups is greater than the amount of acid groups.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups is greater than the amount of acid groups when the total amount of the acid groups and the basic groups is 100 mol%.
  • the basic group possessed by the basic dispersant is preferably an amino group.
  • the resin used as the dispersant is a graft resin.
  • graft resins please refer to the description in paragraphs 0025 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein by reference.
  • the resin used as the dispersant is preferably a polyimine-based dispersant containing nitrogen atoms in at least one of the main chain and side chain.
  • the polyimine-based dispersant is preferably a resin having a main chain with a partial structure having a functional group with a pKa of 14 or less, a side chain with 40 to 10,000 atoms, and having a basic nitrogen atom in at least one of the main chain and side chain.
  • the basic nitrogen atom so long as it is a nitrogen atom that exhibits basicity.
  • polyimine-based dispersants please refer to the description in paragraphs 0102 to 0166 of JP 2012-255128 A, the contents of which are incorporated herein by reference.
  • the resin used as the dispersant is preferably one having a structure in which multiple polymer chains are bonded to a core portion.
  • resins include dendrimers (including star-shaped polymers).
  • dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962A.
  • the resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain.
  • the content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol % or more of the total repeating units of the resin, more preferably 10 to 80 mol %, and even more preferably 20 to 70 mol %.
  • resins described in JP 2018-087939 A, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6,432,077 A, polyethyleneimine having polyester side chains described in WO 2016/104803 A, block copolymers described in WO 2019/125940 A, block polymers having acrylamide structural units described in JP 2020-066687 A, block polymers having acrylamide structural units described in JP 2020-066688 A, and the like can also be used.
  • Dispersants are also available as commercially available products, and specific examples include the DISPERBYK series manufactured by BYK-Chemie, the SOLSPERSE series manufactured by Lubrizol Nippon, the Efka series manufactured by BASF, and the AJISPER series manufactured by Ajinomoto Fine-Techno Co., Ltd.
  • the products described in paragraph 0129 of JP2012-137564A and the products described in paragraph 0235 of JP2017-194662A can also be used as dispersants.
  • the content of the curable compound in the total solid content of the composition is preferably 1 to 95 mass%.
  • the lower limit is preferably 2 mass% or more, more preferably 5 mass% or more, even more preferably 7 mass% or more, and particularly preferably 10 mass% or more.
  • the upper limit is preferably 94 mass% or less, more preferably 90 mass% or less, even more preferably 85 mass% or less, and particularly preferably 80 mass% or less.
  • the content of the polymerizable compound in the total solid content of the composition is preferably 1 to 85 mass%.
  • the lower limit is preferably 2 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more.
  • the upper limit is preferably 80 mass% or less, and more preferably 70 mass% or less.
  • the content of the polymerizable monomer in the total solid content of the composition is preferably 1 to 50 mass%.
  • the lower limit is preferably 2 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more.
  • the upper limit is preferably 30 mass% or less, and more preferably 20 mass% or less.
  • the content of the compound having an ethylenically unsaturated bond-containing group in the total solid content of the composition is preferably 1 to 70 mass%.
  • the lower limit is preferably 2 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more.
  • the upper limit is preferably 65 mass% or less, and more preferably 60 mass% or less.
  • the content of the compound having a cyclic ether group in the total solid content of the composition is preferably 1 to 95 mass%.
  • the lower limit is preferably 2 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more.
  • the upper limit is preferably 80 mass% or less, more preferably 70 mass% or less, and even more preferably 60 mass% or less.
  • the content of the resin in the total solid content of the composition is preferably 1 to 85 mass%.
  • the lower limit is preferably 2 mass% or more, more preferably 5 mass% or more, even more preferably 7 mass% or more, and particularly preferably 10 mass% or more.
  • the upper limit is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, and particularly preferably 40 mass% or less.
  • the content of the resin as a dispersant in the total solid content of the composition is preferably 0.1 to 40 mass%.
  • the upper limit is preferably 25 mass% or less, and more preferably 20 mass% or less.
  • the lower limit is preferably 0.5 mass% or more, and more preferably 1 mass% or more.
  • the content of the resin as a dispersant is preferably 1 to 100 mass parts per 100 mass parts of pigment.
  • the upper limit is preferably 80 mass parts or less, and more preferably 75 mass parts or less.
  • the lower limit is preferably 2.5 mass parts or more, and more preferably 5 mass parts or more.
  • composition of the present invention may contain only one type of curable compound, or may contain two or more types. When two or more types of curable compounds are contained, it is preferable that the total amount thereof is within the above range.
  • the composition of the present invention preferably contains a solvent.
  • the solvent include water and organic solvents, and organic solvents are preferred.
  • the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
  • ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used.
  • organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, butyl acetate ...
  • diacetate examples include ethylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol and 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.
  • diacetone alcohol also known as diacetone alcohol and 4-hydroxy-4-methyl-2-pentanone
  • 2-methoxypropyl acetate 2-methoxy-1-propano
  • the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons, etc. (for example, the amount can be 50 ppm (parts per million) by mass or less, 10 ppm by mass or less, or 1 ppm by mass or less, relative to the total amount of organic solvents).
  • an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent with a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).
  • Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter.
  • the filter used for filtration preferably has a pore size of 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 with the same number of atoms but different structures).
  • the organic solvent may contain only one type of isomer, or multiple types of isomers.
  • the peroxide content in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.
  • the content of the solvent in the composition is preferably 10 to 97% by mass.
  • the lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
  • the upper limit is preferably 96% by mass or less, and more preferably 95% by mass or less.
  • the composition may contain only one type of solvent, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the composition of the present invention may contain an infrared absorbing agent (another infrared absorbing agent) other than the above-mentioned specific compound.
  • an infrared absorbing agent another infrared absorbing agent
  • a film capable of shielding infrared rays in a wider wavelength range can be formed.
  • the other infrared absorbing agent may be a dye or a pigment (particle).
  • Examples of the other infrared absorbing agent include pyrrolopyrrole compounds, polymethine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, etc., and it is preferable that the other infrared absorbing agent is at least one selected from squarylium compounds and phthalocyanine compounds.
  • Examples of pyrrolopyrrole compounds include compounds described in paragraphs 0016 to 0058 of JP-A-2009-263614, compounds described in paragraphs 0037 to 0052 of JP-A-2011-068731, and compounds described in paragraphs 0010 to 0033 of WO 2015/166873.
  • Examples of squarylium compounds include compounds described in paragraphs 0044 to 0049 of JP-A-2011-208101, compounds described in paragraphs 0060 to 0061 of Japanese Patent No. 6065169, compounds described in paragraphs 0040 of WO 2016/181987, compounds described in JP-A-2015-176046, and compounds described in paragraph 0072 of WO 2016/190162.
  • polymethine compounds examples include compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, compounds described in paragraphs 0026 to 0030 of JP-A-2002-194040, compounds described in JP-A-2015-172004, compounds described in JP-A-2015-172102, compounds described in JP-A-2008-088426, compounds described in paragraph 0090 of WO 2016/190162, compounds described in JP-A-2017-031394, compounds described in JP-A-2021-134350, compounds described in WO 2021/085372, and the like.
  • croconium compounds examples include compounds described in JP-A-2017-082029.
  • Examples of the iminium compound include compounds described in JP-T-2008-528706, compounds described in JP-A-2012-012399, compounds described in JP-A-2007-092060, and compounds described in paragraphs 0048 to 0063 of WO 2018/043564.
  • Examples of the phthalocyanine compound include compounds described in paragraph 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, compounds described in paragraphs 0013 to 0029 of JP-A-2013-195480, vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, and compounds described in WO 2020/071470.
  • Examples of the naphthalocyanine compound include the compounds described in paragraph 0093 of JP 2012-077153 A.
  • Examples of the dithiolene metal complex include the compounds described in Japanese Patent No. 5733804 A.
  • Examples of the metal oxide include indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide. For details of tungsten oxide, refer to paragraph 0080 of JP 2016-006476 A, the contents of which are incorporated herein by reference.
  • Examples of the metal boride include lanthanum boride.
  • Examples of commercially available lanthanum boride include LaB 6 -F (manufactured by Japan New Metals Co., Ltd.).
  • compounds described in WO 2017/119394 A can also be used as the metal boride.
  • An example of a commercially available indium tin oxide product is F-ITO (manufactured by Dowa Hightec Co., Ltd.).
  • squarylium compounds described in JP 2017-197437 A As infrared absorbents, squarylium compounds described in JP 2017-197437 A, squarylium compounds described in JP 2017-025311 A, squarylium compounds described in WO 2016/154782 A, squarylium compounds described in Japanese Patent No. 5884953 A, squarylium compounds described in Japanese Patent No. 6036689 A, squarylium compounds described in Japanese Patent No.
  • squarylium compounds described in paragraphs 0090 to 0107 of WO 2017/213047 A pyrrole ring-containing compounds described in paragraphs 0019 to 0075 of JP 2018-054760 A, pyrrole ring-containing compounds described in paragraphs 0078 to 0082 of JP 2018-040955 A, and squarylium compounds described in paragraphs 002773 to 0030 of JP 2018-002773 A are examples of the squarylium compounds described in WO 2017/213047 A.
  • tungsten oxide represented by the following formula described in paragraph 0025 of European Patent No. 3628645 can also be used.
  • M 1 and M 2 each represent an ammonium cation or a metal cation, a is 0.01 to 0.5, b is 0 to 0.5, c is 1, d is 2.5 to 3, e is 0.01 to 0.75, n is 1, 2 or 3, m is 1, 2 or 3, and R represents a hydrocarbon group which may have a substituent.
  • the content of the other infrared absorbent is preferably 1 to 100 parts by mass, more preferably 3 to 60 parts by mass, and even more preferably 5 to 40 parts by mass, relative to 100 parts by mass of the specific compound.
  • the total content of the specific compound and the other infrared absorbing agent is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on the total solid content of the composition.
  • the upper limit of the total content is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
  • the composition of the present invention may contain a pigment derivative.
  • the pigment derivative is used as a dispersing aid.
  • a dispersing aid is a material for enhancing the dispersibility of a pigment in a composition.
  • Pigment derivatives include compounds having at least one structure selected from the group consisting of a dye structure and a triazine structure, and an acid group or a basic group.
  • the above dye structures include squarylium dye structures, pyrrolopyrrole dye structures, diketopyrrolopyrrole dye structures, quinacridone dye structures, anthraquinone dye structures, dianthraquinone dye structures, benzoisoindole dye structures, thiazine indigo dye structures, azo dye structures, quinophthalone dye structures, phthalocyanine dye structures, naphthalocyanine dye structures, dioxazine dye structures, perylene dye structures, perinone dye structures, benzimidazolone dye structures, benzothiazole dye structures, benzimidazole dye structures, and benzoxazole dye structures.
  • Squarylium dye structures pyrrolopyrrole dye structures, diketopyrrolopyrrole dye structures, phthalocyanine dye structures, quinacridone dye structures, and benzimidazolone dye structures are preferred, and squarylium dye structures and pyrrolopyrrole dye structures are more preferred.
  • Examples of the acid group possessed by the pigment derivative include a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imide acid group, and salts thereof.
  • Examples of atoms or atomic groups constituting the salt include an alkali metal ion (Li + , Na + , K + , etc.), an alkaline earth metal ion (Ca 2+ , Mg 2+ , etc.), an ammonium ion, an imidazolium ion, a pyridinium ion, and a phosphonium ion.
  • a preferred example of the carboxylic acid amide group is a group represented by -NHCOR X1 .
  • a preferred example of the sulfonic acid amide group is a group represented by -NHSO 2 R X2 .
  • a preferred example of the imide acid group is a group represented by -SO 2 NHSO 2 R X3 , -CONHSO 2 R X4 , -CONHCOR X5 , or -SO 2 NHCOR X6 , and -SO 2 NHSO 2 R X3 is more preferred.
  • R x1 to R x6 each independently represent an alkyl group or an aryl group.
  • the alkyl group and aryl group represented by R x1 to R x6 may have a substituent.
  • the substituent is preferably a halogen atom, and more preferably a fluorine atom.
  • Basic groups contained in pigment derivatives include amino groups, pyridinyl groups and their salts, salts of ammonium groups, and phthalimidomethyl groups.
  • Atoms or atomic groups that constitute the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
  • pigment derivatives include the compounds described in paragraphs 0037 to 0054 of WO 2016/035695, the compounds described in paragraphs 0061 to 0086 of WO 2017/146092, the compounds described in paragraphs 0017 to 0068 of WO 2018/230387, the compounds described in paragraphs 0085 to 0099 of WO 2020/054718, the compounds described in paragraph 0099 of WO 2020/054718, the compounds described in paragraph 0124 of WO 2022/085485, the benzimidazolone compounds or salts thereof described in JP 2018-168244 A, and the compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6,996,282.
  • the content of the pigment derivative is preferably 1 to 50 parts by mass relative to 100 parts by mass of the pigment.
  • the lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more.
  • the upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. Only one type of pigment derivative may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.
  • the composition of the present invention contains a polymerizable compound
  • the photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators.For example, a compound having photosensitivity to light rays in the ultraviolet range to the visible range is preferable.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • Photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, etc.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
  • acylphosphine compounds e.g., acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, etc.
  • the photopolymerization initiator is preferably 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, a hexaarylbiimidazole compound, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, or a 3-aryl substituted coumarin compound, more preferably a compound selected from an oxime compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound.
  • examples of the photopolymerization initiator include the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A, the compounds described in Japanese Patent No. 6301489 A, and the compounds described in MATERIAL STAGE 37 to 60p, vol. 19, No.
  • hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (all manufactured by BASF), etc.
  • Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF), etc.
  • Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (all manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (all manufactured by BASF), etc.
  • Examples of oxime compounds include the compound described in paragraph 0142 of WO 2022/085485, the compound described in Japanese Patent No. 5,430,746, the compound described in Japanese Patent No. 5,647,738, the compound represented by general formula (1) and the compounds described in paragraphs 0022 to 0024 of JP 2021-173858 A, the compound represented by general formula (1) and the compounds described in paragraphs 0117 to 0120 of JP 2021-170089 A, and the like.
  • oxime compound examples include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like.
  • an oxime compound having a fluorene ring an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, an oxime compound having a fluorine atom, an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton, or a compound described in paragraphs 0143 to 0149 of WO 2022/085485 can also be used.
  • oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited to these.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
  • the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1000 to 300,000, even more preferably 2000 to 300,000, and particularly preferably 5000 to 200,000.
  • the molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using a spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.
  • a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photopolymerization initiator.
  • a photoradical polymerization initiator two or more radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity can be obtained.
  • crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, and improving the stability of the composition over time.
  • Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include the compounds described in paragraph 0148 of WO 2022/065215.
  • the content of the photopolymerization initiator is preferably 0.1 to 40 mass% of the total solid content of the composition, more preferably 0.5 to 35 mass%, and even more preferably 1 to 30 mass%.
  • the composition may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the composition of the present invention contains a compound having a cyclic ether group
  • the composition further contains a curing agent.
  • the curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, polycarboxylic acids, and thiol compounds.
  • Specific examples of the curing agent include succinic acid, trimellitic acid, pyromellitic acid, N,N-dimethyl-4-aminopyridine, and pentaerythritol tetrakis (3-mercaptopropionate).
  • the curing agent may be a compound described in paragraphs 0072 to 0078 of JP-A-2016-075720 or a compound described in JP-A-2017-036379.
  • the content of the curing agent is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.1 to 6.0 parts by mass, relative to 100 parts by mass of the compound having a cyclic ether group.
  • the composition of the present invention may contain a chromatic colorant.
  • the chromatic colorant include a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant.
  • the chromatic colorant may be a pigment or a dye.
  • a pigment and a dye may be used in combination.
  • the pigment may be either an inorganic pigment or an organic pigment.
  • As the pigment a material in which an inorganic pigment or an organic-inorganic pigment is partially substituted with an organic chromophore may also be used. By substituting an inorganic pigment or an organic-inorganic pigment with an organic chromophore, it is possible to easily design the hue.
  • the average primary particle diameter of the pigment is preferably 1 to 200 nm.
  • the lower limit is preferably 5 nm or more, and more preferably 10 nm or more.
  • the upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less.
  • the primary particle diameter of the pigment can be determined from an image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment.
  • the average primary particle diameter is the arithmetic mean value of the primary particle diameters of 400 primary particles of the pigment.
  • the primary particles of the pigment refer to independent particles that are not aggregated.
  • the chromatic colorant preferably contains a pigment.
  • the content of the pigment in the chromatic colorant is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • pigments include the following.
  • a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can also be used. Specific examples include the compounds described in WO 2015/118720.
  • a compound described in paragraph 0029 of WO 2022/085485, an aluminum phthalocyanine compound described in JP 2020-070426 A, a diarylmethane compound described in JP 2020-504758 A, and the like can also be used.
  • Aluminum phthalocyanine compounds having phosphorus atoms can also be used as blue colorants. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A No. 2012-247591 and paragraph 0047 of JP-A No. 2011-157478.
  • the compounds described in paragraphs 0031 to 0033 of WO 2022/085485, the methine dyes described in JP 2019-073695 A, and the methine dyes described in JP 2019-073696 A can be used.
  • the compound described in paragraph 0034 of WO 2022/085485 and the brominated diketopyrrolopyrrole compound described in JP 2020-085947 A can also be used.
  • Dyes can also be used as chromatic colorants.
  • dyes There are no particular limitations on the dyes, and known dyes can be used.
  • pyrazole azo dyes, anilino azo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, pyrromethene dyes, and the like can be mentioned.
  • the thiazole compounds described in JP-A-2012-158649, the azo compounds described in JP-A-2011-184493, and the azo compounds described in JP-A-2011-145540 can also
  • chromatic colorants there are used triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in Japanese Patent Publication No. 2020-117638, phthalocyanine compounds described in International Publication No. 2020/174991, isoindoline compounds or salts thereof described in Japanese Patent Publication No. 2020-160279, and compounds of formula 1 described in Korean Patent Publication No. 10-2020-0069442.
  • 10-2020-0069067 a compound represented by the formula 1 described in Korean Patent Publication No. 10-2020-0069062, a halogenated compound described in Japanese Patent No. 6809649 Zinc phthalocyanine pigments, isoindoline compounds described in JP 2020-180176 A, phenothiazine compounds described in JP 2021-187913 A, halogenated zinc phthalocyanines described in WO 2022/004261 A, halogenated zinc phthalocyanines described in WO 2021/250883 A, quinophthalone compounds represented by formula 1 in Korean Patent Publication No. 10-2020-0030759 A , polymer dyes described in Korean Patent Publication No.
  • the chromatic colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, may be used in the rod-shaped structure, or may be used in both structures.
  • the content of the chromatic colorant in the total solid content of the composition is preferably 1 to 50 mass %.
  • the total amount thereof is preferably within the above range.
  • the composition of the present invention is substantially free of chromatic colorants.
  • the content of chromatic colorants in the total solid content of the composition is 0.5% by mass or less, preferably 0.1% by mass or less, and more preferably free of chromatic colorants.
  • the composition of the present invention may also contain a coloring material that transmits infrared light and blocks visible light (hereinafter, also referred to as a coloring material that blocks visible light).
  • a composition containing a coloring material that blocks visible light is preferably used as a composition for forming an infrared transmission filter.
  • the coloring material that blocks visible light is preferably a coloring material that absorbs light in the purple to red wavelength region. Also, the coloring material that blocks visible light is preferably a coloring material that blocks light in the wavelength region of 450 to 650 nm. Also, the coloring material that blocks visible light is preferably a coloring material that transmits light in the wavelength region of 900 to 1500 nm.
  • the coloring material that blocks visible light preferably satisfies at least one of the following requirements (A) and (B).
  • A) Two or more types of chromatic colorants are included, and black is formed by a combination of two or more types of chromatic colorants.
  • B Contains an organic black colorant.
  • Examples of chromatic colorants include those mentioned above.
  • Examples of organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred.
  • Examples of bisbenzofuranone compounds include compounds described in JP-T-2010-534726, JP-T-2012-515233, and JP-T-2012-515234, and are available as "Irgaphor Black” manufactured by BASF.
  • Examples of perylene compounds include compounds described in paragraphs 0016 to 0020 of JP-A-2017-226821, C.I. Pigment Black 31, 32, and the like.
  • Examples of azomethine compounds include those described in JP-A-01-170601 and JP-A-02-034664, and are available as "Chromofine Black A1103" manufactured by Dainichi Seika Chemicals Co., Ltd.
  • the combination of chromatic colorants may be, for example, the following embodiments (1) to (8).
  • the content of the coloring material that blocks visible light in the total solid content of the composition is preferably 1 to 50 mass%.
  • the lower limit is preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 20 mass% or more, and particularly preferably 30 mass% or more.
  • the composition of the present invention does not substantially contain a coloring material that blocks visible light.
  • the content of the coloring material that blocks visible light in the total solid content of the composition is 0.5 mass % or less, preferably 0.1 mass % or less, and it is more preferable that the composition does not contain a coloring material that blocks visible light.
  • the composition of the present invention may contain a surfactant.
  • a surfactant various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants may be used.
  • the surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant.
  • Nonionic surfactants include the compounds described in paragraph 0174 of WO 2022/085485.
  • silicone surfactants examples include SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419.
  • OIL all manufactured by Dow Toray Co., Ltd.
  • KP-341, KF-6000, KF-6001, KF-6002, KF-6003 all manufactured by Shin-Etsu Chemical Co., Ltd.
  • BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 all manufactured by BYK-Chemie
  • the silicone surfactant a compound having the following structure can also be used.
  • the content of the surfactant in the total solid content of the composition is preferably 0.001 to 1 mass%, more preferably 0.001 to 0.5 mass%, and even more preferably 0.001 to 0.2 mass%.
  • the composition may contain only one type of surfactant, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the composition of the present invention may contain a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.), with p-methoxyphenol being preferred.
  • the content of the polymerization inhibitor in the total solid content of the composition is preferably 0.0001 to 5% by mass.
  • the composition may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the composition of the present invention may contain a silane coupling agent.
  • the silane coupling agent is preferably a silane compound having a hydrolyzable group, more preferably a silane compound having a hydrolyzable group and other functional groups.
  • the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, and an alkoxy group is preferred.
  • the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • examples of functional groups other than the hydrolyzable group include a vinyl group, a styryl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, and a phenyl group, and an (meth)acryloyl group and an epoxy group are preferred.
  • examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP-A-2009-288703 and the compounds described in paragraphs 0056 to 0066 of JP-A-2009-242604.
  • the content of the silane coupling agent in the total solid content of the composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass.
  • the composition may contain only one type of silane coupling agent, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably within the above range.
  • the composition of the present invention may contain an ultraviolet absorbing agent, such as a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or a dibenzoyl compound.
  • an ultraviolet absorbing agent such as a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or a dibenzoyl compound.
  • Such compounds include the compounds described in paragraphs 0038 to 0052 of JP 2009-217221 A, 0052 to 0072 of JP 2012-208374 A, 0317 to 0334 of JP 2013-068814 A, 0061 to 0080 of JP 2016-162946 A, 0052 and 0074 of WO 2021/131355 A, and 0022 to 0024 of WO 2021/132247 A, the contents of which are incorporated herein.
  • Commercially available ultraviolet absorbers include the Tinuvin series and Uvinul series manufactured by BASF Corporation.
  • examples of the benzotriazole compound include the MYUA series manufactured by Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016).
  • the ultraviolet absorber the compounds described in the examples described later, the compounds described in paragraphs 0049-0059 of Japanese Patent No. 6268967, and paragraphs 0059-0076 of International Publication No. 2016/181987 can also be used.
  • the content of the ultraviolet absorber in the total solid content of the composition is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass.
  • the composition may contain only one type of ultraviolet absorber, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the composition of the present invention may contain an antioxidant.
  • the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
  • the phenol-based antioxidant include hindered phenol compounds.
  • the phenol-based antioxidant is preferably a compound having a substituent at the site (ortho position) adjacent to the phenolic hydroxy group.
  • the aforementioned substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
  • phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite, and tris(2,4-di-tert-butylphenyl)phosphite.
  • antioxidants examples include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB 2112, ADK STAB PEP-36, ADK STAB HP-10 (all manufactured by ADEKA CORPORATION), and JP-650 (manufactured by Johoku Chemical Industry Co., Ltd.).
  • the antioxidant may be a compound described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, a compound described in International Publication No.
  • the content of the antioxidant in the total solid content of the composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass.
  • the composition may contain only one type of antioxidant, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • composition of the present invention may contain, as necessary, a sensitizer, a filler, a heat curing accelerator, a plasticizer, and other auxiliaries (e.g., conductive particles, defoamers, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension regulators, chain transfer agents, latent antioxidants, etc.).
  • auxiliaries e.g., conductive particles, defoamers, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension regulators, chain transfer agents, latent antioxidants, etc.
  • the container for storing the composition of the present invention is not particularly limited, and a known container can be used.
  • the container described in paragraph 0187 of WO 2022/085485 can be used as the container.
  • the composition of the present invention can be prepared by mixing the above-mentioned components.
  • all the components may be simultaneously dissolved or dispersed in a solvent to prepare the composition, or, if necessary, two or more solutions or dispersions in which the components are appropriately mixed may be prepared in advance, and these may be mixed at the time of use (at the time of application) to prepare the composition.
  • the preparation of the composition may include a process for dispersing the pigment.
  • mechanical forces used to disperse the pigment include compression, squeezing, impact, shear, and cavitation.
  • Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion.
  • grinding pigments in a sand mill (bead mill) it is preferable to use beads with a small diameter and increase the bead packing rate to perform processing under conditions that increase the grinding efficiency.
  • the process and dispersing machine for dispersing the pigment may be suitably used as described in "Dispersion Technology Encyclopedia, published by Information Technology Co., Ltd., July 15, 2005” or "Dispersion Technology and Industrial Application Practice Focusing on Suspension (Solid/Liquid Dispersion System) - Comprehensive Data Collection, published by Management Development Center Publishing Department, October 10, 1978", and in paragraph number 0022 of JP 2015-157893 A.
  • the pigment in the process for dispersing the pigment, the pigment may be subjected to a fine treatment in a salt milling process. For the materials, equipment, processing conditions, etc.
  • the descriptions in, for example, JP 2015-194521 A and JP 2012-046629 A may be referred to.
  • materials for the beads used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass.
  • the beads may also be made of inorganic compounds with a Mohs hardness of 2 or more.
  • the composition may contain 1 to 10,000 ppm of the above beads.
  • the composition When preparing the composition, it is preferable to filter the composition with a filter for the purpose of removing foreign matter and reducing defects.
  • filters and filtration methods used for filtration include the filters and filtration methods described in paragraphs 0196 to 0199 of WO 2022/085485.
  • the film of the present invention is obtained from the composition of the present invention described above.
  • the film of the present invention can be preferably used as an optical filter.
  • the use of the optical filter is not particularly limited, but examples thereof include an infrared cut filter and an infrared transmission filter.
  • infrared cut filters include an infrared cut filter on the light receiving side of a solid-state imaging element (for example, an infrared cut filter for a wafer level lens), an infrared cut filter on the back side (opposite to the light receiving side) of a solid-state imaging element, and an infrared cut filter for an environmental light sensor (for example, an illuminance sensor that senses the illuminance and color tone of the environment in which an information terminal device is placed and adjusts the color tone of the display, and a color correction sensor that adjusts the color tone).
  • an environmental light sensor for example, an illuminance sensor that senses the illuminance and color tone of the environment in which an information terminal device is placed and adjusts the color tone of the display, and a color correction sensor that adjusts the color tone.
  • it can be preferably used as an infrared cut filter on the light receiving side of a solid-state imaging element.
  • infrared transmission filters include a filter that can block visible light and selectively transmit
  • the film of the present invention may have a pattern, or may be a film without a pattern (flat film).
  • the film of the present invention may be laminated on a support, or may be peeled off from the support.
  • Examples of the support include semiconductor substrates such as silicon substrates, and transparent substrates.
  • a charge-coupled device CCD
  • CMOS complementary metal-oxide semiconductor
  • a transparent conductive film etc.
  • CCD charge-coupled device
  • CMOS complementary metal-oxide semiconductor
  • a black matrix that isolates each pixel may also be formed on the semiconductor substrate.
  • an undercoat layer may be provided on the semiconductor substrate to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface.
  • the transparent substrate used as the support is not particularly limited as long as it is made of a material that can transmit at least visible light.
  • substrates made of materials such as glass and resin can be used.
  • resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer, norbornene resin, acrylic resins such as polyacrylate and polymethyl methacrylate, urethane resin, vinyl chloride resin, fluororesin, polycarbonate resin, polyvinyl butyral resin, and polyvinyl alcohol resin.
  • glass examples include soda lime glass, borosilicate glass, alkali-free glass, quartz glass, and glass containing copper.
  • glass containing copper examples include phosphate glass containing copper and fluorophosphate glass containing copper. Commercially available glass containing copper can also be used. Commercially available glass containing copper includes NF-50 (manufactured by AGC Technoglass Co., Ltd.).
  • the thickness of the film of the present invention can be adjusted appropriately depending on the purpose.
  • the thickness of the film can be 200 ⁇ m or less, 150 ⁇ m or less, 120 ⁇ m or less, 20 ⁇ m or less, 10 ⁇ m or less, or 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, and more preferably 0.2 ⁇ m or more.
  • the film of the present invention When the film of the present invention is used as an infrared cut filter, it is preferred that the film of the present invention has a maximum absorption wavelength in the wavelength range of 650 to 1500 nm (preferably 660 to 1200 nm, more preferably 660 to 1000 nm). Furthermore, the average transmittance in the wavelength range of 700 to 720 nm is preferably 10% or less, more preferably 7% or less, even more preferably 4% or less, and particularly preferably 2% or less. The average transmittance in the wavelength range of 420 to 550 nm is preferably 86% or more, more preferably 89% or more, even more preferably 92% or more, and particularly preferably 95% or more.
  • the transmittance in the entire wavelength range of 420 to 550 nm is preferably 50% or more, more preferably 70% or more, and even more preferably 80% or more.
  • the transmittance at at least one point in the wavelength range of 650 to 1500 nm is preferably 10% or less, more preferably 7% or less, even more preferably 4% or less, and particularly preferably 2% or less.
  • the absorbance at the maximum absorption wavelength of the film of the present invention is taken as 1, the average absorbance in the wavelength range of 420 to 550 nm is preferably less than 0.030, and more preferably less than 0.025.
  • the film of the present invention preferably has, for example, any one of the following spectral characteristics (i1) to (i3).
  • a film having such spectral characteristics can block light in the wavelength range of 400 to 850 nm and transmit light with a wavelength of more than 950 nm.
  • a film having such spectral characteristics can block light in the wavelength range of 400 to 950 nm and transmit light with a wavelength of more than 1050 nm.
  • a film having such spectral characteristics can block light in the wavelength range of 400 to 1050 nm and transmit light with a wavelength of more than 1150 nm.
  • the film of the present invention can also be used in combination with a color filter containing a chromatic colorant.
  • the color filter can be manufactured using a coloring composition containing a chromatic colorant.
  • a color filter is arranged on the optical path of the film of the present invention.
  • the film of the present invention may be formed on a support other than the support on which the color filter is formed, and other members constituting a solid-state imaging device (e.g., microlenses, planarization layers, etc.) may be interposed between the film of the present invention and the color filter.
  • a solid-state imaging device e.g., microlenses, planarization layers, etc.
  • the film of the present invention can be used in various devices such as solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal-oxide semiconductors), infrared sensors, and image display devices.
  • solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal-oxide semiconductors), infrared sensors, and image display devices.
  • CCDs charge-coupled devices
  • CMOSs complementary metal-oxide semiconductors
  • infrared sensors and image display devices.
  • the film of the present invention can be produced through a process of applying the composition of the present invention.
  • the support may be any of those mentioned above.
  • a known method such as spin coating may be used as a method for applying the composition.
  • the application method described in paragraph 0207 of WO 2022/085485 may be used.
  • the composition layer formed by applying the composition may be dried (prebaked).
  • the prebaking temperature is preferably 150°C or less, more preferably 120°C or less, and even more preferably 110°C or less.
  • the lower limit can be, for example, 50°C or more, and can also be 80°C or more.
  • the prebaking time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. Drying can be performed using a hot plate, oven, etc.
  • the film manufacturing method 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, and a pattern forming method using a photolithography method is preferred.
  • the pattern forming step does not need to be performed. The pattern forming step will be described in detail below.
  • the pattern forming method by photolithography preferably includes a step of exposing the composition layer formed by applying the composition of the present invention to light in a pattern (exposure step), and a step of developing and removing the composition layer in the unexposed area to form a pattern (development step). If necessary, a step of baking the developed pattern (post-baking step) may be provided. Each step will be described below.
  • the composition layer is exposed to light in a pattern.
  • the composition layer can be exposed to light in a pattern by using a stepper exposure machine or a scanner exposure machine to expose the layer through a mask having a specific mask pattern. This allows the exposed parts to harden.
  • Radiation (light) that can be used for exposure includes g-line and i-line.
  • Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used.
  • Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), with KrF line (wavelength 248 nm) being preferred.
  • Long-wavelength light sources of 300 nm or more can also be used.
  • Pulse exposure is an exposure method in which light is applied and paused repeatedly in short cycles (e.g., milliseconds or less).
  • the irradiation amount is, for example, preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2.
  • the oxygen concentration during exposure can be appropriately selected, and in addition to being performed under air, exposure may be performed under a low-oxygen atmosphere with an oxygen concentration of 19 volume% or less (e.g., 15 volume%, 5 volume%, or substantially oxygen-free), or under a high-oxygen atmosphere with an oxygen concentration of more than 21 volume% (e.g., 22 volume%, 30 volume%, or 50 volume%).
  • the exposure illuminance can be appropriately set, and can usually be selected from the range of 1000 W/m 2 to 100,000 W/m 2 (e.g., 5,000 W/m 2 , 15,000 W/m 2 , or 35,000 W/m 2 ).
  • the oxygen concentration and exposure illuminance may be appropriately combined.
  • the oxygen concentration can be 10% by volume and the illuminance can be 10,000 W/m 2
  • the oxygen concentration can be 35% by volume and the illuminance can be 20,000 W/m 2 .
  • the composition layer in the unexposed parts of the composition layer after exposure is developed and removed to form a pattern.
  • the composition layer in the unexposed parts can be developed and removed using a developer.
  • the composition layer in the unexposed parts in the exposure process dissolves into the developer, and only the photocured parts remain on the support.
  • the temperature of the developer is preferably, for example, 20 to 30°C.
  • the development time is preferably 20 to 180 seconds.
  • the process of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.
  • the developer may be an organic solvent or an alkaline developer, with an alkaline developer being preferred.
  • the developer and the washing (rinsing) method after development may be as described in paragraph 0214 of WO 2022/085485.
  • Additional exposure processing and post-baking are curing processing after development to complete curing.
  • the heating temperature in post-baking is preferably, for example, 100 to 240°C, more preferably 200 to 240°C.
  • Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater to heat the developed film to the above conditions.
  • a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater to heat the developed film to the above conditions.
  • the light used for exposure has a wavelength of 400 nm or less.
  • additional exposure processing may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
  • the pattern formation by the dry etching method can be performed by a method in which the composition layer formed by applying the composition on a support is cured to form a cured layer, a patterned photoresist layer is formed on the cured layer, and then the patterned photoresist layer is used as a mask to dry etch the cured layer using an etching gas.
  • a pre-bake treatment it is preferable to perform a pre-bake treatment.
  • the description in paragraphs 0010 to 0067 of JP 2013-064993 A can be referred to, and the contents thereof are incorporated herein.
