WO2023042605A1 - Composition, film, optical filter, solid-state imaging element, image display device, and infrared sensor - Google Patents

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

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WO2023042605A1
WO2023042605A1 PCT/JP2022/031413 JP2022031413W WO2023042605A1 WO 2023042605 A1 WO2023042605 A1 WO 2023042605A1 JP 2022031413 W JP2022031413 W JP 2022031413W WO 2023042605 A1 WO2023042605 A1 WO 2023042605A1
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group
formula
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compound
composition
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一成 八木
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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
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415Five-membered rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • C08L101/02Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C08L101/08Carboxyl groups
    • 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
    • C09B57/00Other synthetic dyes of known constitution
    • 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
    • C09B67/0071Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084Dispersions of dyes
    • 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 composition containing a near-infrared absorbing pigment.
  • the present invention also relates to a film, an optical filter, a solid-state imaging device, an image display device and an infrared sensor using the above composition.
  • CCDs charge-coupled devices
  • CMOSs complementary metal-oxide semiconductors
  • CCDs charge-coupled devices
  • CMOSs complementary metal-oxide semiconductors
  • These solid-state imaging devices use silicon photodiodes that are sensitive to infrared rays in their light receiving portions. For this reason, a near-infrared cut filter may be provided to correct visibility.
  • a near-infrared cut filter is manufactured using a composition containing a near-infrared absorbing dye.
  • Pyrrolopyrrole compounds and the like are known as near-infrared absorbing dyes.
  • Patent Document 1 proposes a specific boradiazine compound as a near-infrared absorbing dye.
  • an object of the present invention is to provide a composition capable of forming a film in which foreign matter defects are suppressed.
  • Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, an image display device, and an infrared sensor in which foreign matter defects are suppressed.
  • the present invention provides the following. ⁇ 1> containing a compound represented by formula (1), a near-infrared absorbing pigment, and a curable compound, A composition in which the content of the compound represented by formula (1) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment;
  • R 1 to R 4 each independently represent a substituent, one of R 1 and R 2 is a heteroaryl group, and one of R 3 and R 4 is a heteroaryl group and R5 and R6 each independently represent an alkyl group, an aryl group or a heteroaryl group.
  • one of R 1 and R 2 in the above formula (1) is a heteroaryl group and the other is a cyano group;
  • the heteroaryl group represented by either one of R 1 and R 2 in the above formula (1) and the heteroaryl group represented by either one of R 3 and R 4 in the above formula (1) are independently The composition according to ⁇ 1> or ⁇ 2>, which is a group represented by formula (A-1) or a group represented by formula (A-2);
  • X A1 represents O, S, NR X1 or CR X2 R X3
  • R X1 to R X3 each independently represent a hydrogen atom or a substituent
  • R A1 and R A2 each independently represent a hydrogen atom or a substituent
  • R A1 and R A2 may combine with each other to form a ring
  • * represents a bond
  • Y A1 to Y A4 each independently represent N or CR Y1
  • R Y1 represents a hydrogen atom or a substituent, at least two of Y A1 to Y A4 are CR Y1 ;
  • the compound represented by formula (1) is a compound represented by formula (1-1) or formula (1-2) a composition of In formula (1-1), R 11 and R 12 each independently represent a substituent, R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group; X 11 and X 12 each independently represent O, S, NR X11 or CR X12 R X13 , R X11 to R X13 each independently represent a hydrogen atom or a substituent, R 15 to R 18 each independently represent a hydrogen atom or a substituent, R 15 and R 16 may combine with each other to form a ring, R 17 and R 18 may combine with each other to form a ring; In formula (1-2), R 11 and R 12 each independently represent a substituent, R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group; Y 11 to Y 18 each independently represent N or CR
  • the near-infrared absorbing pigment is a compound represented by formula (P-1);
  • Rp 1 to Rp 4 each independently represent a substituent, one of Rp 1 and Rp 2 is a heteroaryl group, and one of Rp 3 and Rp 4 is a heteroaryl group, Rp 5 and Rp 6 each independently represent an alkyl group, an aryl group or a heteroaryl group;
  • B 1 and B 2 each independently represent BRp 11 Rp 12 , Rp 11 and Rp 12 each independently represent a substituent, Rp 11 and Rp 12 may combine with each other to form a ring.
  • ⁇ 7> The composition according to any one of ⁇ 1> to ⁇ 6>, wherein the curable compound contains a polymerizable compound.
  • ⁇ 8> The composition according to any one of ⁇ 1> to ⁇ 7>, wherein the curable compound contains a resin having an acid group.
  • ⁇ 9> A film obtained using the composition according to any one of ⁇ 1> to ⁇ 8>.
  • ⁇ 10> An optical filter including the film according to ⁇ 9>.
  • ⁇ 11> A solid-state imaging device including the film according to ⁇ 9>.
  • ⁇ 12> An image display device comprising the film according to ⁇ 9>.
  • ⁇ 13> An infrared sensor including the film according to ⁇ 9>.
  • composition capable of forming a film in which foreign matter defects are suppressed, a film in which foreign matter defects are suppressed, an optical filter, a solid-state imaging device, an image display device, and an infrared sensor.
  • FIG. 1 is a schematic diagram illustrating one embodiment of an infrared sensor
  • is used to include the numerical values before and after it as lower and upper limits.
  • a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent.
  • an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • EUV light extreme ultraviolet rays
  • (meth)acrylate” represents both or either acrylate and methacrylate
  • (meth)acryl represents both or either acrylic and methacrylic
  • (meth) ) acryloyl refers to acryloyl and/or methacryloyl.
  • the weight average molecular weight and number average molecular weight are defined as polystyrene equivalent values in gel permeation chromatography (GPC) measurement.
  • GPC gel permeation chromatography
  • near-infrared light refers to light (electromagnetic waves) with a wavelength of 700 to 2500 nm.
  • total solid content refers to the total mass of all components of the composition excluding the solvent.
  • a pigment means a compound that is difficult to dissolve in a solvent.
  • the term "process” includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .
  • composition of the present invention contains a compound represented by formula (1), a near-infrared absorbing pigment, and a curable compound,
  • the content of the compound represented by formula (1) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment.
  • the near-infrared absorbing pigment is designed to absorb light in the long wavelength region, and therefore has a high HOMO (Highest Occupied Molecular Orbital) level and a LUMO (Lowest Unoccupied Molecular Orbital) level. tend to be low. Therefore, a nucleophilic agent such as water or an electrophilic agent such as acid tends to react with the near-infrared absorbing pigment to easily produce decomposition products. It is presumed that crystals of this decomposition product precipitate and grow to become foreign matter. Also, the near-infrared absorbing pigment has a structure with a large ⁇ plane.
  • the decomposition product of the near-infrared absorbing pigment also has the partial structure of the near-infrared absorbing pigment and has a somewhat large ⁇ plane.
  • a compound having a large ⁇ -plane is likely to undergo ⁇ - ⁇ stacking, and is often a highly crystalline compound.
  • the composition of the present invention contains 0.01 to 10 parts by mass of the compound represented by formula (1) with respect to 100 parts by mass of the near-infrared absorbing pigment.
  • the compound represented by the formula (1) is a compound having a large ⁇ -plane structure, it effectively interacts with the near-infrared absorbing pigment or its decomposition product in the composition to form the near-infrared absorbing pigment or It is presumed that the decomposed product is adsorbed on the surface to suppress aggregation and crystallization. Therefore, although the composition of the present invention is a composition containing a near-infrared absorbing pigment, the compound represented by formula (1) is added in an amount of 0.01 to 0.01 per 100 parts by mass of the near-infrared absorbing pigment. By containing 10 parts by mass, it is possible to form a film in which defects are suppressed even when stored for a long period of time under high temperature conditions.
  • composition of the present invention can be used as a composition for optical filters.
  • optical filters include near-infrared cut filters and infrared transmission filters.
  • the composition of the present invention can be preferably used as a composition for pattern formation in photolithography.
  • the composition of the present invention is used as a composition for photolithography, it is preferable to use a resin having an acid group and a polymerizable monomer (monomer type polymerizable compound) as the curable compound, and the acid group and a polymerizable monomer (monomer-type polymerizable compound) having an ethylenically unsaturated bond-containing group.
  • the composition further contains a photopolymerization initiator.
  • composition of the present invention contains a compound represented by formula (1) (hereinafter also referred to as a specific compound).
  • R 1 to R 4 each independently represent a substituent
  • one of R 1 and R 2 is a heteroaryl group
  • one of R 3 and R 4 is a heteroaryl group
  • R5 and R6 each independently represent an alkyl group, an aryl group or a heteroaryl group.
  • Substituents represented by R 1 to R 4 include alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, hetero aryloxycarbonyl group, acyloxy group, amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heteroaryl luthio group, alkylsulfonyl group, arylsulfonyl group, heteroarylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group, ureid
  • Either one of R 1 and R 2 in formula (1) is a heteroaryl group and the other is an electron-withdrawing group, and either one of R 3 and R 4 is a heteroaryl group and the other is an electron-withdrawing group. is preferably a sexual group.
  • a substituent having a positive Hammett's ⁇ p value acts as an electron-withdrawing group.
  • a substituent having a Hammett's ⁇ p value of 0.2 or more can be exemplified as an electron-withdrawing group.
  • the ⁇ p value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more.
  • the upper limit is not particularly limited, it is preferably 0.80 or less.
  • the electron-withdrawing group examples include a cyano group (0.66), a carboxyl group (-COOH: 0.45), an alkoxycarbonyl group (e.g., -COOCH 3 : 0.45), an aryloxycarbonyl group ( For example, —COOCH 3 : 0.44), carbamoyl group (for example —CONH 2 : 0.36), alkylcarbonyl group (for example —COCH 3 : 0.50), arylcarbonyl group (for example —COPh: 0 .43), alkylsulfonyl groups (eg —SO 2 CH 3 : 0.72), arylsulfonyl groups (eg —SO 2 Ph: 0.68), and the like.
  • a cyano group 0.66
  • a carboxyl group -COOH: 0.45
  • an alkoxycarbonyl group e.g., -COOCH 3 : 0.45
  • the electron-withdrawing group is preferably a cyano group, an alkylcarbonyl group, an alkylsulfonyl group and an arylsulfonyl group, more preferably a cyano group. That is, one of R 1 and R 2 and one of R 3 and R 4 in formula (1) are each preferably a cyano group.
  • Ph represents a phenyl group.
  • Hammett's ⁇ p value can be referred to paragraphs 0024 to 0025 of JP-A-2009-263614, the contents of which are incorporated herein.
  • the heteroaryl group represented by either one of R 1 and R 2 in formula (1) and the heteroaryl group represented by either one of R 3 and R 4 in formula (1) are each independently represented by the formula ( A group represented by A-1) or a group represented by formula (A-2) is preferable.
  • the heteroaryl group is a group represented by formula (A-1)
  • a film with more excellent light resistance can be formed.
  • the heteroaryl group is a group represented by formula (A-2)
  • a film with more excellent heat resistance can be formed.
  • X A1 represents O, S, NR X1 or CR X2 R X3 , and R X1 to R X3 each independently represent a hydrogen atom or a substituent, R A1 and R A2 each independently represent a hydrogen atom or a substituent, R A1 and R A2 may combine with each other to form a ring, * represents a bond;
  • Y A1 to Y A4 each independently represent N or CR Y1
  • R Y1 represents a hydrogen atom or a substituent, at least two of Y A1 to Y A4 are CR Y1 ;
  • the R Y1s in the two adjacent CR Y1 may be bonded to each other to form a ring, * represents a bond.
  • X A1 in formula (A-1) represents O, S, NR X1 or CR X2 R X3 , and is preferably O or S because a film with more excellent light resistance can be formed.
  • substituents represented by R X1 to R X3 include the groups exemplified for the substituent T described later and the groups represented by the formula (R-100) described later, and a halogen atom, an alkyl group, an alkenyl group or an alkoxy group. is preferably
  • the number of carbon atoms in the alkyl group and alkoxy group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8.
  • Alkyl groups and alkoxy groups may be linear, branched, or cyclic, but are preferably linear or branched.
  • the alkyl group and alkoxy group may have a substituent or may be unsubstituted. Examples of the substituent include the groups exemplified for the substituent T described below and the groups represented by the formula (R-100) described below.
  • the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 2 to 8 carbon atoms.
  • the alkenyl group may have a substituent or may be unsubstituted.
  • substituent include the groups exemplified for the substituent T described below and the groups represented by the formula (R-100) described below.
  • halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R A1 and R A2 may combine with each other to form a ring.
  • the ring formed may be an aliphatic ring, but is preferably an aromatic ring.
  • the group represented by formula (A-1) includes a group represented by formula (A-1-1) and (A-1 -2) and the like.
  • X A1 represents O, S, NR X1 or CR X2 R X3 , and R X1 to R X3 each independently represent a hydrogen atom or a substituent, R A11 to R A20 each independently represent a hydrogen atom or a substituent, * represents a bond.
  • the substituents represented by R A11 to R A20 include the groups described as the substituents represented by R A1 and R A2 in formula (A-1), and the preferred ranges are also the same.
  • Y A1 to Y A4 in formula (A-2) each independently represent N or CR Y1
  • R Y1 represents a hydrogen atom or a substituent.
  • Examples of the substituent represented by R 1 Y1 include the groups described as the substituent represented by R A1 and R A2 in formula (A-1), and the preferred range is also the same.
  • At least two of Y A1 to Y A4 are CR Y1 .
  • the R Y1s in the two adjacent CR Y1s may combine with each other to form a ring.
  • the ring formed by combining adjacent R Y1s may be an aliphatic ring, but is preferably an aromatic ring.
  • the group represented by formula (A-2) includes groups represented by formulas (A-2-1) to (A-2-3). etc.
  • Y A1 to Y A4 each independently represent N or CR Y1
  • R Y1 represents a hydrogen atom or a substituent
  • R A31 to R A42 each independently represent a hydrogen atom or a substituent
  • * represents a bond.
  • the substituents represented by R A31 to R A42 include the groups described for the substituents represented by R A1 and R A2 in formula (A-1), and the preferred ranges are also the same.
  • R 5 and R 6 in formula (1) each independently represent an alkyl group, an aryl group or a heteroaryl group, preferably an aryl group or a heteroaryl group, more preferably an aryl group.
  • the number of carbon atoms in the alkyl group represented by R 5 and R 6 is preferably 1-30, more preferably 1-20, even more preferably 1-10.
  • the alkyl group may be linear, branched or cyclic, but preferably linear or branched.
  • the aryl group represented by R 5 and R 6 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
  • the number of carbon atoms constituting the ring of the heteroaryl group represented by R 5 and R 6 is preferably 1-30, more preferably 1-12.
  • Types of heteroatoms that constitute the heteroaryl group include, for example, a nitrogen atom, an oxygen atom and a sulfur atom.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1-3, more preferably 1-2.
  • the heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring with 2 to 8 condensed numbers, and still more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers.
  • the heteroaryl group represented by R 5 and R 6 is preferably a group represented by the above formula (A-1) or a group represented by the above formula (A-2).
  • the alkyl group, aryl group and heteroaryl group represented by R5 and R6 may be unsubstituted or may have a substituent.
  • substituents include the groups described below for the substituent T and the groups represented by the formula (R-100).
  • L R1 is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, -O-, -S-, -NR L1 -, -CO-, -COO-, - OCO—, —SO 2 —, or an n+1-valent linking group consisting of a combination thereof
  • R L1 represents a hydrogen atom, an alkyl group or an aryl group
  • X R1 represents an acid group or a basic group
  • n represents an integer of 1 or more, and when n is 1, L R1 may be a single bond
  • * represents a bond.
  • the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-20, more preferably 2-20, still more preferably 2-10, and particularly preferably 2-5.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • the aliphatic hydrocarbon group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
  • the number of carbon atoms in the aromatic hydrocarbon group is preferably 6-18, more preferably 6-14, even more preferably 6-10.
  • the aromatic hydrocarbon group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
  • the heterocyclic group is preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1-3.
  • a heteroatom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 1-30, more preferably 1-18, and more preferably 1-12.
  • heterocyclic groups include piperazine ring group, pyrrolidine ring group, pyrrole ring group, piperidine ring group, pyridine ring group, imidazole ring group, pyrazole ring group, oxazole ring group, thiazole ring group, pyrazine ring group, morpholine ring group, thiazine ring group, indole ring group, isoindole ring group, benzimidazole ring group, purine ring group, quinoline ring group, isoquinoline ring group, quinoxaline ring group, cinnoline ring group, carbazole ring group and the following formula (L- 1) to groups represented by (L-7).
  • * in the formula represents a bond
  • R represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
  • the aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group may have a substituent.
  • substituents include the groups exemplified for the substituent T described later, preferably a halogen atom, more preferably a fluorine atom.
  • the number of carbon atoms in the alkyl group represented by R L1 is preferably 1-20, more preferably 1-15, even more preferably 1-8.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the alkyl group represented by R L1 may further have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
  • the number of carbon atoms in the aryl group represented by R L1 is preferably 6-30, more preferably 6-20, even more preferably 6-12.
  • the aryl group represented by R L1 may further have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
  • Examples of the acid group represented by X R1 of the formula (R-100) include a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imidic acid group and salts thereof.
  • Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ion and the like.
  • a group represented by —NHCOR XR1 is preferable.
  • a group represented by —NHSO 2 R XR2 is preferable.
  • the imidic acid group is preferably a group represented by —SO 2 NHSO 2 R XR3 , —CONHSO 2 R XR4 , —CONHCOR XR5 or —SO 2 NHCOR XR6 , and —CONHSO 2 R XR4 or —SO 2 NHSO 2 R.
  • XR3 is more preferred.
  • R XR1 to R XR6 each independently represent an alkyl group or an aryl group.
  • the alkyl groups and aryl groups represented by R XR1 to R XR6 may have substituents.
  • the substituent is preferably a halogen atom, more preferably a fluorine atom.
  • Basic groups represented by X R1 of formula (R-100) include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups.
  • Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
  • the amino group includes groups represented by —NRx R1 Rx R2 and cyclic amino groups.
  • Rx R1 and Rx R2 each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably an alkyl group.
  • the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, and even more preferably 1-3.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the alkyl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
  • the number of carbon atoms in the aryl group is preferably 6-30, more preferably 6-20, even more preferably 6-12.
  • the aryl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later. Also, Rx R1 and Rx R2 may combine to form a ring. Cyclic amino groups include a pyrrolidine group, a piperidine group, a piperazine group, a morpholine group and the like. These groups may further have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later. Specific examples of substituents include alkyl groups and aryl groups.
  • n in formula (R-100) represents an integer of 1 or more, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
  • R 5 and R 6 in formula (1) at least one of R 5 and R 6 (preferably both R 5 and R 6 ) is a group represented by the above formula (R-100) and an aryl group having as a substituent. According to this aspect, the thermal decomposition temperature of the specific compound is increased, and a film having more excellent heat resistance can be formed.
  • R 5 and R 6 in formula (1) is one in which one of R 5 and R 6 is an aryl group and the other is an alkyl group.
  • the aryl group and the alkyl group may be unsubstituted or may have a substituent. Examples of substituents include alkyl groups, halogen atoms, alkoxy groups, acyloxy groups, and alkoxycarbonyl groups.
  • R 5 and R 6 in formula (1) is an embodiment in which R 5 and R 6 are aryl groups having an alkoxy group having 1 to 16 carbon atoms as a substituent. According to this aspect, a composition with less change in viscosity can be obtained.
  • R 5 and R 6 in formula (1) is an embodiment in which R 5 and R 6 are unsubstituted aryl groups. According to this aspect, the thermal decomposition temperature of the specific compound is increased, and a film having more excellent heat resistance can be formed.
  • the compound represented by Formula (1) is preferably a compound represented by Formula (1-1) or Formula (1-2). By using such a compound, a film having more excellent light resistance can be formed.
  • R 11 and R 12 each independently represent a substituent
  • R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group
  • X 11 and X 12 each independently represent O, S, NR X11 or CR X12 R X13 , R X11 to R X13 each independently represent a hydrogen atom or a substituent
  • R 15 to R 18 each independently represent a hydrogen atom or a substituent
  • R 15 and R 16 may combine with each other to form a ring
  • R 17 and R 18 may combine with each other to form a ring
  • R 11 and R 12 each independently represent a substituent
  • R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group
  • Y 11 to Y 18 each independently represent N or CR Y11
  • R Y11 represents a hydrogen atom or a substituent, at least two of Y 11 to Y 14 and at least two of Y 15 to Y 18
  • the substituents represented by R 11 and R 12 in formula (1-1) and the substituents represented by R 11 and R 12 in formula (1-2) are represented by R 1 to R 4 in formula (1).