  • optical filter of the present invention has the above-mentioned film of the present invention.
  • Types of the optical filter include an infrared cut filter and an infrared transmission filter.
  • the optical filter of the present invention may further include a copper-containing layer, a dielectric multilayer film, an ultraviolet absorbing layer, etc., in addition to the above-mentioned film of the present invention.
  • the ultraviolet absorbing layer include the absorbing layer described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/099060.
  • the dielectric multilayer film include the dielectric multilayer film described in paragraphs 0255 to 0259 of JP 2014-041318 A.
  • the copper-containing layer include a glass substrate (copper-containing glass substrate) made of glass containing copper, and a layer containing a copper complex (copper complex-containing layer).
  • Examples of the copper-containing glass substrate include copper-containing phosphate glass and copper-containing fluorophosphate glass.
  • Examples of commercially available copper-containing glass include NF-50 (manufactured by AGC Technoglass Co., Ltd.), BG-60, BG-61 (all manufactured by Schott Co., Ltd.), CD5000 (manufactured by HOYA Co., Ltd.), etc.
  • the solid-state imaging device of the present invention has the above-mentioned film of the present invention.
  • the configuration of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device. For example, the following configurations can be mentioned.
  • the solid-state imaging device has a support on which a plurality of photodiodes constituting the light receiving area of the solid-state imaging element and a transfer electrode made of polysilicon or the like are disposed, a light shielding film made of tungsten or the like with only the light receiving portion of the photodiode opened on the photodiode and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the light receiving portion of the photodiode, and a film of the present invention on the device protection film.
  • the device protection film may have a light collecting means (e.g., a microlens, etc., the same below) on the device protection film and below the film of the present invention (on the side closer to the support), or a light collecting means on the film of the present invention.
  • the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, it is preferable that the partition walls have a lower refractive index than each pixel. Examples of imaging devices having such a structure include the devices described in JP 2012-227478 A and JP 2014-179577 A.
  • the image display device of the present invention has the film of the present invention.
  • Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device.
  • the definition and details of the image display device are described in, for example, "Electronic Display Device (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990)” and “Display Device (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1989)".
  • 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 image display device may have a white organic EL element.
  • the white organic EL element is preferably a tandem structure.
  • the tandem structure of the organic EL element is described in, for example, JP 2003-045676 A and Akiyoshi Mikami (ed.), "The Frontline of Organic EL Technology Development - High Brightness, High Precision, Long Life, Know-How Collection", Technical Information Association, pp. 326-328, 2008.
  • the spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430-485 nm), green region (530-580 nm), and yellow region (580-620 nm). More preferably, the spectrum has a maximum emission peak in the red region (650-700 nm) in addition to these emission peaks.
  • the infrared sensor of the present invention has the above-mentioned film of the present invention.
  • the configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor.
  • one embodiment of the infrared sensor of the present invention will be described with reference to the drawings.
  • reference numeral 110 denotes a solid-state imaging element.
  • An infrared cut filter 111 and an infrared transmission filter 114 are disposed on the imaging region of the solid-state imaging element 110.
  • a color filter 112 is disposed on the infrared cut filter 111.
  • a microlens 115 is disposed on the incident light h ⁇ side of the color filter 112 and the infrared transmission filter 114.
  • a planarization layer 116 is formed to cover the microlens 115.
  • the infrared cut filter 111 can be formed using the composition of the present invention.
  • the color filter 112 is a color filter in which pixels that transmit and absorb light of specific wavelengths in the visible range are formed, and is not particularly limited, and a conventionally known color filter for forming pixels can be used.
  • a color filter in which red (R), green (G), and blue (B) pixels are formed can be used.
  • R red
  • G green
  • B blue
  • the characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used.
  • the infrared transmission filter 114 can be formed using the composition of the present invention.
  • an infrared cut filter (another infrared cut filter) other than the infrared cut filter 111 may be further disposed on the planarization layer 116.
  • the other infrared cut filter include those having a copper-containing layer and/or a dielectric multilayer film. Details of these are as described above. Also, a dual bandpass filter may be used as the other infrared cut filter.
  • the camera module of the present invention has the above-mentioned film of the present invention.
  • the configuration of the camera module is not particularly limited as long as it has the film of the present invention and functions as a camera module.
  • the camera module may have a configuration having a solid-state image sensor, a lens, and a circuit for processing an image obtained from the solid-state image sensor.
  • the lens used in the camera module and the circuit for processing an image obtained from the solid-state image sensor may be a known one.
  • the camera modules described in JP 2016-006476 A and JP 2014-197190 A can be referred to, and the contents of these are incorporated herein.
  • the MS spectrum (Posi) of the obtained compound A-1 was 649.2 (M-1/2Mg+2H).
  • Compound A-1 was decomposed by wet ashing using UltraWAVE (Milestone General) under the condition of adding 70% nitric acid, and the decomposition product was measured using an ICP (inductively coupled plasma) mass spectrometer (Agilent Technologies, Agilent 7700s).
  • the magnesium content of compound A-1 was quantified by the absolute calibration curve method. Since the theoretical value of the magnesium content contained in compound A-1 and the measured value of the magnesium content obtained by an ICP mass spectrometer were in agreement, it was confirmed that the counter cation of compound A-1 was magnesium.
  • Synthesis Example 2 Synthesis of Compound A-5
  • Compound A-5 was synthesized in the same manner as in Synthesis Example 1, except that compound a-5 was used instead of compound a-1, compound b-5 was used instead of compound b-1, and barium acetate was used instead of magnesium acetate tetrahydrate.
  • the MS spectrum (Posi) of the obtained compound A-5 was 891.3 (M-1/2Ba+2H).
  • the barium content of the obtained compound A-5 was quantified in the same manner as for compound A-1.
  • the theoretical value of the barium content contained in compound A-5 and the measured value of the barium content obtained by an ICP mass spectrometer were in good agreement, confirming that the counter cation of compound A-5 was barium.
  • Synthesis Example 3 Synthesis of Compound A-11
  • Compound A-11 was synthesized in the same manner as in Synthesis Example 1, except that compound a-11 was used instead of compound a-1 and compound b-1 was used instead of compound b-1.
  • the MS spectrum (Posi) of the obtained compound A-11 was 765.2 (M-1/2Mg+2H).
  • the magnesium content of the obtained compound A-11 was quantified in the same manner as for compound A-1.
  • the theoretical value of the magnesium content contained in compound A-11 and the measured value of the magnesium content obtained by an ICP mass spectrometer were in good agreement, confirming that the counter cation of compound A-11 was magnesium.
  • Synthesis Example 4 Synthesis of Compound A-15
  • Compound A-15 was synthesized in the same manner as in Synthesis Example 1, except that compound a-15 was used instead of compound a-1 and compound b-1 was used instead of compound b-1.
  • the MS spectrum (Posi) of the obtained compound A-15 was 1023.1 (M-3/2Mg+4H).
  • the magnesium content of the obtained compound A-15 was quantified in the same manner as for compound A-1.
  • the theoretical value of the magnesium content contained in compound A-15 and the measured value of the magnesium content obtained by an ICP mass spectrometer were in good agreement, confirming that the counter cation of compound A-15 was magnesium.
  • Synthesis Example 5 Synthesis of Compound A-18 Compound A-18 was synthesized in the same manner as in Synthesis Example 1, except that compound c-18 was used instead of magnesium acetate tetrahydrate.
  • the MS spectrum (Posi) of the obtained compound A-18 was 649.2 (M-4C-11H-N+2H).
  • the 1 H NMR (d6DMSO) of the obtained compound A-18 it was confirmed that the molar ratio of the cationic moiety to the anionic moiety of compound A-18 was 1:2, and therefore it was confirmed that the counter cation of compound A-18 was the counter cation having the indicated structure.
  • the numbers attached to the main chain indicate the molar ratio of the repeating unit, and the numbers attached to the side chain indicate the number of repeating units.
  • Examples 101 to 149, Comparative Example 101 The materials were mixed in the ratios shown below to prepare a composition.
  • Infrared absorber listed in the table below ... parts by weight listed in the table Epoxy compound listed in the table below ... 9.3 parts by weight Curing agent listed in the table below (if specified in the table) ... 1.6 parts by weight Surfactant listed in the table below ... 0.01 parts by weight Antioxidant listed in the table below ... 2.0 parts by weight Solvent listed in the table below ... parts by weight listed in the table
  • Dispersions 1 to 29 Dispersions 1 to 29 described above
  • D-Pc-1 to D-Pc-3 Compounds having the following structures (phthalocyanine compounds, infrared absorbers)
  • D-SQ-1 to D-SQ-4 Compounds having the following structures (squarylium compounds, infrared absorbers)
  • PPM-r1 Compound having the following structure (comparative compound, infrared absorber)
  • B001 Resin having the following structure (the numbers added to the main chain are the molar ratios of repeating units, weight average molecular weight 17,000, dispersity 2.3)
  • B002 Resin having the following structure (the numbers added to the main chain are the molar ratios of repeating units, weight average molecular weight 9700, dispersity 1.8)
  • B003 Resin having the following structure (the numbers attached to the main chain are the molar ratios of repeating units, weight average molecular weight 10100, dispersity 1.7)
  • B004 Resin having the following structure (the numbers added to the main chain are the molar ratios of repeating units, weight average molecular weight 25,000, dispersity 2.2)
  • B005 Resin having the following structure (weight average molecular weight 137,000, number average molecular weight 32,000, glass transition temperature 165° C.)
  • B006 Resin having the following structure (weight average molecular weight 188,000, number average molecular weight 75,000, glass transition temperature 285
  • F-1 FTX-218D (manufactured by Neos Co., Ltd., fluorine-based surfactant)
  • F-2 Compound having the following structure (weight average molecular weight: 14,000, the percentages indicating the proportions of repeating units are mol%)
  • F-3 Megafac F-554 (manufactured by DIC Corporation, fluorosurfactant)
  • E-1 Resin having the following structure (the numerical values of the repeating units are mass ratios, weight average molecular weight 20,000, number average molecular weight 8,300, epoxy equivalent 284 g/eq, acid value 130 mgKOH/g, glass transition temperature 136° C.)
  • E-2 Resin having the following structure (the numerical values of the repeating units are mass ratios, weight average molecular weight 26100, number average molecular weight 8600, epoxy equivalent 355 g/eq, acid value 163 mgKOH/g, glass transition temperature 133° C.)
  • E-3 Resin having the following structure (the numerical values of the repeating units are mass ratios, weight average molecular weight 21100, number average molecular weight 8500, epoxy equivalent 355 g/eq, acid value 130 mgKOH/g, glass transition temperature 157° C.)
  • E-4 Resin having the following structure (the numerical values of the repeating units are mass ratios, weight average molecular weight 18300, number average molecular weight 9100
  • UV-1 Uvinul 3050 (manufactured by BASF, compound having the following structure)
  • UV-2 Tinuvin 477 (manufactured by BASF, hydroxyphenyltriazine-based ultraviolet absorber)
  • UV-3 Tinuvin 326 (manufactured by BASF, compound having the following structure)
  • UV-4 Compound having the following structure
  • the obtained film was irradiated with light at 100,000 Lux for 30 hours using a xenon arc lamp type light resistance tester.
  • the spectral transmittance of the film was measured before and after the light irradiation, and the spectral fluctuation rate ⁇ T was calculated using the following formula, and the light resistance was evaluated according to the following criteria.
  • Spectral fluctuation rate ⁇ T ((T02 - T12) / T02) x 100
  • T02 Spectral transmittance at the maximum absorption wavelength of the film before light irradiation
  • T12 Spectral transmittance at the maximum absorption wavelength of the film after light irradiation - Evaluation criteria -
  • D The spectral fluctuation rate ⁇ T is 15% or more.
  • the obtained film was placed in a thermostatic chamber at 150°C and stored for 6 months to carry out a heat resistance test.
  • the ⁇ Eab value of the color difference of the film before and after the heat resistance test was measured using a colorimeter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.), and the heat resistance was evaluated according to the following criteria. The smaller the ⁇ Eab value, the better the heat resistance.
  • the ⁇ Eab value is a value calculated from the following color difference formula according to the CIE1976 (L*, a*, b*) spatial color system (New Color Science Handbook (1985), edited by the Color Science Association of Japan, p. 266).
  • ⁇ Eab ⁇ ( ⁇ L*) 2 +( ⁇ a*) 2 +( ⁇ b*) 2 ⁇ 1/2 -Evaluation criteria- A: ⁇ Eab value ⁇ 5 B: 5 ⁇ Eab value ⁇ 10 C: 10 ⁇ Eab value ⁇ 15 D: 15 ⁇ Eab value
  • Example 201 described in WO 2020/189458 the curable composition of Example 105 was changed to the compositions of Examples 47 to 55, 101 to 110, 201 to 210, and 301 to 310 described herein.
  • An infrared absorbing composition was produced in the same manner as in Example 201 described in WO 2020/189458.
  • the obtained infrared absorbing composition was spin-coated on a glass substrate so that the film thickness after film formation was 1.0 ⁇ m, and a film was formed by any of the methods of Production Examples 1 to 3 described above (Production Example 1 when the composition of Examples 47 to 55 was used, Production Example 2 when the composition of Examples 101 to 110, 201 to 210 was used, and Production Example 3 when the composition of Examples 301 to 310 was used).
  • the obtained film shielded light with a wavelength in the visible light region and transmitted at least a part of light with a wavelength in the infrared region (infrared light). When the heat resistance and light resistance of the obtained films were evaluated by the same method as above, all of them were rated as A.
  • 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 is a composition comprising a compound represented by formula (1) and a curable compound. Provided are a film, an optical filter, a solid-state imaging element, an image display device, an infrared sensor, and a camera module, each of which uses the composition. This compound is represented by formula (1). (1): (PM)(Z)m wherein: PM represents an anion represented by formula (PM1); Z represents a cation having a valency of two or more; and m represents a number exceeding 0 and necessary for neutralization of the charge of PM.

Description

組成物、膜、光学フィルタ、固体撮像素子、画像表示装置、赤外線センサ、カメラモジュールおよび化合物Composition, film, optical filter, solid-state imaging device, image display device, infrared sensor, camera module and compound
 本発明は、ポリメチン化合物、および、それを含む組成物に関する。また、本発明は、ポリメチン化合物を含む組成物を用いた膜、光学フィルタ、固体撮像素子、画像表示装置、赤外線センサおよびカメラモジュールに関する。 The present invention relates to a polymethine compound and a composition containing the same. The present invention also relates to a film, an optical filter, a solid-state imaging device, an image display device, an infrared sensor, and a camera module that use a composition containing a polymethine compound.
 ビデオカメラ、デジタルスチルカメラ、カメラ機能付き携帯電話などには、カラー画像の固体撮像素子である、CCD(電荷結合素子)や、CMOS(相補型金属酸化膜半導体)が用いられている。これら固体撮像素子は、その受光部において赤外線に感度を有するシリコンフォトダイオードを使用している。このため、赤外線カットフィルタを設けて視感度補正を行うことがある。  Video cameras, digital still cameras, mobile phones with cameras, and other devices use solid-state color image sensors such as CCDs (charge-coupled devices) and CMOS (complementary metal-oxide semiconductors). These solid-state image sensors use silicon photodiodes that are sensitive to infrared light in their light receiving section. For this reason, infrared-cut filters are sometimes used to correct visibility.
 赤外線カットフィルタは、赤外線吸収剤を含む組成物を用いて製造されている。赤外線吸収剤としては、ポリメチン化合物などが知られている。 Infrared cut filters are manufactured using a composition that contains an infrared absorbing agent. Polymethine compounds are known examples of infrared absorbing agents.
 特許文献1には、特定のポリメチン化合物などを含む組成物を用いて赤外線カットフィルタなどを製造することが記載されている。 Patent Document 1 describes the production of infrared cut filters and the like using a composition containing a specific polymethine compound.
特開2021-134350号公報JP 2021-134350 A
 しかしながら、ポリメチン化合物は、耐光性や耐熱性が低い傾向にある。このため、これらの化合物を含む組成物を用いて得られる膜の耐光性について、更なる改善の余地があった。 However, polymethine compounds tend to have low light resistance and heat resistance. For this reason, there is room for further improvement in the light resistance of films obtained using compositions containing these compounds.
 よって、本発明の目的は、耐光性および耐熱性に優れた膜を形成できる組成物を提供することにある。また、本発明は、膜、光学フィルタ、固体撮像素子、画像表示装置、赤外線センサ、カメラモジュールおよび化合物を提供することにある。 Therefore, an object of the present invention is to provide a composition capable of forming a film having excellent light resistance and heat resistance. In addition, the present invention is to provide a film, an optical filter, a solid-state imaging device, an image display device, an infrared sensor, a camera module, and a compound.
 本発明者がポリメチン化合物について鋭意検討を進めたところ、式(PM1)で表されるアニオンと、2価以上のカチオンとの塩は、耐熱性や耐光性に優れる化合物であることを見出し、本発明を完成するに至った。よって、本発明は以下を提供する。 The inventors conducted extensive research into polymethine compounds and discovered that a salt of an anion represented by formula (PM1) with a divalent or higher cation is a compound with excellent heat resistance and light resistance, leading to the completion of the present invention. Thus, the present invention provides the following:
 <1> 式(1)で表される化合物と、硬化性化合物とを含む、組成物;
 (PM)(Z)   ・・・(1)
 式(1)中、PMは、式(PM1)で表されるアニオンを表し、
 Zは2価以上のカチオンを表し、
 mは0を超える数であって、PMの電荷を中和するために必要な数を表す;
 式(PM1)中、Rpm~Rpmは、それぞれ独立して水素原子または置換基を表し、
 nは1以上の整数を表し、
 Rpm~Rpmの2つが結合して環を形成していてもよく、RpmとTは結合して環を形成していてもよく、RpmとTは結合して環を形成していてもよく、
 Tは式(T1A)、式(T1B)または式(T1C)で表される基であり、
 Tは式(T2A)、式(T2B)または式(T2C)で表される基であり、
 Rpm~Rpm、TおよびTの少なくとも一つはアニオン性基を含む;
 式中、X~Xはそれぞれ独立して、酸素原子、硫黄原子、セレン原子、テルル原子または-NRX1-を表し、RX1は、水素原子、ハロゲン原子、アルキル基、アリール基または複素環基を表し、
 R~R16、および、R31~R46は、それぞれ独立して、水素原子、アルキル基、ハロゲン原子、アルケニル基、アリール基、複素環基、ニトロ基、シアノ基、-ORL1、-C(=O)RL1、-C(=O)ORL1、-OC(=O)RL1、-NRL1L2、-NHC(=O)RL1、-C(=O)NRL1L2、-NHC(=O)ORL1、-OC(=O)NRL1L2、-NHC(=O)NRL1L2、-SRL1、-S(=O)L1、-S(=O)ORL1、-NHS(=O)L1、-S(=O)NRL1L2またはアニオン性基を表し、RL1およびRL2はそれぞれ独立して、水素原子、アルキル基、アルケニル基、アリール基または複素環基を表し、
 R~R16、および、R31~R46のうち隣接する2つは互いに結合して環を形成してもよい。
 <2> X~Xはそれぞれ独立して、酸素原子または硫黄原子である、<1>に記載の組成物。
 <3> 上記式(1)のPMは、式(PM2)、式(PM3)または式(PM4)で表されるアニオンである、<1>に記載の組成物;
 式(PM2)中、Rpm11~Rpm15はそれぞれ独立して水素原子または置換基を表し、
 Rpm12とRpm14は結合して環を形成していてもよく、
 Rpm11とTは結合して環を形成していてもよく、Rpm15とTは結合して環を形成していてもよく、
 Tは上記式(T1A)、式(T1B)または式(T1C)で表される基であり、
 Tは上記式(T2A)、式(T2B)または式(T2C)で表される基であり、
 Rpm11~Rpm15、TおよびTの少なくとも一つはアニオン性基を含む;
 式(PM3)中、Rpm21~Rpm27はそれぞれ独立して水素原子または置換基を表し、
 Rpm23とRpm25は結合して環を形成していてもよく、
 Rpm21とTは結合して環を形成していてもよく、Rpm27とTは結合して環を形成していてもよく、
 Tは上記式(T1A)、式(T1B)または式(T1C)で表される基であり、
 Tは上記式(T2A)、式(T2B)または式(T2C)で表される基であり、
 Rpm21~Rpm27、TおよびTの少なくとも一つはアニオン性基を含む;
 式(PM4)中、Rpm31~Rpm39はそれぞれ独立して水素原子または置換基を表し、
 Rpm34とRpm36は結合して環を形成していてもよく、
 Rpm31とTは結合して環を形成していてもよく、Rpm39とTは結合して環を形成していてもよく、
 Tは上記式(T1A)、式(T1B)または式(T1C)で表される基であり、
 Tは上記式(T2A)、式(T2B)または式(T2C)で表される基であり、
 Rpm31~Rpm39、TおよびTの少なくとも一つはアニオン性基を含む。
 <4> 上記式(1)で表される化合物以外の赤外線吸収剤を含む、<1>~<3>のいずれか1つに記載の組成物。
 <5> <1>~<4>のいずれか1つに記載の組成物を用いて得られる膜。
 <6> <5>に記載の膜を有する光学フィルタ。
 <7> <5>に記載の膜を有する固体撮像素子。
 <8> <5>に記載の膜を有する画像表示装置。
 <9> <5>に記載の膜を有する赤外線センサ。
 <10> <5>に記載の膜を有するカメラモジュール。
 <11> 式(1)で表される化合物;
 (PM)(Z)   ・・・(1)
 式(1)中、PMは、式(PM1)で表されるアニオンを表し、
 Zは2価以上のカチオンを表し、
 mは0を超える数であって、PMの電荷を中和するために必要な数を表す;
 式(PM1)中、Rpm~Rpmは、それぞれ独立して水素原子または置換基を表し、
 nは1以上の整数を表し、
 Rpm~Rpmの2つが結合して環を形成していてもよく、RpmとTは結合して環を形成していてもよく、RpmとTは結合して環を形成していてもよく、
 Tは式(T1A)、式(T1B)または式(T1C)で表される基であり、
 Tは式(T2A)、式(T2B)または式(T2C)で表される基であり、
 Rpm~Rpm、TおよびTの少なくとも一つはアニオン性基を含む;
 式中、X~Xはそれぞれ独立して、酸素原子、硫黄原子、セレン原子、テルル原子または-NRX1-を表し、RX1は、水素原子、ハロゲン原子、アルキル基、アリール基または複素環基を表し、
 R~R16、および、R31~R46は、それぞれ独立して、水素原子、アルキル基、ハロゲン原子、アルケニル基、アリール基、複素環基、ニトロ基、シアノ基、-ORL1、-C(=O)RL1、-C(=O)ORL1、-OC(=O)RL1、-NRL1L2、-NHC(=O)RL1、-C(=O)NRL1L2、-NHC(=O)ORL1、-OC(=O)NRL1L2、-NHC(=O)NRL1L2、-SRL1、-S(=O)L1、-S(=O)ORL1、-NHS(=O)L1、-S(=O)NRL1L2またはアニオン性基を表し、RL1およびRL2はそれぞれ独立して、水素原子、アルキル基、アルケニル基、アリール基または複素環基を表し、
 R~R16、および、R31~R46のうち隣接する2つは互いに結合して環を形成してもよい。
<1> A composition comprising a compound represented by formula (1) and a curable compound;
(PM) (Z) m ... (1)
In formula (1), PM represents an anion represented by formula (PM1):
Z represents a divalent or higher cation;
m is a number greater than 0 and represents the number required to neutralize the charge of PM;
In formula (PM1), Rpm 1 to Rpm 5 each independently represent a hydrogen atom or a substituent;
n represents an integer of 1 or more;
any two of Rpm 2 to Rpm 4 may be bonded to form a ring, Rpm 1 and T 1 may be bonded to form a ring, and Rpm 5 and T 2 may be bonded to form a ring;
T 1 is a group represented by formula (T 1A ), formula (T 1B ) or formula (T 1C );
T2 is a group represented by formula ( T2A ), formula ( T2B ) or formula ( T2C ),
At least one of Rpm 1 to Rpm 5 , T 1 and T 2 contains an anionic group;
In the formula, X 1 to X 6 each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR X1 -, where R X1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group;
R 1 to R 16 and R 31 to R 46 each independently represent a hydrogen atom, an alkyl group, a halogen atom, an alkenyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, -OR L1 , -C(=O)R L1 , -C(=O)OR L1 , -OC(=O)R L1 , -NR L1 R L2 , -NHC(=O)R L1 , -C(=O)NR L1 R L2 , -NHC(=O)OR L1 , -OC(=O)NR L1 R L2 , -NHC(=O)NR L1 R L2 , -SR L1 , -S (=O) 2R L1 , -S(=O)2OR L1 , -NHS(=O) 2 R L1 represents -S(=O) 2 NR L1 R L2 or an anionic group, and R L1 and R L2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group;
Adjacent two of R 1 to R 16 and R 31 to R 46 may be bonded to each other to form a ring.
<2> The composition according to <1>, wherein X 1 to X 6 each independently represent an oxygen atom or a sulfur atom.
<3> The composition according to <1>, wherein PM in the formula (1) is an anion represented by formula (PM2), formula (PM3) or formula (PM4);
In formula (PM2), Rpm 11 to Rpm 15 each independently represent a hydrogen atom or a substituent;
Rpm 12 and Rpm 14 may be bonded to form a ring;
Rpm 11 and T 1 may be bonded to form a ring, and Rpm 15 and T 2 may be bonded to form a ring;
T 1 is a group represented by the above formula (T 1A ), formula (T 1B ) or formula (T 1C );
T2 is a group represented by the above formula ( T2A ), formula ( T2B ) or formula ( T2C ),
At least one of Rpm 11 to Rpm 15 , T 1 and T 2 contains an anionic group;
In formula (PM3), Rpm 21 to Rpm 27 each independently represent a hydrogen atom or a substituent;
Rpm 23 and Rpm 25 may be bonded to form a ring;
Rpm 21 and T1 may be bonded to form a ring, Rpm 27 and T2 may be bonded to form a ring,
T 1 is a group represented by the above formula (T 1A ), formula (T 1B ) or formula (T 1C );
T2 is a group represented by the above formula ( T2A ), formula ( T2B ) or formula ( T2C ),
At least one of Rpm 21 to Rpm 27 , T 1 and T 2 contains an anionic group;
In formula (PM4), Rpm 31 to Rpm 39 each independently represent a hydrogen atom or a substituent;
Rpm 34 and Rpm 36 may be bonded to form a ring;
Rpm 31 and T1 may be bonded to form a ring, and Rpm 39 and T2 may be bonded to form a ring;
T 1 is a group represented by the above formula (T 1A ), formula (T 1B ) or formula (T 1C );
T2 is a group represented by the above formula ( T2A ), formula ( T2B ) or formula ( T2C ),
At least one of Rpm 31 to Rpm 39 , T 1 and T 2 contains an anionic group.
<4> The composition according to any one of <1> to <3>, further comprising an infrared absorbing agent other than the compound represented by formula (1).
<5> A film obtained by using the composition according to any one of <1> to <4>.
<6> An optical filter having the film according to <5>.
<7> A solid-state imaging device having the film according to <5>.
<8> An image display device having the film according to <5>.
<9> An infrared sensor having the film according to <5>.
<10> A camera module having the film according to <5>.
<11> A compound represented by formula (1);
(PM) (Z) m ... (1)
In formula (1), PM represents an anion represented by formula (PM1):
Z represents a divalent or higher cation;
m is a number greater than 0 and represents the number required to neutralize the charge of PM;
In formula (PM1), Rpm 1 to Rpm 5 each independently represent a hydrogen atom or a substituent;
n represents an integer of 1 or more;
any two of Rpm 2 to Rpm 4 may be bonded to form a ring, Rpm 1 and T 1 may be bonded to form a ring, and Rpm 5 and T 2 may be bonded to form a ring;
T 1 is a group represented by formula (T 1A ), formula (T 1B ) or formula (T 1C );
T2 is a group represented by formula ( T2A ), formula ( T2B ) or formula ( T2C ),
At least one of Rpm 1 to Rpm 5 , T 1 and T 2 contains an anionic group;
In the formula, X 1 to X 6 each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR X1 -, where R X1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group;
R 1 to R 16 and R 31 to R 46 each independently represent a hydrogen atom, an alkyl group, a halogen atom, an alkenyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, -OR L1 , -C(=O)R L1 , -C(=O)OR L1 , -OC(=O)R L1 , -NR L1 R L2 , -NHC(=O)R L1 , -C(=O)NR L1 R L2 , -NHC(=O)OR L1 , -OC(=O)NR L1 R L2 , -NHC(=O)NR L1 R L2 , -SR L1 , -S (=O) 2R L1 , -S(=O)2OR L1 , -NHS(=O) 2 R L1 represents -S(=O) 2 NR L1 R L2 or an anionic group, and R L1 and R L2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group;
Adjacent two of R 1 to R 16 and R 31 to R 46 may be bonded to each other to form a ring.
 本発明によれば、耐光性および耐熱性に優れた膜を形成できる組成物を提供することができる。また、本発明は、膜、光学フィルタ、固体撮像素子、画像表示装置、赤外線センサ、カメラモジュールおよび化合物を提供することができる。 The present invention can provide a composition capable of forming a film having excellent light resistance and heat resistance. The present invention can also provide a film, an optical filter, a solid-state imaging device, an image display device, an infrared sensor, a camera module, and a compound.
赤外線センサの一実施形態を示す概略図である。FIG. 1 is a schematic diagram illustrating an embodiment of an infrared sensor.
 以下において、本発明の内容について詳細に説明する。
 本明細書において、「~」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
 本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さない基(原子団)と共に置換基を有する基(原子団)をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。
 本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線または放射線が挙げられる。
 本明細書において、「(メタ)アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「(メタ)アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「(メタ)アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
 本明細書において、重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)測定でのポリスチレン換算値として定義される。
 本明細書において、化学式中のMeはメチル基を表し、Etはエチル基を表し、Buはブチル基を表し、Phはフェニル基を表す。
 本明細書において、赤外線とは、波長700~2500nmの光(電磁波)をいう。
 本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。
 本明細書において「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。
The present invention will be described in detail below.
In this specification, the use of "to" means that the numerical values before and after it are included as the lower limit and upper limit.
In the description of groups (atomic groups) in this specification, when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
In this specification, unless otherwise specified, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, active rays or radiation such as electron beams.
In this specification, "(meth)acrylate" refers to both or either of acrylate and methacrylate, "(meth)acrylic" refers to both or either of acrylic and methacrylic, and "(meth)acryloyl" refers to both or either of acryloyl and methacryloyl.
In this specification, the weight average molecular weight and the number average molecular weight are defined as values calculated in terms of polystyrene as measured by gel permeation chromatography (GPC).
In this specification, Me in the chemical formulae represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, infrared rays refer to light (electromagnetic waves) with a wavelength of 700 to 2500 nm.
In this specification, the total solids content refers to the total mass of all components of the composition excluding the solvent.
In this specification, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved.
<組成物>
 本発明の組成物は、式(1)で表される化合物と、硬化性化合物と、を含むことを特徴とする。
<Composition>
The composition of the present invention is characterized by containing a compound represented by formula (1) and a curable compound.
 本発明の組成物に含まれる式(1)で表される化合物は、耐熱性や耐光性に優れており、このような化合物を含む本発明の組成物は、耐光性および耐熱性に優れた膜を形成することができる。 The compound represented by formula (1) contained in the composition of the present invention has excellent heat resistance and light resistance, and the composition of the present invention containing such a compound can form a film having excellent light resistance and heat resistance.
 本発明の組成物は、光学フィルタ用の組成物として用いることができる。光学フィルタの種類としては、赤外線カットフィルタおよび赤外線透過フィルタなどが挙げられる。式(1)で表される化合物は、可視光透過性および赤外線遮蔽性に優れているので、本発明の組成物は、赤外線カットフィルタ用の組成物として特に好ましく用いられる。 The composition of the present invention can be used as a composition for an optical filter. Types of optical filters include infrared cut filters and infrared transmission filters. Since the compound represented by formula (1) has excellent visible light transmittance and infrared shielding properties, the composition of the present invention is particularly preferably used as a composition for an infrared cut filter.
 以下、本発明の組成物に用いられる各成分について説明する。 The components used in the composition of the present invention are explained below.
<<特定化合物(式(1)で表される化合物)>>
 本発明の組成物は、式(1)で表される化合物を含む。式(1)で表される化合物は、本発明の化合物でもある。以下、式(1)で表される化合物を特定化合物ともいう。
<<Specific Compound (Compound Represented by Formula (1)>>
The composition of the present invention contains a compound represented by formula (1). The compound represented by formula (1) is also a compound of the present invention. Hereinafter, the compound represented by formula (1) is also referred to as a specific compound.
 (PM)(Z)   ・・・(1)
 式(1)中、PMは、式(PM1)で表されるアニオンを表し、
 Zは2価以上のカチオンを表し、
 mは0を超える数であって、PMの電荷を中和するために必要な数を表す。
(PM) (Z) m ... (1)
In formula (1), PM represents an anion represented by formula (PM1):
Z represents a divalent or higher cation;
m is a number greater than 0 and represents the number required to neutralize the charge of PM.
 -Zについて-
 式(1)のZが表す2価以上のカチオンは、有機カチオンおよび無機カチオンが挙げられる。無機カチオンの場合は、親水性溶剤における分散性に優れている。有機カチオンの場合は、疎水性溶剤における分散性に優れている。
-About Z-
The divalent or higher cation represented by Z in formula (1) may be an organic cation or an inorganic cation. In the case of an inorganic cation, the dispersibility in a hydrophilic solvent is excellent. In the case of an organic cation, the dispersibility in a hydrophobic solvent is excellent.
 式(1)のZは、2価、3価または4価のカチオンであることが好ましく、2価または3価のカチオンであることがより好ましい。 In formula (1), Z is preferably a divalent, trivalent or tetravalent cation, and more preferably a divalent or trivalent cation.
 Zが表す2価以上のカチオンの種類としては、(1)2価以上の金属カチオン、(2)ピリジニウムカチオン、アンモニウムカチオン、イミダゾリウムカチオン、オキサゾリウムカチオン、チアゾリウムカチオン、ピロリジニウムカチオン、ピペリジニウムカチオン、ホスホニウムカチオンなどのカチオンを1分子中に2個以上有する2価以上のカチオンなどが挙げられる。 The types of divalent or higher cations represented by Z include (1) divalent or higher metal cations, and (2) divalent or higher cations having two or more cations in one molecule, such as pyridinium cations, ammonium cations, imidazolium cations, oxazolium cations, thiazolium cations, pyrrolidinium cations, piperidinium cations, and phosphonium cations.