  • the groups described as substituents can be mentioned, and electron-withdrawing groups are preferred.
  • the substituents represented by R 11 and R 12 in formula (1-1) and the substituents represented by R 11 and R 12 in formula (1-2) are a cyano group, An alkylcarbonyl group, an alkylsulfonyl group or an arylsulfonyl group is preferable, and a cyano group is more preferable.
  • R 13 and R 14 in formula (1-1) and R 13 and R 14 in formula (1-2) have the same meanings as R 5 and R 6 in formula (1), and the preferred ranges are also the same. .
  • X 11 and X 12 in formula (1-1) each independently represent O, S, NR X11 or CR X12 R X13 , and are O or S is preferred.
  • the substituents represented by R X11 to R X13 include the groups described as the substituents represented by R X1 to R X3 in formula (A-1) above, and the preferred ranges are also the same.
  • the substituents represented by R 15 to R 18 in formula (1-1) include the groups described as the substituents represented by R A1 and R A2 in formula (A-1), and the preferred ranges are the same.
  • R 15 and R 16 may combine to form a ring
  • R 17 and R 18 may combine to form a ring.
  • the ring formed by combining these groups may be an aliphatic ring, but is preferably an aromatic ring.
  • Y 11 to Y 18 in formula (1-2) each independently represent N or CR Y11
  • R Y11 represents a hydrogen atom or a substituent
  • at least two of Y 11 to Y 14 and Y 15 to Y At least two of 18 are CR Y11
  • Examples of the substituent represented by R 1 Y11 include the groups described for the substituent represented by R A1 and R A2 in formula (A-1), and the preferred range is also the same.
  • R Y11 in two adjacent CR Y11 may be bonded to each other to form a ring
  • the ring formed by combining these groups may be an aliphatic ring, but is preferably an aromatic ring.
  • Substituent T includes the following groups.
  • Halogen atom e.g., fluorine atom, chlorine atom, bromine atom, iodine atom
  • alkyl group preferably alkyl group having 1 to 30 carbon atoms
  • alkenyl group preferably alkenyl group having 2 to 30 carbon atoms
  • 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 heteroaryl group preferably a heteroaryl group having 1 to 30 carbon atoms
  • an amino group preferably amino group having 0 to 30 carbon atoms
  • alkoxy group preferably alkoxy group having 1 to 30 carbon atoms
  • aryloxy group preferably aryloxy group having 6 to 30 carbon atoms
  • heteroaryloxy group preferably carbon 1 to 30 heteroaryloxy groups
  • acyl groups preferably acyl groups having 2 to 30 carbon
  • the solubility of the specific compound in 100 g of propylene glycol methyl ether acetate at 25°C is preferably 0.1 g or more, more preferably 0.2 g or more, and even more preferably 0.5 g or more.
  • Specific examples of the specific compounds include compounds (PP-001 to PP-010) having structures described in Examples described later.
  • the content of the specific compound is 0.01 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment.
  • the upper limit is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.8 parts by mass or less for the reason that the effects of the present invention are exhibited more remarkably.
  • the lower limit is preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more.
  • the content of the specific compound is preferably 0.002% by mass or more, more preferably 0.006% by mass or more, and more preferably 0.01% by mass or more in the total solid content of the composition. More preferred.
  • the upper limit is preferably 2% by mass or less, more preferably 0.2% by mass or less, and even more preferably 0.1% by 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 the composition of the present invention contains two or more specific compounds, precipitation of crystals of the specific compound can be suppressed even if the amount of the specific compound added is increased. When the composition of the present invention contains two or more specific compounds, it is preferable not to use a compound having an acid group and a compound having a basic group together from the viewpoint of preventing crystal precipitation due to salt formation. When the composition of the present invention contains two or more specific compounds, the total amount thereof is preferably within the above range.
  • the composition of the present invention contains a near-infrared absorbing pigment.
  • the near-infrared absorbing pigment is preferably an organic pigment.
  • an organic pigment is a pigment composed of an organic compound.
  • the near-infrared absorbing pigment is preferably a pigment having a maximum absorption wavelength in the near-infrared region (preferably in the range of 700-1800 nm, more preferably in the range of 700-1300 nm, still more preferably in the range of 700-1000 nm).
  • the solubility of the near-infrared absorbing pigment in 100 g of propylene glycol methyl ether acetate at 25°C is preferably less than 1 g, more preferably 0.1 g or less, and even more preferably 0.05 g or less.
  • Near-infrared absorbing pigments include pyrrolopyrrole compounds, cyanine 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, boradiazine compounds, etc., and more preferably at least one selected from pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds and boradiazine compounds; Pyrrole compounds are more preferred.
  • the pyrrolopyrrole compound is preferably a compound represented by formula (P-1).
  • Rp 1 to Rp 4 each independently represent a substituent, one of Rp 1 and Rp 2 is a heteroaryl group, and one of Rp 3 and Rp 4 is a heteroaryl group, Rp 5 and Rp 6 each independently represent an alkyl group, an aryl group or a heteroaryl group; B 1 and B 2 each independently represent BRp 11 Rp 12 , Rp 11 and Rp 12 each independently represent a substituent, Rp 11 and Rp 12 may combine with each other to form a ring.
  • Examples of the substituents represented by Rp 1 to Rp 4 of formula (P-1) include the groups described as the substituents represented by R 1 to R 4 of formula (1).
  • the heteroaryl group represented by either one of Rp 1 and Rp 2 in formula (P-1) and the heteroaryl group represented by either one of Rp 3 and Rp 4 in formula (P-1) are each independently is preferably a group represented by formula (A-1) or a group represented by formula (A-2).
  • Either one of Rp 1 and Rp 2 in formula (P-1) is a heteroaryl group, the other is an electron-withdrawing group, and one of Rp 3 and Rp 4 is a heteroaryl group, the other is an electron An attracting group is preferred.
  • the electron-withdrawing group is preferably a cyano group, an alkylcarbonyl group, an alkylsulfonyl group and an arylsulfonyl group, more preferably a cyano group.
  • Rp 5 and Rp 6 in formula (P-1) each independently represent an alkyl group, an aryl group or a heteroaryl group, preferably an aryl group or a heteroaryl group, more preferably an aryl group. .
  • the number of carbon atoms in the alkyl group represented by Rp 5 and Rp 6 is preferably 1-30, more preferably 1-20, even more preferably 1-10.
  • the alkyl group may be linear, branched or cyclic, but preferably linear or branched.
  • the aryl group represented by Rp 5 and Rp 6 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the number of carbon atoms constituting the ring of the heteroaryl group represented by Rp 5 and Rp 6 is preferably 1-30, more preferably 1-12.
  • Types of heteroatoms that constitute the heteroaryl group include, for example, a nitrogen atom, an oxygen atom and a sulfur atom.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1-3, more preferably 1-2.
  • the heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring with 2 to 8 condensed numbers, and still more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers.
  • the heteroaryl group represented by Rp 5 and Rp 6 is preferably a group represented by the above formula (A-1) or a group represented by the above formula (A-2).
  • B 1 and B 2 in formula (P-1) each independently represent BRp 11 Rp 12
  • Rp 11 and Rp 12 each independently represent a substituent.
  • substituents represented by Rp 11 and Rp 12 include halogen atoms, alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups and heteroaryloxy groups. or is preferably a heteroaryl group, more preferably a halogen atom, an alkyl group or an aryl group, and even more preferably an aryl group.
  • a halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.
  • the number of carbon atoms in the alkyl group and alkoxy group is preferably 1-20, more preferably 1-15, even more preferably 1-8.
  • Alkyl groups and alkoxy groups may be linear, branched or cyclic, but are preferably linear or branched.
  • the alkyl group and alkoxy group may have a substituent or may be unsubstituted. Substituents include aryl groups, heteroaryl groups, halogen atoms, and the like.
  • the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 2 to 8 carbon atoms.
  • the alkenyl group may have a substituent or may be unsubstituted.
  • Substituents include alkoxy groups, aryl groups, heteroaryl groups, halogen atoms and the like.
  • the aryl group and the aryloxy group preferably have 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • the aryl group and aryloxy group may have a substituent or may be unsubstituted. Examples of substituents include alkyl groups, alkoxy groups, and halogen atoms.
  • a heteroaryl group and a heteroaryloxy group may be monocyclic or condensed.
  • the number of heteroatoms constituting the heteroaryl ring of the heteroaryl group and heteroaryloxy group is preferably 1 to 3.
  • a heteroatom constituting the heteroaryl ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the number of carbon atoms constituting the heteroaryl ring is preferably 1-30, more preferably 1-18, even more preferably 1-12.
  • the heteroaryl ring is preferably a 5- or 6-membered ring.
  • a heteroaryl group and a heteroaryloxy group may have a substituent or may be unsubstituted. Examples of substituents include alkyl groups, alkoxy groups, and halogen atoms.
  • Rp 11 and Rp 12 of BRp 11 Rp 12 represented by B 1 and B 2 may combine with each other to form a ring.
  • Examples of the ring to be formed include structures shown in (B-1) to (B-5) below.
  • Rb represents a substituent
  • Rb 1 to Rb 4 each independently represent a hydrogen atom or a substituent
  • b1 to b3 each independently represent an integer of 0 to 4
  • b4 is 0 to It represents an integer of 6
  • * represents a link.
  • Substituents represented by Rb and Rb 1 to Rb 4 include the groups exemplified for the substituent T described above, preferably halogen atoms, alkyl groups and alkoxy groups.
  • pyrrolopyrrole compound examples include compounds having structures described in Examples described later. Further, as the pyrrolopyrrole compound, compounds described in paragraph numbers 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph numbers 0037-0052 of JP-A-2011-068731, International Publication No. 2015/166873 and the compounds described in paragraph numbers 0010 to 0033 of No. Examples of the squarylium compound include compounds described in paragraph numbers 0044 to 0049 of JP-A-2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese Patent No. 6065169, and paragraph number 0040 of WO 2016/181987.
  • the squarylium compound include compounds having structures described in Examples described later. Further, as the squarylium compound and the croconium compound, the squarylium compound described in JP-A-2017-197437, the squarylium compound described in JP-A-2017-025311, the squarylium compound described in International Publication No. 2016/154782, the patent Squarylium compounds described in Japanese Patent No. 5884953, squarylium compounds described in Japanese Patent No. 6036689, squarylium compounds described in Japanese Patent No. 5810604, squarylium compounds described in paragraph numbers 0090 to 0107 of International Publication No.
  • Examples of boradiazine compounds include compounds having structures described in Examples described later. Further, examples of boradiazine compounds include compounds described in paragraphs 0103 to 0117 of JP-A-2015-040231.
  • cyanine compound compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, compounds described in paragraphs 0026-0030 of JP-A-2002-194040, and JP-A-2015-172004.
  • phthalocyanine compound examples include compounds described in paragraph number 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraph numbers 0013 to 0029 of JP-A-2013-195480. compounds, vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, vanadium phthalocyanine compounds described in International Publication No. 2020/071486, and phthalocyanine compounds described in International Publication No. 2020/071470.
  • naphthalocyanine compounds examples include compounds described in paragraph number 0093 of JP-A-2012-077153.
  • the solubility S1 of the near-infrared absorbing pigment in 100 g of propylene glycol methyl ether acetate at 25°C is preferably smaller than the solubility S2 of the specific compound described above in 100 g of propylene glycol methyl ether acetate at 25°C.
  • the value of solubility S2-solubility S1 is preferably 10 g or less, more preferably 5 g or less, and even more preferably 3 g or less, because the surface adsorption to foreign crystals can be enhanced.
  • the content of the near-infrared absorbing pigment is preferably 1 to 50 mass% of the total solid content of the composition.
  • the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the composition of the invention contains a curable compound.
  • curable compounds 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).
  • Polymerizable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.
  • the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred.
  • the epoxy group may be a cycloaliphatic epoxy group.
  • the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
  • the curable compound it is preferable to use one containing at least a resin.
  • the resin preferably contains a resin having an acid group.
  • the composition of the present invention when used as a composition for photolithography, it is preferable to use a resin having an acid group and a polymerizable monomer (monomer type polymerizable compound) as the curable compound. It is more preferable to use a resin having an acid group and a polymerizable monomer (monomer-type polymerizable compound) having an ethylenically unsaturated bond-containing group.
  • polymerizable compound examples include compounds having an ethylenically unsaturated bond-containing group and compounds having a cyclic ether group.
  • a compound having an ethylenically unsaturated bond-containing group can be preferably used as a radically polymerizable compound.
  • a compound having a cyclic ether group can also be preferably used as a cationically polymerizable compound.
  • resin-type polymerizable compounds include resins containing repeating units having polymerizable groups.
  • the molecular weight of the monomer type polymerizable compound is preferably less than 2000, more preferably 1500 or less.
  • the lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 or more.
  • the weight average molecular weight (Mw) of the resin-type polymerizable compound is preferably 2,000 to 2,000,000.
  • the upper limit of the weight average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit of the weight average molecular weight is preferably 3000 or more, more preferably 5000 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, more preferably a 3- to 6-functional (meth)acrylate compound.
  • Specific examples include paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph numbers 0254-0257 of JP-A-2008-292970, and JP-A-2013-253224.
  • Examples of compounds having an ethylenically unsaturated bond-containing group include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetra(meth)acrylate (commercially available).
  • KAYARAD D-320 manufactured by Nippon Kayaku Co., Ltd.
  • dipentaerythritol penta(meth)acrylate commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.
  • dipentaerythritol hexa(meth)acrylate ) Acrylate commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.
  • the (meth)acryloyl groups of these compounds are ethylene glycol and / Or a compound having a structure linked via a propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer).
  • diglycerin EO ethylene oxide modified (meth) acrylate
  • pentaerythritol tetraacrylate Shin-Nakamura Chemical Industry 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.
  • DPHA-40H manufactured by Nippon Kayaku Co., Ltd.
  • Aronix TO-2349 Toagosei Co., Ltd.
  • NK Oligo UA-7200 Shin Nakamura Chemical Co., Ltd.
  • 8UH-1006, 8UH-1012 Taisei Fine Chemical Co., Ltd.
  • Examples of compounds having an ethylenically unsaturated bond-containing group include trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, and isocyanuric acid. It is also preferable to use trifunctional (meth)acrylate compounds such as ethylene oxide-modified tri(meth)acrylate and pentaerythritol tri(meth)acrylate. Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305.
  • M-303, M-452, M-450 manufactured by Toagosei Co., Ltd.
  • a compound having an ethylenically unsaturated bond-containing group a compound having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group can be used.
  • 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 as the compound having an ethylenically unsaturated bond-containing group.
  • the descriptions in paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, the contents of which are incorporated herein.
  • Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd.
  • a compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used as the compound having an ethylenically unsaturated bond-containing group.
  • Such a compound is preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and/or a propyleneoxy group, and is a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group. More preferably, it is a tri- to hexa-functional (meth)acrylate compound having 4 to 20 ethyleneoxy groups.
  • a polymerizable compound having a fluorene skeleton can also be used as the compound having an ethylenically unsaturated bond-containing group.
  • Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).
  • the compound having an ethylenically unsaturated bond-containing group it is also preferable to use a compound such as toluene that does not substantially contain environmentally regulated substances.
  • Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
  • Compounds having a cyclic ether group include compounds having an epoxy group, compounds having an oxetanyl group, and the like, and compounds having an epoxy group are preferred.
  • 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 two or more.
  • a compound having a cyclic ether group may be a low-molecular compound (for example, a molecular weight of less than 1000) or a macromolecule (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight-average molecular weight of 1000 or more).
  • the weight average molecular weight of the cyclic ether group is preferably from 200 to 100,000, more preferably from 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 composition of the present invention can use a resin as a curable compound. It is preferable to use a curable compound containing at least a resin.
  • the resin is blended, for example, for dispersing a pigment or the like in the composition or for a binder.
  • a resin that is mainly used to disperse a pigment or the like in a composition is also called a dispersant.
  • such uses of the resin are only examples, and the resin can be used for purposes other than such uses.
  • a resin having a polymerizable group also corresponds to 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, more preferably 500,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 5000 or more.
  • 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, polyurea resins, and the like.
  • norbornene resin is preferable from the viewpoint of improving heat resistance.
  • Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (for example, ARTON F4520). Further, as the resin, the resin described in the examples of International Publication No.
  • a resin having a fluorene skeleton can also be preferably used.
  • the description of US Patent Application Publication No. 2017/0102610 can be referred to, the content of which is incorporated herein.
  • the resin the resin described in paragraphs 0199 to 0233 of JP-A-2020-186373, the alkali-soluble resin described in JP-A-2020-186325, and the Korean Patent Publication No. 10-2020-0078339.
  • a resin represented by the formula 1 can also be used.
  • a resin having an acid group As the resin.
  • acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. Only one kind of these acid groups may be used, or two or more kinds thereof may be used.
  • a resin having an acid group can be used, for example, as an alkali-soluble resin.
  • the acid value of the resin having acid groups is preferably 30-500 mgKOH/g.
  • the lower limit is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more.
  • the upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.
  • a resin containing a repeating unit derived from a compound represented by the formula (ED1) and/or a compound represented by the formula (ED2) (hereinafter, these compounds may be referred to as an "ether dimer"). It is also preferred to include
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the description in JP-A-2010-168539 can be referred to.
  • paragraph number 0317 of JP-A-2013-029760 can be referred to, the content of which is incorporated herein.
  • the resin it is also preferable to use a resin having a polymerizable group.
  • the polymerizable group includes an ethylenically unsaturated bond-containing group and a cyclic ether group, preferably an ethylenically unsaturated bond-containing group.
  • R 1 represents a hydrogen atom or a methyl group
  • R 21 and R 22 each independently represent an alkylene group
  • n represents an integer of 0-15.
  • the number of carbon atoms in the alkylene group represented by R 21 and R 22 is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly 2 or 3.
  • n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.
  • Examples of the compound represented by formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of paracumylphenol.
  • Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
  • the composition of the present invention preferably contains a resin as a dispersant.
  • Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins).
  • the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups.
  • the acidic dispersant (acidic resin) a resin having an acid group content of 70 mol % or more is preferable when the total amount of the acid group and the basic group is 100 mol %.
  • the acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g.
  • a basic dispersant represents a resin in which the amount of basic groups is greater than the amount of acid groups.
  • a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and 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 also preferably a graft resin.
  • graft resin for details of the graft resin, reference can be made to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
  • the resin used as the dispersant is also preferably a polyimine-based dispersant containing nitrogen atoms in at least one of its main chain and side chains.
  • the polyimine-based dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom.
  • a resin having The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity.
  • the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
  • the resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core.
  • resins include, for example, dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.
  • the resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain.
  • the content of repeating units having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70, of the total repeating units of the resin. More preferably, it is mol %.
  • resins described in JP-A-2018-087939, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, Polyethyleneimine having a polyester side chain described in International Publication No. 2016/104803, a block copolymer described in International Publication No. 2019/125940, a block polymer having an acrylamide structural unit described in JP-A-2020-066687 , a block polymer having an acrylamide structural unit described in JP-A-2020-066688, a dispersant described in WO 2016/104803, and the like can also be used.
  • Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like.
  • Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like.
  • the content of the curable compound is preferably 1 to 95% by mass based on the total solid content of the composition.
  • the lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and particularly preferably 10% by mass or more.
  • the upper limit is preferably 94% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and particularly preferably 80% by mass or less.
  • the content of the polymerizable compound is preferably 1 to 85% by mass based on the total solid content of the composition.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.
  • the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.
  • the content of the polymerizable monomer is preferably 1 to 50% by mass based on the total solid content of the composition.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.
  • the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less.
  • the content of the compound having an ethylenically unsaturated bond-containing group is 1 to 70 mass in the total solid content of the composition. % is preferred.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.
  • the upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
  • the content of the resin is preferably 1 to 85% by mass based on the total solid content of the composition.
  • the lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and particularly preferably 10% by mass or more.