 2価以上の金属カチオンは、第3周期元素、第4周期元素、第5周期元素、第6周期元素、第7周期元素および希土類元素から選ばれる元素のカチオンであることが好ましく、第3周期元素、第4周期元素、第5周期元素および希土類元素から選ばれる元素のカチオンであることがより好ましい。具体的には、マグネシウムカチオン、アルミニウムカチオン、カルシウムカチオン、スカンジウムカチオン、チタンカチオン、バナジウムカチオン、クロムカチオン、マンガンカチオン、鉄カチオン、コバルトカチオン、ニッケルカチオン、銅カチオン、亜鉛カチオン、ガリウムカチオン、ストロンチウムカチオン、イットリウムカチオン、ジルコニウムカチオン、ルテニウムカチオン、ロジウムカチオン、パラジウムカチオン、インジウムカチオン、スズカチオン、バリウムカチオン、ハフニウムカチオン、タンタルカチオン、レニウムカチオン、イリジウムカチオン、白金カチオン、または、希土類元素のカチオンであることが好ましく、マグネシウムカチオン、アルミニウムカチオン、カルシウムカチオン、スカンジウムカチオン、チタンカチオン、バナジウムカチオン、クロムカチオン、マンガンカチオン、鉄カチオン、コバルトカチオン、ニッケルカチオン、銅カチオン、亜鉛カチオン、ガリウムカチオン、ストロンチウムカチオン、バリウムカチオン、ハフニウムカチオン、ラジウムカチオン、または、希土類元素のカチオンであることがより好ましく、マグネシウムカチオン、アルミニウムカチオン、カルシウムカチオン、スカンジウムカチオン、チタンカチオン、バナジウムカチオン、クロムカチオン、マンガンカチオン、鉄カチオン、コバルトカチオン、ニッケルカチオン、銅カチオン、亜鉛カチオン、ガリウムカチオン、ストロンチウムカチオン、バリウムカチオン、ハフニウムカチオン、ラジウムカチオン、ランタンカチオン、セリウムカチオン、プラセオジウムカチオン、ネオジムカチオン、サマリウムカチオン、ユウロピウムカチオン、ガドリニウムカチオン、テルビウムカチオン、ツリウムカチオン、イッテルビウムカチオンまたはルテチウムカチオンであることが更に好ましく、マグネシウムカチオン、アルミニウムカチオン、カルシウムカチオン、チタンカチオン、鉄カチオン、銅カチオン、亜鉛カチオン、ガリウムカチオン、ストロンチウムカチオン、バリウムカチオン、ハフニウムカチオン、ランタンカチオン、セリウムカチオン、ネオジムカチオン、サマリウムカチオン、ユウロピウムカチオンまたはガドリニウムカチオンであることが特に好ましい。 The divalent or higher metal cation is preferably a cation of an element selected from the group consisting of periodic elements, 4th period elements, 5th period elements, 6th period elements, 7th period elements, and rare earth elements, and more preferably a cation of an element selected from the group consisting of periodic elements, 4th period elements, 5th period elements, and rare earth elements. Specifically, magnesium cation, aluminum cation, calcium cation, scandium cation, titanium cation, vanadium cation, chromium cation, manganese cation, iron cation, cobalt cation, nickel cation, copper cation, zinc cation, gallium cation, strontium cation, yttrium cation, zirconium cation, ruthenium cation, rhodium cation, palladium cation, indium cation, tin cation, barium cation, hafnium cation, tantalum cation, rhenium cation, iridium cation, platinum cation, or a cation of a rare earth element is preferable, and magnesium cation, aluminum cation, calcium cation, scandium cation, titanium cation, vanadium cation, chromium cation, manganese cation, iron cation, cobalt cation, nickel cation, copper cation, zinc cation, gallium cation, strontium cation, barium cation, hafnium cation, radium cation, or a cation of a rare earth element is preferable. and more preferably, magnesium cation, aluminum cation, calcium cation, scandium cation, titanium cation, vanadium cation, chromium cation, manganese cation, iron cation, cobalt cation, nickel cation, copper cation, zinc cation, gallium cation, strontium cation, barium cation, hafnium cation, radium cation, lanthanum cation, cerium cation, praseodymium cation, neodymium cation, samarium cation, europium cation, gadolinium cation, terbium cation, thulium cation, ytterbium cation, or lutetium cation. Magnesium cation, aluminum cation, calcium cation, titanium cation, iron cation, copper cation, zinc cation, gallium cation, strontium cation, barium cation, hafnium cation, lanthanum cation, cerium cation, neodymium cation, samarium cation, europium cation, or gadolinium cation is particularly preferred.
 金属カチオン以外の具体例としては、以下に示す構造のカチオンなどが挙げられる。以下の構造式中のMeはメチル基を表し、Etはエチル基を表し、Phはフェニル基を表す。
Specific examples of cations other than metal cations include cations having the structures shown below: In the following structural formulas, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.
 -mについて-
 式(1)のmは0を超える数であって、式(1)のPMの電荷を中和するために必要な数を表す。すなわち、式(1)において、mは以下の関係を満たす数である。
 m×(式(1)のZが表すカチオンの価数)=式(1)のPMが表すアニオンの価数
 例えば、式(1)のPMが表すアニオンの価数が1で、Zが表すカチオンが2価のMg(マグネシウム)カチオンである場合は、mは1/2となる。なお、式(1)において、mは、Zが表すカチオンのモル数をPMが表すアニオン1モルに対する値として表記している。このため、上記の場合、mは分数で表されているが、式(1)で表される化合物は、PMが表すアニオンの2モルに対して、Zが表すアニオンは1モルであることを意味している。
About -m-
In formula (1), m is a number greater than 0 and represents a number necessary to neutralize the charge of the PM of formula (1). That is, in formula (1), m is a number that satisfies the following relationship.
m × (valence of cation represented by Z in formula (1)) = valence of anion represented by PM in formula (1) For example, when the valence of anion represented by PM in formula (1) is 1 and the cation represented by Z is a divalent Mg (magnesium) cation, m is 1/2. In formula (1), m is expressed as the number of moles of cation represented by Z relative to 1 mole of anion represented by PM. Therefore, in the above case, m is expressed as a fraction, but it means that the compound represented by formula (1) has 1 mole of anion represented by Z relative to 2 moles of anion represented by PM.
-式(PM1)で表されるアニオンについて-
 式(1)のPMは、式(PM1)で表されるアニオンを表す。
--Regarding the anion represented by formula (PM1)--
PM in formula (1) represents an anion represented by formula (PM1).
 式(PM1)中、Rpm~Rpmは、それぞれ独立して水素原子または置換基を表し、
 nは1以上の整数を表し、
 Rpm~Rpmの2つが結合して環を形成していてもよく、RpmとTは結合して環を形成していてもよく、RpmとTは結合して環を形成していてもよく、
 Tは式(T1A)、式(T1B)または式(T1C)で表される基であり、
 Tは式(T2A)、式(T2B)または式(T2C)で表される基であり、
 Rpm~Rpm、TおよびTの少なくとも一つはアニオン性基を含む。
In formula (PM1), Rpm 1 to Rpm 5 each independently represent a hydrogen atom or a substituent;
n represents an integer of 1 or more;
any two of Rpm 2 to Rpm 4 may be bonded to form a ring, Rpm 1 and T 1 may be bonded to form a ring, and Rpm 5 and T 2 may be bonded to form a ring;
T 1 is a group represented by formula (T 1A ), formula (T 1B ) or formula (T 1C );
T2 is a group represented by formula ( T2A ), formula ( T2B ) or formula ( T2C ),
At least one of Rpm 1 to Rpm 5 , T 1 and T 2 contains an anionic group.
 式中、X~Xはそれぞれ独立して、酸素原子、硫黄原子、セレン原子、テルル原子または-NRX1-を表し、RX1は、水素原子、ハロゲン原子、アルキル基、アリール基または複素環基を表し、
 R~R16、および、R31~R46は、それぞれ独立して、水素原子、アルキル基、ハロゲン原子、アルケニル基、アリール基、複素環基、ニトロ基、シアノ基、-ORL1、-C(=O)RL1、-C(=O)ORL1、-OC(=O)RL1、-NRL1L2、-NHC(=O)RL1、-C(=O)NRL1L2、-NHC(=O)ORL1、-OC(=O)NRL1L2、-NHC(=O)NRL1L2、-SRL1、-S(=O)L1、-S(=O)ORL1、-NHS(=O)L1、-S(=O)NRL1L2またはアニオン性基を表し、RL1およびRL2はそれぞれ独立して、水素原子、アルキル基、アルケニル基、アリール基または複素環基を表し、
 R~R16、および、R31~R46のうち隣接する2つは互いに結合して環を形成してもよい。
In the formula, X 1 to X 6 each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR X1 -, where R X1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group;
R 1 to R 16 and R 31 to R 46 each independently represent a hydrogen atom, an alkyl group, a halogen atom, an alkenyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, -OR L1 , -C(=O)R L1 , -C(=O)OR L1 , -OC(=O)R L1 , -NR L1 R L2 , -NHC(=O)R L1 , -C(=O)NR L1 R L2 , -NHC(=O)OR L1 , -OC(=O)NR L1 R L2 , -NHC(=O)NR L1 R L2 , -SR L1 , -S (=O) 2R L1 , -S(=O)2OR L1 , -NHS(=O) 2 R L1 represents -S(=O) 2 NR L1 R L2 or an anionic group, and R L1 and R L2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group;
Adjacent two of R 1 to R 16 and R 31 to R 46 may be bonded to each other to form a ring.
 Rpm~Rpmが表す置換基としては、後述する置換基Tで挙げた基、および、アニオン性基が挙げられる。 Examples of the substituents represented by Rpm 1 to Rpm 5 include the groups exemplified as the substituent T described below, and anionic groups.
 Rpm~Rpmが表す置換基のうち、アニオン性基以外の置換基としては、ハロゲン原子、アルキル基、アルケニル基、アリール基、複素環基、ニトロ基、シアノ基、-ORL1、-C(=O)RL1、-C(=O)ORL1、-OC(=O)RL1、-NRL1L2、-NHC(=O)RL1、-C(=O)NRL1L2、-NHC(=O)ORL1、-OC(=O)NRL1L2、-NHC(=O)NRL1L2、-SRL1、-S(=O)L1、-S(=O)ORL1、-NHS(=O)L1または-S(=O)NRL1L2であることが好ましい。RL1およびRL2はそれぞれ独立して、水素原子、アルキル基、アルケニル基、アリール基または複素環基を表す。
 ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
 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、1~10が更に好ましく、1~5が特に好ましい。アルキル基は、直鎖、分岐、環状のいずれであってもよい。
 アルケニル基の炭素数は、2~20が好ましく、2~15がより好ましく、2~10が更に好ましく、2~5が特に好ましい。アルケニル基は、直鎖および分岐のいずれであってもよい。
 アリール基の炭素数は、6~20が好ましく、6~12がより好ましい。
 複素環基は、単環または縮合数が2~8の縮合環の複素環基であることが好ましく、単環または縮合数が2~4の縮合環の複素環基であることがより好ましい。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、酸素原子および硫黄原子が挙げられ、窒素原子であることが好ましい。複素環基の環を構成する炭素原子の数は1~20が好ましく、1~18がより好ましく、1~12がより好ましい。複素環基は、5員環または6員環の複素環基であることが好ましい。
 上記のアルキル基、アルケニル基、アリール基およ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、後述する置換基Tで挙げた基が挙げられる。
Among the substituents represented by Rpm 1 to Rpm 5 , examples of the substituents other than the anionic group include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, -OR L1 , -C(=O)R L1 , -C(=O)OR L1 , -OC(=O)R L1 , -NR L1 R L2 , -NHC(=O)R L1 , -C(=O)NR L1 R L2 , -NHC(=O)OR L1 , -OC(=O)NR L1 R L2 , -NHC(=O)NR L1 R L2 , -SR L1 , -S(=O) 2R L1 , -S(=O) 2OR L1 , -NHS(=O) 2R L1 or -S(=O) 2 NR L1 R L2 is preferred, where R L1 and R L2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may be linear, branched, or cyclic.
The number of carbon atoms in the alkenyl group is preferably from 2 to 20, more preferably from 2 to 15, still more preferably from 2 to 10, and particularly preferably from 2 to 5. The alkenyl group may be either linear or branched.
The aryl group preferably has 6 to 20 carbon atoms, and more preferably has 6 to 12 carbon atoms.
The heterocyclic group is preferably a monocyclic or fused ring heterocyclic group having 2 to 8 fused rings, more preferably a monocyclic or fused ring heterocyclic group having 2 to 4 fused rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. Examples of the heteroatoms constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom, and the nitrogen atom is preferred. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 1 to 20, more preferably 1 to 18, and more preferably 1 to 12. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
The alkyl group, alkenyl group, aryl group and heterocyclic group may have a substituent. Examples of the substituent include the groups exemplified as the substituent T described later.
 アニオン性基としては、式(AN-1)で表される基および式(AN-2)で表される基が挙げられる。
The anionic group includes a group represented by the formula (AN-1) and a group represented by the formula (AN-2).
 式(AN-1)中、LAN1は、単結合またはp+1価の連結基を表し、
 Anは、-SO 、-COO、-PO、-CONSOan1、-SOSOan1または-SOCORan1を表し、Ran1は、アルキル基またはアリール基を表し、pは、1~4の整数を表す。
In formula (AN-1), L AN1 represents a single bond or a p+1-valent linking group.
An1 represents -SO3- , -COO- , -PO3H- , -CON - SO2Ran1 , -SO2N - SO2Ran1 or -SO2N - CORan1 , where Ran1 represents an alkyl group or an aryl group, and p represents an integer of 1 to 4.
 式(AN-2)中、LAN2およびLAN4は、それぞれ独立して単結合または2価の連結基を表し、
 LAN3は、-CONSO-、-SOSO-または-SOCO-を表し、
 RAN1およびRAN2は、それぞれ独立してアルキレン基またはアリーレン基を表し、
 Anは、-SO 、-COOまたは-POを表す。
In formula (AN-2), L AN2 and L AN4 each independently represent a single bond or a divalent linking group.
L AN3 represents -CON - SO 2 -, -SO 2 N - SO 2 - or -SO 2 N - CO-;
R AN1 and R AN2 each independently represent an alkylene group or an arylene group;
An 2 represents -SO 3 - , -COO - or -PO 3 H - .
 式(AN-1)のLAN1が表すp+1価の連結基としては、脂肪族炭化水素基、芳香族炭化水素基、複素環基、-O-、-CO-、-NH-、-COO-、-OCO-、-CONH-、-NHCO-、-SO-、-SONH-、-NHSO-、-S-およびこれらの基を2以上組み合わせた基が挙げられる。
 脂肪族炭化水素基の炭素数は、1~20が好ましく、1~15がより好ましく、1~10が更に好ましく、1~5が特に好ましい。脂肪族炭化水素基は、直鎖、分岐、環状のいずれであってもよい。
 芳香族炭化水素基の炭素数は、6~20が好ましく、6~12がより好ましい。
 複素環基は、単環または縮合数が2~8の縮合環の複素環基であることが好ましく、単環または縮合数が2~4の縮合環の複素環基であることがより好ましい。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、酸素原子および硫黄原子が挙げられ、窒素原子であることが好ましい。複素環基の環を構成する炭素原子の数は1~20が好ましく、1~18がより好ましく、1~12がより好ましい。複素環基は、5員環または6員環の複素環基であることが好ましい。
 脂肪族炭化水素基、芳香族炭化水素基およ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、後述する置換基Tが挙げられる。
Examples of the p+1-valent linking group represented by L AN1 in formula (AN-1) include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, -O-, -CO-, -NH-, -COO-, -OCO-, -CONH-, -NHCO-, -SO 2 -, -SO 2 NH-, -NHSO 2 -, -S-, and groups consisting of a combination of two or more of these groups.
The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 5. The aliphatic hydrocarbon group may be linear, branched, or cyclic.
The aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, and more preferably has 6 to 12 carbon atoms.
The heterocyclic group is preferably a monocyclic or fused ring heterocyclic group having 2 to 8 fused rings, more preferably a monocyclic or fused ring heterocyclic group having 2 to 4 fused rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. Examples of the heteroatoms constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom, and the nitrogen atom is preferred. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 1 to 20, more preferably 1 to 18, and more preferably 1 to 12. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
The aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group may have a substituent. Examples of the substituent include the substituent T described below.
 式(AN-1)のAnは、-SO 、-COO、-PO、-CONSOan1、-SOSOan1、-SOCORan1を表し、Ran1は、アルキル基またはアリール基を表す。Anは、-SO 、-COO、-CONSOan1、-SOSOan1または-SOCORan1であることが好ましく、-SO 、-COO、または-SOSOan1であることがより好ましい。 In formula (AN-1), An 1 represents -SO 3 - , -COO - , -PO 3 H - , -CON - SO 2 R an1 , -SO 2 N - SO 2 R an1 or -SO 2 N - COR an1 , where R an1 represents an alkyl group or an aryl group. An 1 is preferably -SO 3 - , -COO - , -CON - SO 2 R an1 , -SO 2 N - SO 2 R an1 or -SO 2 N - COR an1 , and more preferably -SO 3 - , -COO - or -SO 2 N - SO 2 R an1 .
 Ran1が表すアルキル基の炭素数は、1~15が好ましく、1~10がより好ましく、1~5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い。アルキル基は置換基を有していてもよい。置換基としては、ハロゲン原子、アリール基、アルコキシ基およびアリールオキシ基などが挙げられる。置換基は、複数あっても良い。Ran1が表すアルキル基は、ハロゲン原子を置換基として有するアルキル基であることが好ましく、フッ素原子を置換基として有するアルキル基であることがより好ましい。
 Ran1が表すアリール基の炭素数は、6~20が好ましく、6~12がより好ましい。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、ハロゲン原子、アルキル基、アルコキシ基およびアリールオキシ基などが挙げられる。置換基は、複数あっても良い。Ran1が表すアリール基は、ハロゲン原子を置換基として有するアリール基であることが好ましく、フッ素原子を置換基として有するアリール基であることがより好ましい。
The number of carbon atoms in the alkyl group represented by R an1 is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, and an aryloxy group. The alkyl group may have a plurality of substituents. The alkyl group represented by R an1 is preferably an alkyl group having a halogen atom as a substituent, and more preferably an alkyl group having a fluorine atom as a substituent.
The number of carbon atoms of the aryl group represented by R an1 is preferably 6 to 20, and more preferably 6 to 12. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group. The number of substituents may be multiple. The aryl group represented by R an1 is preferably an aryl group having a halogen atom as a substituent, and more preferably an aryl group having a fluorine atom as a substituent.
 式(AN-2)のLAN2およびLAN4は、それぞれ独立して単結合または2価の連結基を表す。
 LAN2およびLAN4が表す2価の連結基としては、アルキレン基、アリーレン基、複素環基、-O-、-CO-、-NH-、-COO-、-OCO-、-CONH-、-NHCO-、-SO-、-SONH-、-NHSO-、-S-およびこれらの基を2以上組み合わせた基が挙げられる。
 アルキレン基の炭素数は、1~20が好ましく、1~15がより好ましく、1~10が更に好ましく、1~5が特に好ましい。アルキレン基は、直鎖、分岐、環状のいずれであってもよい。
 アリーレン基の炭素数は、6~20が好ましく、6~12がより好ましい。
 複素環基は、単環または縮合数が2~8の縮合環の複素環基であることが好ましく、単環または縮合数が2~4の縮合環の複素環基であることがより好ましい。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、酸素原子および硫黄原子が挙げられ、窒素原子であることが好ましい。複素環基の環を構成する炭素原子の数は1~20が好ましく、1~18がより好ましく、1~12がより好ましい。複素環基は、5員環または6員環の複素環基であることが好ましい。
 アルキレン基、アリーレン基およ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、後述する置換基Tが挙げられる。
L AN2 and L AN4 in formula (AN-2) each independently represent a single bond or a divalent linking group.
Examples of the divalent linking group represented by L AN2 and L AN4 include an alkylene group, an arylene group, a heterocyclic group, -O-, -CO-, -NH-, -COO-, -OCO-, -CONH-, -NHCO-, -SO 2 -, -SO 2 NH-, -NHSO 2 -, -S-, and groups formed by combining two or more of these groups.
The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 5. The alkylene group may be linear, branched, or cyclic.
The arylene group preferably has 6 to 20 carbon atoms, and more preferably has 6 to 12 carbon atoms.
The heterocyclic group is preferably a monocyclic or fused ring heterocyclic group having 2 to 8 fused rings, more preferably a monocyclic or fused ring heterocyclic group having 2 to 4 fused rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. Examples of the heteroatoms constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom, and the nitrogen atom is preferred. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 1 to 20, more preferably 1 to 18, and more preferably 1 to 12. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
The alkylene group, the arylene group and the heterocyclic group may have a substituent. Examples of the substituent include the substituent T described below.
 式(AN-2)のLAN3は、-CONSO-、-SOSO-または-SOCO-を表し、-SOSO-であることが好ましい。 L AN3 in the formula (AN-2) represents -CON - SO 2 -, -SO 2 N - SO 2 - or -SO 2 N - CO-, and is preferably -SO 2 N - SO 2 -.
 式(1)のRAN1およびRAN2は、それぞれ独立してアルキレン基またはアリーレン基を表す。
 RAN1およびRAN2が表すアルキレン基の炭素数は、1~15が好ましく、1~10がより好ましく、1~5が更に好ましい。アルキレン基は、直鎖、分岐、環状のいずれでもよい。アルキレン基は置換基を有していてもよい。置換基としては、ハロゲン原子、アリール基、アルコキシ基およびアリールオキシ基などが挙げられる。置換基は、複数あっても良い。
 RAN2が表すアルキレン基は、ハロゲン原子を置換基として有するアルキレン基であることが好ましく、フッ素原子を置換基として有するアルキレン基であることが更に好ましい。
 RAN1およびRAN2が表すアリーレン基の炭素数は、6~20が好ましく、6~12がより好ましい。アリーレン基は置換基を有していてもよい。置換基としては、ハロゲン原子、アルキル基、アルコキシ基およびアリールオキシ基などが挙げられる。置換基は、複数あっても良い。RAN2が表すアリーレン基は、ハロゲン原子を置換基として有するアリーレン基であることが好ましく、フッ素原子を置換基として有するアリーレン基であることがより好ましい。
In formula (1), R AN1 and R AN2 each independently represent an alkylene group or an arylene group.
The number of carbon atoms in the alkylene group represented by R AN1 and R AN2 is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5. The alkylene group may be linear, branched, or cyclic. The alkylene group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, and an aryloxy group. There may be multiple substituents.
The alkylene group represented by R AN2 is preferably an alkylene group having a halogen atom as a substituent, and more preferably an alkylene group having a fluorine atom as a substituent.
The number of carbon atoms in the arylene group represented by R AN1 and R AN2 is preferably 6 to 20, and more preferably 6 to 12. The arylene group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group. The number of substituents may be multiple. The arylene group represented by R AN2 is preferably an arylene group having a halogen atom as a substituent, and more preferably an arylene group having a fluorine atom as a substituent.
 式(AN-2)のAnは、-SO 、-COOまたは-POを表し、-SO または-COOであることが好ましく、-SO であることがより好ましい。 An 2 in formula (AN-2) represents -SO 3 - , -COO - or -PO 3 H - , preferably -SO 3 - or -COO - , and more preferably -SO 3 - .
 式(PM1)において、Rpm~Rpmの2つが結合して環を形成していてもよく、RpmとTは結合して環を形成していてもよく、RpmとTは結合して環を形成していてもよい。
 形成される環は、5員環または6員環であることが好ましい。形成される環は、置換基を有していてもよい。置換基としては、後述する置換基Tで挙げた基およびアニオン性基が挙げられる。アニオン性基としては、上述した式(AN-1)で表される基および式(AN-2)で表される基が挙げられる。
In formula (PM1), any two of Rpm 2 to Rpm 4 may be bonded to form a ring, Rpm 1 and T 1 may be bonded to form a ring, and Rpm 5 and T 2 may be bonded to form a ring.
The ring formed is preferably a 5-membered or 6-membered ring. The ring formed may have a substituent. Examples of the substituent include the groups listed as the substituent T described below and anionic groups. Examples of the anionic group include the groups represented by the above formula (AN-1) and formula (AN-2).
 式(PM1)のnは1以上の整数を表し、1~3の整数であることが好ましい。 In formula (PM1), n represents an integer of 1 or more, and is preferably an integer of 1 to 3.
 式(1)のTは式(T1A)、式(T1B)または式(T1C)で表される基であり、Tは式(T2A)、式(T2B)または式(T2C)で表される基である。 In formula (1), T1 is a group represented by formula ( T1A ), formula ( T1B ) or formula ( T1C ), and T2 is a group represented by formula ( T2A ), formula ( T2B ) or formula ( T2C ).
 式(T1A)、式(T1B)、式(T1C)、式(T2A)、式(T2B)および式(T2C)において、X~Xはそれぞれ独立して、酸素原子、硫黄原子、セレン原子、テルル原子または-NRX1-を表し、RX1は、水素原子、ハロゲン原子、アルキル基、アリール基または複素環基を表す。 In formulae (T 1A ), (T 1B ), (T 1C ), (T 2A ), (T 2B ) and (T 2C ), X 1 to X 6 each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR X1 -, where R X1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.
 RX1が表すハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
 RX1が表す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、1~10が更に好ましく、1~5が特に好ましい。アルキル基は、直鎖、分岐、環状のいずれであってもよい。
 RX1が表すアリール基の炭素数は、6~20が好ましく、6~12がより好ましい。
 RX1が表す複素環基は、単環または縮合数が2~8の縮合環の複素環基であることが好ましく、単環または縮合数が2~4の縮合環の複素環基であることがより好ましい。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、酸素原子および硫黄原子が挙げられ、窒素原子であることが好ましい。複素環基の環を構成する炭素原子の数は1~20が好ましく、1~18がより好ましく、1~12がより好ましい。複素環基は、5員環または6員環の複素環基であることが好ましい。
 RX1が表すアルキル基、アリール基およ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、後述する置換基Tで挙げた基が挙げられる。
Examples of the halogen atom represented by R X1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The number of carbon atoms in the alkyl group represented by R X1 is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may be linear, branched, or cyclic.
The aryl group represented by R 3 X1 preferably has 6 to 20 carbon atoms, and more preferably has 6 to 12 carbon atoms.
The heterocyclic group represented by R X1 is preferably a monocyclic or fused ring heterocyclic group having 2 to 8 fused rings, more preferably a monocyclic or fused ring heterocyclic group having 2 to 4 fused rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. Examples of the heteroatoms constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom, and are preferably a nitrogen atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 1 to 20, more preferably 1 to 18, and more preferably 1 to 12. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
The alkyl group, aryl group and heterocyclic group represented by R X1 may have a substituent. Examples of the substituent include the groups exemplified as the substituent T described below.
 式(T1A)、式(T1B)、式(T1C)、式(T2A)、式(T2B)および式(T2C)において、X~Xはそれぞれ独立して、酸素原子または硫黄原子であることが好ましく、酸素原子がより好ましい。この態様によれば、耐熱性および耐光性をより向上させることができる。 In formula (T 1A ), formula (T 1B ), formula (T 1C ), formula (T 2A ), formula (T 2B ) and formula (T 2C ), X 1 to X 6 are each preferably independently an oxygen atom or a sulfur atom, more preferably an oxygen atom. According to this embodiment, the heat resistance and light resistance can be further improved.
 式(T1A)、式(T1B)、式(T1C)、式(T2A)、式(T2B)および式(T2C)において、R~R16、および、R31~R46は、それぞれ独立して、水素原子、アルキル基、ハロゲン原子、アルケニル基、アリール基、複素環基、ニトロ基、シアノ基、-ORL1、-C(=O)RL1、-C(=O)ORL1、-OC(=O)RL1、-NRL1L2、-NHC(=O)RL1、-C(=O)NRL1L2、-NHC(=O)ORL1、-OC(=O)NRL1L2、-NHC(=O)NRL1L2、-SRL1、-S(=O)L1、-S(=O)ORL1、-NHS(=O)L1、-S(=O)NRL1L2またはアニオン性基を表し、RL1およびRL2はそれぞれ独立して、水素原子、アルキル基、アルケニル基、アリール基または複素環基を表す。 In formulae (T 1A ), (T 1B ), (T 1C ), (T 2A ), (T 2B ) and (T 2C ), R 1 to R 16 and R 31 to R 46 each independently represent a hydrogen atom, an alkyl group, a halogen atom, an alkenyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, -OR L1 , -C(═O)R L1 , -C(═O)OR L1 , -OC(═O)R L1 , -NR L1 R L2 , -NHC(═O)R L1 , -C(═O)NR L1 R L2 , -NHC(═O)OR L1 , -OC(═O)NR L1 R L2 , -NHC(═O)NR L1 R L2 , -SR L1 , -S(=O) 2 R L1 , -S(=O) 2 OR L1 , -NHS(=O) 2 R L1 , -S(=O) 2 NR L1 R L2 or an anionic group, and R L1 and R L2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.
 R~R16、および、R31~R46が表すアニオン性基としては、上述した式(AN-1)で表される基および式(AN-2)で表される基が挙げられる。 Examples of the anionic group represented by R 1 to R 16 and R 31 to R 46 include the groups represented by the above-mentioned formula (AN-1) and formula (AN-2).
 R~R16およびR31~R46が表すハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。 Examples of the halogen atom represented by R 1 to R 16 and R 31 to R 46 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
 R~R16、R31~R46、RL1およびRL2が表す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、1~10が更に好ましく、1~5が特に好ましい。アルキル基は、直鎖、分岐、環状のいずれであってもよい。
 R~R16、R31~R46、RL1およびRL2が表すアルケニル基の炭素数は、2~20が好ましく、2~15がより好ましく、2~10が更に好ましく、2~5が特に好ましい。アルケニル基は、直鎖および分岐のいずれであってもよい。
 R~R16、R31~R46、RL1およびRL2が表すアリール基の炭素数は、6~20が好ましく、6~12がより好ましい。
 R~R16、R31~R46、RL1およびRL2が表す複素環基は、単環または縮合数が2~8の縮合環の複素環基であることが好ましく、単環または縮合数が2~4の縮合環の複素環基であることがより好ましい。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、酸素原子および硫黄原子が挙げられ、窒素原子であることが好ましい。複素環基の環を構成する炭素原子の数は1~20が好ましく、1~18がより好ましく、1~12がより好ましい。複素環基は、5員環または6員環の複素環基であることが好ましい。
 上記のアルキル基、アルケニル基、アリール基およ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、後述する置換基Tで挙げた基が挙げられる。
The number of carbon atoms in the alkyl group represented by R 1 to R 16 , R 31 to R 46 , R L1 and R L2 is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may be linear, branched or cyclic.
The number of carbon atoms in the alkenyl group represented by R 1 to R 16 , R 31 to R 46 , R L1 and R L2 is preferably 2 to 20, more preferably 2 to 15, still more preferably 2 to 10, and particularly preferably 2 to 5. The alkenyl group may be either linear or branched.
The aryl group represented by R 1 to R 16 , R 31 to R 46 , R L1 and R L2 preferably has 6 to 20 carbon atoms, and more preferably has 6 to 12 carbon atoms.
The heterocyclic group represented by R 1 to R 16 , R 31 to R 46 , R L1 and R L2 is preferably a monocyclic or fused ring heterocyclic group having 2 to 8 fused rings, more preferably a monocyclic or fused ring heterocyclic group having 2 to 4 fused rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. Examples of the heteroatom constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom, and the nitrogen atom is preferable. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 1 to 20, more preferably 1 to 18, and more preferably 1 to 12. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
The alkyl group, alkenyl group, aryl group and heterocyclic group may have a substituent. Examples of the substituent include the groups exemplified as the substituent T described later.
 R~R16、および、R31~R46のうち隣接する2つは互いに結合して環を形成してもよい。形成される環は、5員環または6員環であることが好ましい。形成される環は、置換基を有していてもよい。置換基としては、後述する置換基Tで挙げた基およびアニオン性基が挙げられる。アニオン性基としては、上述した式(AN-1)で表される基および式(AN-2)で表される基が挙げられる。 Any two adjacent groups among R 1 to R 16 and R 31 to R 46 may be bonded to each other to form a ring. The ring formed is preferably a 5-membered or 6-membered ring. The ring formed may have a substituent. Examples of the substituent include the groups listed as the substituent T described below and anionic groups. Examples of the anionic group include the groups represented by the formula (AN-1) and the groups represented by the formula (AN-2) described above.
 式(PM1)において、Rpm~Rpm、TおよびTの少なくとも一つはアニオン性基を含む。TおよびTの少なくとも一つはアニオン性基を含むことが好ましく、TおよびTのそれぞれがアニオン性基を含むことがより好ましい。 In formula (PM1), at least one of Rpm 1 to Rpm 5 , T 1 and T 2 contains an anionic group. It is preferable that at least one of T 1 and T 2 contains an anionic group, and it is more preferable that each of T 1 and T 2 contains an anionic group.
 なお、Tがアニオン性基を含む場合とは、TがR~Rの少なくとも一つがアニオン性基を含む基である式(T1A)で表される基であるか、TがR~R12の少なくとも一つがアニオン性基を含む基である式(T1B)で表される基であるか、または、TがR13~R16の少なくとも一つがアニオン性基を含む基である式(T1C)で表される基であることである。
 また、Tがアニオン性基を含む場合とは、TがR31~R36の少なくとも一つがアニオン性基を含む基である式(T2A)で表される基であるか、TがR37~R42の少なくとも一つがアニオン性基を含む基である式(T2B)で表される基であるか、または、TがR43~R46の少なくとも一つがアニオン性基を含む基である式(T2C)で表される基であることである。
In addition, when T1 contains an anionic group, it means that T1 is a group represented by formula ( T1A ) in which at least one of R1 to R6 is a group containing an anionic group, T1 is a group represented by formula ( T1B ) in which at least one of R7 to R12 is a group containing an anionic group, or T1 is a group represented by formula ( T1C ) in which at least one of R13 to R16 is a group containing an anionic group.
Furthermore, when T2 contains an anionic group, it means that T2 is a group represented by formula ( T2A ) in which at least one of R31 to R36 is a group containing an anionic group, T2 is a group represented by formula ( T2B ) in which at least one of R37 to R42 is a group containing an anionic group, or T2 is a group represented by formula ( T2C ) in which at least one of R43 to R46 is a group containing an anionic group.
 式(PM1)において、Rpm~Rpm、TおよびTに含まれるアニオンの数の合計は、2~20であることが好ましく、2~15であることがより好ましく、2~10であることが更に好ましい。 In formula (PM1), the total number of anions contained in Rpm 1 to Rpm 5 , T 1 and T 2 is preferably 2-20, more preferably 2-15, and even more preferably 2-10.
 式(PM1)で表されるアニオンは、1~19価のアニオンであることが好ましく、1~14価のアニオンであることがより好ましく、1~9価のアニオンであることが更に好ましい。 The anion represented by formula (PM1) is preferably a 1-19 valent anion, more preferably a 1-14 valent anion, and even more preferably a 1-9 valent anion.
 式(1)のPMは、式(PM2)、式(PM3)または式(PM4)で表されるアニオンであることが好ましく、式(PM2)または式(PM3)で表されるアニオンであることがより好ましい。
PM in formula (1) is preferably an anion represented by formula (PM2), formula (PM3) or formula (PM4), and more preferably an anion represented by formula (PM2) or formula (PM3).
 式(PM2)中、Rpm11~Rpm15はそれぞれ独立して水素原子または置換基を表し、
 Rpm12とRpm14は結合して環を形成していてもよく、
 Rpm11とTは結合して環を形成していてもよく、Rpm15とTは結合して環を形成していてもよく、
 Tは上記式(T1A)、式(T1B)または式(T1C)で表される基であり、
 Tは上記式(T2A)、式(T2B)または式(T2C)で表される基であり、
 Rpm11~Rpm15、TおよびTの少なくとも一つはアニオン性基を含む;
 式(PM3)中、Rpm21~Rpm27はそれぞれ独立して水素原子または置換基を表し、
 Rpm23とRpm25は結合して環を形成していてもよく、
 Rpm21とTは結合して環を形成していてもよく、Rpm27とTは結合して環を形成していてもよく、
 Tは上記式(T1A)、式(T1B)または式(T1C)で表される基であり、
 Tは上記式(T2A)、式(T2B)または式(T2C)で表される基であり、
 Rpm21~Rpm27、TおよびTの少なくとも一つはアニオン性基を含む;
 式(PM4)中、Rpm31~Rpm39はそれぞれ独立して水素原子または置換基を表し、
 Rpm34とRpm36は結合して環を形成していてもよく、
 Rpm31とTは結合して環を形成していてもよく、Rpm39とTは結合して環を形成していてもよく、
 Tは上記式(T1A)、式(T1B)または式(T1C)で表される基であり、
 Tは上記式(T2A)、式(T2B)または式(T2C)で表される基であり、
 Rpm31~Rpm39、TおよびTの少なくとも一つはアニオン性基を含む。
In formula (PM2), Rpm 11 to Rpm 15 each independently represent a hydrogen atom or a substituent;
Rpm 12 and Rpm 14 may be bonded to form a ring;
Rpm 11 and T 1 may be bonded to form a ring, and Rpm 15 and T 2 may be bonded to form a ring;
T 1 is a group represented by the above formula (T 1A ), formula (T 1B ) or formula (T 1C );
T2 is a group represented by the above formula ( T2A ), formula ( T2B ) or formula ( T2C ),
At least one of Rpm 11 to Rpm 15 , T 1 and T 2 contains an anionic group;
In formula (PM3), Rpm 21 to Rpm 27 each independently represent a hydrogen atom or a substituent;
Rpm 23 and Rpm 25 may be bonded to form a ring;
Rpm 21 and T1 may be bonded to form a ring, Rpm 27 and T2 may be bonded to form a ring,
T 1 is a group represented by the above formula (T 1A ), formula (T 1B ) or formula (T 1C );
T2 is a group represented by the above formula ( T2A ), formula ( T2B ) or formula ( T2C ),
At least one of Rpm 21 to Rpm 27 , T 1 and T 2 contains an anionic group;
In formula (PM4), Rpm 31 to Rpm 39 each independently represent a hydrogen atom or a substituent;
Rpm 34 and Rpm 36 may be bonded to form a ring;
Rpm 31 and T1 may be bonded to form a ring, and Rpm 39 and T2 may be bonded to form a ring;
T 1 is a group represented by the above formula (T 1A ), formula (T 1B ) or formula (T 1C );
T2 is a group represented by the above formula ( T2A ), formula ( T2B ) or formula ( T2C ),
At least one of Rpm 31 to Rpm 39 , T 1 and T 2 contains an anionic group.
 式(PM2)のRpm11~Rpm15が表す置換基、式(PM3)のRpm21~Rpm27が表す置換基、および、式(PM4)のRpm31~Rpm39が表す置換基としては、後述する置換基Tで挙げた基、および、アニオン性基が挙げられる。 Examples of the substituents represented by Rpm 11 to Rpm 15 in formula (PM2), the substituents represented by Rpm 21 to Rpm 27 in formula (PM3), and the substituents represented by Rpm 31 to Rpm 39 in formula (PM4) include the groups exemplified as the substituent T described later, and anionic groups.
 アニオン性基以外の置換基は、上述した式(PM1)のRpm~Rpmが表すアニオン性基以外の置換基の好ましい例として挙げた基であることが好ましい。 The substituent other than the anionic group is preferably the group given as the preferred examples of the substituent other than the anionic group represented by Rpm 1 to Rpm 5 in the above formula (PM1).
 アニオン性基としては、上述した式(AN-1)で表される基および式(AN-2)で表される基が挙げられる。 Examples of the anionic group include the group represented by the above formula (AN-1) and the group represented by the formula (AN-2).
 式(PM2)において、Rpm12とRpm14は結合して環を形成していてもよく、Rpm11とTは結合して環を形成していてもよく、Rpm15とTは結合して環を形成していてもよい。
 式(PM3)において、Rpm23とRpm25は結合して環を形成していてもよく、Rpm21とTは結合して環を形成していてもよく、Rpm27とTは結合して環を形成していてもよい。
 式(PM4)において、Rpm34とRpm36は結合して環を形成していてもよく、Rpm31とTは結合して環を形成していてもよく、Rpm39とTは結合して環を形成していてもよい。
 上記の基同士が結合して形成される環は、5員環または6員環であることが好ましい。形成される環は、置換基を有していてもよい。置換基としては、後述する置換基Tで挙げた基およびアニオン性基が挙げられる。アニオン性基としては、上述した式(AN-1)で表される基および式(AN-2)で表される基が挙げられる。
In formula (PM2), Rpm 12 and Rpm 14 may be bonded to form a ring, Rpm 11 and T 1 may be bonded to form a ring, and Rpm 15 and T 2 may be bonded to form a ring.
In formula (PM3), Rpm 23 and Rpm 25 may be bonded to form a ring, Rpm 21 and T1 may be bonded to form a ring, and Rpm 27 and T2 may be bonded to form a ring.
In formula (PM4), Rpm 34 and Rpm 36 may be bonded to form a ring, Rpm 31 and T1 may be bonded to form a ring, and Rpm 39 and T2 may be bonded to form a ring.
The ring formed by bonding the above groups together is preferably a 5-membered or 6-membered ring. The ring formed may have a substituent. Examples of the substituent include the groups listed as the substituent T described below and anionic groups. Examples of the anionic group include the group represented by the above formula (AN-1) and the group represented by the formula (AN-2).
 式(PM2)において、Rpm11~Rpm15、TおよびTの少なくとも一つはアニオン性基を含む。TおよびTの少なくとも一つはアニオン性基を含むことが好ましく、TおよびTのそれぞれがアニオン性基を含むことがより好ましい。
 式(PM2)において、Rpm11~Rpm15、TおよびTに含まれるアニオンの数の合計は、2~20であることが好ましく、2~15であることがより好ましく、2~10であることが更に好ましい。
 式(PM2)で表されるアニオンは、1~19価のアニオンであることが好ましく、1~14価のアニオンであることがより好ましく、1~9価のアニオンであることが更に好ましい。
In formula (PM2), at least one of Rpm 11 to Rpm 15 , T 1 and T 2 contains an anionic group. It is preferable that at least one of T 1 and T 2 contains an anionic group, and it is more preferable that each of T 1 and T 2 contains an anionic group.
In formula (PM2), the total number of anions contained in Rpm 11 to Rpm 15 , T 1 and T 2 is preferably 2-20, more preferably 2-15, and even more preferably 2-10.
The anion represented by formula (PM2) is preferably a 1- to 19-valent anion, more preferably a 1- to 14-valent anion, and even more preferably a 1- to 9-valent anion.
 式(PM3)において、Rpm21~Rpm27、TおよびTの少なくとも一つはアニオン性基を含む。TおよびTの少なくとも一つはアニオン性基を含むことが好ましく、TおよびTのそれぞれがアニオン性基を含むことがより好ましい。
 式(PM3)において、Rpm21~Rpm27、TおよびTに含まれるアニオンの数の合計は、2~20であることが好ましく、2~15であることがより好ましく、2~10であることが更に好ましい。
式(PM3)で表されるアニオンは、1~19価のアニオンであることが好ましく、1~14価のアニオンであることがより好ましく、1~9価のアニオンであることが更に好ましい。
In formula (PM3), at least one of Rpm 21 to Rpm 27 , T 1 and T 2 contains an anionic group. It is preferable that at least one of T 1 and T 2 contains an anionic group, and it is more preferable that each of T 1 and T 2 contains an anionic group.
In formula (PM3), the total number of anions contained in Rpm 21 to Rpm 27 , T 1 and T 2 is preferably 2-20, more preferably 2-15, and even more preferably 2-10.
The anion represented by formula (PM3) is preferably a 1- to 19-valent anion, more preferably a 1- to 14-valent anion, and even more preferably a 1- to 9-valent anion.
 式(PM4)において、Rpm31~Rpm39、TおよびTの少なくとも一つはアニオン性基を含む。TおよびTの少なくとも一つはアニオン性基を含むことが好ましく、TおよびTのそれぞれがアニオン性基を含むことがより好ましい。
 式(PM4)において、Rpm31~Rpm39、TおよびTに含まれるアニオンの数の合計は、2~20であることが好ましく、2~15であることがより好ましく、2~10であることが更に好ましい。
 式(PM4)で表されるアニオンは、1~19価のアニオンであることが好ましく、1~14価のアニオンであることがより好ましく、1~9価のアニオンであることが更に好ましい。
In formula (PM4), at least one of Rpm 31 to Rpm 39 , T 1 and T 2 contains an anionic group. It is preferable that at least one of T 1 and T 2 contains an anionic group, and it is more preferable that each of T 1 and T 2 contains an anionic group.
In formula (PM4), the total number of anions contained in Rpm 31 to Rpm 39 , T 1 and T 2 is preferably 2-20, more preferably 2-15, and even more preferably 2-10.
The anion represented by formula (PM4) is preferably a 1- to 19-valent anion, more preferably a 1- to 14-valent anion, and even more preferably a 1- to 9-valent anion.
 -置換基Tについて-
 置換基Tとしては、次の基が挙げられる。ハロゲン原子(例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子)、アルキル基(好ましくは炭素数1~30のアルキル基)、アルケニル基(好ましくは炭素数2~30のアルケニル基)、アルキニル基(好ましくは炭素数2~30のアルキニル基)、アリール基(好ましくは炭素数6~30のアリール基)、複素環基(好ましくは炭素数1~30の複素環基)、アミノ基(好ましくは炭素数0~30のアミノ基)、アルコキシ基(好ましくは炭素数1~30のアルコキシ基)、アリールオキシ基(好ましくは炭素数6~30のアリールオキシ基)、複素環オキシ基(好ましくは炭素数1~30の複素環オキシ基)、アシル基(好ましくは炭素数2~30のアシル基)、アルコキシカルボニル基(好ましくは炭素数2~30のアルコキシカルボニル基)、アリールオキシカルボニル基(好ましくは炭素数7~30のアリールオキシカルボニル基)、複素環オキシカルボニル基(好ましくは炭素数2~30の複素環オキシカルボニル基)、アシルオキシ基(好ましくは炭素数2~30のアシルオキシ基)、アシルアミノ基(好ましくは炭素数2~30のアシルアミノ基)、アミノカルボニルアミノ基(好ましくは炭素数2~30のアミノカルボニルアミノ基)、アルコキシカルボニルアミノ基(好ましくは炭素数2~30のアルコキシカルボニルアミノ基)、アリールオキシカルボニルアミノ基(好ましくは炭素数7~30のアリールオキシカルボニルアミノ基)、スルファモイル基(好ましくは炭素数0~30のスルファモイル基)、スルファモイルアミノ基(好ましくは炭素数0~30のスルファモイルアミノ基)、カルバモイル基(好ましくは炭素数1~30のカルバモイル基)、アルキルチオ基(好ましくは炭素数1~30のアルキルチオ基)、アリールチオ基(好ましくは炭素数6~30のアリールチオ基)、複素環チオ基(好ましくは炭素数1~30の複素環チオ基)、アルキルスルホニル基(好ましくは炭素数1~30のアルキルスルホニル基)、アルキルスルホニルアミノ基(好ましくは炭素数1~30のアルキルスルホニルアミノ基)、アリールスルホニル基(好ましくは炭素数6~30のアリールスルホニル基)、アリールスルホニルアミノ基(好ましくは炭素数6~30のアリールスルホニルアミノ基)、複素環スルホニル基(好ましくは炭素数1~30の複素環スルホニル基)、複素環スルホニルアミノ基(好ましくは炭素数1~30の複素環スルホニルアミノ基)、アルキルスルフィニル基(好ましくは炭素数1~30のアルキルスルフィニル基)、アリールスルフィニル基(好ましくは炭素数6~30のアリールスルフィニル基)、複素環スルフィニル基(好ましくは炭素数1~30の複素環スルフィニル基)、ウレイド基(好ましくは炭素数1~30のウレイド基)、ヒドロキシ基、ニトロ基、カルボキシ基、スルホ基、リン酸基、カルボン酸アミド基、スルホン酸アミド基、イミド基、ホスフィノ基、メルカプト基、シアノ基、アルキルスルフィノ基、アリールスルフィノ基、アリールアゾ基、複素環アゾ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、シリル基、ヒドラジノ基、イミノ基。これらの基は、更に置換可能な基である場合、更に置換基を有してもよい。置換基としては、上述した置換基Tで説明した基が挙げられる。
-Regarding the Substituent T-
Examples of the substituent T include the following groups: a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms), a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms), an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 30 carbon atoms), an acyl group (preferably an acyl group having 2 to 30 carbon atoms), an alkoxycarbonyl group (preferably an alkoxy ... an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), a heterocyclic oxycarbonyl group (preferably a heterocyclic oxycarbonyl group having 2 to 30 carbon atoms), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an aminocarbonylamino group (preferably an aminocarbonylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), a sulfamoylamino group (preferably represents a sulfamoylamino group having 0 to 30 carbon atoms), a carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 30 carbon atoms), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), an alkylsulfonylamino group (preferably an alkylsulfonylamino group having 1 to 30 carbon atoms), an arylsulfonyl group (preferably an arylsulfonylamino group having 6 to 30 carbon atoms), an arylsulfonylamino group (preferably an arylsulfonylamino group having 6 to 30 carbon atoms), a heterocyclic sulfonyl group (preferably a heterocyclic sulfonyl group having 1 to 30 carbon atoms), Ring sulfonylamino group (preferably a heterocyclic sulfonylamino group having 1 to 30 carbon atoms), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 30 carbon atoms), arylsulfinyl group (preferably an arylsulfinyl group having 6 to 30 carbon atoms), heterocyclic sulfinyl group (preferably a heterocyclic sulfinyl group having 1 to 30 carbon atoms), ureido group (preferably a ureido group having 1 to 30 carbon atoms), hydroxy group, nitro group, carboxy group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imido group, phosphino group, mercapto group, cyano group, alkylsulfino group, arylsulfino group, arylazo group, heterocyclic azo group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, hydrazino group, imino group. When these groups are further substitutable groups, they may further have a substituent. Examples of the substituent include the groups described above for the substituent T.
 -具体例について-
 特定化合物の具体例としては、以下に示す構造の化合物が挙げられる。これらの化合物の共鳴構造体も特定化合物の具体例として挙げられる。以下に示す構造式中のMeはメチル基であり、Phはフェニル基である。具体例では、色素アニオンとカチオンのそれぞれの電荷を考慮して、カチオンのモル数を色素アニオン1モルに対する値として表記している。例えば、A-1においては、色素アニオン2モルに対してカチオンが1モルであることを表し、A-3においては色素アニオン2モルに対してカチオンが3モルであることを表している。
- Specific examples -
Specific examples of the specific compound include compounds having the structures shown below. Resonance structures of these compounds are also specific examples of the specific compound. In the structural formulas shown below, Me is a methyl group, and Ph is a phenyl group. In the specific examples, the number of moles of cations is expressed as a value relative to 1 mole of dye anion, taking into account the respective charges of the dye anion and the cation. For example, A-1 indicates that there is 1 mole of cations for 2 moles of dye anion, and A-3 indicates that there are 3 moles of cations for 2 moles of dye anion.
 特定化合物の極大吸収波長は、波長650nm以上に存在することが好ましく、波長650~1500nmの範囲に存在することがより好ましく、波長700~1200nmの範囲に存在することが更に好ましく、波長700~1000nmの範囲に存在することが特に好ましい。 The maximum absorption wavelength of the specific compound is preferably at least 650 nm, more preferably in the wavelength range of 650 to 1500 nm, even more preferably in the wavelength range of 700 to 1200 nm, and particularly preferably in the wavelength range of 700 to 1000 nm.
 特定化合物は、赤外線吸収剤として好ましく用いられる。 The specific compound is preferably used as an infrared absorber.
 組成物の全固形分中における特定化合物(式(1)で表される化合物)の含有量は、0.1質量%以上であることが好ましく、0.5質量%以上であることがより好ましく、3質量%以上であることが更に好ましく、5質量%以上であることが特に好ましい。また、赤外線吸収剤の含有量の上限は、50質量%以下であることが好ましく、40質量%以下であることがより好ましく、30質量%以下であることが更に好ましい。本発明の組成物は特定化合物を1種のみ含んでいてもよく、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the specific compound (compound represented by formula (1)) in the total solid content of the composition is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, even more preferably 3 mass% or more, and particularly preferably 5 mass% or more. The upper limit of the content of the infrared absorber is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less. The composition of the present invention may contain only one type of specific compound, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above range.
<<硬化性化合物>>
 本発明の組成物は硬化性化合物を含有する。硬化性化合物としては、重合性化合物、樹脂等が挙げられる。樹脂は、非重合性の樹脂(重合性基を有さない樹脂)であってもよく、重合性の樹脂(重合性基を有する樹脂)であってもよい。重合性基としては、エチレン性不飽和結合含有基、環状エーテル基、メチロール基、アルコキシメチル基などが挙げられる。エチレン性不飽和結合含有基としては、ビニル基、ビニルフェニル基、(メタ)アリル基、(メタ)アクリロイル基、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミド基などが挙げられ、(メタ)アリル基、(メタ)アクリロイル基および(メタ)アクリロイルオキシ基が好ましく、(メタ)アクリロイルオキシ基がより好ましい。環状エーテル基としては、エポキシ基、オキセタニル基などが挙げられ、エポキシ基が好ましい。
<<Curable Compound>>
The composition of the present invention contains a curable compound. Examples of the curable compound include polymerizable compounds and resins. The resin may be a non-polymerizable resin (a resin having no polymerizable group) or a polymerizable resin (a resin having a polymerizable group). Examples of the polymerizable group include an ethylenically unsaturated bond-containing group, a cyclic ether group, a methylol group, and an alkoxymethyl group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a vinylphenyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a (meth)acryloylamide group, with the (meth)allyl group, the (meth)acryloyl group, and the (meth)acryloyloxy group being preferred, and the (meth)acryloyloxy group being more preferred. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred.
 硬化性化合物としては、樹脂を少なくとも含むものを用いることが好ましい。また、本発明の組成物をフォトリソグラフィ用の組成物とする場合には、硬化性化合物として樹脂と、重合性化合物(好ましくは、モノマータイプの重合性化合物である重合性モノマー)とを用いることが好ましく、樹脂と、エチレン性不飽和結合含有基を有する重合性モノマー(モノマータイプの重合性化合物)とを用いることがより好ましい。 The curable compound preferably contains at least a resin. When the composition of the present invention is used as a composition for photolithography, it is preferable to use a resin and a polymerizable compound (preferably a polymerizable monomer that is a monomer-type polymerizable compound) as the curable compound, and it is more preferable to use a resin and a polymerizable monomer having an ethylenically unsaturated bond-containing group (a monomer-type polymerizable compound).
(重合性化合物)
 重合性化合物としては、エチレン性不飽和結合含有基を有する化合物、環状エーテル基を有する化合物、メチロール基を有する化合物、アルコキシメチル基を有する化合物等が挙げられる。エチレン性不飽和結合含有基を有する化合物はラジカル重合性化合物として好ましく用いることができる。また、環状エーテル基を有する化合物は、カチオン重合性化合物として好ましく用いることができる。
(Polymerizable compound)
The polymerizable compound may include a compound having an ethylenically unsaturated bond-containing group, a compound having a cyclic ether group, a compound having a methylol group, a compound having an alkoxymethyl group, etc. The compound having an ethylenically unsaturated bond-containing group can be preferably used as a radical polymerizable compound. In addition, the compound having a cyclic ether group can be preferably used as a cationic polymerizable compound.
 樹脂タイプの重合性化合物としては、重合性基を有する繰り返し単位を含む樹脂などが挙げられる。 Examples of resin-type polymerizable compounds include resins that contain repeating units with polymerizable groups.
 モノマータイプの重合性化合物(重合性モノマー)の分子量は、2000未満であることが好ましく、1500以下であることがより好ましい。重合性モノマーの分子量の下限は100以上であることが好ましく、200以上であることがより好ましい。樹脂タイプの重合性化合物の重量平均分子量(Mw)は、2000~2000000であることが好ましい。重量平均分子量の上限は、1000000以下であることが好ましく、500000以下であることがより好ましい。重量平均分子量の下限は、3000以上であることが好ましく、5000以上であることがより好ましい。 The molecular weight of the monomer-type polymerizable compound (polymerizable monomer) is preferably less than 2000, and more preferably 1500 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, and more preferably 200 or more. The weight average molecular weight (Mw) of the resin-type polymerizable compound is preferably 2000 to 2,000,000. The upper limit of the weight average molecular weight is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit of the weight average molecular weight is preferably 3,000 or more, and more preferably 5,000 or more.
 重合性モノマーとしてのエチレン性不飽和結合含有基を有する化合物は、3~15官能の(メタ)アクリレート化合物であることが好ましく、3~6官能の(メタ)アクリレート化合物であることがより好ましい。具体例としては、特開2009-288705号公報の段落番号0095~0108、特開2013-029760号公報の段落0227、特開2008-292970号公報の段落番号0254~0257、特開2013-253224号公報の段落番号0034~0038、特開2012-208494号公報の段落番号0477、特開2017-048367号公報、特許第6057891号公報、特許第6031807号公報、特開2017-194662号公報に記載されている化合物が挙げられ、これらの内容は本明細書に組み込まれる。 The compound having an ethylenically unsaturated bond-containing group as a polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, and more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples include compounds described in paragraphs 0095 to 0108 of JP 2009-288705 A, paragraph 0227 of JP 2013-029760 A, paragraphs 0254 to 0257 of JP 2008-292970 A, paragraphs 0034 to 0038 of JP 2013-253224 A, paragraph 0477 of JP 2012-208494 A, JP 2017-048367 A, Japanese Patent No. 6057891 A, Japanese Patent No. 6031807 A, and Japanese Patent No. 2017-194662 A, the contents of which are incorporated herein by reference.
 エチレン性不飽和結合含有基を有する化合物としては、ジペンタエリスリトールトリ(メタ)アクリレート(市販品としてはKAYARAD D-330;日本化薬(株)製)、ジペンタエリスリトールテトラ(メタ)アクリレート(市販品としてはKAYARAD D-320;日本化薬(株)製)、ジペンタエリスリトールペンタ(メタ)アクリレート(市販品としてはKAYARAD D-310;日本化薬(株)製)、ジペンタエリスリトールヘキサ(メタ)アクリレート(市販品としてはKAYARAD DPHA;日本化薬(株)製、NKエステルA-DPH-12E;新中村化学工業(株)製)、およびこれらの化合物の(メタ)アクリロイル基がエチレングリコールおよび/またはプロピレングリコール残基を介して結合している構造の化合物(例えば、サートマー社から市販されている、SR454、SR499)などが挙げられる。また、エチレン性不飽和結合含有基を有する化合物としては、ジグリセリンEO(エチレンオキシド)変性(メタ)アクリレート(市販品としてはM-460;東亞合成製)、ペンタエリスリトールテトラアクリレート(新中村化学工業(株)製、NKエステルA-TMMT)、1,6-ヘキサンジオールジアクリレート(日本化薬(株)製、KAYARAD HDDA)、RP-1040(日本化薬(株)製)、アロニックスTO-2349(東亞合成(株)製)、NKオリゴUA-7200(新中村化学工業(株)製)、8UH-1006、8UH-1012(大成ファインケミカル(株)製)、ライトアクリレートPOB-A0(共栄社化学(株)製)などを用いることもできる。 Examples of compounds having an ethylenically unsaturated bond-containing group include dipentaerythritol tri(meth)acrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds in which the (meth)acryloyl groups of these compounds are bonded via ethylene glycol and/or propylene glycol residues (e.g., SR454, SR499, commercially available from Sartomer Corporation). In addition, examples of compounds having an ethylenically unsaturated bond-containing group include diglycerol EO (ethylene oxide) modified (meth)acrylate (commercially available product is M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), and light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.).
 また、エチレン性不飽和結合含有基を有する化合物としては、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールプロパンプロピレンオキシド変性トリ(メタ)アクリレート、トリメチロールプロパンエチレンオキシド変性トリ(メタ)アクリレート、イソシアヌル酸エチレンオキシド変性トリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレートなどの3官能の(メタ)アクリレート化合物を用いることも好ましい。3官能の(メタ)アクリレート化合物の市販品としては、アロニックスM-309、M-310、M-321、M-350、M-360、M-313、M-315、M-306、M-305、M-303、M-452、M-450(東亞合成(株)製)、NKエステル A9300、A-GLY-9E、A-GLY-20E、A-TMM-3、A-TMM-3L、A-TMM-3LM-N、A-TMPT、TMPT(新中村化学工業(株)製)、KAYARAD GPO-303、TMPTA、THE-330、TPA-330、PET-30(日本化薬(株)製)などが挙げられる。 In addition, as compounds having an ethylenically unsaturated bond-containing group, it is also preferable to use trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. Commercially available trifunctional (meth)acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, and M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, and TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, and PET-30 (manufactured by Nippon Kayaku Co., Ltd.).
 エチレン性不飽和結合含有基を有する化合物は、更に、カルボキシ基、スルホ基、リン酸基等の酸基を有していてもよい。このような化合物の市販品としては、アロニックスM-305、M-510、M-520、アロニックスTO-2349(東亞合成(株)製)等が挙げられる。 The compound having an ethylenically unsaturated bond-containing group may further have an acid group such as a carboxy group, a sulfo group, or a phosphate group. Commercially available products of such compounds include Aronix M-305, M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
 エチレン性不飽和結合含有基を有する化合物としては、カプロラクトン構造を有する化合物を用いることもできる。カプロラクトン構造を有する化合物については、特開2013-253224号公報の段落0042~0045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。カプロラクトン構造を有する化合物は、例えば、日本化薬(株)からシリーズとして市販されている、DPCA-20、DPCA-30、DPCA-60、DPCA-120等が挙げられる。 As a compound having an ethylenically unsaturated bond-containing group, a compound having a caprolactone structure can also be used. For compounds having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP 2013-253224 A can be referred to, the contents of which are incorporated herein by reference. Examples of compounds having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as a series from Nippon Kayaku Co., Ltd.
 エチレン性不飽和結合含有基を有する化合物としては、エチレン性不飽和結合含有基とアルキレンオキシ基を有する化合物を用いることもできる。このような化合物は、エチレン性不飽和結合含有基と、エチレンオキシ基および/またはプロピレンオキシ基とを有する化合物であることが好ましく、エチレン性不飽和結合含有基とエチレンオキシ基とを有する化合物であることがより好ましく、エチレンオキシ基を4~20個有する3~6官能(メタ)アクリレート化合物であることがさらに好ましい。市販品としては、例えばサートマー社製のエチレンオキシ基を4個有する4官能(メタ)アクリレートであるSR-494、日本化薬(株)製のイソブチレンオキシ基を3個有する3官能(メタ)アクリレートであるKAYARAD TPA-330などが挙げられる。 As a compound having an ethylenically unsaturated bond-containing group, a compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used. Such a compound is preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and/or a propyleneoxy group, more preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group, and even more preferably a trifunctional to hexafunctional (meth)acrylate compound having 4 to 20 ethyleneoxy groups. Examples of commercially available products include SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer, and KAYARAD TPA-330, a trifunctional (meth)acrylate having three isobutyleneoxy groups manufactured by Nippon Kayaku Co., Ltd.
 エチレン性不飽和結合含有基を有する化合物としては、フルオレン骨格を有する重合性化合物を用いることもできる。市販品としては、オグソールEA-0200、EA-0300(大阪ガスケミカル(株)製、フルオレン骨格を有する(メタ)アクリレートモノマー)などが挙げられる。 As a compound having an ethylenically unsaturated bond-containing group, a polymerizable compound having a fluorene skeleton can also be used. Commercially available products include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).
 エチレン性不飽和結合含有基を有する化合物としては、トルエンなどの環境規制物質を実質的に含まない化合物を用いることも好ましい。このような化合物の市販品としては、KAYARAD DPHA LT、KAYARAD DPEA-12 LT(日本化薬(株)製)などが挙げられる。 As a compound having an ethylenically unsaturated bond-containing group, it is also preferable to use a compound that is substantially free of environmentally restricted substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
 環状エーテル基を有する化合物としては、エポキシ基を有する化合物、オキセタニル基を有する化合物などが挙げられ、エポキシ基を有する化合物であることが好ましい。エポキシ基を有する化合物としては、1分子内にエポキシ基を1~100個有する化合物が挙げられる。エポキシ基の数の上限は、例えば、10個以下とすることもでき、5個以下とすることもできる。エポキシ基の数の下限は、2個以上が好ましい。 Examples of compounds having a cyclic ether group include compounds having an epoxy group and compounds having an oxetanyl group, and compounds having an epoxy group are preferred. Examples of compounds having an epoxy group include compounds having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably 2 or more.
 環状エーテル基を有する化合物は、低分子化合物(例えば分子量1000未満)でもよいし、高分子化合物(macromolecule)(例えば、分子量1000以上、ポリマーの場合は、重量平均分子量が1000以上)でもよい。環状エーテル基の重量平均分子量は、200~100000が好ましく、500~50000がより好ましい。重量平均分子量の上限は、10000以下が好ましく、5000以下がより好ましく、3000以下が更に好ましい。 The compound having a cyclic ether group may be a low molecular weight compound (e.g., molecular weight less than 1000) or a high molecular weight compound (macromolecule) (e.g., molecular weight 1000 or more, in the case of a polymer, weight average molecular weight 1000 or more). The weight average molecular weight of the cyclic ether group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.
 環状エーテル基を有する化合物としては、特開2013-011869号公報の段落番号0034~0036に記載された化合物、特開2014-043556号公報の段落番号0147~0156に記載された化合物、特開2014-089408号公報の段落番号0085~0092に記載された化合物、特開2017-179172号公報に記載された化合物を用いることもできる。 As compounds having a cyclic ether group, the compounds described in JP 2013-011869 A, paragraphs 0034 to 0036, the compounds described in JP 2014-043556 A, paragraphs 0147 to 0156, the compounds described in JP 2014-089408 A, paragraphs 0085 to 0092, and the compounds described in JP 2017-179172 A can also be used.
 環状エーテル基を有する化合物の市販品としては、デナコール EX-212L、EX-212、EX-214L、EX-214、EX-216L、EX-216、EX-321L、EX-321、EX-850L、EX-850(以上、ナガセケムテックス(株)製)、ADEKA RESIN EP-4000S、EP-4003S、EP-4010S、EP-4011S(以上、(株)ADEKA製)、NC-2000、NC-3000、NC-7300、XD-1000、EPPN-501、EPPN-502(以上、(株)ADEKA製)、セロキサイド2021P、セロキサイド2081、セロキサイド2083、セロキサイド2085、EHPE3150、EPOLEAD PB 3600、PB 4700(以上、(株)ダイセル製)、サイクロマーP ACA 200M、ACA 230AA、ACA Z250、ACA Z251、ACA Z300、ACA Z320(以上、(株)ダイセル製)、jER1031S、jER157S65、jER152、jER154、jER157S70(以上、三菱ケミカル(株)製)、アロンオキセタンOXT-121、OXT-221、OX-SQ、PNOX(以上、東亞合成(株)製)、アデカグリシロール ED-505((株)ADEKA製、エポキシ基含有モノマー)、マープルーフG-0150M、G-0105SA、G-0130SP、G-0250SP、G-1005S、G-1005SA、G-1010S、G-2050M、G-01100、G-01758(日油(株)製、エポキシ基含有ポリマー)、OXT-101、OXT-121、OXT-212、OXT-221(以上、東亞合成(株)製、オキセタニル基含有モノマー)、OXE-10、OXE-30(以上、大阪有機化学工業(株)製、オキセタニル基含有モノマー)などが挙げられる。 Commercially available compounds with cyclic ether groups include Denacol EX-212L, EX-212, EX-214L, EX-214, EX-216L, EX-216, EX-321L, EX-321, EX-850L, and EX-850 (all manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, and EP-4011S (all manufactured by ADEKA Corporation), NC-2000, NC -3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA Corporation), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (all manufactured by DAICEL Corporation), CYCLOMER P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z30 0, ACA Z320 (all manufactured by Daicel Corporation), jER1031S, jER157S65, jER152, jER154, jER157S70 (all manufactured by Mitsubishi Chemical Corporation), Aron Oxetane OXT-121, OXT-221, OX-SQ, PNOX (all manufactured by Toagosei Co., Ltd.), ADEKA GLYCILOR ED-505 (manufactured by ADEKA Corporation, epoxy group-containing monomer), MARPROOF G-0150M, G-0105SA, G-0 Examples include 130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (epoxy group-containing polymers manufactured by NOF Corporation), OXT-101, OXT-121, OXT-212, and OXT-221 (oxetanyl group-containing monomers manufactured by Toagosei Co., Ltd.), and OXE-10 and OXE-30 (oxetanyl group-containing monomers manufactured by Osaka Organic Chemical Industry Co., Ltd.).
 メチロール基を有する化合物(以下、メチロール化合物ともいう)としては、メチロール基が窒素原子または芳香族環を形成する炭素原子に結合している化合物が挙げられる。また、アルコキシメチル基を有する化合物(以下、アルコキシメチル化合物ともいう)としては、アルコキシメチル基が窒素原子または芳香族環を形成する炭素原子に結合している化合物が挙げられる。アルコキシメチル基またはメチロール基が窒素原子に結合している化合物としては、アルコキシメチル化メラミン、メチロール化メラミン、アルコキシメチル化ベンゾグアナミン、メチロール化ベンゾグアナミン、アルコキシメチル化グリコールウリル、メチロール化グリコールウリル、アルコキシメチル化尿素およびメチロール化尿素等が好ましい。また、特開2004-295116号公報の段落0134~0147、特開2014-089408号公報の段落0095~0126に記載された化合物を用いることもできる。 Examples of compounds having a methylol group (hereinafter also referred to as methylol compounds) include compounds in which a methylol group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Examples of compounds having an alkoxymethyl group (hereinafter also referred to as alkoxymethyl compounds) include compounds in which an alkoxymethyl group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Examples of compounds in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxymethylated urea, and methylolated urea. Compounds described in paragraphs 0134 to 0147 of JP 2004-295116 A and paragraphs 0095 to 0126 of JP 2014-089408 A can also be used.
(樹脂)
 本発明の組成物は、硬化性化合物として樹脂を用いることができる。硬化性化合物は、樹脂を少なくとも含むものを用いることが好ましい。樹脂は、例えば、顔料等を組成物中で分散させる用途や、バインダーの用途で配合される。なお、主に顔料等を組成物中で分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外を目的として樹脂を使用することもできる。なお、重合性基を有する樹脂は、重合性化合物にも該当する。
(resin)
The composition of the present invention can use a resin as a curable compound. It is preferable to use a curable compound that contains at least a resin. The resin is blended, for example, for dispersing pigments in the composition or for use as a binder. In addition, a resin that is mainly used for dispersing pigments in the composition is also called a dispersant. However, such uses of the resin are only examples, and the resin can also be used for purposes other than such uses. In addition, a resin having a polymerizable group also falls under the category of a polymerizable compound.
 樹脂の重量平均分子量は、3000~2000000が好ましい。上限は、1000000以下が好ましく、500000以下がより好ましい。下限は、4000以上が好ましく、5000以上がより好ましい。 The weight average molecular weight of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.