  • the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 40% by mass or less.
  • the content of the resin as a dispersant is preferably 0.1 to 40% by mass based on the total solid content of the composition.
  • the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
  • the content of the resin as a dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the above specific compound.
  • the upper limit is preferably 80 parts by mass or less, more preferably 75 parts by mass or less.
  • the lower limit is preferably 2.5 parts by mass or more, more preferably 5 parts by mass 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 curable compounds are included, the total amount thereof is preferably within the above range.
  • composition of the present invention can further contain a dye derivative in addition to the specific compounds described above.
  • Dye derivatives are used as dispersing aids.
  • Examples of dye derivatives include compounds having a structure in which an acid group or a basic group is bonded to a dye skeleton.
  • dye skeletons constituting dye derivatives include squarylium dye skeleton, pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, quinacridone dye skeleton, anthraquinone dye skeleton, dianthraquinone dye skeleton, benzoisoindole dye skeleton, and thiazineindigo dye skeleton.
  • a squarylium dye skeleton, a pyrrolopyrrole dye skeleton, a diketopyrrolopyrrole dye skeleton, a phthalocyanine dye skeleton, a quinacridone dye skeleton and a benzimidazolone dye skeleton are preferred, and a squarylium dye skeleton and a pyrrolopyrrole dye skeleton are more preferred.
  • the acid group includes a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imidic acid group and salts thereof.
  • Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ion and the like.
  • the carboxylic acid amide group a group represented by —NHCOR A1 is preferable.
  • a group represented by —NHSO 2 R A2 is preferable.
  • the imidic acid group is preferably a group represented by -SO 2 NHSO 2 R A3 , -CONHSO 2 R A4 , -CONHCOR A5 or -SO 2 NHCOR A6 , more preferably -SO 2 NHSO 2 R A3 .
  • R A1 to R A6 each independently represent an alkyl group or an aryl group.
  • the alkyl groups and aryl groups represented by R A1 to R A6 may have substituents.
  • the substituent is preferably a halogen atom, more preferably a fluorine atom.
  • Basic groups include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups.
  • Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
  • the dye derivative include the compounds described in Examples described later.
  • JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-009961, JP-A-03-026767, JP-A-03-153780 Publications, JP-A-03-045662, JP-A-04-285669, JP-A-06-145546, JP-A-06-212088, JP-A-06-240158, JP-A-10-030063, JP-A-10-195326, paragraph numbers 0086 to 0098 of International Publication No. 2011/024896, and compounds described in paragraph numbers 0063 to 0094 of International Publication No. 2012/102399, the contents of which are herein incorporated into.
  • the content of the dye derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment.
  • the lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more.
  • the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.
  • the content of the dye derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the above specific compound.
  • the lower limit is preferably 2 parts by mass or more, more preferably 5 parts by mass or more.
  • the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.
  • the composition of the present invention may contain only one dye derivative, or may contain two or more dye derivatives. When two or more dye derivatives are included, the total amount thereof is preferably within the above range.
  • the composition of the invention preferably contains a solvent.
  • the solvent include water and organic solvents, and organic solvents are preferred.
  • Organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.
  • Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups 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, ethylcarbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N
  • aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be better reduced for environmental reasons (e.g., 50 mass ppm (parts per million), 10 mass ppm or less, or 1 mass ppm or less).
  • 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 ppt (parts per trillion) mass level may be used, and such an organic solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).
  • Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore size of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers may be contained.
  • the content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.
  • the content of the solvent in the composition is preferably 10-97% by mass.
  • the lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, even more preferably 60% by mass or more, and 70% by mass. It is particularly preferable that it is above.
  • the upper limit is preferably 96% by mass or less, more preferably 95% by mass or less.
  • the composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are included, the total amount thereof is preferably within the above range.
  • the composition of the invention preferably further contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet region to the visible region are preferred.
  • 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 and the like.
  • 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 and the like.
  • photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbi imidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl-substituted coumarin compounds, oxime compounds, ⁇ -hydroxyketones compounds, ⁇ -aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds.
  • hexaarylbiimidazole compounds include 2,2′,4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1′-biimidazole, etc. is mentioned.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above company) and the like.
  • ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by Irgacure 369E, Irgacure 379EG). made), etc.
  • acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).
  • Examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, compounds described in Patent No.
  • oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy and imino-1-phenylpropan-1-one.
  • An oxime compound having a fluorene ring can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466, compounds described in Japanese Patent No. 6636081, and compounds described in Korean Patent Publication No. 10-2016-0109444. be done.
  • an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
  • Specific examples of such oxime compounds include compounds described in WO2013/083505.
  • An oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of.
  • An oxime compound having a nitro group can be used as the photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.
  • An oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator.
  • Specific examples include OE-01 to OE-75 described in WO 2015/036910.
  • an oxime compound in which a substituent having a hydroxyl group is bonded to the carbazole skeleton can also be used.
  • Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
  • oxime compounds 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 extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1000 to 300000, further preferably 2000 to 300000, even more preferably 5000 to 200000. It is particularly preferred to have
  • the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photopolymerization initiator.
  • a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained.
  • the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation becomes difficult over time, and the stability over time of the composition can be improved.
  • Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
  • the content of the photopolymerization initiator is preferably 0.1 to 40% by mass, more preferably 0.5 to 35% by mass, even more preferably 1 to 30% by mass, based on the total solid content of the composition.
  • the composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more photopolymerization initiators are included, the total amount thereof preferably falls within the above range.
  • composition of the present invention contains a compound having a cyclic ether group, it preferably further contains a curing agent.
  • curing agents include amine compounds, acid anhydrides, amide compounds, phenol compounds, polyvalent carboxylic acids, and thiol compounds.
  • specific examples of curing agents include succinic acid, trimellitic acid, pyromellitic acid, N,N-dimethyl-4-aminopyridine, pentaerythritol tetrakis(3-mercaptopropionate) and the like.
  • the curing agent compounds described in paragraphs 0072 to 0078 of JP-A-2016-075720 and compounds described in JP-A-2017-036379 can also be used.
  • 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 0.1 to 6.0 parts by mass with respect to 100 parts by mass of the compound having a cyclic ether group. is more preferred.
  • the composition of the present invention may contain only one curing agent, or may contain two or more curing agents. When two or more curing agents are included, the total amount thereof is preferably within the above range.
  • the composition of the invention may contain chromatic colorants.
  • a chromatic colorant means a colorant other than a white colorant and a black colorant.
  • the chromatic colorant is preferably a colorant that absorbs in a wavelength range of 400 nm or more and less than 650 nm.
  • the chromatic colorants include red colorants, green colorants, blue colorants, yellow colorants, purple colorants and orange colorants.
  • a 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.
  • an inorganic pigment or a material in which a part of an organic-inorganic pigment is replaced with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be facilitated.
  • the average primary particle size of the pigment is preferably 1 to 200 nm.
  • the lower limit is preferably 5 nm or more, 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 average primary particle size of the pigment can be determined from the 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 obtained, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment.
  • the average primary particle size in the present invention is the arithmetic mean value of the primary particle sizes of 400 primary particles of the pigment.
  • the primary particles of the pigment refer to independent particles without agglomeration.
  • 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, still more preferably 80% by mass or more, and 90% by mass or more. is particularly preferred. Examples of pigments include those shown below.
  • a halogenated zinc phthalocyanine pigment having an average number of halogen atoms of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 per molecule.
  • Specific examples include compounds described in International Publication No. 2015/118720.
  • a phthalocyanine compound a phthalocyanine compound described in JP-A-2018-180023, a compound described in JP-A-2019-038958, a core-shell type dye described in JP-A-2020-076995, and the like can also be used.
  • An aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue pigment.
  • Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A-2012-247591 and paragraph number 0047 of JP-A-2011-157478.
  • red pigments diketopyrrolopyrrole compounds in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, diketopyrrolopyrrole compounds described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, Diketopyrrolopyrrole compounds described in WO 2012/102399, diketopyrrolopyrrole compounds described in WO 2012/117965, naphthol azo compounds described in JP 2012-229344, Patent No. 6516119 Red pigment described in the publication, red pigment described in Patent No. 6525101, brominated diketopyrrolopyrrole compounds described in paragraph number 0229 of JP 2020-090632, Korean Patent No.
  • 10-2019-0140741 Anthraquinone compounds described in publications, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140744, perylene compounds described in JP-A-2020-079396, and the like can also be used. Also, as a red pigment, a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton may be used. can.
  • the pyrrolopyrrole-based pigment has a crystallite size of 140 ⁇ or less in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes of ( ⁇ 1 ⁇ 1 ⁇ 1) among the crystal lattice planes. It is also preferred to use one. Further, the physical properties of the pyrrolopyrrole pigment are preferably set as described in paragraphs 0028 to 0073 of JP-A-2020-097744.
  • Dyes can also be used as chromatic colorants.
  • the dye is not particularly limited, and known dyes can be used.
  • pyrazole azo dyes anilinoazo 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.
  • a pigment multimer can also be used as a chromatic colorant.
  • the dye multimer is preferably a dye dissolved in a solvent and used. Further, the dye multimer may form particles. When the dye multimer is particles, it is usually used in a state of being dispersed in a solvent.
  • the particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in JP-A-2015-214682.
  • a dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less.
  • a plurality of dye structures in one molecule may be the same dye structure or different dye structures.
  • the weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000.
  • the lower limit is more preferably 3000 or more, and even more preferably 6000 or more.
  • the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
  • Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016/031442, etc. Compounds can also be used.
  • the chromatic colorant the thiazole compound described in JP-A-2012-158649, the azo compound described in JP-A-2011-184493, the azo compound described in JP-A-2011-145540, published in Korea Triarylmethane dye polymer described in Patent No. 10-2020-0028160, xanthene compound described in JP-A-2020-117638, phthalocyanine compound described in WO2020/174991, JP-A-2020-160279
  • An isoindoline compound or a salt thereof described in the publication can be used.
  • the content of the chromatic colorant is preferably 1 to 50% by mass based on the total solid content of the composition of the present invention.
  • the composition of the present invention may contain only one type of chromatic colorant, or may contain two or more types. When two or more chromatic colorants are included, the total amount thereof is preferably within the above range.
  • the composition of the present invention can also contain a coloring material that transmits infrared rays 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 colorant that blocks visible light is preferably a colorant that absorbs light in the wavelength range from violet to red. Further, the coloring material that blocks visible light is preferably a coloring material that blocks light in the wavelength range of 450 to 650 nm. Further, the coloring material that blocks visible light is preferably a coloring material that transmits light with a wavelength of 900 to 1500 nm.
  • the colorant that blocks visible light preferably satisfies at least one of the following requirements (A) and (B).
  • B Contains an organic black colorant.
  • organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred.
  • bisbenzofuranone compounds include compounds described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, Japanese Patent Application Publication No. 2012-515234, etc.
  • perylene compounds include compounds described in paragraphs 0016 to 0020 of JP-A-2017-226821, C.I. I. Pigment Black 31, 32 and the like.
  • the azomethine compound include compounds described in JP-A-01-170601, JP-A-02-034664, and the like.
  • the combination of chromatic colorants includes, for example, the following aspects (1) to (8).
  • the content of the coloring material that blocks visible light is preferably 1 to 50 mass% of the total solid content of the composition.
  • the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass or more.
  • the composition of the invention preferably contains a surfactant.
  • a surfactant various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants can be used.
  • the surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant.
  • Surfactants include those described in paragraphs 0238-0245 of WO2015/166779, the contents of which are incorporated herein.
  • JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-132503 and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein.
  • Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 and F-144.
  • fluorine-based surfactant there is also an acrylic compound that has a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes. It can be used preferably.
  • fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafac and DS-21.
  • fluorosurfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant.
  • fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.
  • a block polymer can also be used as the fluorosurfactant.
  • a fluorosurfactant a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta)
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol%.
  • a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in a side chain can also be used as the fluorine-based surfactant.
  • Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, MEGAFACE RS-101, RS-102 and RS-718K manufactured by DIC Corporation, and RS-72-K. Further, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used as the fluorosurfactant.
  • a fluorine-containing imide salt compound represented by formula (fi-1) is also preferable to use as a surfactant.
  • m represents 1 or 2
  • n represents an integer of 1 to 4
  • a represents 1 or 2
  • X a+ is an a-valent metal ion, primary ammonium ion, Represents secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH 4 + .
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure
  • Cationic surfactants include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridium salts, imidazolium salts, and the like. Specific examples include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, stearamidomethylpyridinium chloride and the like.
  • Anionic surfactants include dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyletherdisulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl Sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, t-octylphenoxyethoxypolyethoxyethyl sodium sulfate and the like.
  • silicone surfactants examples include SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), TSF-4440, and TSF-4300. , TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (Shin-Etsu Chemical Co., Ltd. Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (manufactured by BYK-Chemie) and the like.
  • a compound having the following structure can also be used as the silicone-based surfactant.
  • the content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and still more preferably 0.001 to 0.2% by mass of the total solid content of the composition.
  • the composition of the present invention may contain only one type of surfactant, or may contain two or more types. When two or more surfactants are included, the total amount thereof is preferably within the above range.
  • the composition of the invention may contain a polymerization inhibitor.
  • Polymerization inhibitors 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), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.), and p-methoxyphenol is preferred.
  • the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the composition.
  • the composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more polymerization inhibitors are included, the total amount thereof is preferably within the above range.
  • the composition of the invention can contain a silane coupling agent.
  • a silane coupling agent means 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 capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction.
  • Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group, isocyanate group, and phenyl group. with (meth)acryloyl groups and epoxy groups being preferred.
  • the silane coupling agent includes compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. incorporated into the specification.
  • the content of the silane coupling agent is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass, based on the total solid content of the composition.
  • the composition of the present invention may contain only one type of silane coupling agent, or may contain two or more types. When two or more silane coupling agents are included, the total amount thereof is preferably within the above range.
  • the composition of the invention may contain an ultraviolet absorber.
  • ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and merocyanine dyes. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, paragraph numbers 0317-0317 of JP-A-2013-068814.
  • UV absorbers include Tinuvin series and Uvinul series manufactured by BASF. Moreover, as a benzotriazole compound, the MYUA series made from Miyoshi oil and fats (Chemical Daily, February 1, 2016) is mentioned. Further, as the ultraviolet absorber, compounds described in paragraph numbers 0049 to 0059 of Japanese Patent No. 6268967 and paragraph numbers 0059 to 0076 of International Publication No. 2016/181987 can also be used.
  • the content of the ultraviolet absorber is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, based on the total solid content of the composition.
  • the composition of the present invention may contain only one type of ultraviolet absorber, or may contain two or more types. When two or more ultraviolet absorbers are included, the total amount thereof is preferably within the above range.
  • the compositions of the invention may contain antioxidants.
  • Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound.
  • Preferred phenolic compounds include hindered phenolic compounds.
  • a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
  • Phosphorus-based antioxidants can also be suitably used as antioxidants.
  • a phosphorus antioxidant 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 the like.
  • antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like.
  • antioxidants are compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, and compounds described in WO 2017/164024. can also be used.
  • the content of the antioxidant is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass, based on the total solid content of the composition.
  • the composition of the present invention may contain only one kind of antioxidant, or may contain two or more kinds. When two or more kinds of antioxidants are included, the total amount thereof is preferably within the above range.
  • composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, etc.). agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc.
  • the composition of the present invention may also contain latent antioxidants, if desired.
  • the latent antioxidant is a compound in which the site functioning as an antioxidant is protected by a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst.
  • a compound that functions as an antioxidant by removing the protective group by the reaction is exemplified.
  • Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
  • Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
  • the storage container for the composition of the present invention is not particularly limited, and known storage containers can be used.
  • a storage container a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resin and a bottle with a 7-layer structure of 6 types of resin are used for the purpose of suppressing the contamination of raw materials and compositions with impurities. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351.
  • the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the stability of the composition over time, and suppressing deterioration of components.
  • compositions of the present invention can be prepared by mixing the aforementioned ingredients.
  • the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time, or if necessary, two or more solutions or dispersions in which each component is appropriately blended are prepared in advance. They may be prepared and mixed at the time of use (at the time of application) to prepare a composition.
  • the preparation of the composition may include a process of dispersing the pigment.
  • mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like.
  • 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, ultrasonic dispersion, and the like.
  • pulverizing the pigment in a sand mill (bead mill) it is preferable to use beads with a small diameter or to increase the filling rate of the beads so as to increase the pulverization efficiency.
  • the process and dispersing machine for dispersing pigments are described in "Dispersion Technology Complete Works, Information Organization Co., Ltd., July 15, 2005” and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial Practical Application General Documents, Published by Management Development Center Publishing Department, October 10, 1978", the process and dispersing machine described in paragraph number 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used.
  • the pigment may be finely divided in the salt milling process. Materials, equipment, processing conditions, etc.
  • Beads used for dispersion can be zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, glass, or combinations thereof.
  • An inorganic compound having a Mohs hardness of 2 or more can also be used as beads.
  • the composition may contain 1 to 10000 ppm of the beads.
  • any filter that has been conventionally used for filtration or the like can be used without particular limitation.
  • fluorine resin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene, polypropylene (PP) (high density, ultra high molecular weight (including polyolefin resin).
  • PTFE polytetrafluoroethylene
  • nylon eg nylon-6, nylon-6,6)
  • polyolefin resin such as polyethylene
  • PP polypropylene
  • polypropylene including high density polypropylene
  • nylon are preferred.
  • the pore size of the filter is preferably 0.01-7.0 ⁇ m, more preferably 0.01-3.0 ⁇ m, and even more preferably 0.05-0.5 ⁇ m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably.
  • the pore size value of the filter reference can be made to the filter manufacturer's nominal value.
  • Various filters provided by Nihon Pall Co., Ltd. (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used as the filter. .
  • fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers.
  • Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.
  • filters When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed.
  • filters eg, a first filter and a second filter, etc.
  • the membrane of the invention is obtained from the composition of the invention described above.
  • the film of the present invention can be preferably used as an optical filter.
  • Applications of the optical filter are not particularly limited, but examples thereof include a near-infrared cut filter and an infrared transmission filter.
  • a near-infrared cut filter for example, a near-infrared cut filter on the light receiving side of the solid-state image sensor (for example, a near-infrared cut filter for a wafer level lens, etc.), a back side of the solid-state image sensor (opposite to the light receiving side)
  • Infrared cut filter near-infrared cut filter for ambient light sensor (e.g., illuminance sensor that detects the illuminance and color tone of the environment in which the information terminal device is placed and adjusts the color tone of the display, color correction sensor that adjusts the color tone ) and the like.
  • the infrared transmission filter include a filter capable of blocking visible light and selectively transmitting infrared light having a specific wavelength or longer.
  • the film of the present invention may have a pattern or may be a film without a pattern (flat film). Moreover, the film of the present invention may be used by laminating it on a support, or may be used by peeling the film of the present invention from the support. Examples of the support include semiconductor substrates such as silicon substrates and transparent substrates.
  • a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the semiconductor substrate used as the support. Also, a black matrix that isolates each pixel may be formed on the semiconductor substrate. Further, if necessary, an undercoat layer may be provided on the semiconductor substrate for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the surface of the substrate.
  • CMOS complementary metal oxide semiconductor
  • a transparent conductive film or the like
  • an undercoat layer may be provided on the semiconductor substrate for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the surface of the substrate.
  • the transparent substrate used as the support is not particularly limited as long as it is composed of a material that can transmit at least visible light.
  • Examples thereof include base materials made of materials such as glass and resin.
  • resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer, acrylic resins such as norbornene resin, polyacrylate, and polymethyl methacrylate, urethane resins, and vinyl chloride resins. , fluororesin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin, and the like.
  • glass examples include soda-lime glass, borosilicate glass, alkali-free glass, quartz glass, glass containing copper, and the like.
  • Glass containing copper includes phosphate glass containing copper, fluorophosphate glass containing copper, and the like.
  • a commercially available glass containing copper can also be used.
  • Commercially available glass containing copper includes NF-50 (manufactured by AGC Techno Glass Co., Ltd.).
  • the thickness of the film of the present invention can be adjusted as appropriate according to the purpose.
  • the thickness of the film is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more.
  • the film of the present invention When the film of the present invention is used as a near-infrared cut filter, 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). preferable.