 樹脂としては、(メタ)アクリル樹脂、エポキシ樹脂、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、酢酸ビニル樹脂、ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、ポリウレタン樹脂、ポリウレア樹脂などが挙げられる。これらの樹脂から1種を単独で使用してもよく、2種以上を混合して使用してもよい。環状オレフィン樹脂としては、耐熱性向上の観点からノルボルネン樹脂が好ましい。ノルボルネン樹脂の市販品としては、例えば、JSR(株)製のARTONシリーズ(例えば、ARTON F4520)などが挙げられる。また、樹脂としては、国際公開第2022/065215号の段落番号0091~0099に記載の樹脂、特開2016-222891号公報に記載されたブロックポリイソシアネート樹脂、特開2020-122052号公報に記載された樹脂、特開2020-111656号公報に記載された樹脂、特開2020-139021号公報に記載された樹脂、特開2017-138503号公報に記載の主鎖に環構造を有する構成単位と側鎖にビフェニル基を有する構成単位とを含む樹脂、特開2020-186373号公報の段落0199~0233に記載の樹脂、特開2020-186325号公報に記載のアルカリ可溶性樹脂、韓国公開特許第10-2020-0078339号公報に記載の式1で表される樹脂、国際公開第2022/030445号に記載のエポキシ基と酸基を含む共重合体、特開2020-186373号公報の段落0199~0233に記載の樹脂、特開2020-186325号公報に記載のアルカリ可溶性樹脂、韓国公開特許第10-2020-0078339号公報に記載の式1で表される樹脂、特開2021-134350号公報に記載された樹脂を用いることもできる。また、樹脂としては、フルオレン骨格を有する樹脂を好ましく用いることもできる。フルオレン骨格を有する樹脂としては、米国特許出願公開第2017/0102610号明細書の記載された樹脂が挙げられる。 The resins include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyurethane resins, and polyurea resins. One of these resins may be used alone, or two or more may be mixed and used. As the cyclic olefin resin, norbornene resin is preferred from the viewpoint of improving heat resistance. Commercially available norbornene resins include, for example, the ARTON series (e.g., ARTON F4520) manufactured by JSR Corporation. Further, as the resin, there are resins described in paragraphs 0091 to 0099 of WO 2022/065215, blocked polyisocyanate resins described in JP 2016-222891 A, resins described in JP 2020-122052 A, resins described in JP 2020-111656 A, resins described in JP 2020-139021 A, resins having a ring structure in the main chain and a biphenyl group in the side chain described in JP 2017-138503 A, and resins described in paragraphs 0199 to 0233 of JP 2020-186373 A Resins described in the above, alkali-soluble resins described in JP 2020-186325 A, resins represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339 A, copolymers containing epoxy groups and acid groups described in WO 2022/030445 A, resins described in paragraphs 0199 to 0233 of JP 2020-186373 A, alkali-soluble resins described in JP 2020-186325 A, resins represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339 A, and resins described in JP 2021-134350 A can also be used. In addition, resins having a fluorene skeleton can also be preferably used as the resin. Examples of resins having a fluorene skeleton include resins described in U.S. Patent Application Publication No. 2017/0102610 A.
 樹脂として、酸基を有する樹脂を用いることが好ましい。酸基としては、例えば、カルボキシ基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられる。これら酸基は、1種のみであってもよいし、2種以上であってもよい。酸基を有する樹脂は分散剤として用いることもできる。酸基を有する樹脂の酸価は、30~500mgKOH/gが好ましい。下限は、50mgKOH/g以上が好ましく、70mgKOH/g以上がより好ましい。上限は、400mgKOH/g以下が好ましく、200mgKOH/g以下がより好ましく、150mgKOH/g以下が更に好ましく、120mgKOH/g以下が最も好ましい。 As the resin, it is preferable to use a resin having an acid group. Examples of the acid group include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group. These acid groups may be of only one type, or of two or more types. The resin having an acid group can also be used as a dispersant. The acid value of the resin having an acid group is preferably 30 to 500 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more. The upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, even more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.
 樹脂としては、重合性基を有する樹脂を用いることも好ましい。重合性基は、エチレン性不飽和結合含有基および環状エーテル基であることが好ましく、エチレン性不飽和結合含有基であることがより好ましい。 As the resin, it is also preferable to use a resin having a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated bond-containing group or a cyclic ether group, and more preferably an ethylenically unsaturated bond-containing group.
 樹脂は、分散剤としての樹脂を含むことも好ましい。分散剤としては、酸性分散剤(酸性樹脂)、塩基性分散剤(塩基性樹脂)が挙げられる。ここで、酸性分散剤(酸性樹脂)とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤(酸性樹脂)としては、酸基の量と塩基性基の量の合計量を100モル%としたときに、酸基の量が70モル%以上である樹脂が好ましい。酸性分散剤(酸性樹脂)が有する酸基は、カルボキシ基が好ましい。酸性分散剤(酸性樹脂)の酸価は、10~105mgKOH/gが好ましい。また、塩基性分散剤(塩基性樹脂)とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤(塩基性樹脂)としては、酸基の量と塩基性基の量の合計量を100モル%としたときに、塩基性基の量が50モル%を超える樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミノ基が好ましい。 The resin preferably contains a resin as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more when the total amount of the acid groups and the basic groups is 100 mol%. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. The basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups is greater than the amount of acid groups when the total amount of the acid groups and the basic groups is 100 mol%. The basic group possessed by the basic dispersant is preferably an amino group.
 分散剤として用いる樹脂は、グラフト樹脂であることも好ましい。グラフト樹脂の詳細については、特開2012-255128号公報の段落番号0025~0094の記載を参酌でき、この内容は本明細書に組み込まれる。 It is also preferable that the resin used as the dispersant is a graft resin. For details on graft resins, please refer to the description in paragraphs 0025 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein by reference.
 分散剤として用いる樹脂は、主鎖及び側鎖の少なくとも一方に窒素原子を含むポリイミン系分散剤であることも好ましい。ポリイミン系分散剤としては、pKa14以下の官能基を有する部分構造を有する主鎖と、原子数40~10000の側鎖とを有し、かつ主鎖及び側鎖の少なくとも一方に塩基性窒素原子を有する樹脂が好ましい。塩基性窒素原子は、塩基性を呈する窒素原子であれば特に制限はない。ポリイミン系分散剤については、特開2012-255128号公報の段落番号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。 The resin used as the dispersant is preferably a polyimine-based dispersant containing nitrogen atoms in at least one of the main chain and side chain. The polyimine-based dispersant is preferably a resin having a main chain with a partial structure having a functional group with a pKa of 14 or less, a side chain with 40 to 10,000 atoms, and having a basic nitrogen atom in at least one of the main chain and side chain. There are no particular restrictions on the basic nitrogen atom, so long as it is a nitrogen atom that exhibits basicity. For details of polyimine-based dispersants, please refer to the description in paragraphs 0102 to 0166 of JP 2012-255128 A, the contents of which are incorporated herein by reference.
 分散剤として用いる樹脂は、コア部に複数個のポリマー鎖が結合した構造の樹脂であることも好ましい。このような樹脂としては、例えば、デンドリマー(星型ポリマーを含む)が挙げられる。また、デンドリマーの具体例としては、特開2013-043962号公報の段落番号0196~0209に記載された高分子化合物C-1~C-31などが挙げられる。 The resin used as the dispersant is preferably one having a structure in which multiple polymer chains are bonded to a core portion. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962A.
 分散剤として用いる樹脂は、エチレン性不飽和結合含有基を側鎖に有する繰り返し単位を含む樹脂であることも好ましい。エチレン性不飽和結合含有基を側鎖に有する繰り返し単位の含有量は、樹脂の全繰り返し単位中10モル%以上であることが好ましく、10~80モル%であることがより好ましく、20~70モル%であることが更に好ましい。 The resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol % or more of the total repeating units of the resin, more preferably 10 to 80 mol %, and even more preferably 20 to 70 mol %.
 分散剤として、特開2018-087939号公報に記載された樹脂、特許第6432077号公報の段落番号0219~0221に記載されたブロック共重合体(EB-1)~(EB-9)、国際公開第2016/104803号に記載のポリエステル側鎖を有するポリエチレンイミン、国際公開第2019/125940号に記載のブロック共重合体、特開2020-066687号公報に記載のアクリルアミド構造単位を有するブロックポリマー、特開2020-066688号公報に記載のアクリルアミド構造単位を有するブロックポリマーなどを用いることもできる。 As dispersants, resins described in JP 2018-087939 A, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6,432,077 A, polyethyleneimine having polyester side chains described in WO 2016/104803 A, block copolymers described in WO 2019/125940 A, block polymers having acrylamide structural units described in JP 2020-066687 A, block polymers having acrylamide structural units described in JP 2020-066688 A, and the like can also be used.
 分散剤は、市販品としても入手可能であり、そのような具体例としては、ビックケミー社製のDISPERBYKシリーズ、日本ルーブリゾール社製のSOLSPERSEシリーズ、BASF社製のEfkaシリーズ、味の素ファインテクノ(株)製のアジスパーシリーズ等が挙げられる。また、特開2012-137564号公報の段落番号0129に記載された製品、特開2017-194662号公報の段落番号0235に記載された製品を分散剤として用いることもできる。 Dispersants are also available as commercially available products, and specific examples include the DISPERBYK series manufactured by BYK-Chemie, the SOLSPERSE series manufactured by Lubrizol Nippon, the Efka series manufactured by BASF, and the AJISPER series manufactured by Ajinomoto Fine-Techno Co., Ltd. In addition, the products described in paragraph 0129 of JP2012-137564A and the products described in paragraph 0235 of JP2017-194662A can also be used as dispersants.
 組成物の全固形分中における硬化性化合物の含有量は、1~95質量%が好ましい。下限は2質量%以上が好ましく、5質量%以上がより好ましく、7質量%以上が更に好ましく、10質量%以上が特に好ましい。上限は、94質量%以下が好ましく、90質量%以下がより好ましく、85質量%以下が更に好ましく、80質量%以下が特に好ましい。 The content of the curable compound in the total solid content of the composition is preferably 1 to 95 mass%. The lower limit is preferably 2 mass% or more, more preferably 5 mass% or more, even more preferably 7 mass% or more, and particularly preferably 10 mass% or more. The upper limit is preferably 94 mass% or less, more preferably 90 mass% or less, even more preferably 85 mass% or less, and particularly preferably 80 mass% or less.
 本発明の組成物が硬化性化合物として重合性化合物を含む場合、組成物の全固形分中における重合性化合物の含有量は、1~85質量%が好ましい。下限は、2質量%以上が好ましく、3質量%以上がより好ましく、5質量%以上が更に好ましい。上限は、80質量%以下が好ましく、70質量%以下がより好ましい。 When the composition of the present invention contains a polymerizable compound as a curable compound, the content of the polymerizable compound in the total solid content of the composition is preferably 1 to 85 mass%. The lower limit is preferably 2 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more. The upper limit is preferably 80 mass% or less, and more preferably 70 mass% or less.
 本発明の組成物が硬化性化合物として重合性モノマーを含む場合、組成物の全固形分中における重合性モノマーの含有量は、1~50質量%が好ましい。下限は、2質量%以上が好ましく、3質量%以上がより好ましく、5質量%以上が更に好ましい。上限は、30質量%以下が好ましく、20質量%以下がより好ましい。 When the composition of the present invention contains a polymerizable monomer as a curable compound, the content of the polymerizable monomer in the total solid content of the composition is preferably 1 to 50 mass%. The lower limit is preferably 2 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more. The upper limit is preferably 30 mass% or less, and more preferably 20 mass% or less.
 本発明の組成物が硬化性化合物としてエチレン性不飽和結合含有基を有する化合物を含む場合、組成物の全固形分中におけるエチレン性不飽和結合含有基を有する化合物の含有量は、1~70質量%が好ましい。下限は、2質量%以上が好ましく、3質量%以上がより好ましく、5質量%以上が更に好ましい。上限は、65質量%以下が好ましく、60質量%以下がより好ましい。 When the composition of the present invention contains a compound having an ethylenically unsaturated bond-containing group as a curable compound, the content of the compound having an ethylenically unsaturated bond-containing group in the total solid content of the composition is preferably 1 to 70 mass%. The lower limit is preferably 2 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more. The upper limit is preferably 65 mass% or less, and more preferably 60 mass% or less.
 本発明の組成物が硬化性化合物として環状エーテル基を有する化合物を含む場合、組成物の全固形分中における環状エーテル基を有する化合物の含有量は、1~95質量%が好ましい。下限は、2質量%以上が好ましく、3質量%以上がより好ましく、5質量%以上が更に好ましい。上限は、80質量%以下が好ましく、70質量%以下がより好ましく、60質量%以下が更に好ましい。 When the composition of the present invention contains a compound having a cyclic ether group as a curable compound, the content of the compound having a cyclic ether group in the total solid content of the composition is preferably 1 to 95 mass%. The lower limit is preferably 2 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more. The upper limit is preferably 80 mass% or less, more preferably 70 mass% or less, and even more preferably 60 mass% or less.
 本発明の組成物が硬化性化合物として樹脂を含む場合、組成物の全固形分中における樹脂の含有量は、1~85質量%が好ましい。下限は2質量%以上が好ましく、5質量%以上がより好ましく、7質量%以上が更に好ましく、10質量%以上が特に好ましい。上限は、80質量%以下が好ましく、75質量%以下がより好ましく、70質量%以下が更に好ましく、40質量%以下が特に好ましい。 When the composition of the present invention contains a resin as a curable compound, the content of the resin in the total solid content of the composition is preferably 1 to 85 mass%. The lower limit is preferably 2 mass% or more, more preferably 5 mass% or more, even more preferably 7 mass% or more, and particularly preferably 10 mass% or more. The upper limit is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, and particularly preferably 40 mass% or less.
 本発明の組成物が分散剤としての樹脂を含有する場合、組成物の全固形分中における分散剤としての樹脂の含有量は、0.1~40質量%が好ましい。上限は、25質量%以下が好ましく、20質量%以下が更に好ましい。下限は、0.5質量%以上が好ましく、1質量%以上が更に好ましい。また、分散剤としての樹脂の含有量は、顔料100質量部に対して、1~100質量部が好ましい。上限は、80質量部以下が好ましく、75質量部以下がより好ましい。下限は、2.5質量部以上が好ましく、5質量部以上がより好ましい。 When the composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant in the total solid content of the composition is preferably 0.1 to 40 mass%. The upper limit is preferably 25 mass% or less, and more preferably 20 mass% or less. The lower limit is preferably 0.5 mass% or more, and more preferably 1 mass% or more. The content of the resin as a dispersant is preferably 1 to 100 mass parts per 100 mass parts of pigment. The upper limit is preferably 80 mass parts or less, and more preferably 75 mass parts or less. The lower limit is preferably 2.5 mass parts or more, and more preferably 5 mass parts or more.
 本発明の組成物は、硬化性化合物を1種のみ含んでいてもよいし、2種以上含んでいてもよい。硬化性化合物を2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The composition of the present invention may contain only one type of curable compound, or may contain two or more types. When two or more types of curable compounds are contained, it is preferable that the total amount thereof is within the above range.
<<溶剤>>
 本発明の組成物は溶剤を含有することが好ましい。溶剤としては、水、有機溶剤が挙げられ、有機溶剤であることが好ましい。有機溶剤としては、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤などが挙げられる。これらの詳細については、国際公開第2015/166779号の段落番号0223を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤も好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、ジクロロメタン、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、3-メトキシプロピオン酸メチル、2-ヘプタノン、2-ペンタノン、3-ペンタノン、4-ヘプタノン、シクロヘキサノン、2-メチルシクロヘキサノン、3-メチルシクロヘキサノン、4-メチルシクロヘキサノン、シクロヘプタノン、シクロオクタノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、3-メトキシ-N,N-ジメチルプロパンアミド、3-ブトキシ-N,N-ジメチルプロパンアミド、プロピレングリコールジアセテート、3-メトキシブタノール、メチルエチルケトン、ガンマブチロラクトン、スルホラン、アニソール、1,4-ジアセトキシブタン、ジエチレングリコールモノエチルエーテルアセタート、二酢酸ブタン-1,3-ジイル、ジプロピレングリコールメチルエーテルアセタート、ジアセトンアルコール(別名としてダイアセトンアルコール、4-ヒドロキシ-4-メチル-2-ペンタノン)、2-メトキシプロピルアセテート、2-メトキシ-1-プロパノール、イソプロピルアルコールなどが挙げられる。ただし有機溶剤としての芳香族炭化水素類(ベンゼン、トルエン、キシレン、エチルベンゼン等)は、環境面等の理由により低減したほうがよい場合がある(例えば、有機溶剤全量に対して、50質量ppm(parts per million)以下とすることもでき、10質量ppm以下とすることもでき、1質量ppm以下とすることもできる)。
<<Solvent>>
The composition of the present invention preferably contains a solvent. Examples of the solvent include water and organic solvents, and organic solvents are preferred. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For details, refer to paragraph 0223 of International Publication No. 2015/166779, the contents of which are incorporated herein by reference. In addition, ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, butyl acetate ... Examples of the diacetate include ethylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol and 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol. However, there are cases where it is better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons, etc. (for example, the amount can be 50 ppm (parts per million) by mass or less, 10 ppm by mass or less, or 1 ppm by mass or less, relative to the total amount of organic solvents).
 本発明においては、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10質量ppb(parts per billion)以下であることが好ましい。必要に応じて質量ppt(parts per trillion)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社が提供している(化学工業日報、2015年11月13日)。 In the present invention, it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent with a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided, for example, by 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、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。 Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter. The filter used for filtration preferably has a pore size of 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 with the same number of atoms but different structures). In addition, the organic solvent may contain only one type of isomer, or multiple types of isomers.
 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 peroxide content in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.
 組成物中における溶剤の含有量は、10~97質量%であることが好ましい。下限は、30質量%以上であることが好ましく、40質量%以上であることがより好ましく、50質量%以上であることが更に好ましく、60質量%以上であることがより一層好ましく、70質量%以上であることが特に好ましい。上限は、96質量%以下であることが好ましく、95質量%以下であることがより好ましい。組成物は溶剤を1種のみ含んでいてもよく、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the solvent in the composition is preferably 10 to 97% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit is preferably 96% by mass or less, and more preferably 95% by mass or less. The composition may contain only one type of solvent, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
<<他の赤外線吸収剤>>
 本発明の組成物は、上述した特定化合物以外の赤外線吸収剤(他の赤外線吸収剤)を含有することができる。更に他の赤外線吸収剤を含有することで、より幅広い波長範囲の赤外線を遮蔽できる膜を形成することができる。他の赤外線吸収剤は、染料であってもよく、顔料(粒子)であってもよい。他の赤外線吸収剤としては、ピロロピロール化合物、ポリメチン化合物、スクアリリウム化合物、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、ジチオレン金属錯体、金属酸化物、金属ホウ化物等が挙げられ、スクアリリウム化合物およびフタロシアニン化合物から選ばれる少なくとも1種であることが好ましい。
<<Other infrared absorbing agents>>
The composition of the present invention may contain an infrared absorbing agent (another infrared absorbing agent) other than the above-mentioned specific compound. By further containing another infrared absorbing agent, a film capable of shielding infrared rays in a wider wavelength range can be formed. The other infrared absorbing agent may be a dye or a pigment (particle). Examples of the other infrared absorbing agent include pyrrolopyrrole compounds, polymethine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, etc., and it is preferable that the other infrared absorbing agent is at least one selected from squarylium compounds and phthalocyanine compounds.
 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2011-068731号公報の段落番号0037~0052に記載の化合物、国際公開第2015/166873号の段落番号0010~0033に記載の化合物などが挙げられる。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、特開2015-176046号公報に記載の化合物、国際公開第2016/190162号の段落番号0072に記載の化合物、特開2016-074649号公報の段落番号0196~0228に記載の化合物、特開2017-067963号公報の段落番号0124に記載の化合物、国際公開第2017/135359号に記載の化合物、特開2017-114956号公報に記載の化合物、特許6197940号公報に記載の化合物、国際公開第2016/120166号に記載の化合物などが挙げられる。ポリメチン化合物としては、特開2009-108267号公報の段落番号0044~0045に記載の化合物、特開2002-194040号公報の段落番号0026~0030に記載の化合物、特開2015-172004号公報に記載の化合物、特開2015-172102号公報に記載の化合物、特開2008-088426号公報に記載の化合物、国際公開第2016/190162号の段落番号0090に記載の化合物、特開2017-031394号公報に記載の化合物、特開2021-134350号公報に記載の化合物、国際公開第2021/085372号に記載の化合物などが挙げられる。クロコニウム化合物としては、特開2017-082029号公報に記載の化合物が挙げられる。イミニウム化合物としては、例えば、特表2008-528706号公報に記載の化合物、特開2012-012399号公報に記載の化合物、特開2007-092060号公報に記載の化合物、国際公開第2018/043564号の段落番号0048~0063に記載の化合物が挙げられる。フタロシアニン化合物としては、特開2012-077153号公報の段落番号0093に記載の化合物、特開2006-343631号公報に記載のオキシチタニウムフタロシアニン、特開2013-195480号公報の段落番号0013~0029に記載の化合物、特許第6081771号公報に記載のバナジウムフタロシアニン化合物、国際公開第2020/071470号に記載の化合物が挙げられる。ナフタロシアニン化合物としては、特開2012-077153号公報の段落番号0093に記載の化合物が挙げられる。ジチオレン金属錯体としては、特許第5733804号公報に記載の化合物が挙げられる。金属酸化物としては、例えば、酸化インジウムスズ、酸化アンチモンスズ、酸化亜鉛、Alドープ酸化亜鉛、フッ素ドープ二酸化スズ、ニオブドープ二酸化チタン、酸化タングステンなどが挙げられる。酸化タングステンの詳細については、特開2016-006476号公報の段落番号0080を参酌でき、この内容は本明細書に組み込まれる。金属ホウ化物としては、ホウ化ランタンなどが挙げられる。ホウ化ランタンの市販品としては、LaB-F(日本新金属(株)製)などが挙げられる。また、金属ホウ化物としては、国際公開第2017/119394号に記載の化合物を用いることもできる。酸化インジウムスズの市販品としては、F-ITO(DOWAハイテック(株)製)などが挙げられる。 Examples of pyrrolopyrrole compounds include compounds described in paragraphs 0016 to 0058 of JP-A-2009-263614, compounds described in paragraphs 0037 to 0052 of JP-A-2011-068731, and compounds described in paragraphs 0010 to 0033 of WO 2015/166873. Examples of squarylium compounds include compounds described in paragraphs 0044 to 0049 of JP-A-2011-208101, compounds described in paragraphs 0060 to 0061 of Japanese Patent No. 6065169, compounds described in paragraphs 0040 of WO 2016/181987, compounds described in JP-A-2015-176046, and compounds described in paragraph 0072 of WO 2016/190162. Compounds, compounds described in paragraphs 0196 to 0228 of JP-A-2016-074649, compounds described in paragraph 0124 of JP-A-2017-067963, compounds described in WO 2017/135359, compounds described in JP-A-2017-114956, compounds described in Japanese Patent No. 6197940, compounds described in WO 2016/120166, and the like. Examples of polymethine compounds include compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, compounds described in paragraphs 0026 to 0030 of JP-A-2002-194040, compounds described in JP-A-2015-172004, compounds described in JP-A-2015-172102, compounds described in JP-A-2008-088426, compounds described in paragraph 0090 of WO 2016/190162, compounds described in JP-A-2017-031394, compounds described in JP-A-2021-134350, compounds described in WO 2021/085372, and the like. Examples of croconium compounds include compounds described in JP-A-2017-082029. Examples of the iminium compound include compounds described in JP-T-2008-528706, compounds described in JP-A-2012-012399, compounds described in JP-A-2007-092060, and compounds described in paragraphs 0048 to 0063 of WO 2018/043564. Examples of the phthalocyanine compound include compounds described in paragraph 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, compounds described in paragraphs 0013 to 0029 of JP-A-2013-195480, vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, and compounds described in WO 2020/071470. Examples of the naphthalocyanine compound include the compounds described in paragraph 0093 of JP 2012-077153 A. Examples of the dithiolene metal complex include the compounds described in Japanese Patent No. 5733804 A. Examples of the metal oxide include indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide. For details of tungsten oxide, refer to paragraph 0080 of JP 2016-006476 A, the contents of which are incorporated herein by reference. Examples of the metal boride include lanthanum boride. Examples of commercially available lanthanum boride include LaB 6 -F (manufactured by Japan New Metals Co., Ltd.). In addition, compounds described in WO 2017/119394 A can also be used as the metal boride. An example of a commercially available indium tin oxide product is F-ITO (manufactured by Dowa Hightec Co., Ltd.).
 赤外線吸収剤としては、特開2017-197437号公報に記載のスクアリリウム化合物、特開2017-025311号公報に記載のスクアリリウム化合物、国際公開第2016/154782号に記載のスクアリリウム化合物、特許第5884953号公報に記載のスクアリリウム化合物、特許第6036689号公報に記載のスクアリリウム化合物、特許第5810604号公報に記載のスクアリリウム化合物、国際公開第2017/213047号の段落番号0090~0107に記載のスクアリリウム化合物、特開2018-054760号公報の段落番号0019~0075に記載のピロール環含有化合物、特開2018-040955号公報の段落番号0078~0082に記載のピロール環含有化合物、特開2018-002773号公報の段落番号0043~0069に記載のピロール環含有化合物、特開2018-041047号公報の段落番号0024~0086に記載のアミドα位に芳香環を有するスクアリリウム化合物、特開2017-179131号公報に記載のアミド連結型スクアリリウム化合物、特開2017-141215号公報に記載のピロールビス型スクアリリウム骨格又はクロコニウム骨格を有する化合物、特開2017-082029号公報に記載されたジヒドロカルバゾールビス型のスクアリリウム化合物、特開2017-068120号公報の段落番号0027~0114に記載の非対称型の化合物、特開2017-067963号公報に記載されたピロール環含有化合物(カルバゾール型)、特許第6251530号公報に記載されたフタロシアニン化合物などを用いることもできる。 As infrared absorbents, squarylium compounds described in JP 2017-197437 A, squarylium compounds described in JP 2017-025311 A, squarylium compounds described in WO 2016/154782 A, squarylium compounds described in Japanese Patent No. 5884953 A, squarylium compounds described in Japanese Patent No. 6036689 A, squarylium compounds described in Japanese Patent No. 5810604 A, squarylium compounds described in paragraphs 0090 to 0107 of WO 2017/213047 A, pyrrole ring-containing compounds described in paragraphs 0019 to 0075 of JP 2018-054760 A, pyrrole ring-containing compounds described in paragraphs 0078 to 0082 of JP 2018-040955 A, and squarylium compounds described in paragraphs 002773 to 0030 of JP 2018-002773 A are examples of the squarylium compounds described in WO 2017/213047 A. Pyrrole ring-containing compounds described in JP 2018-041047 A, squarylium compounds having an aromatic ring at the amide α-position described in paragraphs 0024 to 0086, amide-linked squarylium compounds described in JP 2017-179131 A, compounds having a pyrrole bis-type squarylium skeleton or a croconium skeleton described in JP 2017-141215 A, dihydrocarbazole bis-type squarylium compounds described in JP 2017-082029 A, asymmetric compounds described in paragraphs 0027 to 0114 of JP 2017-068120 A, pyrrole ring-containing compounds (carbazole type) described in JP 2017-067963 A, and phthalocyanine compounds described in Japanese Patent No. 6251530 can also be used.
 他の赤外線吸収剤として、欧州特許第3628645号明細書の段落番号0025に記載の下記式で表される酸化タングステンを用いることもできる。
 M (P(O)
 M、Mはアンモニウムカチオンまたは金属カチオンを表し、aは0.01~0.5であり、bは0~0.5であり、cは1であり、dは2.5~3であり、eは0.01~0.75であり、nは1、2または3であり、mは1、2または3であり、Rは、置換基を有していてもよい炭化水素基を表す。
As another infrared absorbing agent, tungsten oxide represented by the following formula described in paragraph 0025 of European Patent No. 3628645 can also be used.
M 1 a M 2 b W c O d (P (O) n R m ) e
M 1 and M 2 each represent an ammonium cation or a metal cation, a is 0.01 to 0.5, b is 0 to 0.5, c is 1, d is 2.5 to 3, e is 0.01 to 0.75, n is 1, 2 or 3, m is 1, 2 or 3, and R represents a hydrocarbon group which may have a substituent.
 他の赤外線吸収剤の含有量は、上述した特定化合物100質量部に対し1~100質量部であることが好ましく、3~60質量部であることがより好ましく、5~40質量部であることが更に好ましい。
 上述した特定化合物と他の赤外線吸収剤との合計の含有量は、組成物の全固形分中1質量%以上であることが好ましく、3質量%以上であることがより好ましく、5質量%以上であることが更に好ましい。上記合計の含有量の上限は、50質量%以下であることが好ましく、40質量%以下であることがより好ましく、30質量%以下であることが更に好ましい。
The content of the other infrared absorbent is preferably 1 to 100 parts by mass, more preferably 3 to 60 parts by mass, and even more preferably 5 to 40 parts by mass, relative to 100 parts by mass of the specific compound.
The total content of the specific compound and the other infrared absorbing agent is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on the total solid content of the composition. The upper limit of the total content is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
<<顔料誘導体>>
 本発明の組成物は、顔料誘導体を含有することができる。顔料誘導体は分散助剤として用いられる。分散助剤とは、組成物中において顔料の分散性を高めるための素材のことである。
<<Pigment derivatives>>
The composition of the present invention may contain a pigment derivative. The pigment derivative is used as a dispersing aid. A dispersing aid is a material for enhancing the dispersibility of a pigment in a composition.
 顔料誘導体としては、色素構造およびトリアジン構造からなる群より選ばれる少なくとも1種の構造と、酸基または塩基性基とを有する化合物が挙げられる。 Pigment derivatives include compounds having at least one structure selected from the group consisting of a dye structure and a triazine structure, and an acid group or a basic group.
 上記色素構造としては、スクアリリウム色素構造、ピロロピロール色素構造、ジケトピロロピロール色素構造、キナクリドン色素構造、アントラキノン色素構造、ジアントラキノン色素構造、ベンゾイソインドール色素構造、チアジンインジゴ色素構造、アゾ色素構造、キノフタロン色素構造、フタロシアニン色素構造、ナフタロシアニン色素構造、ジオキサジン色素構造、ペリレン色素構造、ペリノン色素構造、ベンゾイミダゾロン色素構造、ベンゾチアゾール色素構造、ベンゾイミダゾール色素構造およびベンゾオキサゾール色素構造が挙げられ、スクアリリウム色素構造、ピロロピロール色素構造、ジケトピロロピロール色素構造、フタロシアニン色素構造、キナクリドン色素構造およびベンゾイミダゾロン色素構造が好ましく、スクアリリウム色素構造およびピロロピロール色素構造がより好ましい。 The above dye structures include squarylium dye structures, pyrrolopyrrole dye structures, diketopyrrolopyrrole dye structures, quinacridone dye structures, anthraquinone dye structures, dianthraquinone dye structures, benzoisoindole dye structures, thiazine indigo dye structures, azo dye structures, quinophthalone dye structures, phthalocyanine dye structures, naphthalocyanine dye structures, dioxazine dye structures, perylene dye structures, perinone dye structures, benzimidazolone dye structures, benzothiazole dye structures, benzimidazole dye structures, and benzoxazole dye structures. Squarylium dye structures, pyrrolopyrrole dye structures, diketopyrrolopyrrole dye structures, phthalocyanine dye structures, quinacridone dye structures, and benzimidazolone dye structures are preferred, and squarylium dye structures and pyrrolopyrrole dye structures are more preferred.
 顔料誘導体が有する酸基としては、カルボキシ基、スルホ基、リン酸基、ボロン酸基、カルボン酸アミド基、スルホン酸アミド基、イミド酸基及びこれらの塩等が挙げられる。塩を構成する原子または原子団としては、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。カルボン酸アミド基としては、-NHCORX1で表される基が好ましい。スルホン酸アミド基としては、-NHSOX2で表される基が好ましい。イミド酸基としては、-SONHSOX3、-CONHSOX4、-CONHCORX5または-SONHCORX6で表される基が好ましく、-SONHSOX3がより好ましい。RX1~RX6は、それぞれ独立に、アルキル基またはアリール基を表す。RX1~RX6が表すアルキル基及びアリール基は、置換基を有してもよい。置換基としてはハロゲン原子であることが好ましく、フッ素原子であることがより好ましい。 Examples of the acid group possessed by the pigment derivative include a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imide acid group, and salts thereof. Examples of atoms or atomic groups constituting the salt include an alkali metal ion (Li + , Na + , K + , etc.), an alkaline earth metal ion (Ca 2+ , Mg 2+ , etc.), an ammonium ion, an imidazolium ion, a pyridinium ion, and a phosphonium ion. A preferred example of the carboxylic acid amide group is a group represented by -NHCOR X1 . A preferred example of the sulfonic acid amide group is a group represented by -NHSO 2 R X2 . A preferred example of the imide acid group is a group represented by -SO 2 NHSO 2 R X3 , -CONHSO 2 R X4 , -CONHCOR X5 , or -SO 2 NHCOR X6 , and -SO 2 NHSO 2 R X3 is more preferred. R x1 to R x6 each independently represent an alkyl group or an aryl group. The alkyl group and aryl group represented by R x1 to R x6 may have a substituent. The substituent is preferably a halogen atom, and more preferably a fluorine atom.
 顔料誘導体が有する塩基性基としては、アミノ基、ピリジニル基およびその塩、アンモニウム基の塩、並びにフタルイミドメチル基が挙げられる。塩を構成する原子または原子団としては、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。 Basic groups contained in pigment derivatives include amino groups, pyridinyl groups and their salts, salts of ammonium groups, and phthalimidomethyl groups. Atoms or atomic groups that constitute the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
 顔料誘導体の具体例としては、国際公開第2016/035695号の段落番号0037~0054に記載の化合物、国際公開第2017/146092号の段落番号0061~0086に記載の化合物、国際公開第2018/230387号の段落番号0017~0068に記載の化合物、国際公開第2020/054718号の段落番号0085~0099に記載の化合物、国際公開第2020/054718号の段落番号0099に記載の化合物、国際公開第2022/085485号の段落0124に記載の化合物、特開2018-168244号公報に記載のベンゾイミダゾロン化合物又はそれらの塩、特許第6996282号の一般式(1)に記載のイソインドリン骨格を有する化合物などが挙げられる。 Specific examples of pigment derivatives include the compounds described in paragraphs 0037 to 0054 of WO 2016/035695, the compounds described in paragraphs 0061 to 0086 of WO 2017/146092, the compounds described in paragraphs 0017 to 0068 of WO 2018/230387, the compounds described in paragraphs 0085 to 0099 of WO 2020/054718, the compounds described in paragraph 0099 of WO 2020/054718, the compounds described in paragraph 0124 of WO 2022/085485, the benzimidazolone compounds or salts thereof described in JP 2018-168244 A, and the compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6,996,282.
 顔料誘導体の含有量は、顔料100質量部に対し、1~50質量部が好ましい。下限値は、3質量部以上が好ましく、5質量部以上がより好ましい。上限値は、40質量部以下が好ましく、30質量部以下がより好ましい。顔料誘導体は1種のみを用いてもよく、2種以上を用いてもよい。2種以上を用いる場合は、合計量が上記範囲となることが好ましい。 The content of the pigment derivative is preferably 1 to 50 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. Only one type of pigment derivative may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.
<<光重合開始剤>>
 本発明の組成物が重合性化合物を含む場合、本発明の組成物は更に光重合開始剤を含有することが好ましい。光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する化合物が好ましい。光重合開始剤は、光ラジカル重合開始剤であることが好ましい。
<<Photopolymerization initiator>>
When the composition of the present invention contains a polymerizable compound, it is preferable that the composition of the present invention further contains a photopolymerization initiator.The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators.For example, a compound having photosensitivity to light rays in the ultraviolet range to the visible range is preferable.The photopolymerization initiator is preferably a photoradical polymerization initiator.
 光重合開始剤としては、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化合物、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、ヘキサアリールビイミダゾール化合物、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および3-アリール置換クマリン化合物であることが好ましく、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、および、アシルホスフィン化合物から選ばれる化合物であることがより好ましく、オキシム化合物であることが更に好ましい。また、光重合開始剤としては、特開2014-130173号公報の段落0065~0111に記載された化合物、特許第6301489号公報に記載された化合物、MATERIAL STAGE 37~60p,vol.19,No.3,2019に記載されたパーオキサイド系光重合開始剤、国際公開第2018/221177号に記載の光重合開始剤、国際公開第2018/110179号に記載の光重合開始剤、特開2019-043864号公報に記載の光重合開始剤、特開2019-044030号公報に記載の光重合開始剤、特開2019-167313号公報に記載の過酸化物系開始剤、特開2020-055992号公報に記載のオキサゾリジン基を有するアミノアセトフェノン系開始剤、特開2013-190459号公報に記載のオキシム系光重合開始剤、特開2020-172619号公報に記載の重合体、国際公開第2020/152120号に記載の式1で表される化合物、特開2021-181406号公報に記載の化合物、特開2022-013379号公報に記載の光重合開始剤、特開2022-015747号公報に記載の式(1)で表される化合物、特表2021-507058号公報に記載のフッ素含有フルオレンオキシムエステル系光開始剤、中国特許出願公開第110764367号明細書に記載の開始剤、特表2022-518535号公報に記載の開始剤、国際公開第2021/175855号に記載の開始剤などが挙げられ、これらの内容は本明細書に組み込まれる。 Photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably 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, a hexaarylbiimidazole compound, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, or a 3-aryl substituted coumarin compound, more preferably a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. In addition, examples of the photopolymerization initiator include the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A, the compounds described in Japanese Patent No. 6301489 A, and the compounds described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, photopolymerization initiators described in WO 2018/221177, photopolymerization initiators described in WO 2018/110179, photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, peroxide-based initiators described in JP 2019-167313 A, aminoacetophenone-based initiators having an oxazolidine group described in JP 2020-055992 A, oxime-based photopolymerization initiators described in JP 2013-190459 A, polymerization initiators described in JP 2020-172619 A Examples of the compound include compounds represented by formula 1 described in WO 2020/152120, compounds described in JP 2021-181406 A, photopolymerization initiators described in JP 2022-013379 A, compounds represented by formula (1) described in JP 2022-015747 A, fluorine-containing fluorene oxime ester photoinitiators described in JP 2021-507058 A, initiators described in China Patent Application Publication No. 110764367, initiators described in JP 2022-518535 A, and initiators described in WO 2021/175855, the contents of which are incorporated herein by reference.
 ヘキサアリールビイミダゾール化合物の具体例としては、2,2’,4-トリス(2-クロロフェニル)-5-(3,4-ジメトキシフェニル)-4,5-ジフェニル-1,1’-ビイミダゾールなどが挙げられる。 Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.
 α-ヒドロキシケトン化合物の市販品としては、Omnirad 184、Omnirad 1173、Omnirad 2959、Omnirad 127(以上、IGM Resins B.V.社製)、Irgacure 184、Irgacure 1173、Irgacure 2959、Irgacure 127(以上、BASF社製)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、Omnirad 907、Omnirad 369、Omnirad 369E、Omnirad 379EG(以上、IGM Resins B.V.社製)、Irgacure 907、Irgacure 369、Irgacure 369E、Irgacure 379EG(以上、BASF社製)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、Omnirad 819、Omnirad TPO(以上、IGM Resins B.V.社製)、Irgacure 819、Irgacure TPO(以上、BASF社製)などが挙げられる。 Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (all manufactured by BASF), etc. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF), etc. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (all manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (all manufactured by BASF), etc.
 オキシム化合物としては、国際公開第2022/085485号の段落番号0142に記載の化合物、特許第5430746号に記載の化合物、特許第5647738号に記載の化合物、特開2021-173858号公報の一般式(1)で表される化合物や段落0022から0024に記載の化合物、特開2021-170089号公報の一般式(1)で表される化合物や段落0117から0120に記載の化合物などが挙げられる。オキシム化合物の具体例としては、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、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、1-[4-(フェニルチオ)フェニル]-3-シクロヘキシル-プロパン-1,2-ジオン-2-(O-アセチルオキシム)などが挙げられる。市販品としては、Irgacure OXE01、Irgacure OXE02、Irgacure OXE03、Irgacure OXE04(以上、BASF社製)、TR-PBG-301、TR-PBG-304、TR-PBG-327(TRONLY社製)、アデカオプトマーN-1919((株)ADEKA製、特開2012-014052号公報に記載の光重合開始剤2)が挙げられる。また、オキシム化合物としては、着色性が無い化合物や、透明性が高く変色し難い化合物を用いることも好ましい。市販品としては、アデカアークルズNCI-730、NCI-831、NCI-930(以上、(株)ADEKA製)などが挙げられる。 Examples of oxime compounds include the compound described in paragraph 0142 of WO 2022/085485, the compound described in Japanese Patent No. 5,430,746, the compound described in Japanese Patent No. 5,647,738, the compound represented by general formula (1) and the compounds described in paragraphs 0022 to 0024 of JP 2021-173858 A, the compound represented by general formula (1) and the compounds described in paragraphs 0117 to 0120 of JP 2021-170089 A, and the like. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, and Irgacure OXE04 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, and TR-PBG-327 (manufactured by TRONLY), and Adeka Optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP 2012-014052 A). In addition, it is also preferable to use a compound that is not colorable or a compound that is highly transparent and does not easily discolor as the oxime compound. Commercially available products include Adeka Arcles NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).
 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、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、フッ素原子を有するオキシム化合物、ニトロ基を有するオキシム化合物、ベンゾフラン骨格を有するオキシム化合物、カルバゾール骨格にヒドロキシ基を有する置換基が結合したオキシム化合物、国際公開第2022/085485号の段落0143~0149に記載の化合物を用いることもできる。 As the photopolymerization initiator, an oxime compound having a fluorene ring, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, an oxime compound having a fluorine atom, an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton, or a compound described in paragraphs 0143 to 0149 of WO 2022/085485 can also be used.
 本発明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、本発明はこれらに限定されるものではない。 Specific examples of oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited to these.
 オキシム化合物は、波長350~500nmの範囲に極大吸収波長を有する化合物が好ましく、波長360~480nmの範囲に極大吸収波長を有する化合物がより好ましい。また、オキシム化合物の波長365nm又は波長405nmにおけるモル吸光係数は、感度の観点から、高いことが好ましく、1000~300000であることがより好ましく、2000~300000であることが更に好ましく、5000~200000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、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 oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1000 to 300,000, even more preferably 2000 to 300,000, and particularly preferably 5000 to 200,000. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using a spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.
 光重合開始剤としては、2官能あるいは3官能以上の光ラジカル重合開始剤を用いてもよい。そのような光ラジカル重合開始剤を用いることにより、光ラジカル重合開始剤の1分子から2つ以上のラジカルが発生するため、良好な感度が得られる。また、非対称構造の化合物を用いた場合においては、結晶性が低下して溶剤などへの溶解性が向上して、経時で析出しにくくなり、組成物の経時安定性を向上させることができる。2官能あるいは3官能以上の光ラジカル重合開始剤の具体例としては、国際公開第2022/065215号の段落0148に記載の化合物が挙げられる。 As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, and improving the stability of the composition over time. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include the compounds described in paragraph 0148 of WO 2022/065215.
 光重合開始剤の含有量は、組成物の全固形分中0.1~40質量%が好ましく、0.5~35質量%がより好ましく、1~30質量%が更に好ましい。組成物は光重合開始剤を1種のみ含んでいてもよく、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the photopolymerization initiator is preferably 0.1 to 40 mass% of the total solid content of the composition, more preferably 0.5 to 35 mass%, and even more preferably 1 to 30 mass%. The composition may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
<<硬化剤>>
 本発明の組成物が環状エーテル基を有する化合物を含む場合、硬化剤をさらに含むことが好ましい。硬化剤としては、例えばアミン系化合物、酸無水物系化合物、アミド系化合物、フェノール化合物、多価カルボン酸、チオール化合物などが挙げられる。硬化剤の具体例としては、コハク酸、トリメリット酸、ピロメリット酸、N,N-ジメチル-4-アミノピリジン、ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)などが挙げられる。硬化剤は、特開2016-075720号公報の段落番号0072~0078に記載の化合物、特開2017-036379号公報に記載の化合物を用いることもできる。硬化剤の含有量は、環状エーテル基を有する化合物の100質量部に対し、0.01~20質量部が好ましく、0.01~10質量部がより好ましく、0.1~6.0質量部がさらに好ましい。
<<Curing agent>>
When the composition of the present invention contains a compound having a cyclic ether group, it is preferable that the composition further contains a curing agent. Examples of the curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, polycarboxylic acids, and thiol compounds. Specific examples of the curing agent include succinic acid, trimellitic acid, pyromellitic acid, N,N-dimethyl-4-aminopyridine, and pentaerythritol tetrakis (3-mercaptopropionate). The curing agent may be a compound described in paragraphs 0072 to 0078 of JP-A-2016-075720 or a compound described in JP-A-2017-036379. The content of the curing agent is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.1 to 6.0 parts by mass, relative to 100 parts by mass of the compound having a cyclic ether group.
<<有彩色着色剤>>
 本発明の組成物は、有彩色着色剤を含有することができる。有彩色着色剤としては、赤色着色剤、緑色着色剤、青色着色剤、黄色着色剤、紫色着色剤およびオレンジ色着色剤が挙げられる。有彩色着色剤は、顔料であってもよく、染料であってもよい。顔料と染料とを併用してもよい。また、顔料は、無機顔料、有機顔料のいずれでもよい。また、顔料には、無機顔料または有機-無機顔料の一部を有機発色団で置換した材料を用いることもできる。無機顔料や有機-無機顔料を有機発色団で置換することで、色相設計をしやすくできる。
<<Chromatic colorants>>
The composition of the present invention may contain a chromatic colorant. Examples of the chromatic colorant include a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant. The chromatic colorant may be a pigment or a dye. A pigment and a dye may be used in combination. The pigment may be either an inorganic pigment or an organic pigment. As the pigment, a material in which an inorganic pigment or an organic-inorganic pigment is partially substituted with an organic chromophore may also be used. By substituting an inorganic pigment or an organic-inorganic pigment with an organic chromophore, it is possible to easily design the hue.
 顔料の平均一次粒子径は、1~200nmが好ましい。下限は5nm以上が好ましく、10nm以上がより好ましい。上限は、180nm以下が好ましく、150nm以下がより好ましく、100nm以下が更に好ましい。なお、本明細書において、顔料の一次粒子径は、顔料の一次粒子を透過型電子顕微鏡により観察し、得られた画像写真から求めることができる。具体的には、顔料の一次粒子の投影面積を求め、それに対応する円相当径を顔料の一次粒子径として算出する。また、本明細書における平均一次粒子径は、400個の顔料の一次粒子についての一次粒子径の算術平均値とする。また、顔料の一次粒子とは、凝集のない独立した粒子をいう。 The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, and more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. In this specification, the primary particle diameter of the pigment can be determined from an image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment. In this specification, the average primary particle diameter is the arithmetic mean value of the primary particle diameters of 400 primary particles of the pigment. Furthermore, the primary particles of the pigment refer to independent particles that are not aggregated.
 有彩色着色剤は、顔料を含むものであることが好ましい。有彩色着色剤中における顔料の含有量は、50質量%以上であることが好ましく、70質量%以上であることがより好ましく、80質量%以上であることが更に好ましく、90質量%以上であることが特に好ましい。顔料としては以下に示すものが挙げられる。 The chromatic colorant preferably contains a pigment. The content of the pigment in the chromatic colorant is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Examples of pigments include the following.
 カラーインデックス(C.I.)Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,215,228,231,232(メチン系),233(キノリン系),234(アミノケトン系),235(アミノケトン系),236(アミノケトン系)等(以上、黄色顔料)、
 C.I.Pigment Orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73等(以上、オレンジ色顔料)、
 C.I.Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291,294(キサンテン系、Organo Ultramarine、Bluish Red),295(モノアゾ系),296(ジアゾ系),297(アミノケトン系)等(以上、赤色顔料)、
 C.I.Pigment Green 7,10,36,37,58,59,62,63,64(フタロシアニン系),65(フタロシアニン系),66(フタロシアニン系)等(以上、緑色顔料)、
 C.I.Pigment Violet 1,19,23,27,32,37,42,60(トリアリールメタン系),61(キサンテン系)等(以上、紫色顔料)、
 C.I.Pigment Blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,29,60,64,66,79,80,87(モノアゾ系),88(メチン系)等(以上、青色顔料)。
Color Index (C.I.) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 13 8, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232 (methine type), 233 (quinoline type), 234 (aminoketone type), 235 (aminoketone type), 236 (aminoketone type) etc. (all yellow pigments),
C.I. Pigment Orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73, etc. (orange pigments)
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294 (xanthene type, Organo Ultramarine, Bluish Red), 295 (monoazo type), 296 (diazo type), 297 (aminoketone type) and the like (all red pigments),
C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine type), 65 (phthalocyanine type), 66 (phthalocyanine type) etc. (all green pigments),
C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane type), 61 (xanthene type) etc. (all purple pigments),
C. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo type), 88 (methine type), etc. (all blue pigments).
 緑色着色剤として、1分子中のハロゲン原子数が平均10~14個であり、臭素原子数が平均8~12個であり、塩素原子数が平均2~5個であるハロゲン化亜鉛フタロシアニン顔料を用いることもできる。具体例としては、国際公開第2015/118720号に記載の化合物が挙げられる。また、緑色着色剤として国際公開第2022/085485号の段落番号0029に記載の化合物、特開2020-070426号公報に記載のアルミニウムフタロシアニン化合物、特表2020-504758号公報に記載のジアリールメタン化合物などを用いることもできる。 As a green colorant, a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can also be used. Specific examples include the compounds described in WO 2015/118720. In addition, as a green colorant, a compound described in paragraph 0029 of WO 2022/085485, an aluminum phthalocyanine compound described in JP 2020-070426 A, a diarylmethane compound described in JP 2020-504758 A, and the like can also be used.
 青色着色剤として、リン原子を有するアルミニウムフタロシアニン化合物を用いることもできる。具体例としては、特開2012-247591号公報の段落番号0022~0030、特開2011-157478号公報の段落番号0047に記載の化合物が挙げられる。 Aluminum phthalocyanine compounds having phosphorus atoms can also be used as blue colorants. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A No. 2012-247591 and paragraph 0047 of JP-A No. 2011-157478.
 黄色着色剤として、国際公開第2022/085485号の段落番号0031~0033に記載の化合物、特開2019-073695号公報に記載のメチン染料、特開2019-073696号公報に記載のメチン染料を用いることができる。 As yellow colorants, the compounds described in paragraphs 0031 to 0033 of WO 2022/085485, the methine dyes described in JP 2019-073695 A, and the methine dyes described in JP 2019-073696 A can be used.
 赤色着色剤として、国際公開第2022/085485号の段落番号0034に記載の化合物、特開2020-085947号公報に記載の臭素化ジケトピロロピロール化合物を用いることもできる。 As a red colorant, the compound described in paragraph 0034 of WO 2022/085485 and the brominated diketopyrrolopyrrole compound described in JP 2020-085947 A can also be used.
 有彩色着色剤には染料を用いることもできる。染料としては特に制限はなく、公知の染料を使用できる。例えば、ピラゾールアゾ系染料、アニリノアゾ系染料、トリアリールメタン系染料、アントラキノン系染料、アントラピリドン系染料、ベンジリデン系染料、オキソノール系染料、ピラゾロトリアゾールアゾ系染料、ピリドンアゾ系染料、シアニン系染料、フェノチアジン系染料、ピロロピラゾールアゾメチン系染料、キサンテン系染料、フタロシアニン系染料、ベンゾピラン系染料、インジゴ系染料、ピロメテン系染料等が挙げられる。また、染料には、特開2012-158649号公報に記載のチアゾール化合物、特開2011-184493号公報に記載のアゾ化合物、特開2011-145540号公報に記載のアゾ化合物を用いることもできる。 Dyes can also be used as chromatic colorants. There are no particular limitations on the dyes, and known dyes can be used. For example, pyrazole azo dyes, anilino azo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, pyrromethene dyes, and the like can be mentioned. In addition, the thiazole compounds described in JP-A-2012-158649, the azo compounds described in JP-A-2011-184493, and the azo compounds described in JP-A-2011-145540 can also be used as dyes.
 有彩色着色剤として、韓国公開特許第10-2020-0028160号公報に記載されたトリアリールメタン染料ポリマー、特開2020-117638号公報に記載のキサンテン化合物、国際公開第2020/174991号に記載のフタロシアニン化合物、特開2020-160279号公報に記載のイソインドリン化合物又はそれらの塩、韓国公開特許第10-2020-0069442号公報に記載の式1で表される化合物、韓国公開特許第10-2020-0069730号公報に記載の式1で表される化合物、韓国公開特許第10-2020-0069070号公報に記載の式1で表される化合物、韓国公開特許第10-2020-0069067号公報に記載の式1で表される化合物、韓国公開特許第10-2020-0069062号公報に記載の式1で表される化合物、特許第6809649号に記載のハロゲン化亜鉛フタロシアニン顔料、特開2020-180176号公報に記載のイソインドリン化合物、特開2021-187913号公報に記載のフェノチアジン系化合物、国際公開第2022/004261号に記載のハロゲン化亜鉛フタロシアニン、国際公開第2021/250883号に記載のハロゲン化亜鉛フタロシアニン、韓国公開特許第10-2020-0030759号公報の式1で表されるキノフタロン化合物、韓国公開特許第10-2020-0061793号公報に記載の高分子染料、特開2022-029701号公報に記載の着色剤、国際公開第2022/014635号に記載のイソインドリン化合物、国際公開第2022/024926号に記載のアルミニウムフタロシアニン化合物、特開2022-045895号公報に記載の化合物、国際公開第2022/050051号に記載の化合物を用いることもできる。有彩色着色剤は、ロタキサンであってもよく、色素骨格はロタキサンの環状構造に使用されていてもよく、棒状構造に使用されていてもよく、両方の構造に使用されていてもよい。 As chromatic colorants, there are used triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in Japanese Patent Publication No. 2020-117638, phthalocyanine compounds described in International Publication No. 2020/174991, isoindoline compounds or salts thereof described in Japanese Patent Publication No. 2020-160279, and compounds of formula 1 described in Korean Patent Publication No. 10-2020-0069442. A compound represented by the formula 1 described in Korean Patent Publication No. 10-2020-0069730, a compound represented by the formula 1 described in Korean Patent Publication No. 10-2020-0069070, a compound represented by the formula 1 described in Korean Patent Publication No. 10-2020-0069067, a compound represented by the formula 1 described in Korean Patent Publication No. 10-2020-0069062, a halogenated compound described in Japanese Patent No. 6809649 Zinc phthalocyanine pigments, isoindoline compounds described in JP 2020-180176 A, phenothiazine compounds described in JP 2021-187913 A, halogenated zinc phthalocyanines described in WO 2022/004261 A, halogenated zinc phthalocyanines described in WO 2021/250883 A, quinophthalone compounds represented by formula 1 in Korean Patent Publication No. 10-2020-0030759 A , polymer dyes described in Korean Patent Publication No. 10-2020-0061793, colorants described in JP 2022-029701, isoindoline compounds described in WO 2022/014635, aluminum phthalocyanine compounds described in WO 2022/024926, compounds described in JP 2022-045895, and compounds described in WO 2022/050051 can also be used. The chromatic colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, may be used in the rod-shaped structure, or may be used in both structures.
 本発明の組成物が、有彩色着色剤を含有する場合、組成物の全固形分中における有彩色着色剤の含有量は、1~50質量%が好ましい。本発明の組成物が、有彩色着色剤を2種以上含む場合、それらの合計量が上記範囲内であることが好ましい。 When the composition of the present invention contains a chromatic colorant, the content of the chromatic colorant in the total solid content of the composition is preferably 1 to 50 mass %. When the composition of the present invention contains two or more chromatic colorants, the total amount thereof is preferably within the above range.
 本発明の組成物を赤外線カットフィルタ用として用いる場合には、本発明の組成物は有彩色着色剤を実質的に含有しないことが好ましい。なお、本発明の組成物が有彩色着色剤を実質的に含有しない場合とは、組成物の全固形分中における有彩色着色剤の含有量が、0.5質量%以下であることを意味し、0.1質量%以下であることが好ましく、有彩色着色剤を含有しないことがより好ましい。 When the composition of the present invention is used as an infrared cut filter, it is preferable that the composition of the present invention is substantially free of chromatic colorants. Note that when the composition of the present invention is substantially free of chromatic colorants, this means that the content of chromatic colorants in the total solid content of the composition is 0.5% by mass or less, preferably 0.1% by mass or less, and more preferably free of chromatic colorants.
<<赤外線を透過させて可視光を遮光する色材>>
 本発明の組成物は、赤外線を透過させて可視光を遮光する色材(以下、可視光を遮光する色材ともいう)を含有することもできる。可視光を遮光する色材を含む組成物は、赤外線透過フィルタ形成用の組成物として好ましく用いられる。
<<Coloring material that transmits infrared rays but blocks visible light>>
The composition of the present invention may also contain a coloring material that transmits infrared light and blocks visible light (hereinafter, also referred to as a coloring material that blocks visible light). A composition containing a coloring material that blocks visible light is preferably used as a composition for forming an infrared transmission filter.
 可視光を遮光する色材は、紫色から赤色の波長領域の光を吸収する色材であることが好ましい。また、可視光を遮光する色材は、波長450~650nmの波長領域の光を遮光する色材であることが好ましい。また、可視光を遮光する色材は、波長900~1500nmの光を透過させる色材であることが好ましい。可視光を遮光する色材は、以下の(A)および(B)の少なくとも一方の要件を満たすことが好ましい。
(A):2種類以上の有彩色着色剤を含み、2種以上の有彩色着色剤の組み合わせで黒色を形成している。
(B):有機系黒色着色剤を含む。
The coloring material that blocks visible light is preferably a coloring material that absorbs light in the purple to red wavelength region. Also, the coloring material that blocks visible light is preferably a coloring material that blocks light in the wavelength region of 450 to 650 nm. Also, the coloring material that blocks visible light is preferably a coloring material that transmits light in the wavelength region of 900 to 1500 nm. The coloring material that blocks visible light preferably satisfies at least one of the following requirements (A) and (B).
(A): Two or more types of chromatic colorants are included, and black is formed by a combination of two or more types of chromatic colorants.
(B): Contains an organic black colorant.
 有彩色着色剤としては、上述したものが挙げられる。有機系黒色着色剤としては、例えば、ビスベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物、アゾ化合物などが挙げられ、ビスベンゾフラノン化合物、ペリレン化合物が好ましい。ビスベンゾフラノン化合物としては、特表2010-534726号公報、特表2012-515233号公報、特表2012-515234号公報などに記載の化合物が挙げられ、例えば、BASF社製の「Irgaphor Black」として入手可能である。ペリレン化合物としては、特開2017-226821号公報の段落番号0016~0020に記載の化合物、C.I.Pigment Black 31、32などが挙げられる。アゾメチン化合物としては、特開平01-170601号公報、特開平02-034664号公報などに記載の化合物が挙げられ、例えば、大日精化社製の「クロモファインブラックA1103」として入手できる。 Examples of chromatic colorants include those mentioned above. Examples of organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. Examples of bisbenzofuranone compounds include compounds described in JP-T-2010-534726, JP-T-2012-515233, and JP-T-2012-515234, and are available as "Irgaphor Black" manufactured by BASF. Examples of perylene compounds include compounds described in paragraphs 0016 to 0020 of JP-A-2017-226821, C.I. Pigment Black 31, 32, and the like. Examples of azomethine compounds include those described in JP-A-01-170601 and JP-A-02-034664, and are available as "Chromofine Black A1103" manufactured by Dainichi Seika Chemicals Co., Ltd.
 2種以上の有彩色着色剤の組み合わせで黒色を形成する場合の、有彩色着色剤の組み合わせとしては、例えば以下の(1)~(8)の態様が挙げられる。
(1)黄色着色剤、青色着色剤、紫色着色剤および赤色着色剤を含有する態様。
(2)黄色着色剤、青色着色剤および赤色着色剤を含有する態様。
(3)黄色着色剤、紫色着色剤および赤色着色剤を含有する態様。
(4)黄色着色剤および紫色着色剤を含有する態様。
(5)緑色着色剤、青色着色剤、紫色着色剤および赤色着色剤を含有する態様。
(6)紫色着色剤およびオレンジ色着色剤を含有する態様。
(7)緑色着色剤、紫色着色剤および赤色着色剤を含有する態様。
(8)緑色着色剤および赤色着色剤を含有する態様。
When black is formed by combining two or more chromatic colorants, the combination of chromatic colorants may be, for example, the following embodiments (1) to (8).
(1) An embodiment containing a yellow colorant, a blue colorant, a purple colorant, and a red colorant.
(2) An embodiment containing a yellow colorant, a blue colorant, and a red colorant.
(3) An embodiment containing a yellow colorant, a purple colorant, and a red colorant.
(4) An embodiment containing a yellow colorant and a purple colorant.
(5) An embodiment containing a green colorant, a blue colorant, a purple colorant, and a red colorant.
(6) An embodiment containing a purple colorant and an orange colorant.
(7) An embodiment containing a green colorant, a purple colorant, and a red colorant.
(8) An embodiment containing a green colorant and a red colorant.
 本発明の組成物が可視光を遮光する色材を含有する場合、組成物の全固形分中における可視光を遮光する色材の含有量は、1~50質量%が好ましい。下限は5質量%以上であることが好ましく、10質量%以上であることがより好ましく、20質量%以上であることが更に好ましく、30質量%以上であることが特に好ましい。 When the composition of the present invention contains a coloring material that blocks visible light, the content of the coloring material that blocks visible light in the total solid content of the composition is preferably 1 to 50 mass%. The lower limit is preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 20 mass% or more, and particularly preferably 30 mass% or more.
 本発明の組成物を赤外線カットフィルタ用として用いる場合には、本発明の組成物は可視光を遮光する色材を実質的に含有しないことが好ましい。なお、本発明の組成物が可視光を遮光する色材を実質的に含有しない場合とは、組成物の全固形分中における可視光を遮光する色材の含有量が、0.5質量%以下であることを意味し、0.1質量%以下であることが好ましく、可視光を遮光する色材を含有しないことがより好ましい。 When the composition of the present invention is used as an infrared cut filter, it is preferable that the composition of the present invention does not substantially contain a coloring material that blocks visible light. Note that when the composition of the present invention does not substantially contain a coloring material that blocks visible light, this means that the content of the coloring material that blocks visible light in the total solid content of the composition is 0.5 mass % or less, preferably 0.1 mass % or less, and it is more preferable that the composition does not contain a coloring material that blocks visible light.
<<界面活性剤>>
 本発明の組成物は界面活性剤を含有することができる。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用することができる。界面活性剤はシリコーン系界面活性剤またはフッ素系界面活性剤であることが好ましい。界面活性剤については、国際公開第2015/166779号の段落番号0238~0245に記載された界面活性剤を参照することができ、この内容は本明細書に組み込まれる。
<<Surfactants>>
The composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants may be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant. For the surfactant, reference may be made to the surfactants described in paragraphs 0238 to 0245 of WO 2015/166779, the contents of which are incorporated herein by reference.
 フッ素系界面活性剤としては、国際公開第2022/085485号の段落番号0167~0173に記載の化合物を用いることができる。 As fluorosurfactants, the compounds described in paragraphs 0167 to 0173 of WO 2022/085485 can be used.
 ノニオン系界面活性剤としては、国際公開第2022/085485号の段落0174に記載の化合物が挙げられる。 Nonionic surfactants include the compounds described in paragraph 0174 of WO 2022/085485.
 シリコーン系界面活性剤としては、例えば、SH8400、SH8400 FLUID、FZ-2122、67 Additive、74 Additive、M Additive、SF 8419 OIL(以上、ダウ・東レ(株)製)、TSF-4440、TSF-4300、TSF-4445、TSF-4460、TSF-4452(以上、モメンティブ・パフォーマンス・マテリアルズ社製)、KP-341、KF-6000、KF-6001、KF-6002、KF-6003(以上、信越化学工業(株)製)、BYK-307、BYK-322、BYK-323、BYK-330、BYK-3760、BYK-UV3510(以上、ビックケミー社製)等が挙げられる。シリコーン系界面活性剤には下記構造の化合物を用いることもできる。
Examples of silicone surfactants include SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. OIL (all manufactured by Dow Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie), etc. As the silicone surfactant, a compound having the following structure can also be used.
 組成物の全固形分中における界面活性剤の含有量は、0.001~1質量%が好ましく、0.001~0.5質量%がより好ましく、0.001~0.2質量%が更に好ましい。組成物は界面活性剤を1種のみ含んでいてもよく、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the surfactant in the total solid content of the composition is preferably 0.001 to 1 mass%, more preferably 0.001 to 0.5 mass%, and even more preferably 0.001 to 0.2 mass%. The composition may contain only one type of surfactant, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
<<重合禁止剤>>
 本発明の組成物は重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、p-メトキシフェノール、ジ-tert-ブチル-p-クレゾール、ピロガロール、tert-ブチルカテコール、ベンゾキノン、4,4’-チオビス(3-メチル-6-tert-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、N-ニトロソフェニルヒドロキシアミン塩(アンモニウム塩、第一セリウム塩等)が挙げられ、p-メトキシフェノールが好ましい。組成物の全固形分中における重合禁止剤の含有量は、0.0001~5質量%が好ましい。組成物は重合禁止剤を1種のみ含んでいてもよく、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。
<<Polymerization inhibitor>>
The composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.), with p-methoxyphenol being preferred. The content of the polymerization inhibitor in the total solid content of the composition is preferably 0.0001 to 5% by mass. The composition may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
<<シランカップリング剤>>
 本発明の組成物はシランカップリング剤を含有することができる。シランカップリング剤は、加水分解性基を有するシラン化合物であることが好ましく、加水分解性基とそれ以外の官能基とを有するシラン化合物であることがより好ましい。加水分解性基とは、ケイ素原子に直結し、加水分解反応および縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。シランカップリング剤は、アルコキシシリル基を有する化合物であることが好ましい。また、加水分解性基以外の官能基としては、例えば、ビニル基、スチリル基、(メタ)アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基、フェニル基などが挙げられ、(メタ)アクリロイル基およびエポキシ基が好ましい。シランカップリング剤は、特開2009-288703号公報の段落番号0018~0036に記載の化合物、特開2009-242604号公報の段落番号0056~0066に記載の化合物が挙げられる。組成物の全固形分中におけるシランカップリング剤の含有量は、0.01~15.0質量%が好ましく、0.05~10.0質量%がより好ましい。組成物はシランカップリング剤を1種のみ含んでいてもよく、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。
<<Silane coupling agents>>
The composition of the present invention may contain a silane coupling agent. The silane coupling agent is preferably a silane compound having a hydrolyzable group, more preferably a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, and an alkoxy group is preferred. The silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, examples of functional groups other than the hydrolyzable group include a vinyl group, a styryl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, and a phenyl group, and an (meth)acryloyl group and an epoxy group are preferred. Examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP-A-2009-288703 and the compounds described in paragraphs 0056 to 0066 of JP-A-2009-242604. The content of the silane coupling agent in the total solid content of the composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass. The composition may contain only one type of silane coupling agent, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably within the above range.
<<紫外線吸収剤>>
 本発明の組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤としては、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物、ジベンゾイル化合物などが挙げられる。このような化合物の具体例としては、特開2009-217221号公報の段落番号0038~0052、特開2012-208374号公報の段落番号0052~0072、特開2013-068814号公報の段落番号0317~0334、特開2016-162946号公報の段落番号0061~0080、国際公開第2021/131355号の段落番号0052、0074、国際公開第2021/132247号の段落番号0022~0024に記載された化合物が挙げられ、これらの内容は本明細書に組み込まれる。紫外線吸収剤の市販品としては、BASF社製のTinuvinシリーズ、Uvinul(ユビナール)シリーズなどが挙げられる。また、ベンゾトリアゾール化合物としては、ミヨシ油脂製のMYUAシリーズ(化学工業日報、2016年2月1日)が挙げられる。紫外線吸収剤は、後述する実施例に記載の化合物、特許第6268967号公報の段落番号0049~0059、国際公開第2016/181987号の段落番号0059~0076に記載された化合物を用いることもできる。組成物の全固形分中における紫外線吸収剤の含有量は、0.01~30質量%が好ましく、0.05~25質量%がより好ましい。組成物は紫外線吸収剤を1種のみ含んでいてもよく、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。
<<Ultraviolet absorbing agent>>
The composition of the present invention may contain an ultraviolet absorbing agent, such as a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or a dibenzoyl compound. Specific examples of such compounds include the compounds described in paragraphs 0038 to 0052 of JP 2009-217221 A, 0052 to 0072 of JP 2012-208374 A, 0317 to 0334 of JP 2013-068814 A, 0061 to 0080 of JP 2016-162946 A, 0052 and 0074 of WO 2021/131355 A, and 0022 to 0024 of WO 2021/132247 A, the contents of which are incorporated herein. Commercially available ultraviolet absorbers include the Tinuvin series and Uvinul series manufactured by BASF Corporation. In addition, examples of the benzotriazole compound include the MYUA series manufactured by Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016). As the ultraviolet absorber, the compounds described in the examples described later, the compounds described in paragraphs 0049-0059 of Japanese Patent No. 6268967, and paragraphs 0059-0076 of International Publication No. 2016/181987 can also be used. The content of the ultraviolet absorber in the total solid content of the composition is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass. The composition may contain only one type of ultraviolet absorber, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
<<酸化防止剤>>
 本発明の組成物は、酸化防止剤を含有することができる。酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤などが挙げられる。フェノール系酸化防止剤としては、ヒンダードフェノール化合物が挙げられる。フェノール系酸化防止剤は、フェノール性ヒドロキシ基に隣接する部位(オルト位)に置換基を有する化合物が好ましい。前述の置換基としては炭素数1~22の置換又は無置換のアルキル基が好ましい。酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。リン系酸化防止剤としては、トリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン、トリス[2-[(4,6,9,11-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-2-イル)オキシ]エチル]アミン、亜リン酸エチルビス(2,4-ジ-tert-ブチル-6-メチルフェニル)、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイトなどが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブAO-20、アデカスタブAO-30、アデカスタブAO-40、アデカスタブAO-50、アデカスタブAO-50F、アデカスタブAO-60、アデカスタブAO-60G、アデカスタブAO-80、アデカスタブAO-330、アデカスタブAO-412S、アデカスタブ2112、アデカスタブPEP-36、アデカスタブHP-10(以上、(株)ADEKA製)、JP-650(城北化学工業(株)製)などが挙げられる。酸化防止剤は、特許第6268967号公報の段落番号0023~0048に記載された化合物、国際公開第2017/006600号に記載された化合物、国際公開第2017/164024号に記載された化合物、韓国公開特許第10-2019-0059371号公報に記載された化合物を使用することもできる。組成物の全固形分中における酸化防止剤の含有量は、0.01~20質量%であることが好ましく、0.3~15質量%であることがより好ましい。組成物は酸化防止剤を1種のみ含んでいてもよく、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。
<<Antioxidants>>
The composition of the present invention may contain an antioxidant. Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of the phenol-based antioxidant include hindered phenol compounds. The phenol-based antioxidant is preferably a compound having a substituent at the site (ortho position) adjacent to the phenolic hydroxy group. The aforementioned substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite, and tris(2,4-di-tert-butylphenyl)phosphite. Examples of commercially available antioxidants include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB 2112, ADK STAB PEP-36, ADK STAB HP-10 (all manufactured by ADEKA CORPORATION), and JP-650 (manufactured by Johoku Chemical Industry Co., Ltd.). The antioxidant may be a compound described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, a compound described in International Publication No. WO 2017/006600, a compound described in International Publication No. WO 2017/164024, or a compound described in Korean Patent Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. The composition may contain only one type of antioxidant, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
<<その他成分>>
 本発明の組成物は、必要に応じて、増感剤、フィラー、熱硬化促進剤、可塑剤及びその他の助剤類(例えば、導電性粒子、消泡剤、難燃剤、レベリング剤、剥離促進剤、香料、表面張力調整剤、連鎖移動剤、潜在酸化防止剤など)を含有してもよい。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、国際公開第2022/085485号の段落0182に記載の化合物を用いることができる。
<<Other ingredients>>
The composition of the present invention may contain, as necessary, a sensitizer, a filler, a heat curing accelerator, a plasticizer, and other auxiliaries (e.g., conductive particles, defoamers, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension regulators, chain transfer agents, latent antioxidants, etc.). By appropriately incorporating these components, properties such as film properties can be adjusted. As these components, the compounds described in paragraph 0182 of WO 2022/085485 can be used.