  • the average transmittance of light with a wavelength of 420 to 550 nm is preferably 50% or more, more preferably 70% or more, still more preferably 80% or more, and particularly 85% or more. preferable.
  • 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 film of the present invention preferably has a transmittance of 15% or less at at least one point in the wavelength range of 650 to 1500 nm (preferably 660 to 1200 nm, more preferably 660 to 1000 nm). The following is more preferable, and 5% or less is even more preferable.
  • the film of the present invention preferably has an average absorbance of less than 0.030, more preferably less than 0.025 in the wavelength range of 420 to 550 nm when the absorbance at the maximum absorption wavelength is 1.
  • 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 in the wavelength range of 950 nm or more.
  • the maximum transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1100 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • a film having such spectral characteristics can block light in the wavelength range of 400 to 950 nm and transmit light in the wavelength range of 1050 nm or more.
  • the maximum transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1200 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • a film having such spectral characteristics can block light in the wavelength range of 400 to 1050 nm and transmit light in the wavelength range of 1150 nm or more.
  • the film of the present invention can also be used in combination with a color filter containing a chromatic colorant.
  • a color filter can be produced using a coloring composition containing a chromatic colorant.
  • the color filter is preferably 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.
  • Other members for example, a microlens, a planarization layer, etc. constituting the solid-state imaging device may be interposed between the film and the color filter.
  • 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.
  • the film of the present invention can be produced through the step of applying the composition of the present invention.
  • Examples of the support include those mentioned above.
  • a method for applying the composition a known method can be used. For example, drop method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); methods described in publications); inkjet (e.g., on-demand method, piezo method, thermal method), discharge system printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like.
  • the application method for inkjet is not particularly limited.
  • the composition layer formed by applying the composition may be dried (pre-baked).
  • the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower.
  • the lower limit can be, for example, 50° C. or higher, and can also be 80° C. or higher.
  • the prebaking time is preferably 10 seconds to 3000 seconds, more preferably 40 seconds to 2500 seconds, and even more preferably 80 seconds to 220 seconds. Drying can be performed using a hot plate, an oven, or the like.
  • the film manufacturing method may further include a step of forming a pattern.
  • the pattern forming method include a pattern forming method using a photolithographic method and a pattern forming method using a dry etching method, and the pattern forming method using the photolithographic method is preferable.
  • the step of forming a pattern may not be performed. The process of forming the pattern will be described in detail below.
  • the pattern formation method by photolithography comprises a step of patternwise exposing the composition layer formed by coating the composition of the present invention (exposure step), and developing and removing the unexposed portion of the composition layer. and a step of forming 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 in a pattern.
  • the composition layer can be exposed in a pattern by exposing through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.
  • Radiation (light) that can be used for exposure includes g-line, i-line, and the like.
  • Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used.
  • Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferable.
  • a long-wave light source of 300 nm or more can also be used.
  • the light when exposing, the light may be continuously irradiated and exposed, or may be irradiated and exposed in pulses (pulse exposure).
  • pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and rest in short-time (for example, millisecond level or less) cycles.
  • 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 at the time of exposure can be selected as appropriate, and in addition to exposure in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free) or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume).
  • the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W/m 2 to 100000 W/m 2 (eg, 5000 W/m 2 , 15000 W/m 2 or 35000 W/m 2 ). can be done. Oxygen concentration and exposure illuminance may be appropriately combined. For example, illuminance of 10000 W/m 2 at oxygen concentration of 10% by volume and illuminance of 20000 W/m 2 at oxygen concentration of 35% by volume.
  • an unexposed portion of the composition layer after exposure is removed by development to form a pattern.
  • the development and removal of the composition layer in the unexposed area can be carried out using a developer.
  • the unexposed portion of the composition layer in the exposure step is eluted into the developer, leaving only the photocured portion on the support.
  • the temperature of the developer is preferably 20 to 30° C., for example.
  • the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the step of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.
  • the developer includes an organic solvent, an alkaline developer, etc., and an alkaline developer is preferably used.
  • an alkaline developer an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable.
  • alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
  • alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate and sodium metasilicate.
  • concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
  • the developer may further contain a surfactant.
  • a nonionic surfactant is preferable as the surfactant.
  • the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times.
  • wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse liquid to the composition layer after development while rotating the support on which the composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support.
  • the moving speed of the nozzle may be gradually decreased.
  • in-plane variations in rinsing can be suppressed.
  • a similar effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the periphery.
  • Additional exposure processing and post-baking are post-development curing treatments for complete curing.
  • the heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree.
  • Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. .
  • the light used for exposure preferably has a wavelength of 400 nm or less.
  • the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
  • Pattern formation by a dry etching method includes curing the composition layer formed by coating the composition on a support to form a cured product layer, and then forming a photoresist layer patterned on the cured product layer. is formed, and then dry etching is performed on the cured product layer using an etching gas using the patterned photoresist layer as a mask. In forming the photoresist layer, pre-baking is preferably performed.
  • description in paragraphs 0010 to 0067 of JP-A-2013-064993 can be referred to, and the contents thereof are incorporated into this specification.
  • optical filter of the present invention has the film of the present invention as described above.
  • Types of optical filters include near-infrared cut filters and infrared transmission filters.
  • the optical filter of the present invention may further have a layer containing copper, a dielectric multilayer film, an ultraviolet absorbing layer, etc., in addition to the film of the present invention described above.
  • the ultraviolet absorbing layer include the absorbing layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/099060.
  • Dielectric multilayer films include dielectric multilayer films described in paragraphs 0255 to 0259 of JP-A-2014-041318.
  • the layer containing copper a glass substrate made of glass containing copper (copper-containing glass substrate) or a layer containing a copper complex (copper complex-containing layer) can be used.
  • Copper-containing glass substrates include copper-containing phosphate glass, copper-containing fluorophosphate glass, and the like.
  • Commercially available copper-containing glasses include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (manufactured by Schott), CD5000 (manufactured by HOYA Corporation), and the like.
  • the solid-state imaging device of the present invention includes the film of the present invention described above.
  • 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 configuration can be mentioned.
  • a plurality of photodiodes constituting the light receiving area of the solid-state imaging device and transfer electrodes made of polysilicon or the like are provided on the support, and light shielding made of tungsten or the like with only the light receiving portions of the photodiodes being opened on the photodiodes and the transfer electrodes.
  • a device protective film made of silicon nitride or the like is formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion, and the film of the present invention is provided on the device protective film. be.
  • the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.
  • the partition in this case preferably has a lower refractive index than each pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478 and JP-A-2014-179577.
  • the image display device of the invention comprises the film of the invention.
  • image display devices include liquid crystal display devices and organic electroluminescence (organic EL) display devices.
  • organic EL organic electroluminescence
  • For the definition and details of the image display device see, for example, “Electronic Display Device (written by Akio Sasaki, Industrial Research Institute, 1990)", “Display Device (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd., 1989). issued)”, etc.
  • Liquid crystal display devices are described, for example, in “Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied.
  • the image display device may have a white organic EL element.
  • a white organic EL device preferably has a tandem structure. Regarding the tandem structure of organic EL elements, see Japanese Patent Application Laid-Open No. 2003-045676, supervised by Akiyoshi Mikami, "Forefront of Organic EL Technology Development -High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, 326-328, 2008, and others.
  • the spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430-485 nm), the green region (530-580 nm) and the yellow region (580-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 to 700 nm) are more preferred.
  • the infrared sensor of the invention comprises the membrane of the invention as described above.
  • the configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. An embodiment of the infrared sensor of the present invention will be described below with reference to the drawings.
  • reference numeral 110 is a solid-state imaging device.
  • a near-infrared cut filter 111 and an infrared transmission filter 114 are arranged on the imaging area of the solid-state imaging device 110 .
  • a color filter 112 is arranged on the near-infrared cut filter 111 .
  • a microlens 115 is arranged on the incident light h ⁇ side of the color filter 112 and the infrared transmission filter 114 .
  • a planarization layer 116 is formed to cover the microlens 115 .
  • the near-infrared cut filter 111 can be formed using the composition of the present invention.
  • the color filter 112 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible region, and is not particularly limited, and conventionally known color filters for forming pixels can be used. For example, a color filter having red (R), green (G), and blue (B) pixels is used. For example, paragraph numbers 0214 to 0263 of JP-A-2014-043556 can be referred to, and the contents thereof are incorporated herein.
  • the characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used. Infrared transmission filter 114 can be formed using the composition of the present invention.
  • a near-infrared cut filter different from the near-infrared cut filter 111 may be further arranged on the flattening layer 116 .
  • Other near-infrared cut filters include those having copper-containing layers and/or dielectric multilayer films. These details are given above.
  • a dual bandpass filter may be used as another near-infrared cut filter.
  • the weight-average molecular weight of the resin is determined by using HPC-8220GPC (manufactured by Tosoh Corporation) as a measuring device, TSKguardcolumn SuperHZ-L as a guard column, and TSKgel SuperHZM-M, TSKgel SuperHZ4000, TSKgel SuperHZ3000, and TSKgel SuperHZ2000 as columns.
  • the column temperature is set to 40 ° C., 10 ⁇ L of a tetrahydrofuran solution with a sample concentration of 0.1% by mass is injected into the column, tetrahydrofuran is flowed at a flow rate of 0.35 mL per minute as an elution solvent, and an RI (differential refractive index) detector. A sample peak was detected at , and measured using a calibration curve prepared using standard polystyrene.
  • the viscosity of the pigment dispersion liquid was obtained by adjusting the temperature of the pigment dispersion liquid to 25° C. and measuring it using an E-type viscometer at a rotation speed of 1000 rpm.
  • the average particle diameter D50 value of the pigment is obtained by measuring the particle size distribution of the pigment in the pigment dispersion on a volume basis using MICROTRACUPA 150 manufactured by Nikkiso Co., Ltd., and the particle diameter at which the cumulative volume in the particle size distribution becomes 50%. Measured and sought.
  • Pigment Compounds having the following structures (near-infrared absorbing pigments, pyrrolopyrrole compounds, and the solubility of Pig-001 to Pig-005 in 100 g of propylene glycol methyl ether acetate at 25° C. are all 0.05 g or less.
  • Pig-101 compound having the following structure (near-infrared absorbing pigment, squarylium compound, solubility in 100 g of propylene glycol methyl ether acetate at 25°C is 0.05 g or less)
  • Pig-102 compound having the following structure (near-infrared absorbing pigment, boradiazine compound, solubility in 100 g of propylene glycol methyl ether acetate at 25°C is 0.1 g or less)
  • PY150 C.I. I. Pigment Yellow150 (yellow pigment)
  • PR254 C.I. I. Pigment Red254 (red pigment)
  • Dis-001 Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight 25000, dispersion degree 2.0)
  • Dis-002 Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 32,000, dispersity: 2.5)
  • Dis-003 Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 15,000, dispersity: 2.8)
  • composition Materials other than the solvent shown in the table below are mixed in the ratio shown in the table below, and the solvent shown in the table below is added to adjust the solid content concentration to 20% by mass, then stirred and nylon with a pore size of 0.45 ⁇ m. filter (manufactured by Nippon Pall Co., Ltd.) to prepare a composition.
  • Numerical values in the columns of compounding amounts in the table are values in parts by mass in terms of solid content. Also, the value of parts by mass of the specific compound with respect to 100 parts by mass of the near-infrared absorbing pigment is shown in the column of "content of specific compound".
  • B003 Resin having the following structure (the numerical values attached to the main chain are the molar ratios of the repeating units, the weight average molecular weight is 15,000, the degree of dispersion is 2.1)
  • C-1 Irgacure OXE01 (manufactured by BASF, oxime ester initiator)
  • C-2 Irgacure OXE02 (manufactured by BASF, oxime ester initiator)
  • M-1 Aronix M-305 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate. The content of pentaerythritol triacrylate is 55% by mass to 63% by mass.)
  • M-2 KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd., ethylene oxide-modified pentaerythritol tetraacrylate)
  • M-3 Aronix M-510 (manufactured by Toagosei Co., Ltd., polybasic acid-modified acrylic oligomer)
  • F-1 Megafac RS-72-K (manufactured by DIC Corporation, fluorine-based surfactant)
  • F-2 A compound having the following structure (weight average molecular weight: 14,000, % indicating the ratio of repeating units is mol %)
  • F-3 KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., carbinol-modified polydimethylsiloxane at both ends, hydroxyl value 62 mgKOH/g)
  • U-1 Uvinul 3050 (manufactured by BASF, UV absorber)
  • U-2 Tinuvin477 (manufactured by BASF, hydroxyphenyltriazine-based UV absorber)
  • U-3 Tinuvin326 (manufactured by BASF, UV absorber)
  • i-line stepper exposure apparatus FPA-3000i5+ manufactured by Canon Inc.
  • exposure was performed at an exposure amount of 1000 mJ/cm 2 through a mask having a Bayer pattern of 1 ⁇ m.
  • TMAH tetramethylammonium hydroxide
  • puddle development was performed at 23° C. for 60 seconds.
  • the substrate was rinsed with a spin shower, washed with pure water, and then heated at 200° C. for 5 minutes on a hot plate to form a pattern (pixels).
  • the glass substrate on which the pixels are formed is observed with a microscope at a magnification of 10,000 times, and the number of foreign crystals having a size of 1 ⁇ m or more present in the pixels formed on the glass substrate is counted. Defects were evaluated.
  • E The number of foreign crystals is 1000 more than one
  • Viscosity change rate ((composition after storage at 50°C for 3 months - viscosity of composition immediately after production)/viscosity of composition immediately after production) x 100
  • the glass substrate on which the film was formed was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2,000,000 lux ⁇ h), and the transmittance of the film after irradiation with the xenon lamp was measured.
  • the change in average transmittance ( ⁇ T) in the wavelength range of 600 to 800 nm before and after irradiation with the xenon lamp was measured. Based on the largest change in transmittance ( ⁇ T) in the entire measurement wavelength range, the light resistance was evaluated according to the following criteria. The smaller the value of ⁇ T, the better the light resistance.
  • the compositions of the examples were able to form films in which foreign matter defects were suppressed.
  • the composition of the example when the same pixel as described above was formed on a glass substrate using the composition immediately after production and microscopic observation was performed, no foreign matter was observed.
  • the composition of Example 22 had a higher liquid permeation rate in filter filtration during preparation of the composition than the compositions of other Examples, but was superior in liquid permeation.
  • 110 solid-state imaging device
  • 111 near-infrared cut filter
  • 112 color filter
  • 114 infrared transmission filter
  • 115 microlens
  • 116 flattening layer

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Abstract

The present invention provides a composition that can form a film in which foreign matter defects are suppressed. Provided are a film, an optical filter, a solid-state imaging element, an image display device, and an infrared sensor that use said composition. This composition contains a compound represented by formula (1), a near-infrared absorbing pigment, and a curable compound, and the content of the compound represented by formula (1) is 0.01-10 parts by mass per 100 parts by mass of the near-infrared absorbing pigment.

Description

組成物、膜、光学フィルタ、固体撮像素子、画像表示装置および赤外線センサComposition, film, optical filter, solid-state imaging device, image display device, and infrared sensor
 本発明は、近赤外線吸収顔料を含む組成物に関する。また、本発明は、前述の組成物を用いた膜、光学フィルタ、固体撮像素子、画像表示装置および赤外線センサに関する。 The present invention relates to a composition containing a near-infrared absorbing pigment. The present invention also relates to a film, an optical filter, a solid-state imaging device, an image display device and an infrared sensor using the above composition.
 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、近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。 CCDs (charge-coupled devices) and CMOSs (complementary metal-oxide semiconductors), which are solid-state imaging devices for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. These solid-state imaging devices use silicon photodiodes that are sensitive to infrared rays in their light receiving portions. For this reason, a near-infrared cut filter may be provided to correct visibility.
 近赤外線カットフィルタは、近赤外線吸収色素を含む組成物を用いて製造されている。近赤外線吸収色素としてはピロロピロール化合物などが知られている。また、特許文献1には、近赤外線吸収色素として特定のボラジアジン化合物が提案されている。 A near-infrared cut filter is manufactured using a composition containing a near-infrared absorbing dye. Pyrrolopyrrole compounds and the like are known as near-infrared absorbing dyes. Further, Patent Document 1 proposes a specific boradiazine compound as a near-infrared absorbing dye.
特開2015-040231号公報JP 2015-040231 A
 しかしながら、近赤外線吸収色素として近赤外線吸収顔料を用いた組成物を使用して膜を形成した場合、膜中に異物欠陥が生じやすい傾向にある。特に、長期保管後の組成物を用いて膜を形成した場合において、膜中に異物欠陥がより生じやすい傾向にあった。 However, when a film is formed using a composition using a near-infrared absorbing pigment as a near-infrared absorbing dye, foreign matter defects tend to occur in the film. In particular, when a film was formed using a composition after long-term storage, there was a tendency for foreign matter defects to occur more easily in the film.
 よって、本発明の目的は、異物欠陥の抑制された膜を形成できる組成物を提供することにある。また、本発明の目的は、異物欠陥の抑制された膜、光学フィルタ、固体撮像素子、画像表示装置および赤外線センサを提供することにある。 Accordingly, an object of the present invention is to provide a composition capable of forming a film in which foreign matter defects are suppressed. Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, an image display device, and an infrared sensor in which foreign matter defects are suppressed.
 本発明は以下を提供する。
 <1> 式(1)で表される化合物と、近赤外線吸収顔料と、硬化性化合物と、を含有し、
 上記式(1)で表される化合物の含有量が上記近赤外線吸収顔料の100質量部に対して、0.01~10質量部である、組成物;
Figure JPOXMLDOC01-appb-C000005
 式(1)中、R~Rは、それぞれ独立して置換基を表し、RおよびRのいずれか一方はヘテロアリール基で、RおよびRのいずれか一方はヘテロアリール基であり、
 RおよびRは、それぞれ独立してアルキル基、アリール基またはヘテロアリール基を表す。
 <2> 上記式(1)のRおよびRのいずれか一方はヘテロアリール基で、他方はシアノ基であり、
 上記式(1)のRおよびRのいずれか一方はヘテロアリール基で、他方はシアノ基である、<1>に記載の組成物。
 <3> 上記式(1)のRおよびRのいずれか一方が表すヘテロアリール基、ならびに、上記式(1)のRおよびRのいずれか一方が表すヘテロアリール基が、それぞれ独立して、式(A-1)で表される基または式(A-2)で表される基である、<1>または<2>に記載の組成物;
Figure JPOXMLDOC01-appb-C000006
 式(A-1)中、XA1はO、S、NRX1またはCRX2X3を表し、RX1~RX3は、それぞれ独立して水素原子または置換基を表し、
 RA1およびRA2は、それぞれ独立して水素原子または置換基を表し、
 RA1とRA2は互いに結合して環を形成してよく、
 *は結合手を表す;
 式(A-2)中、YA1~YA4は、それぞれ独立してNまたはCRY1を表し、RY1は水素原子または置換基を表し、
 YA1~YA4の少なくとも2つはCRY1であり、
 YA1~YA4のうち隣接する2つがCRY1である場合、隣接する2つのCRY1におけるRY1同士は互いに結合して環を形成してよく、
 *は結合手を表す。
 <4> 上記式(1)で表される化合物が、式(1-1)または式(1-2)で表される化合物である、<1>~<3>のいずれか1つに記載の組成物;
Figure JPOXMLDOC01-appb-C000007
 式(1-1)中、R11およびR12は、それぞれ独立して置換基を表し、
 R13およびR14は、それぞれ独立してアルキル基、アリール基またはヘテロアリール基を表し、
 X11およびX12は、それぞれ独立してO、S、NRX11またはCRX12X13を表し、RX11~RX13は、それぞれ独立して水素原子または置換基を表し、
 R15~R18は、それぞれ独立して水素原子または置換基を表し、
 R15とR16は互いに結合して環を形成してよく、
 R17とR18は互いに結合して環を形成してよい;
 式(1-2)中、R11およびR12は、それぞれ独立して置換基を表し、
 R13およびR14は、それぞれ独立してアルキル基、アリール基またはヘテロアリール基を表し、
 Y11~Y18は、それぞれ独立してNまたはCRY11を表し、RY11は水素原子または置換基を表し、
 Y11~Y14の少なくとも2つと、Y15~Y18の少なくとも2つは、CRY11であり、
 Y11~Y14のうち隣接する2つがCRY11である場合、隣接する2つのCRY11におけるRY11同士は互いに結合して環を形成してよく、
 Y15~Y18のうち隣接する2つがCRY11である場合、隣接する2つのCRY11におけるRY11同士は互いに結合して環を形成してよい。
 <5> 上記近赤外線吸収顔料がピロロピロール化合物である、<1>~<4>のいずれか1つに記載の組成物。
 <6> 上記近赤外線吸収顔料が、式(P-1)で表される化合物である、<1>~<5>のいずれか1つに記載の組成物;
Figure JPOXMLDOC01-appb-C000008
 式(P-1)中、Rp~Rpはそれぞれ独立して置換基を表し、かつ、RpおよびRpのいずれか一方はヘテロアリール基で、RpおよびRpのいずれか一方はヘテロアリール基であり、
 RpおよびRpは、それぞれ独立してアルキル基、アリール基またはヘテロアリール基を表し、
 BおよびBは、それぞれ独立してBRp11Rp12を表し、Rp11およびRp12は、それぞれ独立して置換基を表し、
 Rp11とRp12は互いに結合して環を形成してよい。
 <7> 上記硬化性化合物は、重合性化合物を含有する、<1>~<6>のいずれか1つに記載の組成物。
 <8> 上記硬化性化合物は、酸基を有する樹脂を含有する、<1>~<7>のいずれか1つに記載の組成物。
 <9> <1>~<8>のいずれか1つに記載の組成物を用いて得られる膜。
 <10> <9>に記載の膜を含む光学フィルタ。
 <11> <9>に記載の膜を含む固体撮像素子。
 <12> <9>に記載の膜を含む画像表示装置。
 <13> <9>に記載の膜を含む赤外線センサ。
The present invention provides the following.