<収容容器>
 本発明の組成物の収容容器としては、特に限定はなく、公知の収容容器を用いることができる。また、収容容器として、国際公開第2022/085485号の段落0187に記載の容器を用いることができる。
<Containment container>
The container for storing the composition of the present invention is not particularly limited, and a known container can be used. In addition, the container described in paragraph 0187 of WO 2022/085485 can be used as the container.
<組成物の調製方法>
 本発明の組成物は、前述の成分を混合して調製できる。組成物の調製に際しては、全成分を同時に溶剤に溶解または分散して組成物を調製してもよいし、必要に応じては、各成分を適宜配合した2つ以上の溶液または分散液をあらかじめ調製し、使用時(塗布時)にこれらを混合して組成物として調製してもよい。
<Method of preparing the composition>
The composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the composition, all the components may be simultaneously dissolved or dispersed in a solvent to prepare the composition, or, if necessary, two or more solutions or dispersions in which the components are appropriately mixed may be prepared in advance, and these may be mixed at the time of use (at the time of application) to prepare the composition.
 組成物の調製に際して、顔料を分散させるプロセスを含んでいてもよい。顔料を分散させるプロセスにおいて、顔料の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断、キャビテーションなどが挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、ボールミル、ペイントシェーカー、マイクロフルイダイザー、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化、超音波分散などが挙げられる。またサンドミル(ビーズミル)における顔料の粉砕においては、径の小さいビーズを使用する、ビーズの充填率を大きくする事等により粉砕効率を高めた条件で処理することが好ましい。また、粉砕処理後にろ過、遠心分離などで粗粒子を除去することが好ましい。また、顔料を分散させるプロセスおよび分散機は、「分散技術大全集、株式会社情報機構発行、2005年7月15日」や「サスペンション(固/液分散系)を中心とした分散技術と工業的応用の実際 総合資料集、経営開発センター出版部発行、1978年10月10日」、特開2015-157893号公報の段落番号0022に記載のプロセス及び分散機を好適に使用出来る。また顔料を分散させるプロセスにおいては、ソルトミリング工程にて顔料の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器、処理条件等は、例えば特開2015-194521号公報、特開2012-046629号公報の記載を参酌できる。分散に使用するビーズの素材としては、ジルコニア、メノウ、石英、チタニア、タングステンカーバイト、窒化ケイ素、アルミナ、ステンレス鋼およびガラスが挙げられる。また、ビーズには、モース硬度が2以上の無機化合物を使用することもできる。組成物中に上記ビーズが1~10000ppm含まれていてもよい。 The preparation of the composition may include a process for dispersing the pigment. In the process for dispersing the pigment, mechanical forces used to disperse the pigment include compression, squeezing, impact, shear, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion. In addition, when grinding pigments in a sand mill (bead mill), it is preferable to use beads with a small diameter and increase the bead packing rate to perform processing under conditions that increase the grinding efficiency. In addition, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the grinding process. In addition, the process and dispersing machine for dispersing the pigment may be suitably used as described in "Dispersion Technology Encyclopedia, published by Information Technology Co., Ltd., July 15, 2005" or "Dispersion Technology and Industrial Application Practice Focusing on Suspension (Solid/Liquid Dispersion System) - Comprehensive Data Collection, published by Management Development Center Publishing Department, October 10, 1978", and in paragraph number 0022 of JP 2015-157893 A. In addition, in the process for dispersing the pigment, the pigment may be subjected to a fine treatment in a salt milling process. For the materials, equipment, processing conditions, etc. used in the salt milling process, the descriptions in, for example, JP 2015-194521 A and JP 2012-046629 A may be referred to. Examples of materials for the beads used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. The beads may also be made of inorganic compounds with a Mohs hardness of 2 or more. The composition may contain 1 to 10,000 ppm of the above beads.
 組成物の調製にあたり、異物の除去や欠陥の低減などの目的で、組成物をフィルタでろ過することが好ましい。ろ過に用いるフィルタの種類およびろ過方法としては、国際公開第2022/085485号の段落番号0196~0199に記載のフィルタおよびろ過方法が挙げられる。 When preparing the composition, it is preferable to filter the composition with a filter for the purpose of removing foreign matter and reducing defects. Examples of the types of filters and filtration methods used for filtration include the filters and filtration methods described in paragraphs 0196 to 0199 of WO 2022/085485.
<膜>
 次に、本発明の膜について説明する。本発明の膜は、上述した本発明の組成物から得られるものである。本発明の膜は、光学フィルタとして好ましく用いることができる。光学フィルタの用途は、特に限定されないが、赤外線カットフィルタ、赤外線透過フィルタなどが挙げられる。赤外線カットフィルタとしては、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、環境光センサー用の赤外線カットフィルタ(例えば、情報端末装置が置かれた環境の照度や色調を感知してディスプレイの色調を調整する照度センサーや、色調を調整する色補正用センサー)などが挙げられる。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。赤外線透過フィルタとしては、可視光を遮光し、特定の波長以上の赤外線を選択的に透過可能なフィルタが挙げられる。
<Membrane>
Next, the film of the present invention will be described. The film of the present invention is obtained from the composition of the present invention described above. The film of the present invention can be preferably used as an optical filter. The use of the optical filter is not particularly limited, but examples thereof include an infrared cut filter and an infrared transmission filter. Examples of infrared cut filters include an infrared cut filter on the light receiving side of a solid-state imaging element (for example, an infrared cut filter for a wafer level lens), an infrared cut filter on the back side (opposite to the light receiving side) of a solid-state imaging element, and an infrared cut filter for an environmental light sensor (for example, an illuminance sensor that senses the illuminance and color tone of the environment in which an information terminal device is placed and adjusts the color tone of the display, and a color correction sensor that adjusts the color tone). In particular, it can be preferably used as an infrared cut filter on the light receiving side of a solid-state imaging element. Examples of infrared transmission filters include a filter that can block visible light and selectively transmit infrared rays of a specific wavelength or more.
 本発明の膜は、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。また、本発明の膜は、支持体上に積層して用いてもよく、本発明の膜を支持体から剥離して用いてもよい。支持体としては、シリコン基板などの半導体基材や、透明基材が挙げられる。 The film of the present invention may have a pattern, or may be a film without a pattern (flat film). The film of the present invention may be laminated on a support, or may be peeled off from the support. Examples of the support include semiconductor substrates such as silicon substrates, and transparent substrates.
 支持体として用いられる半導体基材上には、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、半導体基材上には、各画素を隔離するブラックマトリクスが形成されていてもよい。また、半導体基材上には、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表面の平坦化のために下塗り層が設けられていてもよい。 A charge-coupled device (CCD), a complementary metal-oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the semiconductor substrate used as a support. A black matrix that isolates each pixel may also be formed on the semiconductor substrate. If necessary, an undercoat layer may be provided on the semiconductor substrate to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface.
 支持体として用いられる透明基材としては、少なくとも可視光を透過できる材料で構成されたものであれば特に限定されない。例えば、ガラス、樹脂などの材質で構成された基材が挙げられる。樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル樹脂、ポリエチレン、ポリプロピレン、エチレン酢酸ビニル共重合体等のポリオレフィン樹脂、ノルボルネン樹脂、ポリアクリレート、ポリメチルメタクリレート等のアクリル樹脂、ウレタン樹脂、塩化ビニル樹脂、フッ素樹脂、ポリカーボネート樹脂、ポリビニルブチラール樹脂、ポリビニルアルコール樹脂等が挙げられる。ガラスとしては、ソーダライムガラス、ホウケイ酸ガラス、無アルカリガラス、石英ガラス、銅を含有するガラスなどが挙げられる。銅を含有するガラスとしては、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。銅を含有するガラスは、市販品を用いることもできる。銅を含有するガラスの市販品としては、NF-50(AGCテクノグラス(株)製)等が挙げられる。 The transparent substrate used as the support is not particularly limited as long as it is made of a material that can transmit at least visible light. For example, substrates made of materials such as glass and resin can be used. Examples of resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer, norbornene resin, acrylic resins such as polyacrylate and polymethyl methacrylate, urethane resin, vinyl chloride resin, fluororesin, polycarbonate resin, polyvinyl butyral resin, and polyvinyl alcohol resin. Examples of glass include soda lime glass, borosilicate glass, alkali-free glass, quartz glass, and glass containing copper. Examples of glass containing copper include phosphate glass containing copper and fluorophosphate glass containing copper. Commercially available glass containing copper can also be used. Commercially available glass containing copper includes NF-50 (manufactured by AGC Technoglass Co., Ltd.).
 本発明の膜の厚さは、目的に応じて適宜調整できる。膜の厚さは200μm以下とすることができ、150μm以下とすることもでき、120μm以下とすることもでき、20μm以下とすることもでき、10μm以下とすることもでき、5μm以下とすることもできる。膜の厚さの下限は0.1μm以上が好ましく、0.2μm以上がより好ましい。 The thickness of the film of the present invention can be adjusted appropriately depending on the purpose. The thickness of the film can be 200 μm or less, 150 μm or less, 120 μm or less, 20 μm or less, 10 μm or less, or 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, and more preferably 0.2 μm or more.
 本発明の膜を赤外線カットフィルタとして用いる場合、本発明の膜は、波長650~1500nm(好ましくは波長660~1200nm、より好ましくは波長660~1000nm)の範囲に極大吸収波長が存在することが好ましい。
 また、波長700~720nmの範囲における平均透過率は10%以下であることが好ましく、7%以下であることがより好ましく、4%以下であることが更に好ましく、2%以下であることが特に好ましい。
 また、波長420~550nmの範囲における平均透過率が86%以上であることが好ましく、89%以上であることがより好ましく、92%以上であることが更に好ましく、95%以上であることが特に好ましい。また、波長420~550nmの全ての範囲での透過率は50%以上であることが好ましく、70%以上であることがより好ましく、80%以上であることが更に好ましい。
 また、波長650~1500nm(好ましくは波長660~1200nm、より好ましくは波長660~1000nm)の範囲の少なくとも1点での透過率が10%以下であることが好ましく、7%以下であることがより好ましく、4%以下であることが更に好ましく、2%以下であることが特に好ましい。
 また、本発明の膜は、極大吸収波長における吸光度を1とした時、波長420~550nmの範囲における平均吸光度が0.030未満であることが好ましく、0.025未満であることがより好ましい。
When the film of the present invention is used as an infrared cut filter, it is preferred that the film of the present invention has a maximum absorption wavelength in the wavelength range of 650 to 1500 nm (preferably 660 to 1200 nm, more preferably 660 to 1000 nm).
Furthermore, the average transmittance in the wavelength range of 700 to 720 nm is preferably 10% or less, more preferably 7% or less, even more preferably 4% or less, and particularly preferably 2% or less.
The average transmittance in the wavelength range of 420 to 550 nm is preferably 86% or more, more preferably 89% or more, even more preferably 92% or more, and particularly preferably 95% or more. The transmittance in the entire wavelength range of 420 to 550 nm is preferably 50% or more, more preferably 70% or more, and even more preferably 80% or more.
In addition, the transmittance at at least one point in the wavelength range of 650 to 1500 nm (preferably a wavelength range of 660 to 1200 nm, more preferably a wavelength range of 660 to 1000 nm) is preferably 10% or less, more preferably 7% or less, even more preferably 4% or less, and particularly preferably 2% or less.
Furthermore, when the absorbance at the maximum absorption wavelength of the film of the present invention is taken as 1, the average absorbance in the wavelength range of 420 to 550 nm is preferably less than 0.030, and more preferably less than 0.025.
 本発明の膜を赤外線透過フィルタとして用いる場合、本発明の膜は、例えば、以下の(i1)~(i3)のいずれかの分光特性を有することが好ましい。
 (i1):波長400~850nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1000~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ。このような分光特性を有する膜は、波長400~850nmの範囲の光を遮光して、波長950nmを超える光を透過させることができる。
 (i2):波長400~950nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1100~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ。このような分光特性を有する膜は、波長400~950nmの範囲の光を遮光して、波長1050nmを超える光を透過させることができる。
 (i3):波長400~1050nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1200~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ。このような分光特性を有する膜は、波長400~1050nmの範囲の光を遮光して、波長1150nmを超える光を透過させることができる。
When the film of the present invention is used as an infrared transmission filter, the film of the present invention preferably has, for example, any one of the following spectral characteristics (i1) to (i3).
(i1): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 850 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1500 nm. A film having such spectral characteristics can block light in the wavelength range of 400 to 850 nm and transmit light with a wavelength of more than 950 nm.
(i2): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1500 nm. A film having such spectral characteristics can block light in the wavelength range of 400 to 950 nm and transmit light with a wavelength of more than 1050 nm.
(i3): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 1050 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1200 to 1500 nm. A film having such spectral characteristics can block light in the wavelength range of 400 to 1050 nm and transmit light with a wavelength of more than 1150 nm.
 本発明の膜は、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。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。本発明の膜を赤外線カットフィルタとして用い、かつ、本発明の膜とカラーフィルタと組み合わせて用いる場合、本発明の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、本発明の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好ましい。積層体においては、本発明の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。本発明の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上に、本発明の膜が形成されていてもよく、本発明の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。 The film of the present invention can also be used in combination with a color filter containing a chromatic colorant. The color filter can be manufactured using a coloring composition containing a chromatic colorant. When the film of the present invention is used as an infrared cut filter and is used in combination with the film of the present invention and a color filter, it is preferable that a color filter is arranged on the optical path of the film of the present invention. For example, it is preferable to use the film of the present invention and a color filter as a laminate by laminating them. In the laminate, the film of the present invention and the color filter may or may not be adjacent to each other in the thickness direction. When the film of the present invention and the color filter are not adjacent to each other in the thickness direction, the film of the present invention may be formed on a support other than the support on which the color filter is formed, and other members constituting a solid-state imaging device (e.g., microlenses, planarization layers, etc.) may be interposed between the film of the present invention and the color filter.
 本発明の膜は、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 of the present invention can be used in various devices such as solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal-oxide semiconductors), infrared sensors, and image display devices.
<膜の製造方法>
 本発明の膜は、本発明の組成物を塗布する工程を経て製造できる。
<Membrane manufacturing method>
The film of the present invention can be produced through a process of applying the composition of the present invention.
 支持体としては、上述したものが挙げられる。組成物の塗布方法としては、スピンコート法などの公知の方法を用いることができる。例えば、国際公開第2022/085485号の段落番号0207に記載の塗布方法を用いることができる。 The support may be any of those mentioned above. A known method such as spin coating may be used as a method for applying the composition. For example, the application method described in paragraph 0207 of WO 2022/085485 may be used.
 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。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℃以上とすることができ、80℃以上とすることもできる。プリベーク時間は、10秒~3000秒が好ましく、40~2500秒がより好ましく、80~220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). When prebaking is performed, the prebaking temperature is preferably 150°C or less, more preferably 120°C or less, and even more preferably 110°C or less. The lower limit can be, for example, 50°C or more, and can also be 80°C or more. The prebaking time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. Drying can be performed using a hot plate, oven, etc.
 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、フォトリソグラフィ法を用いたパターン形成方法が好ましい。なお、本発明の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 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, and a pattern forming method using a photolithography method is preferred. When the film of the present invention is used as a flat film, the pattern forming step does not need to be performed. The pattern forming step will be described in detail below.
(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、本発明の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 by photolithography preferably includes a step of exposing the composition layer formed by applying the composition of the present invention to light in a pattern (exposure step), and a step of developing and removing the composition layer in the unexposed area to form a pattern (development step). If necessary, a step of baking the developed pattern (post-baking step) may be provided. Each step will be described below.
 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、ステッパー露光機やスキャナ露光機などを用いて、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、パターン状に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。 In the exposure process, the composition layer is exposed to light in a pattern. For example, the composition layer can be exposed to light in a pattern by using a stepper exposure machine or a scanner exposure machine to expose the layer through a mask having a specific mask pattern. This allows the exposed parts to harden.
 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線等が挙げられる。また、波長300nm以下の光(好ましくは波長180~300nmの光)を用いることもできる。波長300nm以下の光としては、KrF線(波長248nm)、ArF線(波長193nm)などが挙げられ、KrF線(波長248nm)が好ましい。また、300nm以上の長波な光源も利用できる。 Radiation (light) that can be used for exposure includes g-line and i-line. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), with KrF line (wavelength 248 nm) being preferred. Long-wavelength light sources of 300 nm or more can also be used.
 また、露光に際して、光を連続的に照射して露光してもよく、パルス的に照射して露光(パルス露光)してもよい。なお、パルス露光とは、短時間(例えば、ミリ秒レベル以下)のサイクルで光の照射と休止を繰り返して露光する方式の露光方法のことである。 In addition, during exposure, light may be applied continuously or in pulses (pulse exposure). Pulse exposure is an exposure method in which light is applied and paused repeatedly in short cycles (e.g., milliseconds or less).
 照射量(露光量)は、例えば、0.03~2.5J/cmが好ましく、0.05~1.0J/cmがより好ましい。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%、または、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%、または、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、通常1000W/m~100000W/m(例えば、5000W/m、15000W/m、または、35000W/m)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10000W/m、酸素濃度35体積%で照度20000W/mなどとすることができる。 The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2. The oxygen concentration during exposure can be appropriately selected, and in addition to being performed under air, exposure may be performed under a low-oxygen atmosphere with an oxygen concentration of 19 volume% or less (e.g., 15 volume%, 5 volume%, or substantially oxygen-free), or under a high-oxygen atmosphere with an oxygen concentration of more than 21 volume% (e.g., 22 volume%, 30 volume%, or 50 volume%). The exposure illuminance can be appropriately set, and can usually be selected from the range of 1000 W/m 2 to 100,000 W/m 2 (e.g., 5,000 W/m 2 , 15,000 W/m 2 , or 35,000 W/m 2 ). The oxygen concentration and exposure illuminance may be appropriately combined. For example, the oxygen concentration can be 10% by volume and the illuminance can be 10,000 W/m 2 , and the oxygen concentration can be 35% by volume and the illuminance can be 20,000 W/m 2 .
 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。現像液の温度は、例えば、20~30℃が好ましい。現像時間は、20~180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。 Next, the composition layer in the unexposed parts of the composition layer after exposure is developed and removed to form a pattern. The composition layer in the unexposed parts can be developed and removed using a developer. As a result, the composition layer in the unexposed parts in the exposure process dissolves into the developer, and only the photocured parts remain on the support. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, in order to improve the removability of residues, the process of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.
 現像液は、有機溶剤、アルカリ現像液などが挙げられ、アルカリ現像液が好ましく用いられる。現像液、および、現像後の洗浄(リンス)方法については、国際公開第2022/085485号の段落番号0214に記載の現像液や洗浄方法を用いることができる。 The developer may be an organic solvent or an alkaline developer, with an alkaline developer being preferred. The developer and the washing (rinsing) method after development may be as described in paragraph 0214 of WO 2022/085485.
 現像後、乾燥を施した後に追加露光処理や加熱処理(ポストベーク)を行うことが好ましい。追加露光処理やポストベークは、硬化を完全なものとするための現像後の硬化処理である。ポストベークにおける加熱温度は、例えば100~240℃が好ましく、200~240℃がより好ましい。ポストベークは、現像後の膜を、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、連続式あるいはバッチ式で行うことができる。追加露光処理を行う場合、露光に用いられる光は、波長400nm以下の光であることが好ましい。また、追加露光処理は、韓国公開特許第10-2017-0122130号公報に記載された方法で行ってもよい。 After development and drying, it is preferable to perform additional exposure processing or heating processing (post-baking). Additional exposure processing and post-baking are curing processing after development to complete curing. The heating temperature in post-baking is preferably, for example, 100 to 240°C, more preferably 200 to 240°C. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater to heat the developed film to the above conditions. When additional exposure processing is performed, it is preferable that the light used for exposure has a wavelength of 400 nm or less. In addition, additional exposure processing may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
(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、上記組成物を支持体上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、プリベーク処理を施すことが好ましい。ドライエッチング法でのパターン形成については、特開2013-064993号公報の段落番号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)
The pattern formation by the dry etching method can be performed by a method in which the composition layer formed by applying the composition on a support is cured to form a cured layer, a patterned photoresist layer is formed on the cured layer, and then the patterned photoresist layer is used as a mask to dry etch the cured layer using an etching gas. In forming the photoresist layer, it is preferable to perform a pre-bake treatment. For the pattern formation by the dry etching method, the description in paragraphs 0010 to 0067 of JP 2013-064993 A can be referred to, and the contents thereof are incorporated herein.
<光学フィルタ>
 本発明の光学フィルタは、上述した本発明の膜を有する。光学フィルタの種類としては、赤外線カットフィルタおよび赤外線透過フィルタなどが挙げられる。
<Optical filter>
The optical filter of the present invention has the above-mentioned film of the present invention. Types of the optical filter include an infrared cut filter and an infrared transmission filter.
 本発明の光学フィルタは、上述した本発明の膜の他に、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。紫外線吸収層としては、例えば、国際公開第2015/099060号の段落番号0040~0070、0119~0145に記載された吸収層が挙げられる。誘電体多層膜としては、特開2014-041318号公報の段落番号0255~0259に記載された誘電体多層膜が挙げられる。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板(銅含有ガラス基板)や、銅錯体を含む層(銅錯体含有層)を用いることもできる。銅含有ガラス基板としては、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 optical filter of the present invention may further include a copper-containing layer, a dielectric multilayer film, an ultraviolet absorbing layer, etc., in addition to the above-mentioned film of the present invention. Examples of the ultraviolet absorbing layer include the absorbing layer described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/099060. Examples of the dielectric multilayer film include the dielectric multilayer film described in paragraphs 0255 to 0259 of JP 2014-041318 A. Examples of the copper-containing layer include a glass substrate (copper-containing glass substrate) made of glass containing copper, and a layer containing a copper complex (copper complex-containing layer). Examples of the copper-containing glass substrate include copper-containing phosphate glass and copper-containing fluorophosphate glass. Examples of commercially available copper-containing glass include NF-50 (manufactured by AGC Technoglass Co., Ltd.), BG-60, BG-61 (all manufactured by Schott Co., Ltd.), CD5000 (manufactured by HOYA Co., Ltd.), etc.
<固体撮像素子>
 本発明の固体撮像素子は、上述した本発明の膜を有する。固体撮像素子の構成としては、本発明の膜を有する構成であり、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-state imaging element>
The solid-state imaging device of the present invention has the above-mentioned film of the present invention. The configuration of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device. For example, the following configurations 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およびポリシリコン等からなる転送電極を有し、フォトダイオードおよ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およ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、本発明の膜を有する構成である。更に、デバイス保護膜上であって、本発明の膜の下(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、本発明の膜上に集光手段を有する構成等であってもよい。また、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撮像装置の例としては、特開2012-227478号公報、特開2014-179577号公報に記載された装置が挙げられる。 The solid-state imaging device has a support on which a plurality of photodiodes constituting the light receiving area of the solid-state imaging element and a transfer electrode made of polysilicon or the like are disposed, a light shielding film made of tungsten or the like with only the light receiving portion of the photodiode opened on the photodiode and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the light receiving portion of the photodiode, and a film of the present invention on the device protection film. Furthermore, the device protection film may have a light collecting means (e.g., a microlens, etc., the same below) on the device protection film and below the film of the present invention (on the side closer to the support), or a light collecting means on the film of the present invention. The color filter may have a structure in which a film forming each pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, it is preferable that the partition walls have a lower refractive index than each pixel. Examples of imaging devices having such a structure include the devices described in JP 2012-227478 A and JP 2014-179577 A.
<画像表示装置>
 本発明の画像表示装置は、本発明の膜を有する。画像表示装置としては、液晶表示装置や有機エレクトロルミネッセンス(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。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。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2003-045676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(430~485nm)、緑色領域(530~580nm)及び黄色領域(580~620nm)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(650~700nm)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 of the present invention has the film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. The definition and details of the image display device are described in, for example, "Electronic Display Device (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990)" and "Display Device (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1989)". 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)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied, and the present invention 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 is preferably a tandem structure. The tandem structure of the organic EL element is described in, for example, JP 2003-045676 A and Akiyoshi Mikami (ed.), "The Frontline of Organic EL Technology Development - High Brightness, High Precision, Long Life, Know-How Collection", Technical Information Association, pp. 326-328, 2008. The spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430-485 nm), green region (530-580 nm), and yellow region (580-620 nm). More preferably, the spectrum has a maximum emission peak in the red region (650-700 nm) in addition to these emission peaks.
<赤外線センサ>
 本発明の赤外線センサは、上述した本発明の膜を有する。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、本発明の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 of the present invention has the above-mentioned film of the present invention. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. Hereinafter, one embodiment of the infrared sensor of the present invention 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の撮像領域上には、赤外線カットフィルタ111と、赤外線透過フィルタ114とが配置されている。また、赤外線カットフィルタ111上には、カラーフィルタ112が配置されている。カラーフィルタ112およ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 denotes a solid-state imaging element. An infrared cut filter 111 and an infrared transmission filter 114 are disposed on the imaging region of the solid-state imaging element 110. A color filter 112 is disposed on the infrared cut filter 111. A microlens 115 is disposed on the incident light hν side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed to cover the microlens 115.
 赤外線カットフィルタ111は本発明の組成物を用いて形成することができる。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2014-043556号公報の段落番号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。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。赤外線透過フィルタ114は本発明の組成物を用いて形成することができる。 The infrared cut filter 111 can be formed using the composition of the present invention. The color filter 112 is a color filter in which pixels that transmit and absorb light of specific wavelengths in the visible range are formed, and is not particularly limited, and a conventionally known color filter for forming pixels can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed can be used. For example, the description in paragraphs 0214 to 0263 of JP 2014-043556 A can be referred to, and the contents of this specification can be incorporated herein. The characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used. The infrared transmission filter 114 can be formed using the composition of the present invention.
 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、銅を含有する層および/または誘電体多層膜を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。 In the infrared sensor shown in FIG. 1, an infrared cut filter (another infrared cut filter) other than the infrared cut filter 111 may be further disposed on the planarization layer 116. Examples of the other infrared cut filter include those having a copper-containing layer and/or a dielectric multilayer film. Details of these are as described above. Also, a dual bandpass filter may be used as the other infrared cut filter.
<カメラモジュール>
 本発明のカメラモジュールは、上述した本発明の膜を有する。カメラモジュールの構成としては、本発明の膜を有する構成であり、カメラモジュールとして機能する構成であれば特に限定はない。例えば、カメラモジュールとしては、固体撮像素子、レンズ、及び、固体撮像素子から得られる撮像を処理する回路を有する構成が挙げられる。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2016-006476号公報、及び、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 of the present invention has the above-mentioned film of the present invention. The configuration of the camera module is not particularly limited as long as it has the film of the present invention and functions as a camera module. For example, the camera module may have a configuration having a solid-state image sensor, a lens, and a circuit for processing an image obtained from the solid-state image sensor. The lens used in the camera module and the circuit for processing an image obtained from the solid-state image sensor may be a known one. As examples of the camera module, the camera modules described in JP 2016-006476 A and JP 2014-197190 A can be referred to, and the contents of these are incorporated herein.
 以下に実施例を挙げて本発明を更に具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。なお、以下に示す構造式中、Meはメチル基であり、Etはエチル基である The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. In the structural formula shown below, Me is a methyl group, and Et is an ethyl group.
<合成例>
 (合成例1)化合物A-1の合成
 化合物A-1は、以下のスキームに従い、合成した。
<Synthesis Example>
Synthesis Example 1 Synthesis of Compound A-1 Compound A-1 was synthesized according to the following scheme.
 フラスコに、国際公開第2019/067180号に記載の方法を参考にして合成した化合物a-1を5.0g、化合物b-1を2.4g、イソプロパノールを27.3g加えて、20℃で10分撹拌した後、無水酢酸を5.2g、トリエチルアミンを3.5g加えて、20℃で4時間撹拌した。得られた反応液に酢酸マグネシウム4水和物を3.7g、水を3.9g、メタノールを6.7g加えた。反応液中で析出した結晶をろ過することで、化合物A-1を4.4g得た。
 得られた化合物A-1のMSスペクトル(Pоsi)は649.2(M-1/2Mg+2H)であった。
 また化合物A-1について、UltraWAVE(マイルストーンゼネラル社製)を用い、70%硝酸を添加した条件で湿式灰化によって分解し、得られた分解物をICP(高周波誘導結合プラズマ)質量分析装置(アジレントテクノロジー社製、Agilent7700s)を用いて測定した。また、絶対検量線法にて、化合物A-1が含有するマグネシウム含有量の定量を行った。
 化合物A-1に含まれるマグネシウム含有量の理論値と、ICP質量分析装置により得られたマグネシウム含有量の測定値が一致したため、化合物A-1の対カチオンはマグネシウムであることが確認された。
In a flask, 5.0 g of compound a-1 synthesized with reference to the method described in WO 2019/067180, 2.4 g of compound b-1, and 27.3 g of isopropanol were added, and the mixture was stirred at 20 ° C. for 10 minutes, and then 5.2 g of acetic anhydride and 3.5 g of triethylamine were added and stirred at 20 ° C. for 4 hours. 3.7 g of magnesium acetate tetrahydrate, 3.9 g of water, and 6.7 g of methanol were added to the obtained reaction solution. The crystals precipitated in the reaction solution were filtered to obtain 4.4 g of compound A-1.
The MS spectrum (Posi) of the obtained compound A-1 was 649.2 (M-1/2Mg+2H).
Compound A-1 was decomposed by wet ashing using UltraWAVE (Milestone General) under the condition of adding 70% nitric acid, and the decomposition product was measured using an ICP (inductively coupled plasma) mass spectrometer (Agilent Technologies, Agilent 7700s). The magnesium content of compound A-1 was quantified by the absolute calibration curve method.
Since the theoretical value of the magnesium content contained in compound A-1 and the measured value of the magnesium content obtained by an ICP mass spectrometer were in agreement, it was confirmed that the counter cation of compound A-1 was magnesium.
 (合成例2) 化合物A-5の合成
 化合物a-1の代わりに化合物a-5を用い、化合物b-1の代わりに化合物b-5を用い、酢酸マグネシウム4水和物の代わりに酢酸バリウムを用いた以外は、合成例1の方法と同様の方法で化合物A-5を合成した。
 得られた化合物A-5のMSスペクトル(Pоsi)は891.3(M-1/2Ba+2H)であった。
 また、得られた化合物A-5について、化合物A-1と同様の方法でバリウム含有量の定量を行った。その結果、化合物A-5に含まれるバリウム含有量の理論値と、ICP質量分析装置により得られたバリウム含有量の測定値がよく一致したため、化合物A-5の対カチオンはバリウムであることが確認された。
Synthesis Example 2 Synthesis of Compound A-5 Compound A-5 was synthesized in the same manner as in Synthesis Example 1, except that compound a-5 was used instead of compound a-1, compound b-5 was used instead of compound b-1, and barium acetate was used instead of magnesium acetate tetrahydrate.
The MS spectrum (Posi) of the obtained compound A-5 was 891.3 (M-1/2Ba+2H).
The barium content of the obtained compound A-5 was quantified in the same manner as for compound A-1. As a result, the theoretical value of the barium content contained in compound A-5 and the measured value of the barium content obtained by an ICP mass spectrometer were in good agreement, confirming that the counter cation of compound A-5 was barium.
 (合成例3) 化合物A-11の合成
 化合物a-1の代わりに化合物a-11を用い、化合物b-1の代わりに化合物b-11を用いた以外は、合成例1の方法と同様の方法で化合物A-11を合成した。
 得られた化合物A-11のMSスペクトル(Pоsi)は765.2(M-1/2Mg+2H)であった。
 また、得られた化合物A-11を、化合物A-1と同様の方法でマグネシウム含有量の定量を行った。その結果、化合物A-11に含まれるマグネシウム含有量の理論値と、ICP質量分析装置により得られたマグネシウム含有量の測定値がよく一致したため、化合物A-11の対カチオンはマグネシウムであることが確認された。
Synthesis Example 3 Synthesis of Compound A-11 Compound A-11 was synthesized in the same manner as in Synthesis Example 1, except that compound a-11 was used instead of compound a-1 and compound b-1 was used instead of compound b-1.
The MS spectrum (Posi) of the obtained compound A-11 was 765.2 (M-1/2Mg+2H).
The magnesium content of the obtained compound A-11 was quantified in the same manner as for compound A-1. As a result, the theoretical value of the magnesium content contained in compound A-11 and the measured value of the magnesium content obtained by an ICP mass spectrometer were in good agreement, confirming that the counter cation of compound A-11 was magnesium.
 (合成例4) 化合物A-15の合成
 化合物a-1の代わりに化合物a-15を用い、化合物b-1の代わりに化合物b-15を用いた以外は、合成例1の方法と同様の方法で化合物A-15を合成した。
 得られた化合物A-15のMSスペクトル(Pоsi)は1023.1(M-3/2Mg+4H)であった。
 また、得られた化合物A-15を、化合物A-1と同様の方法でマグネシウム含有量の定量を行った。その結果、化合物A-15に含まれるマグネシウム含有量の理論値と、ICP質量分析装置により得られたマグネシウム含有量の測定値がよく一致したため、化合物A-15の対カチオンはマグネシウムであることが確認された。
Synthesis Example 4 Synthesis of Compound A-15 Compound A-15 was synthesized in the same manner as in Synthesis Example 1, except that compound a-15 was used instead of compound a-1 and compound b-1 was used instead of compound b-1.
The MS spectrum (Posi) of the obtained compound A-15 was 1023.1 (M-3/2Mg+4H).
The magnesium content of the obtained compound A-15 was quantified in the same manner as for compound A-1. As a result, the theoretical value of the magnesium content contained in compound A-15 and the measured value of the magnesium content obtained by an ICP mass spectrometer were in good agreement, confirming that the counter cation of compound A-15 was magnesium.
 (合成例5) 化合物A-18の合成
 酢酸マグネシウム4水和物の代わりに化合物c-18を用いた以外は、合成例1の方法と同様の方法で化合物A-18を合成した。
 得られた化合物A-18のMSスペクトル(Pоsi)は649.2(M-4C-11H-N+2H)であった。
 また、得られた化合物A-18のH NMR (重DMSO)を測定した結果、化合物A-18のカチオン部位とアニオン部位のモル比率は1:2であることが確認されたため、化合物A-18の対カチオンは表記構造の対カチオンであることが確認された。
Synthesis Example 5 Synthesis of Compound A-18 Compound A-18 was synthesized in the same manner as in Synthesis Example 1, except that compound c-18 was used instead of magnesium acetate tetrahydrate.
The MS spectrum (Posi) of the obtained compound A-18 was 649.2 (M-4C-11H-N+2H).
In addition, as a result of measuring the 1 H NMR (d6DMSO) of the obtained compound A-18, it was confirmed that the molar ratio of the cationic moiety to the anionic moiety of compound A-18 was 1:2, and therefore it was confirmed that the counter cation of compound A-18 was the counter cation having the indicated structure.