<1> containing a compound represented by formula (1), a near-infrared absorbing pigment, and a curable compound,
A composition in which the content of the compound represented by formula (1) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment;
Figure JPOXMLDOC01-appb-C000005
In formula (1), R 1 to R 4 each independently represent a substituent, one of R 1 and R 2 is a heteroaryl group, and one of R 3 and R 4 is a heteroaryl group and
R5 and R6 each independently represent an alkyl group, an aryl group or a heteroaryl group.
<2> one of R 1 and R 2 in the above formula (1) is a heteroaryl group and the other is a cyano group;
The composition according to <1>, wherein one of R 3 and R 4 in formula (1) is a heteroaryl group and the other is a cyano group.
<3> The heteroaryl group represented by either one of R 1 and R 2 in the above formula (1) and the heteroaryl group represented by either one of R 3 and R 4 in the above formula (1) are independently The composition according to <1> or <2>, which is a group represented by formula (A-1) or a group represented by formula (A-2);
Figure JPOXMLDOC01-appb-C000006
In formula (A-1), X A1 represents O, S, NR X1 or CR X2 R X3 , and R X1 to R X3 each independently represent a hydrogen atom or a substituent,
R A1 and R A2 each independently represent a hydrogen atom or a substituent,
R A1 and R A2 may combine with each other to form a ring,
* represents a bond;
In formula (A-2), Y A1 to Y A4 each independently represent N or CR Y1 , R Y1 represents a hydrogen atom or a substituent,
at least two of Y A1 to Y A4 are CR Y1 ;
When adjacent two of Y A1 to Y A4 are CR Y1 , the R Y1s in the two adjacent CR Y1 may be bonded to each other to form a ring,
* represents a bond.
<4> Any one of <1> to <3>, wherein the compound represented by formula (1) is a compound represented by formula (1-1) or formula (1-2) a composition of
Figure JPOXMLDOC01-appb-C000007
In formula (1-1), R 11 and R 12 each independently represent a substituent,
R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group;
X 11 and X 12 each independently represent O, S, NR X11 or CR X12 R X13 , R X11 to R X13 each independently represent a hydrogen atom or a substituent,
R 15 to R 18 each independently represent a hydrogen atom or a substituent,
R 15 and R 16 may combine with each other to form a ring,
R 17 and R 18 may combine with each other to form a ring;
In formula (1-2), R 11 and R 12 each independently represent a substituent,
R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group;
Y 11 to Y 18 each independently represent N or CR Y11 , R Y11 represents a hydrogen atom or a substituent,
at least two of Y 11 to Y 14 and at least two of Y 15 to Y 18 are CR Y11 ;
When adjacent two of Y 11 to Y 14 are CR Y11 , R Y11 in the two adjacent CR Y11 may combine with each other to form a ring,
When adjacent two of Y 15 to Y 18 are CR Y11 , R Y11 in the two adjacent CR Y11 may combine with each other to form a ring.
<5> The composition according to any one of <1> to <4>, wherein the near-infrared absorbing pigment is a pyrrolopyrrole compound.
<6> The composition according to any one of <1> to <5>, wherein the near-infrared absorbing pigment is a compound represented by formula (P-1);
Figure JPOXMLDOC01-appb-C000008
In formula (P-1), Rp 1 to Rp 4 each independently represent a substituent, one of Rp 1 and Rp 2 is a heteroaryl group, and one of Rp 3 and Rp 4 is a heteroaryl group,
Rp 5 and Rp 6 each independently represent an alkyl group, an aryl group or a heteroaryl group;
B 1 and B 2 each independently represent BRp 11 Rp 12 , Rp 11 and Rp 12 each independently represent a substituent,
Rp 11 and Rp 12 may combine with each other to form a ring.
<7> The composition according to any one of <1> to <6>, wherein the curable compound contains a polymerizable compound.
<8> The composition according to any one of <1> to <7>, wherein the curable compound contains a resin having an acid group.
<9> A film obtained using the composition according to any one of <1> to <8>.
<10> An optical filter including the film according to <9>.
<11> A solid-state imaging device including the film according to <9>.
<12> An image display device comprising the film according to <9>.
<13> An infrared sensor including the film according to <9>.
 本発明によれば、異物欠陥の抑制された膜を形成できる組成物、異物欠陥の抑制された膜、光学フィルタ、固体撮像素子、画像表示装置および赤外線センサを提供することができる。 According to the present invention, it is possible to provide a composition capable of forming a film in which foreign matter defects are suppressed, a film in which foreign matter defects are suppressed, an optical filter, a solid-state imaging device, an image display device, and an infrared sensor.
赤外線センサの一実施形態を示す概略図である。1 is a schematic diagram illustrating one embodiment of an infrared sensor; FIG.
 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、近赤外線とは、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、顔料とは、溶剤に対して溶解しにくい化合物を意味する。
 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 contents of the present invention will be described in detail below.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents both or either acrylate and methacrylate, "(meth)acryl" represents both or either acrylic and methacrylic, and "(meth) ) acryloyl” refers to acryloyl and/or methacryloyl.
In this specification, the weight average molecular weight and number average molecular weight are defined as polystyrene equivalent values in gel permeation chromatography (GPC) measurement.
As used herein, near-infrared light refers to light (electromagnetic waves) with a wavelength of 700 to 2500 nm.
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent.
As used herein, a pigment means a compound that is difficult to dissolve in a solvent.
As used herein, the term "process" includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .
<組成物>
 本発明の組成物は、式(1)で表される化合物と、近赤外線吸収顔料と、硬化性化合物と、を含有し、
 式(1)で表される化合物の含有量が近赤外線吸収顔料の100質量部に対して、0.01~10質量部であることを特徴とする。
<Composition>
The composition of the present invention contains a compound represented by formula (1), a near-infrared absorbing pigment, and a curable compound,
The content of the compound represented by formula (1) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment.
 ここで、一般的に、近赤外線吸収顔料は、長波長領域の光を吸収するように設計されているためHOMO(Highest Occupied Molecular Orbital)準位が高く、LUMO(Lowest Unoccupied Molecular Orbital)準位が低い傾向にある。それゆえ、水等の求核剤や酸等の求電子剤と、近赤外線吸収顔料とが反応して分解物を生じやすい傾向にある。この分解物の結晶が析出し、結晶成長することで異物となると推測される。また、近赤外線吸収顔料は大きなπ平面をもつ構造を有している。従って、近赤外線吸収顔料の分解物も、近赤外線吸収顔料の部分構造を有しており、ある程度大きなπ平面をもつと推測される。大きなπ平面を持つ化合物は、π-πスタッキングしやすく、また、結晶性の高い化合物であることが多いことから、分解物も結晶性が高いと推測される。このため、近赤外線吸収顔料を用いた組成物を使用して膜を形成した場合、膜中に異物欠陥が生じやすいと考えられる。
 これに対し、本発明の組成物は、式(1)で表される化合物を、近赤外線吸収顔料の100質量部に対して、0.01~10質量部含有する。式(1)で表される化合物は、大きなπ平面構造を有する化合物であるため、組成物中において、近赤外線吸収顔料やその分解物などと効果的に相互作用して、近赤外線吸収顔料やその分解物の表面に吸着し、これらの凝集を抑えて、結晶化を抑制することができると推測される。
 このため、本発明の組成物は、近赤外線吸収顔料を含む組成物であるにもかかわらず、式(1)で表される化合物を近赤外線吸収顔料の100質量部に対して0.01~10質量部含有することにより、高温条件下で長期間保管した場合であっても、欠陥の抑制された膜を形成することができる。
Here, in general, the near-infrared absorbing pigment is designed to absorb light in the long wavelength region, and therefore has a high HOMO (Highest Occupied Molecular Orbital) level and a LUMO (Lowest Unoccupied Molecular Orbital) level. tend to be low. Therefore, a nucleophilic agent such as water or an electrophilic agent such as acid tends to react with the near-infrared absorbing pigment to easily produce decomposition products. It is presumed that crystals of this decomposition product precipitate and grow to become foreign matter. Also, the near-infrared absorbing pigment has a structure with a large π plane. Therefore, it is presumed that the decomposition product of the near-infrared absorbing pigment also has the partial structure of the near-infrared absorbing pigment and has a somewhat large π plane. A compound having a large π-plane is likely to undergo π-π stacking, and is often a highly crystalline compound. For this reason, when a film is formed using a composition using a near-infrared absorbing pigment, foreign matter defects are likely to occur in the film.
In contrast, the composition of the present invention contains 0.01 to 10 parts by mass of the compound represented by formula (1) with respect to 100 parts by mass of the near-infrared absorbing pigment. Since the compound represented by the formula (1) is a compound having a large π-plane structure, it effectively interacts with the near-infrared absorbing pigment or its decomposition product in the composition to form the near-infrared absorbing pigment or It is presumed that the decomposed product is adsorbed on the surface to suppress aggregation and crystallization.
Therefore, although the composition of the present invention is a composition containing a near-infrared absorbing pigment, the compound represented by formula (1) is added in an amount of 0.01 to 0.01 per 100 parts by mass of the near-infrared absorbing pigment. By containing 10 parts by mass, it is possible to form a film in which defects are suppressed even when stored for a long period of time under high temperature conditions.
 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、近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。 The composition of the present invention can be used as a composition for optical filters. Types of optical filters include near-infrared cut filters and infrared transmission filters.
 また、本発明の組成物は、フォトリソグラフィ法でのパターン形成用の組成物として好ましく用いることができる。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、酸基を有する樹脂と、重合性モノマー(モノマータイプの重合性化合物)とを用いることが好ましく、酸基を有する樹脂と、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。また、組成物は更に光重合開始剤を含むことが好ましい。 In addition, the composition of the present invention can be preferably used as a composition for pattern formation in photolithography. When the composition of the present invention is used as a composition for photolithography, it is preferable to use a resin having an acid group and a polymerizable monomer (monomer type polymerizable compound) as the curable compound, and the acid group and a polymerizable monomer (monomer-type polymerizable compound) having an ethylenically unsaturated bond-containing group. Moreover, it is preferable that the composition further contains a photopolymerization initiator.
 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。 Each component used in the composition of the present invention will be described below.
<<式(1)で表される化合物(特定化合物)>>
 本発明の組成物は、式(1)で表される化合物(以下、特定化合物ともいう)を含む。
Figure JPOXMLDOC01-appb-C000009
<<Compound represented by formula (1) (specific compound)>>
The composition of the present invention contains a compound represented by formula (1) (hereinafter also referred to as a specific compound).
Figure JPOXMLDOC01-appb-C000009
 式(1)中、R~Rは、それぞれ独立して置換基を表し、RおよびRのいずれか一方はヘテロアリール基で、RおよびRのいずれか一方はヘテロアリール基であり、
 RおよびRは、それぞれ独立してアルキル基、アリール基またはヘテロアリール基を表す。
In formula (1), R 1 to R 4 each independently represent a substituent, one of R 1 and R 2 is a heteroaryl group, and one of R 3 and R 4 is a heteroaryl group and
R5 and R6 each independently represent an alkyl group, an aryl group or a heteroaryl group.
 R~Rが表す置換基としては、アルキル基、アルケニル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、ヘテロアリールオキシカルボニル基、アシルオキシ基、アミノ基、アシルアミノ基、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、ヘテロアリールオキシカルボニルアミノ基、スルホニルアミノ基、スルファモイル基、カルバモイル基、アルキルチオ基、アリールチオ基、ヘテロアリールチオ基、アルキルスルホニル基、アリールスルホニル基、ヘテロアリールスルホニル基、アルキルスルフィニル基、アリールスルフィニル基、ヘテロアリールスルフィニル基、ウレイド基、リン酸アミド基、メルカプト基、スルホ基、カルボキシル基、ニトロ基、ヒドロキサム酸基、スルフィノ基、ヒドラジノ基、イミノ基、シリル基、ヒドロキシ基、ハロゲン原子、シアノ基などが挙げられる。 Substituents represented by R 1 to R 4 include alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, hetero aryloxycarbonyl group, acyloxy group, amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heteroaryl luthio group, alkylsulfonyl group, arylsulfonyl group, heteroarylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group, ureido group, phosphoramide group, mercapto group, sulfo group, carboxyl group, nitro group, hydroxam Acid group, sulfino group, hydrazino group, imino group, silyl group, hydroxy group, halogen atom, cyano group and the like.
 式(1)のRおよびRのいずれか一方はヘテロアリール基で、他方は電子求引性基であり、RおよびRのいずれか一方はヘテロアリール基で、他方は電子求引性基であることが好ましい。 Either one of R 1 and R 2 in formula (1) is a heteroaryl group and the other is an electron-withdrawing group, and either one of R 3 and R 4 is a heteroaryl group and the other is an electron-withdrawing group. is preferably a sexual group.
 ここで、Hammettのσp値(シグマパラ値)が正の置換基は、電子求引性基として作用する。本明細書においては、Hammettのσp値が0.2以上の置換基を電子求引性基として例示することができる。σp値は、好ましくは0.25以上であり、より好ましくは0.3以上であり、特に好ましくは0.35以上である。上限は特に制限はないが、好ましくは0.80以下である。電子求引性基の具体例としては、シアノ基(0.66)、カルボキシル基(-COOH:0.45)、アルコキシカルボニル基(例えば、-COOCH:0.45)、アリールオキシカルボニル基(例えば、-COOCH:0.44)、カルバモイル基(例えば、-CONH:0.36)、アルキルカルボニル基(例えば、-COCH:0.50)、アリールカルボニル基(例えば、-COPh:0.43)、アルキルスルホニル基(例えば、-SOCH:0.72)、アリールスルホニル基(例えば、-SOPh:0.68)などが挙げられる。電子求引性基は、シアノ基、アルキルカルボニル基、アルキルスルホニル基およびアリールスルホニル基であることが好ましく、シアノ基であることがより好ましい。すなわち、式(1)のRおよびRの一方、ならびに、RおよびRの一方はそれぞれシアノ基であることが好ましい。ここで、Phはフェニル基を表す。Hammettのσp値については、特開2009-263614号公報の段落0024~0025を参酌でき、この内容は本明細書に組み込まれる。 Here, a substituent having a positive Hammett's σp value (sigma para value) acts as an electron-withdrawing group. In the present specification, a substituent having a Hammett's σp value of 0.2 or more can be exemplified as an electron-withdrawing group. The σp value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more. Although the upper limit is not particularly limited, it is preferably 0.80 or less. Specific examples of the electron-withdrawing group include a cyano group (0.66), a carboxyl group (-COOH: 0.45), an alkoxycarbonyl group (e.g., -COOCH 3 : 0.45), an aryloxycarbonyl group ( For example, —COOCH 3 : 0.44), carbamoyl group (for example —CONH 2 : 0.36), alkylcarbonyl group (for example —COCH 3 : 0.50), arylcarbonyl group (for example —COPh: 0 .43), alkylsulfonyl groups (eg —SO 2 CH 3 : 0.72), arylsulfonyl groups (eg —SO 2 Ph: 0.68), and the like. The electron-withdrawing group is preferably a cyano group, an alkylcarbonyl group, an alkylsulfonyl group and an arylsulfonyl group, more preferably a cyano group. That is, one of R 1 and R 2 and one of R 3 and R 4 in formula (1) are each preferably a cyano group. Here, Ph represents a phenyl group. Hammett's σp value can be referred to paragraphs 0024 to 0025 of JP-A-2009-263614, the contents of which are incorporated herein.
 式(1)のRおよびRのいずれか一方が表すヘテロアリール基、ならびに、式(1)のRおよびRのいずれか一方が表すヘテロアリール基は、それぞれ独立して、式(A-1)で表される基または式(A-2)で表される基であることが好ましい。ヘテロアリール基が式(A-1)で表される基である場合は、より耐光性に優れた膜を形成することができる。また、ヘテロアリール基が式(A-2)で表される基である場合は、より耐熱性に優れた膜を形成することができる。
Figure JPOXMLDOC01-appb-C000010
The heteroaryl group represented by either one of R 1 and R 2 in formula (1) and the heteroaryl group represented by either one of R 3 and R 4 in formula (1) are each independently represented by the formula ( A group represented by A-1) or a group represented by formula (A-2) is preferable. When the heteroaryl group is a group represented by formula (A-1), a film with more excellent light resistance can be formed. In addition, when the heteroaryl group is a group represented by formula (A-2), a film with more excellent heat resistance can be formed.
Figure JPOXMLDOC01-appb-C000010
 式(A-1)中、XA1はO、S、NRX1またはCRX2X3を表し、RX1~RX3は、それぞれ独立して水素原子または置換基を表し、
 RA1およびRA2は、それぞれ独立して水素原子または置換基を表し、
 RA1とRA2は互いに結合して環を形成してよく、
 *は結合手を表す;
 式(A-2)中、YA1~YA4は、それぞれ独立してNまたはCRY1を表し、RY1は水素原子または置換基を表し、
 YA1~YA4の少なくとも2つはCRY1であり、
 YA1~YA4のうち隣接する2つがCRY1である場合、隣接する2つのCRY1におけるRY1同士は互いに結合して環を形成してよく、
 *は結合手を表す。
In formula (A-1), X A1 represents O, S, NR X1 or CR X2 R X3 , and R X1 to R X3 each independently represent a hydrogen atom or a substituent,
R A1 and R A2 each independently represent a hydrogen atom or a substituent,
R A1 and R A2 may combine with each other to form a ring,
* represents a bond;
In formula (A-2), Y A1 to Y A4 each independently represent N or CR Y1 , R Y1 represents a hydrogen atom or a substituent,
at least two of Y A1 to Y A4 are CR Y1 ;
When adjacent two of Y A1 to Y A4 are CR Y1 , the R Y1s in the two adjacent CR Y1 may be bonded to each other to form a ring,
* represents a bond.
 まず、式(A-1)で表される基について説明する。式(A-1)のRA1およびRA2が表す置換基としては、後述する置換基Tとして挙げた基および後述する式(R-100)で表される基が挙げられ、ハロゲン原子、アルキル基、アルケニル基またはアルコキシ基であることが好ましい。 First, the group represented by formula (A-1) will be described. Examples of the substituents represented by R A1 and R A2 in formula (A-1) include the groups exemplified as substituent T described later and the groups represented by formula (R-100) described later. is preferably a group, an alkenyl group or an alkoxy group.
 式(A-1)のXA1はO、S、NRX1またはCRX2X3を表し、より耐光性に優れた膜を形成することができるという理由からOまたはSであることが好ましい。RX1~RX3が表す置換基としては、後述する置換基Tで挙げた基および後述する式(R-100)で表される基が挙げられ、ハロゲン原子、アルキル基、アルケニル基またはアルコキシ基であることが好ましい。 X A1 in formula (A-1) represents O, S, NR X1 or CR X2 R X3 , and is preferably O or S because a film with more excellent light resistance can be formed. Examples of substituents represented by R X1 to R X3 include the groups exemplified for the substituent T described later and the groups represented by the formula (R-100) described later, and a halogen atom, an alkyl group, an alkenyl group or an alkoxy group. is preferably
 上記アルキル基およびアルコキシ基の炭素数は、1~20が好ましく、1~15がより好ましく、1~8が更に好ましい。アルキル基およびアルコキシ基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐であることが好ましい。アルキル基およびアルコキシ基は、置換基を有してもよく、無置換であってもよい。置換基としては、後述する置換基Tで挙げた基および後述する式(R-100)で表される基等が挙げられる。
 上記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、2~8が更に好ましい。アルケニル基は、置換基を有してもよく、無置換であってもよい。置換基としては、後述する置換基Tで挙げた基および後述する式(R-100)で表される基等が挙げられる。
 上記ハロゲン原子は、フッ素原子、塩素原子、臭素原子、ヨウ素原子などが挙げられる。
The number of carbon atoms in the alkyl group and alkoxy group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. Alkyl groups and alkoxy groups may be linear, branched, or cyclic, but are preferably linear or branched. The alkyl group and alkoxy group may have a substituent or may be unsubstituted. Examples of the substituent include the groups exemplified for the substituent T described below and the groups represented by the formula (R-100) described below.
The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 2 to 8 carbon atoms. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups exemplified for the substituent T described below and the groups represented by the formula (R-100) described below.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
 式(A-1)において、RA1とRA2は互いに結合して環を形成してよい。形成される環は脂肪族環であってもよいが、芳香族環であることが好ましい。 In formula (A-1), R A1 and R A2 may combine with each other to form a ring. The ring formed may be an aliphatic ring, but is preferably an aromatic ring.
 RA1とRA2とが結合して環を形成する場合、式(A-1)で表される基としては、式(A-1-1)で表される基、および、(A-1-2)で表される基などが挙げられる。
Figure JPOXMLDOC01-appb-C000011
When R A1 and R A2 combine to form a ring, the group represented by formula (A-1) includes a group represented by formula (A-1-1) and (A-1 -2) and the like.
Figure JPOXMLDOC01-appb-C000011
 式中、XA1はO、S、NRX1またはCRX2X3を表し、RX1~RX3は、それぞれ独立して水素原子または置換基を表し、
 RA11~RA20は、それぞれ独立して水素原子または置換基を表し、
 *は結合手を表す。
In the formula, X A1 represents O, S, NR X1 or CR X2 R X3 , and R X1 to R X3 each independently represent a hydrogen atom or a substituent,
R A11 to R A20 each independently represent a hydrogen atom or a substituent,
* represents a bond.
 RA11~RA20が表す置換基としては、式(A-1)のRA1およびRA2が表す置換基として説明した基が挙げられ、好ましい範囲も同様である。 The substituents represented by R A11 to R A20 include the groups described as the substituents represented by R A1 and R A2 in formula (A-1), and the preferred ranges are also the same.
 次に、式(A-2)で表される基について説明する。式(A-2)のYA1~YA4は、それぞれ独立してNまたはCRY1を表し、RY1は水素原子または置換基を表す。RY1が表す置換基としては、式(A-1)のRA1およびRA2が表す置換基として説明した基が挙げられ、好ましい範囲も同様である。 Next, the group represented by formula (A-2) will be described. Y A1 to Y A4 in formula (A-2) each independently represent N or CR Y1 , and R Y1 represents a hydrogen atom or a substituent. Examples of the substituent represented by R 1 Y1 include the groups described as the substituent represented by R A1 and R A2 in formula (A-1), and the preferred range is also the same.
 式(A-2)において、YA1~YA4の少なくとも2つはCRY1である。YA1~YA4のうち隣接する2つがCRY1である場合、隣接する2つのCRY1におけるRY1同士は互いに結合して環を形成してよい。隣接するRY1同士が結合して形成する環は、脂肪族環であってもよいが、芳香族環であることが好ましい。隣接するRY1同士が結合して環を形成する場合、式(A-2)で表される基としては、式(A-2-1)~(A-2-3)で表される基などが挙げられる。
Figure JPOXMLDOC01-appb-C000012
In formula (A-2), at least two of Y A1 to Y A4 are CR Y1 . When adjacent two of Y A1 to Y A4 are CR Y1 , the R Y1s in the two adjacent CR Y1s may combine with each other to form a ring. The ring formed by combining adjacent R Y1s may be an aliphatic ring, but is preferably an aromatic ring. When adjacent R Y1s are bonded to form a ring, the group represented by formula (A-2) includes groups represented by formulas (A-2-1) to (A-2-3). etc.
Figure JPOXMLDOC01-appb-C000012
 式中、YA1~YA4は、それぞれ独立してNまたはCRY1を表し、RY1は水素原子または置換基を表し、
 RA31~RA42は、それぞれ独立して水素原子または置換基を表し、
 *は結合手を表す。
In the formula, Y A1 to Y A4 each independently represent N or CR Y1 , R Y1 represents a hydrogen atom or a substituent,
R A31 to R A42 each independently represent a hydrogen atom or a substituent,
* represents a bond.
 RA31~RA42が表す置換基としては、式(A-1)のRA1およびRA2が表す置換基で説明した基が挙げられ、好ましい範囲も同様である。 The substituents represented by R A31 to R A42 include the groups described for the substituents represented by R A1 and R A2 in formula (A-1), and the preferred ranges are also the same.
 式(1)のRおよびRは、それぞれ独立してアルキル基、アリール基またはヘテロアリール基を表し、アリール基またはヘテロアリール基であることが好ましく、アリール基であることがより好ましい。
 RおよびRが表すアルキル基の炭素数は、1~30が好ましく、1~20がより好ましく、1~10が更に好ましい。アルキル基は、直鎖、分岐および環状のいずれでもよいが、直鎖または分岐であることが好ましい。
 RおよびRが表すアリール基の炭素数は、6~30が好ましく、6~20がより好ましく、6~12が更に好ましい。
 RおよびRが表すヘテロアリール基の環を構成する炭素原子の数は、1~30が好ましく、1~12がより好ましい。ヘテロアリール基を構成するヘテロ原子の種類としては、例えば、窒素原子、酸素原子および硫黄原子を挙げることができる。ヘテロアリール基を構成するヘテロ原子の数としては、1~3が好ましく、1~2がより好ましい。ヘテロアリール基は、単環または縮合環が好ましく、単環または縮合数が2~8の縮合環がより好ましく、単環または縮合数が2~4の縮合環が更に好ましい。RおよびRが表すヘテロアリール基は、上述した式(A-1)で表される基または上述した式(A-2)で表される基であることが好ましい。
R 5 and R 6 in formula (1) each independently represent an alkyl group, an aryl group or a heteroaryl group, preferably an aryl group or a heteroaryl group, more preferably an aryl group.
The number of carbon atoms in the alkyl group represented by R 5 and R 6 is preferably 1-30, more preferably 1-20, even more preferably 1-10. The alkyl group may be linear, branched or cyclic, but preferably linear or branched.
The aryl group represented by R 5 and R 6 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
The number of carbon atoms constituting the ring of the heteroaryl group represented by R 5 and R 6 is preferably 1-30, more preferably 1-12. Types of heteroatoms that constitute the heteroaryl group include, for example, a nitrogen atom, an oxygen atom and a sulfur atom. The number of heteroatoms constituting the heteroaryl group is preferably 1-3, more preferably 1-2. The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring with 2 to 8 condensed numbers, and still more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers. The heteroaryl group represented by R 5 and R 6 is preferably a group represented by the above formula (A-1) or a group represented by the above formula (A-2).
 RおよびRが表すアルキル基、アリール基およびヘテロアリール基は、無置換であってもよく、置換基を有していてもよい。置換基としては、後述する置換基Tで説明した基および式(R-100)で表される基が挙げられる。 The alkyl group, aryl group and heteroaryl group represented by R5 and R6 may be unsubstituted or may have a substituent. Examples of the substituent include the groups described below for the substituent T and the groups represented by the formula (R-100).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
 式(R-100)中、LR1は、脂肪族炭化水素基、芳香族炭化水素基、複素環基、-O-、-S-、-NRL1-、-CO-、-COO-、-OCO-、-SO-もしくはこれらの組み合わせからなるn+1価の連結基を表し、RL1は、水素原子、アルキル基またはアリール基を表し、XR1は、酸基または塩基性基を表し、nは1以上の整数を表し、nが1の場合、LR1は単結合でもよく、*は結合手を表す。 In formula (R-100), L R1 is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, -O-, -S-, -NR L1 -, -CO-, -COO-, - OCO—, —SO 2 —, or an n+1-valent linking group consisting of a combination thereof, R L1 represents a hydrogen atom, an alkyl group or an aryl group, X R1 represents an acid group or a basic group, n represents an integer of 1 or more, and when n is 1, L R1 may be a single bond, and * represents a bond.
 脂肪族炭化水素基の炭素数は、1~20が好ましく、2~20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。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。脂肪族炭化水素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 aliphatic hydrocarbon group is preferably 1-20, more preferably 2-20, still more preferably 2-10, and particularly preferably 2-5. The aliphatic hydrocarbon group may be linear, branched or cyclic. The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
 芳香族炭化水素基の炭素数は6~18が好ましく、6~14がより好ましく、6~10が更に好ましい。芳香族炭化水素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 aromatic hydrocarbon group is preferably 6-18, more preferably 6-14, even more preferably 6-10. The aromatic hydrocarbon group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
 複素環基は、単環または縮合数が2~4の縮合環が好ましい。複素環基の環を構成するヘテロ原子の数は1~3が好ましい。複素環基の環を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。複素環基の環を構成する炭素原子の数は1~30が好ましく、1~18がより好ましく、1~12がより好ましい。複素環基の具体例としては、ピペラジン環基、ピロリジン環基、ピロール環基、ピペリジン環基、ピリジン環基、イミダゾール環基、ピラゾール環基、オキサゾール環基、チアゾール環基、ピラジン環基、モルホリン環基、チアジン環基、インドール環基、イソインドール環基、ベンズイミダゾール環基、プリン環基、キノリン環基、イソキノリン環基、キノキサリン環基、シンノリン環基、カルバゾール環基および下記式(L-1)~(L-7)で表される基が挙げられる。
Figure JPOXMLDOC01-appb-C000014
 式中の*は結合手を表し、Rは水素原子または置換基を表す。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 heterocyclic group is preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1-3. A heteroatom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 1-30, more preferably 1-18, and more preferably 1-12. Specific examples of heterocyclic groups include piperazine ring group, pyrrolidine ring group, pyrrole ring group, piperidine ring group, pyridine ring group, imidazole ring group, pyrazole ring group, oxazole ring group, thiazole ring group, pyrazine ring group, morpholine ring group, thiazine ring group, indole ring group, isoindole ring group, benzimidazole ring group, purine ring group, quinoline ring group, isoquinoline ring group, quinoxaline ring group, cinnoline ring group, carbazole ring group and the following formula (L- 1) to groups represented by (L-7).
Figure JPOXMLDOC01-appb-C000014
* in the formula represents a bond, and R represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
 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で挙げた基が挙げられ、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。 The aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later, preferably a halogen atom, more preferably a fluorine atom.
 RL1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、1~8が更に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましく、直鎖がより好ましい。RL1が表すアルキル基は更に置換基を有していてもよい。置換基としては後述する置換基Tで挙げた基が挙げられる。 The number of carbon atoms in the alkyl group represented by R L1 is preferably 1-20, more preferably 1-15, even more preferably 1-8. The alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear. The alkyl group represented by R L1 may further have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
 RL1が表すアリール基の炭素数は、6~30が好ましく、6~20がより好ましく、6~12が更に好ましい。RL1が表すアリール基は更に置換基を有していてもよい。置換基としては後述する置換基Tで挙げた基が挙げられる。 The number of carbon atoms in the aryl group represented by R L1 is preferably 6-30, more preferably 6-20, even more preferably 6-12. The aryl group represented by R L1 may further have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
 式(R-100)のXR1が表す酸基としては、カルボキシル基、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、-NHCORXR1で表される基が好ましい。スルホンアミド基としては、-NHSOXR2で表される基が好ましい。イミド酸基としては、-SONHSOXR3、-CONHSOXR4、-CONHCORXR5または-SONHCORXR6で表される基が好ましく、-CONHSOXR4、または-SONHSOXR3がより好ましい。RXR1~RXR6は、それぞれ独立してアルキル基またはアリール基を表す。RXR1~RXR6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 represented by X R1 of the formula (R-100) include a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imidic acid group and salts thereof. . Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ion and the like. As the carboxylic acid amide group, a group represented by —NHCOR XR1 is preferable. As the sulfonamide group, a group represented by —NHSO 2 R XR2 is preferable. The imidic acid group is preferably a group represented by —SO 2 NHSO 2 R XR3 , —CONHSO 2 R XR4 , —CONHCOR XR5 or —SO 2 NHCOR XR6 , and —CONHSO 2 R XR4 or —SO 2 NHSO 2 R. XR3 is more preferred. R XR1 to R XR6 each independently represent an alkyl group or an aryl group. The alkyl groups and aryl groups represented by R XR1 to R XR6 may have substituents. The substituent is preferably a halogen atom, more preferably a fluorine atom.
 式(R-100)のXR1が表す塩基性基としては、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 represented by X R1 of formula (R-100) include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups. Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
 アミノ基としては、-NRxR1RxR2で表される基、および、環状アミノ基が挙げられる。-NRxR1RxR2で表される基において、RxR1およびRxR2は、それぞれ独立して、水素原子、アルキル基またはアリール基を表し、アルキル基であることが好ましい。アルキル基の炭素数は、1~10が好ましく、1~5がより好ましく、1~3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が、直鎖または分岐が好ましく、直鎖がより好ましい。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、後述する置換基Tで挙げた基が挙げられる。アリール基の炭素数は、6~30が好ましく、6~20がより好ましく、6~12が更に好ましい。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、後述する置換基Tで挙げた基が挙げられる。また、RxR1とRxR2とは結合して環を形成していてもよい。環状アミノ基としては、ピロリジン基、ピペリジン基、ピペラジン基、モルホリン基などが挙げられる。これらの基は更に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。置換基の具体例としては、アルキル基およびアリール基などが挙げられる。 The amino group includes groups represented by —NRx R1 Rx R2 and cyclic amino groups. In the group represented by -NRx R1 Rx R2 , Rx R1 and Rx R2 each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably an alkyl group. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, and even more preferably 1-3. The alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear. The alkyl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later. The number of carbon atoms in the aryl group is preferably 6-30, more preferably 6-20, even more preferably 6-12. The aryl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later. Also, Rx R1 and Rx R2 may combine to form a ring. Cyclic amino groups include a pyrrolidine group, a piperidine group, a piperazine group, a morpholine group and the like. These groups may further have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later. Specific examples of substituents include alkyl groups and aryl groups.
 式(R-100)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く、1または2であることがより好ましく、1であることが更に好ましい。 n in formula (R-100) represents an integer of 1 or more, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
 式(1)のRおよびRの好ましい態様として、RおよびRの少なくとも一方(好ましくは、RおよびRの両方)が、上述する式(R-100)で表される基を置換基として有するアリール基である態様が挙げられる。この態様によれば、特定化合物の熱分解温度が高くなり、より耐熱性に優れた膜を形成することができる。 As a preferred embodiment of R 5 and R 6 in formula (1), at least one of R 5 and R 6 (preferably both R 5 and R 6 ) is a group represented by the above formula (R-100) and an aryl group having as a substituent. According to this aspect, the thermal decomposition temperature of the specific compound is increased, and a film having more excellent heat resistance can be formed.
 式(1)のRおよびRの別の好ましい態様として、RおよびRの一方が、アリール基で、他方がアルキル基である態様が挙げられる。この態様によれば、特定化合物の可視光領域の吸収が少なくなり、可視光領域の透過率に優れた膜を形成することができる。この態様において、アリール基及びアルキル基は、無置換であってもよく、置換基を有していてもよい。置換基としては、アルキル基、ハロゲン原子、アルコキシ基、アシルオキシ基、アルコキシカルボニル基などが挙げられる。 Another preferred embodiment of R 5 and R 6 in formula (1) is one in which one of R 5 and R 6 is an aryl group and the other is an alkyl group. According to this aspect, absorption of the specific compound in the visible light region is reduced, and a film having excellent transmittance in the visible light region can be formed. In this aspect, the aryl group and the alkyl group may be unsubstituted or may have a substituent. Examples of substituents include alkyl groups, halogen atoms, alkoxy groups, acyloxy groups, and alkoxycarbonyl groups.
 式(1)のRおよびRの別の好ましい態様として、RおよびRが、炭素数1~16のアルコキシ基を置換基として有するアリール基である態様が挙げられる。この態様によれば、より粘度変化の少ない組成物を得ることが出来る。 Another preferred embodiment of R 5 and R 6 in formula (1) is an embodiment in which R 5 and R 6 are aryl groups having an alkoxy group having 1 to 16 carbon atoms as a substituent. According to this aspect, a composition with less change in viscosity can be obtained.
 式(1)のRおよびRの別の好ましい態様として、RおよびRが、無置換のアリール基である態様が挙げられる。この態様によれば、特定化合物の熱分解温度が高くなり、より耐熱性に優れた膜を形成することができる。 Another preferred embodiment of R 5 and R 6 in formula (1) is an embodiment in which R 5 and R 6 are unsubstituted aryl groups. According to this aspect, the thermal decomposition temperature of the specific compound is increased, and a film having more excellent heat resistance can be formed.
 式(1)で表される化合物は、式(1-1)または式(1-2)で表される化合物であることが好ましい。このような化合物を用いることで、より耐光性に優れた膜を形成することができる。
Figure JPOXMLDOC01-appb-C000015
The compound represented by Formula (1) is preferably a compound represented by Formula (1-1) or Formula (1-2). By using such a compound, a film having more excellent light resistance can be formed.
Figure JPOXMLDOC01-appb-C000015
 式(1-1)中、R11およびR12は、それぞれ独立して置換基を表し、
 R13およびR14は、それぞれ独立してアルキル基、アリール基またはヘテロアリール基を表し、
 X11およびX12は、それぞれ独立してO、S、NRX11またはCRX12X13を表し、RX11~RX13は、それぞれ独立して水素原子または置換基を表し、
 R15~R18は、それぞれ独立して水素原子または置換基を表し、
 R15とR16は互いに結合して環を形成してよく、
 R17とR18は互いに結合して環を形成してよい;
 式(1-2)中、R11およびR12はそれぞれ独立して置換基を表し、
 R13およびR14はそれぞれ独立してアルキル基、アリール基またはヘテロアリール基を表し、
 Y11~Y18は、それぞれ独立してNまたはCRY11を表し、RY11は水素原子または置換基を表し、
 Y11~Y14の少なくとも2つと、Y15~Y18の少なくとも2つは、CRY11であり、
 Y11~Y14のうち隣接する2つがCRY11である場合、隣接する2つのCRY11におけるRY11同士は互いに結合して環を形成してよく、
 Y15~Y18のうち隣接する2つがCRY11である場合、隣接する2つのCRY11におけるRY11同士は互いに結合して環を形成してよい。
In formula (1-1), R 11 and R 12 each independently represent a substituent,
R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group;
X 11 and X 12 each independently represent O, S, NR X11 or CR X12 R X13 , R X11 to R X13 each independently represent a hydrogen atom or a substituent,
R 15 to R 18 each independently represent a hydrogen atom or a substituent,
R 15 and R 16 may combine with each other to form a ring,
R 17 and R 18 may combine with each other to form a ring;
In formula (1-2), R 11 and R 12 each independently represent a substituent,
R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group;
Y 11 to Y 18 each independently represent N or CR Y11 , R Y11 represents a hydrogen atom or a substituent,
at least two of Y 11 to Y 14 and at least two of Y 15 to Y 18 are CR Y11 ;
When adjacent two of Y 11 to Y 14 are CR Y11 , R Y11 in the two adjacent CR Y11 may combine with each other to form a ring,
When adjacent two of Y 15 to Y 18 are CR Y11 , R Y11 in the two adjacent CR Y11 may combine with each other to form a ring.