<分散液の製造>
 下記表に記載の種類の赤外線吸収剤、顔料誘導体、分散樹脂および溶剤を、それぞれ下記の表に記載の質量部で混合し、更に直径0.3mmのジルコニアビーズ117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。なお、赤外線吸収剤は以下の条件で混練研磨処理を施したものを用いた。
<Preparation of Dispersion>
The infrared absorbing agent, pigment derivative, dispersing resin, and solvent of the types shown in the table below were mixed in the parts by mass shown in the table below, and 117 parts by mass of zirconia beads having a diameter of 0.3 mm were further added, and a dispersion liquid was produced by dispersing for 5 hours using a paint shaker, and the beads were separated by filtration. Note that the infrared absorbing agent used had been subjected to a kneading and grinding treatment under the following conditions.
(混練研磨処理条件) 
 赤外線吸収剤10.6質量部、摩砕剤149.4質量部および粘結剤28質量部をラボプラストミル((株)東洋精機製作所製)に添加し、装置中の混練物の温度が70℃になるように温度コントロールして、2時間混練した。摩砕剤は中性無水芒硝E(平均粒子径(体積基準の50%径(D50))=20μm、三田尻化学製)、粘結剤はジエチレングリコールを使用した。混練研磨後の混練物を、24℃の水20Lで水洗処理して摩砕剤および粘結剤を取り除き、加熱オーブンで80℃24時間の処理を行った。
(Kneading and polishing treatment conditions)
10.6 parts by mass of infrared absorber, 149.4 parts by mass of grinding agent and 28 parts by mass of binder were added to a Labo Plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the temperature of the kneaded material in the device was controlled to 70° C., and kneaded for 2 hours. Neutral anhydrous Glauber's salt E (average particle size (volume-based 50% diameter (D50)) = 20 μm, manufactured by Mitajiri Chemical Industry Co., Ltd.) was used as the grinding agent, and diethylene glycol was used as the binder. After kneading and polishing, the kneaded material was washed with 20 L of water at 24° C. to remove the grinding agent and binder, and then treated in a heating oven at 80° C. for 24 hours.
(赤外線吸収剤)
 A-1~A-29:式(1)で表される化合物(特定化合物)の具体例として挙げた化合物A-1~A-29
(Infrared absorber)
A-1 to A-29: Compounds A-1 to A-29 listed as specific examples of the compound represented by formula (1) (specific compound)
(分散樹脂)
 D-1:下記構造の樹脂(酸価=99.1mgKOH/g、重量平均分子量=38000)。主鎖に付記した数値は繰り返し単位のモル比を表し、側鎖に付記した数値は、繰り返し単位の数を表す。
 D-2:下記構造の樹脂(酸価=87.0mgKOH/g、重量平均分子量=18000)。主鎖に付記した数値は繰り返し単位のモル比を表し、側鎖に付記した数値は、繰り返し単位の数を表す。
 D-3:下記構造の樹脂(酸価=85.0mgKOH/g、重量平均分子量=22000)。主鎖に付記した数値は繰り返し単位のモル比を表し、側鎖に付記した数値は、繰り返し単位の数を表す。
 D-4:下記構造の樹脂(酸価=43mgKOH/g、重量平均分子量=9000)。側鎖に付記した数値は繰り返し単位のモル比を表す。
 D-5:下記構造のブロック型樹脂(アミン価=90mgKOH/g、4級アンモニウム塩価=30mgKOH/g、重量平均分子量=9800)。主鎖に付記した数値は繰り返し単位のモル比を表す。
 D-6:下記構造の樹脂(酸価=32.3mgKOH/g、アミン価=45.0mgKOH/g、重量平均分子量=22900)。主鎖に付記した数値は繰り返し単位のモル比を表し、側鎖に付記した数値は、繰り返し単位の数を表す。
(Dispersion Resin)
D-1: Resin having the following structure (acid value = 99.1 mg KOH/g, weight average molecular weight = 38,000). The numbers attached to the main chain indicate the molar ratio of the repeating unit, and the numbers attached to the side chain indicate the number of repeating units.
D-2: Resin having the following structure (acid value = 87.0 mg KOH/g, weight average molecular weight = 18,000). The numbers attached to the main chain indicate the molar ratio of the repeating unit, and the numbers attached to the side chain indicate the number of repeating units.
D-3: Resin having the following structure (acid value = 85.0 mg KOH/g, weight average molecular weight = 22000). The numbers attached to the main chain indicate the molar ratio of the repeating unit, and the numbers attached to the side chain indicate the number of repeating units.
D-4: Resin having the following structure (acid value = 43 mg KOH/g, weight average molecular weight = 9000). The numbers added to the side chains indicate the molar ratio of the repeating units.
D-5: Block type resin having the following structure (amine value = 90 mg KOH/g, quaternary ammonium salt value = 30 mg KOH/g, weight average molecular weight = 9800). The values added to the main chain indicate the molar ratio of the repeating unit.
D-6: Resin having the following structure (acid value = 32.3 mg KOH/g, amine value = 45.0 mg KOH/g, weight average molecular weight = 22900). The numbers attached to the main chain indicate the molar ratio of the repeating unit, and the numbers attached to the side chain indicate the number of repeating units.
(溶剤)
 S-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)
(solvent)
S-1: Propylene glycol monomethyl ether acetate (PGMEA)
<組成物の製造>
(実施例1~62、比較例1)
 下記表に記載の成分を、それぞれ下記の表に記載の質量部で混合して、組成物を製造した。
<Production of Composition>
(Examples 1 to 62, Comparative Example 1)
The components shown in the table below were mixed in the parts by weight shown in the table below to prepare compositions.
(実施例101~149、比較例101)
 各素材を、以下に示す割合で混合して組成物を製造した。
(処方)
 下記表に記載の赤外線吸収剤  ・・・表に記載の質量部
 下記表に記載のエポキシ化合物  ・・・9.3質量部
 下記表に記載の硬化剤(表中に記載がある場合)  ・・・1.6質量部
 下記表に記載の界面活性剤  ・・・0.01質量部
 下記表に記載の酸化防止剤  ・・・2.0質量部
 下記表に記載の溶剤  ・・・表に記載の質量部
(Examples 101 to 149, Comparative Example 101)
The materials were mixed in the ratios shown below to prepare a composition.
(Prescription)
Infrared absorber listed in the table below ... parts by weight listed in the table Epoxy compound listed in the table below ... 9.3 parts by weight Curing agent listed in the table below (if specified in the table) ... 1.6 parts by weight Surfactant listed in the table below ... 0.01 parts by weight Antioxidant listed in the table below ... 2.0 parts by weight Solvent listed in the table below ... parts by weight listed in the table
(実施例201~249、比較例201)
 各素材を、以下に示す割合で混合し、組成物を製造した。
(処方)
 下記表に記載の赤外線吸収剤  ・・・表に記載の質量部
 下記表に記載のエポキシ化合物  ・・・9.3質量部
 下記表に記載の紫外線吸収剤(表中に記載がある場合)  ・・・1.6質量部
 下記表に記載の界面活性剤  ・・・0.01質量部
 下記表に記載の酸化防止剤  ・・・2.0質量部
 下記表に記載の溶剤  ・・・表に記載の質量部
(Examples 201 to 249, Comparative Example 201)
The materials were mixed in the ratios shown below to prepare compositions.
(Prescription)
Infrared absorber listed in the table below ... parts by weight listed in the table Epoxy compound listed in the table below ... 9.3 parts by weight Ultraviolet absorber listed in the table below (if listed in the table) ... 1.6 parts by weight Surfactant listed in the table below ... 0.01 parts by weight Antioxidant listed in the table below ... 2.0 parts by weight Solvent listed in the table below ... parts by weight listed in the table
(実施例301~349、比較例301)
 各素材を、以下に示す割合で混合し、組成物を製造した。
(処方)
 下記表に記載の赤外線吸収剤  ・・・表に記載の質量部
 下記表に記載の樹脂  ・・・10.9質量部
 下記表に記載の酸化防止剤  ・・・2.0質量部
 下記表に記載の溶剤  ・・・表に記載の質量部
(Examples 301 to 349, Comparative Example 301)
The materials were mixed in the ratios shown below to prepare compositions.
(Prescription)
Infrared absorbing agent shown in the table below ... parts by weight shown in the table Resin shown in the table below ... 10.9 parts by weight Antioxidant shown in the table below ... 2.0 parts by weight Solvent shown in the table below ... parts by weight shown in the table
 表中の略語で示す素材の詳細は下記の通りである。 Details of the materials indicated by the abbreviations in the table are as follows:
(分散液、赤外線吸収剤)
 分散液1~29:上述した分散液1~29
 D-Pc-1~D-Pc-3:下記構造の化合物(フタロシアニン化合物、赤外線吸収剤)
 D-SQ-1~D-SQ-4:下記構造の化合物(スクアリリウム化合物、赤外線吸収剤)
 PPM-r1:下記構造の化合物(比較化合物、赤外線吸収剤)
(Dispersion liquid, infrared absorber)
Dispersions 1 to 29: Dispersions 1 to 29 described above
D-Pc-1 to D-Pc-3: Compounds having the following structures (phthalocyanine compounds, infrared absorbers)
D-SQ-1 to D-SQ-4: Compounds having the following structures (squarylium compounds, infrared absorbers)
PPM-r1: Compound having the following structure (comparative compound, infrared absorber)
(樹脂)
 B001:下記構造の樹脂(主鎖に付記した数値は繰り返し単位のモル比である、重量平均分子量17000、分散度2.3)
 B002:下記構造の樹脂(主鎖に付記した数値は繰り返し単位のモル比である、重量平均分子量9700、分散度1.8)
 B003: 下記構造の樹脂(主鎖に付記した数値は繰り返し単位のモル比である、重量平均分子量10100、分散度1.7)
 B004:下記構造の樹脂(主鎖に付記した数値は繰り返し単位のモル比である、重量平均分子量25000、分散度2.2)
 B005:下記構造の樹脂(重量平均分子量137000、数平均分子量32000、ガラス転移温度165℃)
 B006:下記構造の樹脂(重量平均分子量188000、数平均分子量75000、ガラス転移温度285℃)
 B007:下記構造の樹脂(ガラス転移温度310℃、対数粘度0.87)
(resin)
B001: Resin having the following structure (the numbers added to the main chain are the molar ratios of repeating units, weight average molecular weight 17,000, dispersity 2.3)
B002: Resin having the following structure (the numbers added to the main chain are the molar ratios of repeating units, weight average molecular weight 9700, dispersity 1.8)
B003: Resin having the following structure (the numbers attached to the main chain are the molar ratios of repeating units, weight average molecular weight 10100, dispersity 1.7)
B004: Resin having the following structure (the numbers added to the main chain are the molar ratios of repeating units, weight average molecular weight 25,000, dispersity 2.2)
B005: Resin having the following structure (weight average molecular weight 137,000, number average molecular weight 32,000, glass transition temperature 165° C.)
B006: Resin having the following structure (weight average molecular weight 188,000, number average molecular weight 75,000, glass transition temperature 285° C.)
B007: Resin having the following structure (glass transition temperature 310°C, inherent viscosity 0.87)
(光重合開始剤)
 C-1~C-3、C-7、C-22、C-23:下記構造の化合物
(Photopolymerization initiator)
C-1 to C-3, C-7, C-22, C-23: Compounds having the following structures
(重合性化合物)
 M-1:KAYARAD DPHA(日本化薬(株)製、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の混合物)
 M-3:アロニックスM-510(東亞合成(株)製、多塩基酸変性アクリルオリゴマー)
(Polymerizable compound)
M-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
M-3: Aronix M-510 (manufactured by Toagosei Co., Ltd., polybasic acid modified acrylic oligomer)
(界面活性剤)
 F-1:FTX-218D(ネオス社製、フッ素系界面活性剤)
 F-2: 下記構造の化合物(重量平均分子量14000、繰り返し単位の割合を示す%の数値はモル%である)
 F-3:メガファックF-554(DIC(株)製、フッ素系界面活性剤)
(Surfactant)
F-1: FTX-218D (manufactured by Neos Co., Ltd., fluorine-based surfactant)
F-2: Compound having the following structure (weight average molecular weight: 14,000, the percentages indicating the proportions of repeating units are mol%)
F-3: Megafac F-554 (manufactured by DIC Corporation, fluorosurfactant)
(重合禁止剤)
 G-1:p-メトキシフェノール
(Polymerization inhibitor)
G-1: p-Methoxyphenol
(酸化防止剤)
 U-1~U-6:下記構造の化合物
(Antioxidant)
U-1 to U-6: Compounds having the following structures
(エポキシ化合物)
 E-1:下記構造の樹脂(繰り返し単位の数値は質量比である、重量平均分子量20000、数平均分子量8300、エポキシ当量284g/eq、酸価130mgKOH/g、ガラス転移温度136℃)
 E-2:下記構造の樹脂(繰り返し単位の数値は質量比である、重量平均分子量26100、数平均分子量8600、エポキシ当量355g/eq、酸価163mgKOH/g、ガラス転移温度133℃)
 E-3:下記構造の樹脂(繰り返し単位の数値は質量比である、重量平均分子量21100、数平均分子量8500、エポキシ当量355g/eq、酸価130mgKOH/g、ガラス転移温度157℃)
 E-4:下記構造の樹脂(繰り返し単位の数値は質量比である、重量平均分子量18300、数平均分子量9100、エポキシ当量284g/eq、酸価98mgKOH/g、ガラス転移温度134℃)
 E-5:下記構造の樹脂(繰り返し単位の数値は質量比である、重量平均分子量22900、数平均分子量8800、エポキシ当量316g/eq、酸価130mgKOH/g、ガラス転移温度124℃)
(Epoxy Compound)
E-1: Resin having the following structure (the numerical values of the repeating units are mass ratios, weight average molecular weight 20,000, number average molecular weight 8,300, epoxy equivalent 284 g/eq, acid value 130 mgKOH/g, glass transition temperature 136° C.)
E-2: Resin having the following structure (the numerical values of the repeating units are mass ratios, weight average molecular weight 26100, number average molecular weight 8600, epoxy equivalent 355 g/eq, acid value 163 mgKOH/g, glass transition temperature 133° C.)
E-3: Resin having the following structure (the numerical values of the repeating units are mass ratios, weight average molecular weight 21100, number average molecular weight 8500, epoxy equivalent 355 g/eq, acid value 130 mgKOH/g, glass transition temperature 157° C.)
E-4: Resin having the following structure (the numerical values of the repeating units are mass ratios, weight average molecular weight 18300, number average molecular weight 9100, epoxy equivalent 284 g/eq, acid value 98 mgKOH/g, glass transition temperature 134° C.)
E-5: Resin having the following structure (the numerical values of the repeating units are mass ratios, weight average molecular weight 22900, number average molecular weight 8800, epoxy equivalent 316 g/eq, acid value 130 mgKOH/g, glass transition temperature 124° C.)
(硬化剤)
 P-1:トリメリット酸
 P-2:2-エチル-4-メチルイミダゾール
 P-3:メチルテトラヒドロ無水フタル酸
(Hardening agent)
P-1: Trimellitic acid P-2: 2-ethyl-4-methylimidazole P-3: Methyltetrahydrophthalic anhydride
(紫外線吸収剤)
 UV-1:Uvinul3050(BASF製、下記構造の化合物)
 UV-2:Tinuvin477(BASF製、ヒドロキシフェニルトリアジン系紫外線吸収剤)
 UV-3:Tinuvin326(BASF製、下記構造の化合物)
 UV-4:下記構造の化合物
(Ultraviolet absorber)
UV-1: Uvinul 3050 (manufactured by BASF, compound having the following structure)
UV-2: Tinuvin 477 (manufactured by BASF, hydroxyphenyltriazine-based ultraviolet absorber)
UV-3: Tinuvin 326 (manufactured by BASF, compound having the following structure)
UV-4: Compound having the following structure
(溶剤)
 S-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)
 S-2:プロピレングリコールモノメチルエーテル(PGME)
 S-3:シクロペンタノン
 S-4:シクロヘキサノン
 S-5:ジクロロメタン
 S-6:ジメチルアセトアミド
 S-7:3-メトキシプロピオン酸メチル
(solvent)
S-1: Propylene glycol monomethyl ether acetate (PGMEA)
S-2: Propylene glycol monomethyl ether (PGME)
S-3: Cyclopentanone S-4: Cyclohexanone S-5: Dichloromethane S-6: Dimethylacetamide S-7: Methyl 3-methoxypropionate
<膜の製造>
(製造例1) 実施例1~62、比較例1の組成物を用いた膜の製造方法
 各組成物をガラス基板上にスピンコート法で塗布し、ホットプレートを用いて100℃で2分間加熱して組成物層を得た。得られた組成物層を、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を用い、1000mJ/cmの露光量で全面露光した。次いで、ホットプレートを用いて、180℃で5分間加熱し、厚さ1.0μmの膜を製造した。
<Membrane Production>
(Production Example 1) Production method of film using the composition of Examples 1 to 62 and Comparative Example 1 Each composition was applied to a glass substrate by spin coating, and heated at 100°C for 2 minutes using a hot plate to obtain a composition layer. The obtained composition layer was exposed to light at an exposure dose of 1000 mJ/ cm2 using an i-line stepper exposure device FPA-3000i5+ (Canon Corporation). Next, the layer was heated at 180°C for 5 minutes using a hot plate to produce a film having a thickness of 1.0 μm.
(製造例2) 実施例101~149、201~249、比較例101、201の組成物を用いた膜の製造方法
 各組成物をガラス基板上にスピンコート法で塗布し、ホットプレートを用いて100℃で2分間加熱し、次いで200℃で8分間加熱して硬化処理を行い、厚さ1.0μmの膜を得た。
(Production Example 2) Method for producing a film using the composition of Examples 101 to 149, 201 to 249, and Comparative Examples 101 and 201 Each composition was applied onto a glass substrate by spin coating, heated at 100° C. for 2 minutes using a hot plate, and then heated at 200° C. for 8 minutes for hardening treatment to obtain a film having a thickness of 1.0 μm.
(製造例3) 実施例301~349、比較例301の組成物を用いた膜の製造方法
 各組成物を、ガラス基板上にキャストし、20℃で8時間乾燥した後、ガラス基板から剥離した。剥離した塗膜をさらに減圧下100℃で8時間乾燥して、厚さ1.0μm、縦60mm、横60mmの膜を得た。
(Production Example 3) Production method of film using the composition of Examples 301 to 349 and Comparative Example 301 Each composition was cast on a glass substrate, dried at 20° C. for 8 hours, and then peeled off from the glass substrate. The peeled coating film was further dried at 100° C. under reduced pressure for 8 hours to obtain a film having a thickness of 1.0 μm, a length of 60 mm, and a width of 60 mm.
<耐光性の評価>
 得られた膜をキセノンアークランプ式の耐光性試験機を用いて、10万Luxで30時間光照射を行った。光照射前後の膜の分光透過率を測定して下記式より分光変動率ΔTを求め、以下の基準で耐光性を評価した。
 分光変動率ΔT=((T02-T12)/T02)×100
 T02:光照射前の膜の最大吸収波長における分光透過率、
 T12:光照射後の膜の最大吸収波長における分光透過率
-評価基準-
 A:分光変動率ΔTが5%未満である
 B:分光変動率ΔTが5%以上、10%未満である
 C:分光変動率ΔTが10%以上、15%未満である
 D:分光変動率ΔTが15%以上である 
<Evaluation of Light Fastness>
The obtained film was irradiated with light at 100,000 Lux for 30 hours using a xenon arc lamp type light resistance tester. The spectral transmittance of the film was measured before and after the light irradiation, and the spectral fluctuation rate ΔT was calculated using the following formula, and the light resistance was evaluated according to the following criteria.
Spectral fluctuation rate ΔT = ((T02 - T12) / T02) x 100
T02: Spectral transmittance at the maximum absorption wavelength of the film before light irradiation,
T12: Spectral transmittance at the maximum absorption wavelength of the film after light irradiation - Evaluation criteria -
A: The spectral fluctuation rate ΔT is less than 5%. B: The spectral fluctuation rate ΔT is 5% or more and less than 10%. C: The spectral fluctuation rate ΔT is 10% or more and less than 15%. D: The spectral fluctuation rate ΔT is 15% or more.
<耐熱性の評価>
 得られた膜を150℃の恒温器に入れて6ヵ月間保管して耐熱性試験を行い、色度計MCPD-1000(大塚電子(株)製)にて、耐熱性試験前後の膜の色差のΔEab値を測定し、以下の基準で耐熱性を評価した。ΔEab値が小さいほど耐熱性に優れることを意味する。なお、ΔEab値は、CIE1976(L*,a*,b*)空間表色系による以下の色差公式から求められる値である(日本色彩学会編 新編色彩科学ハンドブック(昭和60年)p.266)。
 ΔEab={(ΔL*)+(Δa*)+(Δb*)1/2
-評価基準-
 A:ΔEab値<5
 B:5≦ΔEab値<10
 C:10≦ΔEab値<15
 D:15≦ΔEab値
<Evaluation of heat resistance>
The obtained film was placed in a thermostatic chamber at 150°C and stored for 6 months to carry out a heat resistance test. The ΔEab value of the color difference of the film before and after the heat resistance test was measured using a colorimeter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.), and the heat resistance was evaluated according to the following criteria. The smaller the ΔEab value, the better the heat resistance. The ΔEab value is a value calculated from the following color difference formula according to the CIE1976 (L*, a*, b*) spatial color system (New Color Science Handbook (1985), edited by the Color Science Association of Japan, p. 266).
ΔEab={(ΔL*) 2 +(Δa*) 2 +(Δb*) 2 } 1/2
-Evaluation criteria-
A: ΔEab value < 5
B: 5≦ΔEab value<10
C: 10≦ΔEab value<15
D: 15≦ΔEab value
 上記表に示すように、実施例は、比較例よりも耐光性および耐熱性の評価が優れていた。 As shown in the table above, the examples were rated as superior in light resistance and heat resistance to the comparative examples.
<赤外線吸収組成物の製造>
 国際公開第2020/189458号に記載の実施例201において、実施例105の硬化性組成物を、本明細書に記載の実施例47~55、101~110、201~210、301~310の組成物に変更した以外は、国際公開第2020/189458号に記載の実施例201と同様にして赤外線吸収組成物を製造した。
 得られた赤外線吸収組成物をガラス基材に製膜後の膜厚が1.0μmとなるようにスピンコート塗布し、上述した製造例1~3のいずれかの方法(実施例47~55の組成物を用いた場合は製造例1、実施例101~110、201~210の組成物を用いた場合は製造例2、実施例301~310の組成物を用いた場合は製造例3)で膜を形成した。得られた膜は、可視光領域の波長の光を遮蔽し、赤外領域の波長の光(赤外線)の少なくとも一部を透過させるものであった。得られた膜について、上記と同様の方法で耐熱性および耐光性を評価したところ、すべてAの評価であった。
<Production of infrared absorbing composition>
In Example 201 described in WO 2020/189458, the curable composition of Example 105 was changed to the compositions of Examples 47 to 55, 101 to 110, 201 to 210, and 301 to 310 described herein. An infrared absorbing composition was produced in the same manner as in Example 201 described in WO 2020/189458.
The obtained infrared absorbing composition was spin-coated on a glass substrate so that the film thickness after film formation was 1.0 μm, and a film was formed by any of the methods of Production Examples 1 to 3 described above (Production Example 1 when the composition of Examples 47 to 55 was used, Production Example 2 when the composition of Examples 101 to 110, 201 to 210 was used, and Production Example 3 when the composition of Examples 301 to 310 was used). The obtained film shielded light with a wavelength in the visible light region and transmitted at least a part of light with a wavelength in the infrared region (infrared light). When the heat resistance and light resistance of the obtained films were evaluated by the same method as above, all of them were rated as A.
 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 (11)

  1.  式(1)で表される化合物と、硬化性化合物とを含む、組成物;
     (PM)(Z)   ・・・(1)
     式(1)中、PMは、式(PM1)で表されるアニオンを表し、
     Zは2価以上のカチオンを表し、
     mは0を超える数であって、PMの電荷を中和するために必要な数を表す;
     式(PM1)中、Rpm~Rpmは、それぞれ独立して水素原子または置換基を表し、
     nは1以上の整数を表し、
     Rpm~Rpmの2つが結合して環を形成していてもよく、RpmとTは結合して環を形成していてもよく、RpmとTは結合して環を形成していてもよく、
     Tは式(T1A)、式(T1B)または式(T1C)で表される基であり、
     Tは式(T2A)、式(T2B)または式(T2C)で表される基であり、
     Rpm~Rpm、TおよびTの少なくとも一つはアニオン性基を含む;
     式中、X~Xはそれぞれ独立して、酸素原子、硫黄原子、セレン原子、テルル原子または-NRX1-を表し、RX1は、水素原子、ハロゲン原子、アルキル基、アリール基または複素環基を表し、
     R~R16、および、R31~R46は、それぞれ独立して、水素原子、アルキル基、ハロゲン原子、アルケニル基、アリール基、複素環基、ニトロ基、シアノ基、-ORL1、-C(=O)RL1、-C(=O)ORL1、-OC(=O)RL1、-NRL1L2、-NHC(=O)RL1、-C(=O)NRL1L2、-NHC(=O)ORL1、-OC(=O)NRL1L2、-NHC(=O)NRL1L2、-SRL1、-S(=O)L1、-S(=O)ORL1、-NHS(=O)L1、-S(=O)NRL1L2またはアニオン性基を表し、RL1およびRL2はそれぞれ独立して、水素原子、アルキル基、アルケニル基、アリール基または複素環基を表し、
     R~R16、および、R31~R46のうち隣接する2つは互いに結合して環を形成してもよい。
    A composition comprising a compound represented by formula (1) and a curable compound;
    (PM) (Z) m ... (1)
    In formula (1), PM represents an anion represented by formula (PM1):
    Z represents a divalent or higher cation;
    m is a number greater than 0 and represents the number required to neutralize the charge of PM;
    In formula (PM1), Rpm 1 to Rpm 5 each independently represent a hydrogen atom or a substituent;
    n represents an integer of 1 or more;
    any two of Rpm 2 to Rpm 4 may be bonded to form a ring, Rpm 1 and T 1 may be bonded to form a ring, and Rpm 5 and T 2 may be bonded to form a ring;
    T 1 is a group represented by formula (T 1A ), formula (T 1B ) or formula (T 1C );
    T2 is a group represented by formula ( T2A ), formula ( T2B ) or formula ( T2C ),
    At least one of Rpm 1 to Rpm 5 , T 1 and T 2 contains an anionic group;
    In the formula, X 1 to X 6 each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR X1 -, where R X1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group;
    R 1 to R 16 and R 31 to R 46 each independently represent a hydrogen atom, an alkyl group, a halogen atom, an alkenyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, -OR L1 , -C(=O)R L1 , -C(=O)OR L1 , -OC(=O)R L1 , -NR L1 R L2 , -NHC(=O)R L1 , -C(=O)NR L1 R L2 , -NHC(=O)OR L1 , -OC(=O)NR L1 R L2 , -NHC(=O)NR L1 R L2 , -SR L1 , -S (=O) 2R L1 , -S(=O)2OR L1 , -NHS(=O) 2 R L1 represents -S(=O) 2 NR L1 R L2 or an anionic group, and R L1 and R L2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group;
    Adjacent two of R 1 to R 16 and R 31 to R 46 may be bonded to each other to form a ring.
  2.  X~Xはそれぞれ独立して、酸素原子または硫黄原子である、請求項1に記載の組成物。 The composition according to claim 1, wherein X 1 to X 6 are each independently an oxygen atom or a sulfur atom.
  3.  前記式(1)のPMは、式(PM2)、式(PM3)または式(PM4)で表されるアニオンである、請求項1に記載の組成物;
     式(PM2)中、Rpm11~Rpm15はそれぞれ独立して水素原子または置換基を表し、
     Rpm12とRpm14は結合して環を形成していてもよく、
     Rpm11とTは結合して環を形成していてもよく、Rpm15とTは結合して環を形成していてもよく、
     Tは前記式(T1A)、式(T1B)または式(T1C)で表される基であり、
     Tは前記式(T2A)、式(T2B)または式(T2C)で表される基であり、
     Rpm11~Rpm15、TおよびTの少なくとも一つはアニオン性基を含む;
     式(PM3)中、Rpm21~Rpm27はそれぞれ独立して水素原子または置換基を表し、
     Rpm23とRpm25は結合して環を形成していてもよく、
     Rpm21とTは結合して環を形成していてもよく、Rpm27とTは結合して環を形成していてもよく、
     Tは前記式(T1A)、式(T1B)または式(T1C)で表される基であり、
     Tは前記式(T2A)、式(T2B)または式(T2C)で表される基であり、
     Rpm21~Rpm27、TおよびTの少なくとも一つはアニオン性基を含む;
     式(PM4)中、Rpm31~Rpm39はそれぞれ独立して水素原子または置換基を表し、
     Rpm34とRpm36は結合して環を形成していてもよく、
     Rpm31とTは結合して環を形成していてもよく、Rpm39とTは結合して環を形成していてもよく、
     Tは前記式(T1A)、式(T1B)または式(T1C)で表される基であり、
     Tは前記式(T2A)、式(T2B)または式(T2C)で表される基であり、
     Rpm31~Rpm39、TおよびTの少なくとも一つはアニオン性基を含む。
    The composition according to claim 1, wherein PM in the formula (1) is an anion represented by the formula (PM2), the formula (PM3), or the formula (PM4);
    In formula (PM2), Rpm 11 to Rpm 15 each independently represent a hydrogen atom or a substituent;
    Rpm 12 and Rpm 14 may be bonded to form a ring;
    Rpm 11 and T 1 may be bonded to form a ring, and Rpm 15 and T 2 may be bonded to form a ring;
    T 1 is a group represented by the formula (T 1A ), (T 1B ) or (T 1C );
    T2 is a group represented by the formula ( T2A ), ( T2B ) or ( T2C );
    At least one of Rpm 11 to Rpm 15 , T 1 and T 2 contains an anionic group;
    In formula (PM3), Rpm 21 to Rpm 27 each independently represent a hydrogen atom or a substituent;
    Rpm 23 and Rpm 25 may be bonded to form a ring;
    Rpm 21 and T1 may be bonded to form a ring, Rpm 27 and T2 may be bonded to form a ring,
    T 1 is a group represented by the formula (T 1A ), (T 1B ) or (T 1C );
    T2 is a group represented by the formula ( T2A ), ( T2B ) or ( T2C );
    At least one of Rpm 21 to Rpm 27 , T 1 and T 2 contains an anionic group;
    In formula (PM4), Rpm 31 to Rpm 39 each independently represent a hydrogen atom or a substituent;
    Rpm 34 and Rpm 36 may be bonded to form a ring;
    Rpm 31 and T1 may be bonded to form a ring, and Rpm 39 and T2 may be bonded to form a ring;
    T 1 is a group represented by the formula (T 1A ), (T 1B ) or (T 1C );
    T2 is a group represented by the formula ( T2A ), ( T2B ) or ( T2C );
    At least one of Rpm 31 to Rpm 39 , T 1 and T 2 contains an anionic group.
  4.  前記式(1)で表される化合物以外の赤外線吸収剤を含む、請求項1~3のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 3, which contains an infrared absorbing agent other than the compound represented by formula (1).
  5.  請求項1~3のいずれか1項に記載の組成物を用いて得られる膜。 A film obtained using the composition according to any one of claims 1 to 3.
  6.  請求項5に記載の膜を有する光学フィルタ。 An optical filter having the film according to claim 5.
  7.  請求項5に記載の膜を有する固体撮像素子。 A solid-state imaging device having the film according to claim 5.
  8.  請求項5に記載の膜を有する画像表示装置。 An image display device having the film according to claim 5.
  9.  請求項5に記載の膜を有する赤外線センサ。 An infrared sensor having the film according to claim 5.
  10.  請求項5に記載の膜を有するカメラモジュール。 A camera module having the film according to claim 5.
  11.  式(1)で表される化合物;
     (PM)(Z)   ・・・(1)
     式(1)中、PMは、式(PM1)で表されるアニオンを表し、
     Zは2価以上のカチオンを表し、
     mは0を超える数であって、PMの電荷を中和するために必要な数を表す;
     式(PM1)中、Rpm~Rpmは、それぞれ独立して水素原子または置換基を表し、
     nは1以上の整数を表し、
     Rpm~Rpmの2つが結合して環を形成していてもよく、RpmとTは結合して環を形成していてもよく、RpmとTは結合して環を形成していてもよく、
     Tは式(T1A)、式(T1B)または式(T1C)で表される基であり、
     Tは式(T2A)、式(T2B)または式(T2C)で表される基であり、
     Rpm~Rpm、TおよびTの少なくとも一つはアニオン性基を含む;
     式中、X~Xはそれぞれ独立して、酸素原子、硫黄原子、セレン原子、テルル原子または-NRX1-を表し、RX1は、水素原子、ハロゲン原子、アルキル基、アリール基または複素環基を表し、
     R~R16、および、R31~R46は、それぞれ独立して、水素原子、アルキル基、ハロゲン原子、アルケニル基、アリール基、複素環基、ニトロ基、シアノ基、-ORL1、-C(=O)RL1、-C(=O)ORL1、-OC(=O)RL1、-NRL1L2、-NHC(=O)RL1、-C(=O)NRL1L2、-NHC(=O)ORL1、-OC(=O)NRL1L2、-NHC(=O)NRL1L2、-SRL1、-S(=O)L1、-S(=O)ORL1、-NHS(=O)L1、-S(=O)NRL1L2またはアニオン性基を表し、RL1およびRL2はそれぞれ独立して、水素原子、アルキル基、アルケニル基、アリール基または複素環基を表し、
     R~R16、および、R31~R46のうち隣接する2つは互いに結合して環を形成してもよい。
    A compound represented by formula (1);
    (PM) (Z) m ... (1)
    In formula (1), PM represents an anion represented by formula (PM1):
    Z represents a divalent or higher cation;
    m is a number greater than 0 and represents the number required to neutralize the charge of PM;
    In formula (PM1), Rpm 1 to Rpm 5 each independently represent a hydrogen atom or a substituent;
    n represents an integer of 1 or more;
    any two of Rpm 2 to Rpm 4 may be bonded to form a ring, Rpm 1 and T 1 may be bonded to form a ring, and Rpm 5 and T 2 may be bonded to form a ring;
    T 1 is a group represented by formula (T 1A ), formula (T 1B ) or formula (T 1C );
    T2 is a group represented by formula ( T2A ), formula ( T2B ) or formula ( T2C ),
    At least one of Rpm 1 to Rpm 5 , T 1 and T 2 contains an anionic group;
    In the formula, X 1 to X 6 each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or -NR X1 -, where R X1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group;
    R 1 to R 16 and R 31 to R 46 each independently represent a hydrogen atom, an alkyl group, a halogen atom, an alkenyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, -OR L1 , -C(=O)R L1 , -C(=O)OR L1 , -OC(=O)R L1 , -NR L1 R L2 , -NHC(=O)R L1 , -C(=O)NR L1 R L2 , -NHC(=O)OR L1 , -OC(=O)NR L1 R L2 , -NHC(=O)NR L1 R L2 , -SR L1 , -S (=O) 2R L1 , -S(=O)2OR L1 , -NHS(=O) 2 R L1 represents -S(=O) 2 NR L1 R L2 or an anionic group, and R L1 and R L2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group;
    Adjacent two of R 1 to R 16 and R 31 to R 46 may be bonded to each other to form a ring.
PCT/JP2023/033368 2022-09-26 2023-09-13 Composition, film, optical filter, solid-state imaging element, image display device, infrared sensor, camera module, and compound WO2024070694A1 (en)

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