 式(1-1)のR11およびR12が表す置換基、ならびに、式(1-2)のR11およびR12が表す置換基としては、式(1)のR~Rが表す置換基として説明した基が挙げられ、電子求引性基であることが好ましい。式(1-1)のR11およびR12が表す置換基、ならびに、式(1-2)のR11およびR12が表す置換基は、シアノ基、
アルキルカルボニル基、アルキルスルホニル基またはアリールスルホニル基であることが好ましく、シアノ基であることがより好ましい。
The substituents represented by R 11 and R 12 in formula (1-1) and the substituents represented by R 11 and R 12 in formula (1-2) are represented by R 1 to R 4 in formula (1). The groups described as substituents can be mentioned, and electron-withdrawing groups are preferred. The substituents represented by R 11 and R 12 in formula (1-1) and the substituents represented by R 11 and R 12 in formula (1-2) are a cyano group,
An alkylcarbonyl group, an alkylsulfonyl group or an arylsulfonyl group is preferable, and a cyano group is more preferable.
 式(1-1)のR13およびR14、ならびに、式(1-2)のR13およびR14は、式(1)のRおよびRと同義であり、好ましい範囲も同様である。 R 13 and R 14 in formula (1-1) and R 13 and R 14 in formula (1-2) have the same meanings as R 5 and R 6 in formula (1), and the preferred ranges are also the same. .
 式(1-1)のX11およびX12は、それぞれ独立してO、S、NRX11またはCRX12X13を表し、より耐光性に優れた膜を形成することができるという理由からOまたはSであることが好ましい。RX11~RX13が表す置換基としては、上述した式(A-1)のRX1~RX3が表す置換基として説明した基が挙げられ、好ましい範囲も同様である。 X 11 and X 12 in formula (1-1) each independently represent O, S, NR X11 or CR X12 R X13 , and are O or S is preferred. The substituents represented by R X11 to R X13 include the groups described as the substituents represented by R X1 to R X3 in formula (A-1) above, and the preferred ranges are also the same.
 式(1-1)のR15~R18が表す置換基としては、式(A-1)のRA1およびRA2が表す置換基として説明した基が挙げられ、好ましい範囲も同様である。 The substituents represented by R 15 to R 18 in formula (1-1) include the groups described as the substituents represented by R A1 and R A2 in formula (A-1), and the preferred ranges are the same.
 式(1-1)において、R15とR16は互いに結合して環を形成してよく、R17とR18は互いに結合して環を形成してよい。これらの基同士が結合して形成される環は脂肪族環であってもよいが、芳香族環であることが好ましい。 In formula (1-1), R 15 and R 16 may combine to form a ring, and R 17 and R 18 may combine to form a ring. The ring formed by combining these groups may be an aliphatic ring, but is preferably an aromatic ring.
 式(1-2)のY11~Y18は、それぞれ独立してNまたはCRY11を表し、RY11は水素原子または置換基を表し、Y11~Y14の少なくとも2つと、Y15~Y18の少なくとも2つは、CRY11である。RY11が表す置換基としては、式(A-1)のRA1およびRA2が表す置換基で説明した基が挙げられ、好ましい範囲も同様である。 Y 11 to Y 18 in formula (1-2) each independently represent N or CR Y11 , R Y11 represents a hydrogen atom or a substituent, and at least two of Y 11 to Y 14 and Y 15 to Y At least two of 18 are CR Y11 . Examples of the substituent represented by R 1 Y11 include the groups described for the substituent represented by R A1 and R A2 in formula (A-1), and the preferred range is also the same.
 式(1-2)において、Y11~Y14のうち隣接する2つがCRY11である場合、隣接する2つのCRY11におけるRY11同士は互いに結合して環を形成してよく、Y15~Y18のうち隣接する2つがCRY11である場合、隣接する2つのCRY11におけるRY11同士は互いに結合して環を形成してよい。これらの基同士が結合して形成される環は脂肪族環であってもよいが、芳香族環であることが好ましい。 In formula (1-2), when adjacent two of Y 11 to Y 14 are CR Y11 , R Y11 in two adjacent CR Y11 may be bonded to each other to form a ring, and Y 15 to When adjacent two of Y18 are CR Y11 , R Y11 in two adjacent CR Y11 may be bonded to each other to form a ring. The ring formed by combining these groups may be an aliphatic ring, but is preferably an aromatic ring.
(置換基T)
 置換基Tとして、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)、ヘテロアリール基(好ましくは炭素数1~30のヘテロアリール基)、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)、ヘテロアリールオキシ基(好ましくは炭素数1~30のヘテロアリールオキシ基)、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)、ヘテロアリールオキシカルボニル基(好ましくは炭素数2~30のヘテロアリール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)、ヘテロアリールチオ基(好ましくは炭素数1~30のヘテロアリールチオ基)、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)、ヘテロアリールスルホニル基(好ましくは炭素数1~30のヘテロアリールスルホニル基)、ヘテロアリールスルホニルアミノ基(好ましくは炭素数1~30のヘテロアリール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)、ヘテロアリールスルフィニル基(好ましくは炭素数1~30のヘテロアリールスルフィニル基)、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、カルボキシル基、スルホ基、リン酸基、カルボン酸アミド基、スルホンアミド基、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、ヘテロアリールアゾ基、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。
(substituent T)
Substituent T includes the following groups. Halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (preferably alkyl group having 1 to 30 carbon atoms), alkenyl group (preferably alkenyl group having 2 to 30 carbon atoms), 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 heteroaryl group (preferably a heteroaryl group having 1 to 30 carbon atoms), an amino group (preferably amino group having 0 to 30 carbon atoms), alkoxy group (preferably alkoxy group having 1 to 30 carbon atoms), aryloxy group (preferably aryloxy group having 6 to 30 carbon atoms), heteroaryloxy group (preferably carbon 1 to 30 heteroaryloxy groups), acyl groups (preferably acyl groups having 2 to 30 carbon atoms), alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 30 carbon atoms), aryloxycarbonyl groups (preferably aryloxycarbonyl group having 7 to 30 carbon atoms), heteroaryloxycarbonyl group (preferably heteroaryloxycarbonyl group having 2 to 30 carbon atoms), acyloxy group (preferably acyloxy group having 2 to 30 carbon atoms), acylamino group (preferably acylamino group having 2 to 30 carbon atoms), aminocarbonylamino group (preferably aminocarbonylamino group having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably alkoxycarbonylamino group having 2 to 30 carbon atoms) , aryloxycarbonylamino group (preferably aryloxycarbonylamino group having 7 to 30 carbon atoms), sulfamoyl group (preferably sulfamoyl group having 0 to 30 carbon atoms), sulfamoylamino group (preferably 0 to 30 carbon atoms sulfamoylamino group), carbamoyl group (preferably carbamoyl group having 1 to 30 carbon atoms), alkylthio group (preferably alkylthio group having 1 to 30 carbon atoms), arylthio group (preferably arylthio group having 6 to 30 carbon atoms) group), heteroarylthio group (preferably heteroarylthio group having 1 to 30 carbon atoms), alkylsulfonyl group (preferably alkylsulfonyl group having 1 to 30 carbon atoms), alkylsulfonylamino group (preferably 1 to 30 alkylsulfonylamino groups), arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 30 carbon atoms), arylsulfonylamino groups (preferably arylsulfonylamino groups having 6 to 30 carbon atoms), heteroaryls Sulfonyl group (preferably heteroarylsulfonyl group having 1 to 30 carbon atoms), heteroarylsulfonylamino group (preferably heteroarylsulfonylamino group having 1 to 30 carbon atoms), alkylsulfinyl group (preferably having 1 to 30 carbon atoms) alkylsulfinyl group), arylsulfinyl group (preferably arylsulfinyl group having 6 to 30 carbon atoms), heteroarylsulfinyl group (preferably heteroarylsulfinyl group having 1 to 30 carbon atoms), ureido group (preferably 1 to ureido group of 30), hydroxy group, nitro group, carboxyl group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonamide group, imide group, phosphino group, mercapto group, cyano group, alkylsulphino group, arylsulphino group a fino group, an arylazo group, a heteroarylazo group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group, a hydrazino group and an imino group; These groups may further have substituents if they are substitutable groups. Examples of the substituent include the groups described for the substituent T described above.
 特定化合物は、25℃のプロピレングリコールメチルエーテルアセテート100gに対する溶解度が、0.1g以上であることが好ましく、0.2g以上であることがより好ましく、0.5g以上であることがさらに好ましい。 The solubility of the specific compound in 100 g of propylene glycol methyl ether acetate at 25°C is preferably 0.1 g or more, more preferably 0.2 g or more, and even more preferably 0.5 g or more.
 特定化合物の具体例としては、後述する実施例に記載の構造の化合物(PP-001~PP-010)が挙げられる。 Specific examples of the specific compounds include compounds (PP-001 to PP-010) having structures described in Examples described later.
 特定化合物の含有量は、近赤外線吸収顔料100質量部に対して、0.01~10質量部である。上限は、3質量部以下であることが好ましく、1質量部以下であることがより好ましく、本発明の効果がより顕著に奏されるという理由から0.8質量部以下であることが更に好ましい。下限は、0.03質量部以上であることが好ましく、0.05質量部以上であることがより好ましい。
 また、特定化合物の含有量は組成物の全固形分中0.002質量%以上であることが好ましく、0.006質量%以上であることがより好ましく、0.01質量%以上であることが更に好ましい。上限は、2質量%以下であることが好ましく、0.2質量%以下であることがより好ましく、0.1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。本発明の組成物が特定化合物を2種以上含む場合は、特定化合物の添加量を増やしても、特定化合物の結晶の析出を抑制することができる。また、本発明の組成物が特定化合物を2種以上含む場合は、酸基を有する化合物と、塩基性基を持つものを併用しないことが塩形成による結晶析出を防ぐ観点で好ましい。
 本発明の組成物が特定化合物を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 content of the specific compound is 0.01 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment. The upper limit is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.8 parts by mass or less for the reason that the effects of the present invention are exhibited more remarkably. . The lower limit is preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more.
The content of the specific compound is preferably 0.002% by mass or more, more preferably 0.006% by mass or more, and more preferably 0.01% by mass or more in the total solid content of the composition. More preferred. The upper limit is preferably 2% by mass or less, more preferably 0.2% by mass or less, and even more preferably 0.1% by 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 the composition of the present invention contains two or more specific compounds, precipitation of crystals of the specific compound can be suppressed even if the amount of the specific compound added is increased. When the composition of the present invention contains two or more specific compounds, it is preferable not to use a compound having an acid group and a compound having a basic group together from the viewpoint of preventing crystal precipitation due to salt formation.
When the composition of the present invention contains two or more specific compounds, the total amount thereof is preferably within the above range.
<<近赤外線吸収顔料>>
 本発明の組成物は、近赤外線吸収顔料を含む。近赤外線吸収顔料は、有機顔料であることが好ましい。なお、有機顔料とは、有機化合物で構成された顔料である。近赤外線吸収顔料は、近赤外線領域(好ましくは700~1800nmの範囲、より好ましくは700~1300nmの範囲、更に好ましくは700~1000nmの範囲)に極大吸収波長を有する顔料であることが好ましい。
<<Near-infrared absorption pigment>>
The composition of the present invention contains a near-infrared absorbing pigment. The near-infrared absorbing pigment is preferably an organic pigment. In addition, an organic pigment is a pigment composed of an organic compound. The near-infrared absorbing pigment is preferably a pigment having a maximum absorption wavelength in the near-infrared region (preferably in the range of 700-1800 nm, more preferably in the range of 700-1300 nm, still more preferably in the range of 700-1000 nm).
 近赤外線吸収顔料は、25℃のプロピレングリコールメチルエーテルアセテート100gへの溶解度が、1g未満であることが好ましく、0.1g以下であることがより好ましく、0.05g以下であることがさらに好ましい。 The solubility of the near-infrared absorbing pigment in 100 g of propylene glycol methyl ether acetate at 25°C is preferably less than 1 g, more preferably 0.1 g or less, and even more preferably 0.05 g or less.
 近赤外線吸収顔料としては、ピロロピロール化合物、シアニン化合物、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、ボラジアジン化合物などが挙げられ、ピロロピロール化合物、シアニン化合物、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およびボラジアジン化合物から選ばれる少なくとも1種であることがより好ましく、ピロロピロール化合物であることが更に好ましい。ピロロピロール化合物としては、式(P-1)で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000016
Near-infrared absorbing pigments include pyrrolopyrrole compounds, cyanine 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, boradiazine compounds, etc., and more preferably at least one selected from pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds and boradiazine compounds; Pyrrole compounds are more preferred. The pyrrolopyrrole compound is preferably a compound represented by formula (P-1).
Figure JPOXMLDOC01-appb-C000016
 式(P-1)中、Rp~Rpはそれぞれ独立して置換基を表し、かつ、RpおよびRpのいずれか一方はヘテロアリール基で、RpおよびRpのいずれか一方はヘテロアリール基であり、
 RpおよびRpは、それぞれ独立してアルキル基、アリール基またはヘテロアリール基を表し、
 BおよびBは、それぞれ独立してBRp11Rp12を表し、Rp11およびRp12は、それぞれ独立して置換基を表し、
 Rp11とRp12は互いに結合して環を形成してよい。
In formula (P-1), Rp 1 to Rp 4 each independently represent a substituent, one of Rp 1 and Rp 2 is a heteroaryl group, and one of Rp 3 and Rp 4 is a heteroaryl group,
Rp 5 and Rp 6 each independently represent an alkyl group, an aryl group or a heteroaryl group;
B 1 and B 2 each independently represent BRp 11 Rp 12 , Rp 11 and Rp 12 each independently represent a substituent,
Rp 11 and Rp 12 may combine with each other to form a ring.
 式(P-1)のRp~Rpが表す置換基としては、式(1)のR~Rが表す置換基として説明した基が挙げられる。 Examples of the substituents represented by Rp 1 to Rp 4 of formula (P-1) include the groups described as the substituents represented by R 1 to R 4 of formula (1).
 式(P-1)のRpおよびRpのいずれか一方が表すヘテロアリール基、ならびに、式(P-1)のRpおよびRpのいずれか一方が表すヘテロアリール基は、それぞれ独立して、上述した式(A-1)で表される基または式(A-2)で表される基であることが好ましい。 The heteroaryl group represented by either one of Rp 1 and Rp 2 in formula (P-1) and the heteroaryl group represented by either one of Rp 3 and Rp 4 in formula (P-1) are each independently is preferably a group represented by formula (A-1) or a group represented by formula (A-2).
 式(P-1)のRpおよびRpのいずれか一方はヘテロアリール基で、他方は電子求引性基であり、RpおよびRpのいずれか一方はヘテロアリール基で、他方は電子求引性基であることが好ましい。また、電子求引性基は、シアノ基、アルキルカルボニル基、アルキルスルホニル基およびアリールスルホニル基であることが好ましく、シアノ基であることがより好ましい。 Either one of Rp 1 and Rp 2 in formula (P-1) is a heteroaryl group, the other is an electron-withdrawing group, and one of Rp 3 and Rp 4 is a heteroaryl group, the other is an electron An attracting group is preferred. Further, the electron-withdrawing group is preferably a cyano group, an alkylcarbonyl group, an alkylsulfonyl group and an arylsulfonyl group, more preferably a cyano group.
 式(P-1)のRpおよびRpは、それぞれ独立してアルキル基、アリール基またはヘテロアリール基を表し、アリール基またはヘテロアリール基であることが好ましく、アリール基であることがより好ましい。
 RpおよびRpが表すアルキル基の炭素数は、1~30が好ましく、1~20がより好ましく、1~10が更に好ましい。アルキル基は、直鎖、分岐および環状のいずれでもよいが、直鎖または分岐であることが好ましい。
 RpおよびRpが表すアリール基の炭素数は、6~30が好ましく、6~20がより好ましく、6~12が更に好ましい。
 RpおよびRpが表すヘテロアリール基の環を構成する炭素原子の数は、1~30が好ましく、1~12がより好ましい。ヘテロアリール基を構成するヘテロ原子の種類としては、例えば、窒素原子、酸素原子および硫黄原子を挙げることができる。ヘテロアリール基を構成するヘテロ原子の数としては、1~3が好ましく、1~2がより好ましい。ヘテロアリール基は、単環または縮合環が好ましく、単環または縮合数が2~8の縮合環がより好ましく、単環または縮合数が2~4の縮合環が更に好ましい。RpおよびRpが表すヘテロアリール基は、上述した式(A-1)で表される基または上述した式(A-2)で表される基であることが好ましい。
Rp 5 and Rp 6 in formula (P-1) each independently represent an alkyl group, an aryl group or a heteroaryl group, preferably an aryl group or a heteroaryl group, more preferably an aryl group. .
The number of carbon atoms in the alkyl group represented by Rp 5 and Rp 6 is preferably 1-30, more preferably 1-20, even more preferably 1-10. The alkyl group may be linear, branched or cyclic, but preferably linear or branched.
The aryl group represented by Rp 5 and Rp 6 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
The number of carbon atoms constituting the ring of the heteroaryl group represented by Rp 5 and Rp 6 is preferably 1-30, more preferably 1-12. Types of heteroatoms that constitute the heteroaryl group include, for example, a nitrogen atom, an oxygen atom and a sulfur atom. The number of heteroatoms constituting the heteroaryl group is preferably 1-3, more preferably 1-2. The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring with 2 to 8 condensed numbers, and still more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers. The heteroaryl group represented by Rp 5 and Rp 6 is preferably a group represented by the above formula (A-1) or a group represented by the above formula (A-2).
 式(P-1)のBおよびBは、それぞれ独立してBRp11Rp12を表し、Rp11およびRp12は、それぞれ独立して置換基を表す。
 Rp11およびRp12が表す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、ヘテロアリール基、アルコキシ基、アリールオキシ基およびヘテロアリールオキシ基が挙げられ、ハロゲン原子、アルキル基、アリール基またはヘテロアリール基であることが好ましく、ハロゲン原子、アルキル基またはアリール基であることがより好ましく、アリール基であることが更に好ましい。
B 1 and B 2 in formula (P-1) each independently represent BRp 11 Rp 12 , and Rp 11 and Rp 12 each independently represent a substituent.
Examples of substituents represented by Rp 11 and Rp 12 include halogen atoms, alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups and heteroaryloxy groups. or is preferably a heteroaryl group, more preferably a halogen atom, an alkyl group or an aryl group, and even more preferably an aryl group.
 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、フッ素原子が好ましい。
 アルキル基およびアルコキシ基の炭素数は、1~20が好ましく、1~15がより好ましく、1~8が更に好ましい。アルキル基およびアルコキシ基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐であることが好ましい。アルキル基およびアルコキシ基は、置換基を有してもよく、無置換であってもよい。置換基としては、アリール基、ヘテロアリール基、ハロゲン原子などが挙げられる。
 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、2~8が更に好ましい。アルケニル基は、置換基を有してもよく、無置換であってもよい。置換基としては、アルコキシ基、アリール基、ヘテロアリール基、ハロゲン原子などが挙げられる。
 アリール基およびアリールオキシ基の炭素数は、6~20が好ましく、6~12がより好ましい。アリール基およびアリールオキシ基は、置換基を有していてもよく、無置換であってもよい。置換基としては、アルキル基、アルコキシ基、ハロゲン原子などが挙げられる。
 ヘテロアリール基およびヘテロアリールオキシ基は、単環であってもよく、縮合環であってもよい。ヘテロアリール基およびヘテロアリールオキシ基のヘテロアリール環を構成するヘテロ原子の数は1~3が好ましい。ヘテロアリール環を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。ヘテロアリール環の環を構成する炭素原子の数は1~30が好ましく、1~18がより好ましく、1~12が更に好ましい。ヘテロアリール環は、5員環または6員環が好ましい。ヘテロアリール基およびヘテロアリールオキシ基は、置換基を有していてもよく、無置換であってもよい。置換基としては、アルキル基、アルコキシ基、ハロゲン原子などが挙げられる。
A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.
The number of carbon atoms in the alkyl group and alkoxy group is preferably 1-20, more preferably 1-15, even more preferably 1-8. Alkyl groups and alkoxy groups may be linear, branched or cyclic, but are preferably linear or branched. The alkyl group and alkoxy group may have a substituent or may be unsubstituted. Substituents include aryl groups, heteroaryl groups, halogen atoms, and the like.
The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 2 to 8 carbon atoms. The alkenyl group may have a substituent or may be unsubstituted. Substituents include alkoxy groups, aryl groups, heteroaryl groups, halogen atoms and the like.
The aryl group and the aryloxy group preferably have 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. The aryl group and aryloxy group may have a substituent or may be unsubstituted. Examples of substituents include alkyl groups, alkoxy groups, and halogen atoms.
A heteroaryl group and a heteroaryloxy group may be monocyclic or condensed. The number of heteroatoms constituting the heteroaryl ring of the heteroaryl group and heteroaryloxy group is preferably 1 to 3. A heteroatom constituting the heteroaryl ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the heteroaryl ring is preferably 1-30, more preferably 1-18, even more preferably 1-12. The heteroaryl ring is preferably a 5- or 6-membered ring. A heteroaryl group and a heteroaryloxy group may have a substituent or may be unsubstituted. Examples of substituents include alkyl groups, alkoxy groups, and halogen atoms.
 BおよびBが表すBRp11Rp12のRp11とRp12は互いに結合して環を形成してよい。形成される環としては、例えば、下記(B-1)~(B-5)に示す構造などが挙げられる。以下において、Rbは置換基を表し、Rb~Rbは、それぞれ独立して水素原子又は置換基を表し、b1~b3は、それぞれ独立して0~4の整数を表し、b4は0~6の整数を表し、*は連結手を表す。RbおよびRb~Rbが表す置換基としては、上述した置換基Tで挙げた基が挙げられ、ハロゲン原子、アルキル基、アルコキシ基が好ましい。
Figure JPOXMLDOC01-appb-C000017
Rp 11 and Rp 12 of BRp 11 Rp 12 represented by B 1 and B 2 may combine with each other to form a ring. Examples of the ring to be formed include structures shown in (B-1) to (B-5) below. In the following, Rb represents a substituent, Rb 1 to Rb 4 each independently represent a hydrogen atom or a substituent, b1 to b3 each independently represent an integer of 0 to 4, b4 is 0 to It represents an integer of 6, and * represents a link. Substituents represented by Rb and Rb 1 to Rb 4 include the groups exemplified for the substituent T described above, preferably halogen atoms, alkyl groups and alkoxy groups.
Figure JPOXMLDOC01-appb-C000017
 ピロロピロール化合物の具体例としては、後述する実施例に記載の構造の化合物が挙げられる。また、ピロロピロール化合物としては、特開2009-263614号公報の段落番号0016~0058に記載の化合物、特開2011-068731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。 Specific examples of the pyrrolopyrrole compound include compounds having structures described in Examples described later. Further, as the pyrrolopyrrole compound, compounds described in paragraph numbers 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph numbers 0037-0052 of JP-A-2011-068731, International Publication No. 2015/166873 and the compounds described in paragraph numbers 0010 to 0033 of No. Examples of the squarylium compound include compounds described in paragraph numbers 0044 to 0049 of JP-A-2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese Patent No. 6065169, and paragraph number 0040 of WO 2016/181987. Compounds described in, compounds described in JP-A-2015-176046, compounds described in paragraph No. 0072 of WO 2016/190162, compounds described in paragraph Nos. 0196 to 0228 of JP-A-2016-074649 , the compound described in paragraph number 0124 of JP 2017-067963, the compound described in WO 2017/135359, the compound described in JP 2017-114956, the compound described in Patent 6197940, Examples include compounds described in International Publication No. 2016/120166.
 スクアリリウム化合物の具体例としては、後述する実施例に記載の構造の化合物が挙げられる。また、スクアリリウム化合物およびクロコニウム化合物としては、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に記載の化合物、特開2018-040955号公報の段落番号0078~0082に記載の化合物、特開2018-002773号公報の段落番号0043~0069に記載の化合物、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に記載の化合物、特開2017-067963号公報に記載の化合物などが挙げられる。 Specific examples of the squarylium compound include compounds having structures described in Examples described later. Further, as the squarylium compound and the croconium compound, the squarylium compound described in JP-A-2017-197437, the squarylium compound described in JP-A-2017-025311, the squarylium compound described in International Publication No. 2016/154782, the patent Squarylium compounds described in Japanese Patent No. 5884953, squarylium compounds described in Japanese Patent No. 6036689, squarylium compounds described in Japanese Patent No. 5810604, squarylium compounds described in paragraph numbers 0090 to 0107 of International Publication No. 2017/213047 , Compounds described in paragraphs 0019 to 0075 of JP 2018-054760, compounds described in paragraphs 0078 to 0082 of JP 2018-040955, paragraphs 0043 to 0069 of JP 2018-002773 , a squarylium compound having an aromatic ring at the amide α-position described in paragraphs 0024 to 0086 of JP-A-2018-041047, an amide-linked squarylium compound described in JP-A-2017-179131, JP-A Compounds having a pyrrole bis-type squarylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazole-bis-type squarylium compounds described in JP-A-2017-082029, paragraph numbers 0027 to 0027 of JP-A-2017-068120 0114, compounds described in JP-A-2017-067963, and the like.
 ボラジアジン化合物としては、後述する実施例に記載の構造の化合物が挙げられる。また、ボラジアジン化合物としては、特開2015-040231号公報の段落番号0103~0117に記載の化合物が挙げられる。 Examples of boradiazine compounds include compounds having structures described in Examples described later. Further, examples of boradiazine compounds include compounds described in paragraphs 0103 to 0117 of JP-A-2015-040231.
 シアニン化合物としては、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などが挙げられる。 As the cyanine compound, compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, compounds described in paragraphs 0026-0030 of JP-A-2002-194040, and JP-A-2015-172004. The compound, the compound described in JP-A-2015-172102, the compound described in JP-A-2008-088426, the compound described in paragraph number 0090 of WO 2016/190162, JP-A-2017-031394 and the like compounds described in.
 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2020/071486号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号に記載のフタロシアニン化合物が挙げられる。 Examples of the phthalocyanine compound include compounds described in paragraph number 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraph numbers 0013 to 0029 of JP-A-2013-195480. compounds, vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, vanadium phthalocyanine compounds described in International Publication No. 2020/071486, and phthalocyanine compounds described in International Publication No. 2020/071470.
 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。 Examples of naphthalocyanine compounds include compounds described in paragraph number 0093 of JP-A-2012-077153.
 近赤外線吸収顔料の25℃のプロピレングリコールメチルエーテルアセテート100gへの溶解度S1は、上述した特定化合物の25℃のプロピレングリコールメチルエーテルアセテート100gへの溶解度S2よりも小さいことが好ましい。異物結晶への表面吸着性を高めることができるという理由から、溶解度S2-溶解度S1の値は10g以下であることが好ましく、5g以下であることがより好ましく、3g以下であることが更に好ましい。 The solubility S1 of the near-infrared absorbing pigment in 100 g of propylene glycol methyl ether acetate at 25°C is preferably smaller than the solubility S2 of the specific compound described above in 100 g of propylene glycol methyl ether acetate at 25°C. The value of solubility S2-solubility S1 is preferably 10 g or less, more preferably 5 g or less, and even more preferably 3 g or less, because the surface adsorption to foreign crystals can be enhanced.
 近赤外線吸収顔料の含有量は、組成物の全固形分中1~50質量%であることが好ましい。下限は、3質量%以上であることが好ましく、5質量%以上であることがより好ましく、10質量%以上であることが更に好ましい。上限は、40質量%以下であることが好ましく、30質量%以下であることがより好ましい。 The content of the near-infrared absorbing pigment is preferably 1 to 50 mass% of the total solid content of the composition. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
<<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および環状エーテ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、(メタ)アリル基、(メタ)アクリロイル基などが挙げられる。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。エポキシ基は、脂環式エポキシ基であってもよい。なお、脂環式エポキシ基とは、エポキシ環と飽和炭化水素環とが縮合した環状構造を有する1価の官能基のことを意味する。
<<Curable compound>>
The composition of the invention contains a curable compound. Examples of curable compounds 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). Polymerizable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred. The epoxy group may be a cycloaliphatic epoxy group. The alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
 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、樹脂は、酸基を有する樹脂を含むものであることが好ましい。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、酸基を有する樹脂と、重合性モノマー(モノマータイプの重合性化合物)とを用いることが好ましく、酸基を有する樹脂と、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。 As the curable compound, it is preferable to use one containing at least a resin. Moreover, the resin preferably contains a resin having an acid group. Further, when the composition of the present invention is used as a composition for photolithography, it is preferable to use a resin having an acid group and a polymerizable monomer (monomer type polymerizable compound) as the curable compound. It is more preferable to use a resin having an acid group and a polymerizable monomer (monomer-type polymerizable compound) having an ethylenically unsaturated bond-containing group.
(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および環状エーテ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)
Examples of the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group and compounds having a cyclic ether group. A compound having an ethylenically unsaturated bond-containing group can be preferably used as a radically polymerizable compound. A compound having a cyclic ether group can also be preferably used as a cationically 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 containing repeating units having 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, more preferably 1500 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 or more. The weight average molecular weight (Mw) of the resin-type polymerizable compound is preferably 2,000 to 2,000,000. The upper limit of the weight average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit of the weight average molecular weight is preferably 3000 or more, more preferably 5000 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, more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples include paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph numbers 0254-0257 of JP-A-2008-292970, and JP-A-2013-253224. Paragraph numbers 0034 to 0038 of the publication, paragraph number 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, JP 6031807, JP 2017-194662 and the contents of which are incorporated herein.
 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。 Examples of compounds having an ethylenically unsaturated bond-containing group include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetra(meth)acrylate (commercially available). KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate ) Acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and the (meth)acryloyl groups of these compounds are ethylene glycol and / Or a compound having a structure linked via a propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer).
 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(エチレンオキサイド)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)、DPHA-40H(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、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600、LINC-202UA(以上、共栄社化学(株)製)などを用いることもできる。 Further, as compounds having an ethylenically unsaturated bond-containing group, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (Shin-Nakamura Chemical Industry 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.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) Nippon Kayaku Co., Ltd.), Aronix TO-2349 (Toagosei Co., Ltd.), NK Oligo UA-7200 (Shin Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (Taisei Fine Chemical Co., Ltd.) ), light acrylate POB-A0, UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), etc. can also
 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サイド変性トリ(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サイド変性トリ(メタ)アクリレート、イソシアヌル酸エチレンオキサイド変性トリ(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。 Examples of compounds having an ethylenically unsaturated bond-containing group include trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, and isocyanuric acid. It is also preferable to use trifunctional (meth)acrylate compounds such as ethylene oxide-modified tri(meth)acrylate and pentaerythritol tri(meth)acrylate. Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305. , M-303, M-452, 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, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) etc.
 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、カルボキシル基、スルホ基、リン酸基等の酸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。 Also, as the compound having an ethylenically unsaturated bond-containing group, a compound having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group can be used. 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KAYARAD DPCA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。 A compound having a caprolactone structure can also be used as the compound having an ethylenically unsaturated bond-containing group. For compounds having a caprolactone structure, the descriptions in paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, the contents of which are incorporated herein. Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as KAYARAD DPCA 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。 A compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used as the compound having an ethylenically unsaturated bond-containing group. Such a compound is preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and/or a propyleneoxy group, and is a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group. More preferably, it is a tri- to hexa-functional (meth)acrylate compound having 4 to 20 ethyleneoxy groups. Commercially available products include, for example, SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer Co., Ltd., and a trifunctional (meth)acrylate having three isobutyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. KAYARAD TPA-330, etc.
 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。 A polymerizable compound having a fluorene skeleton can also be used as the compound having an ethylenically unsaturated bond-containing group. Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomer 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 the compound having an ethylenically unsaturated bond-containing group, it is also preferable to use a compound such as toluene that does not substantially contain environmentally regulated substances. 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。 Compounds having a cyclic ether group include compounds having an epoxy group, compounds having an oxetanyl group, and the like, and compounds having an epoxy group are preferred. 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 two 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。 A compound having a cyclic ether group may be a low-molecular compound (for example, a molecular weight of less than 1000) or a macromolecule (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight-average molecular weight of 1000 or more). The weight average molecular weight of the cyclic ether group is preferably from 200 to 100,000, more preferably from 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 the compound having a cyclic ether group, compounds described in paragraph numbers 0034 to 0036 of JP-A-2013-011869, compounds described in paragraph numbers 0147-0156 of JP-A-2014-043556, JP 2014 The compounds described in paragraphs 0085 to 0092 of JP-A-089408 and the compounds described in JP-A-2017-179172 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 having a cyclic ether group include Denacol EX-212L, EX-212, EX-214L, EX-214, EX-216L, EX-216, EX-321L, EX-321, EX-850L, EX -850 (manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC -7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (manufactured by ADEKA Corporation) Daicel), Cychromer P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (manufactured by Daicel Co., Ltd.), jER1031S, jER157S65, jER152, jER154, jER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.) ), Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.), ADEKA GLYCIROL ED-505 (manufactured by ADEKA Co., Ltd., epoxy group-containing monomer), Proof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation, epoxy group containing polymer), OXT-101, OXT-121, OXT-212, OXT-221 (manufactured by Toagosei Co., Ltd., oxetanyl group-containing monomer), OXE-10, OXE-30 (above, Osaka Organic Chemical Industry ( Co., Ltd., oxetanyl group-containing monomer), and the like.
(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 containing at least a resin. The resin is blended, for example, for dispersing a pigment or the like in the composition or for a binder. A resin that is mainly used to disperse a pigment or the like in a composition is also called a dispersant. However, such uses of the resin are only examples, and the resin can be used for purposes other than such uses. A resin having a polymerizable group also corresponds to 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, more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 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2016/088645号の実施例に記載された樹脂、特開2017-057265号公報に記載された樹脂、特開2017-032685号公報に記載された樹脂、特開2017-075248号公報に記載された樹脂、特開2017-066240号公報に記載された樹脂、特開2017-167513号公報に記載された樹脂、特開2017-173787号公報に記載された樹脂、特開2017-206689号公報の段落番号0041~0060に記載された樹脂、特開2018-010856号公報の段落番号0022~0071に記載された樹脂、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については、米国特許出願公開第2017/0102610号明細書の記載を参酌でき、この内容は本明細書に組み込まれる。また、樹脂としては、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で表される樹脂を用いることもできる。 Examples of 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, polyurea resins, and the like. 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 preferable from the viewpoint of improving heat resistance. Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (for example, ARTON F4520). Further, as the resin, the resin described in the examples of International Publication No. 2016/088645, the resin described in JP-A-2017-057265, the resin described in JP-A-2017-032685, JP Resins described in JP-A-2017-075248, resins described in JP-A-2017-066240, resins described in JP-A-2017-167513, resins described in JP-A-2017-173787, Resins described in paragraph numbers 0041 to 0060 of JP-A-2017-206689, resins described in paragraph numbers 0022-0071 of JP-A-2018-010856, blocks described in JP-A-2016-222891 Polyisocyanate resin, resin described in JP-A-2020-122052, resin described in JP-A-2020-111656, resin described in JP-A-2020-139021, JP-A-2017-138503 A resin containing a structural unit having a ring structure in its main chain and a structural unit having a biphenyl group in its side chain as described in 1) can also be used. As the resin, a resin having a fluorene skeleton can also be preferably used. Regarding the resin having a fluorene skeleton, the description of US Patent Application Publication No. 2017/0102610 can be referred to, the content of which is incorporated herein. In addition, as the resin, the resin described in paragraphs 0199 to 0233 of JP-A-2020-186373, the alkali-soluble resin described in JP-A-2020-186325, and the Korean Patent Publication No. 10-2020-0078339. A resin represented by the formula 1 can also be used.
 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、カルボキシル基、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、例えば、アルカリ可溶性樹脂として用いることができる。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。 It is preferable to use a resin having an acid group as the resin. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. Only one kind of these acid groups may be used, or two or more kinds thereof may be used. A resin having an acid group can be used, for example, as an alkali-soluble resin. The acid value of the resin having acid groups is preferably 30-500 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more. The upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.
 樹脂としては、式(ED1)で示される化合物および/または式(ED2)で表される化合物(以下、これらの化合物を「エーテルダイマー」と称することもある。)由来の繰り返し単位を含む樹脂を含むことも好ましい。 As the resin, a resin containing a repeating unit derived from a compound represented by the formula (ED1) and/or a compound represented by the formula (ED2) (hereinafter, these compounds may be referred to as an "ether dimer"). It is also preferred to include
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
 式(ED1)中、RおよびRは、それぞれ独立して、水素原子または置換基を有していてもよい炭素数1~25の炭化水素基を表す。
Figure JPOXMLDOC01-appb-C000019
 式(ED2)中、Rは、水素原子または炭素数1~30の有機基を表す。式(ED2)の具体例としては、特開2010-168539号公報の記載を参酌できる。
In formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
Figure JPOXMLDOC01-appb-C000019
In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description in JP-A-2010-168539 can be referred to.
 エーテルダイマーの具体例については、特開2013-029760号公報の段落番号0317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。 For specific examples of ether dimers, paragraph number 0317 of JP-A-2013-029760 can be referred to, the content of which is incorporated herein.
 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が挙げられ、エチレン性不飽和結合含有基であることが好ましい。 As the resin, it is also preferable to use a resin having a polymerizable group. The polymerizable group includes an ethylenically unsaturated bond-containing group and a cyclic ether group, preferably an ethylenically unsaturated bond-containing group.
 樹脂としては、式(X)で表される化合物由来の繰り返し単位を含む樹脂を用いることも好ましい。
Figure JPOXMLDOC01-appb-C000020
 式中、Rは水素原子またはメチル基を表し、R21およびR22はそれぞれ独立してアルキレン基を表し、nは0~15の整数を表す。R21およびR22が表すアルキレン基の炭素数は1~10であることが好ましく、1~5であることがより好ましく、1~3であることが更に好ましく、2または3であることが特に好ましい。nは0~15の整数を表し、0~5の整数であることが好ましく、0~4の整数であることがより好ましく、0~3の整数であることが更に好ましい。
As the resin, it is also preferable to use a resin containing a repeating unit derived from the compound represented by formula (X).
Figure JPOXMLDOC01-appb-C000020
In the formula, R 1 represents a hydrogen atom or a methyl group, R 21 and R 22 each independently represent an alkylene group, and n represents an integer of 0-15. The number of carbon atoms in the alkylene group represented by R 21 and R 22 is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly 2 or 3. preferable. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.
 式(X)で表される化合物としては、パラクミルフェノールのエチレンオキサイドまたはプロピレンオキサイド変性(メタ)アクリレートなどが挙げられる。市販品としては、アロニックスM-110(東亞合成(株)製)などが挙げられる。 Examples of the compound represented by formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of paracumylphenol. Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
 本発明の組成物は、分散剤としての樹脂を含有することが好ましい。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、カルボキシル基が好ましい。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 composition of the present invention preferably contains a resin as a dispersant. Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups. As the acidic dispersant (acidic resin), a resin having an acid group content of 70 mol % or more is preferable when the total amount of the acid group and the basic group is 100 mol %. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g. Further, a basic dispersant (basic resin) represents a resin in which the amount of basic groups is greater than the amount of acid groups. As the basic dispersant (basic resin), a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and 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。 The resin used as the dispersant is also preferably a graft resin. For details of the graft resin, reference can be made to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
 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 also preferably a polyimine-based dispersant containing nitrogen atoms in at least one of its main chain and side chains. The polyimine-based dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom. A resin having The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. Regarding the polyimine-based dispersant, the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
 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 also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core. Such resins include, for example, dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.
 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 its side chain. The content of repeating units having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70, of the total repeating units of the resin. More preferably, it is mol %.
 また、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、国際公開第2016/104803号に記載の分散剤などを用いることもできる。 Further, as a dispersant, resins described in JP-A-2018-087939, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, Polyethyleneimine having a polyester side chain described in International Publication No. 2016/104803, a block copolymer described in International Publication No. 2019/125940, a block polymer having an acrylamide structural unit described in JP-A-2020-066687 , a block polymer having an acrylamide structural unit described in JP-A-2020-066688, a dispersant described in WO 2016/104803, 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(例えば、Disperbyk-111、161、2001など)、日本ルーブリゾール(株)製のソルスパースシリーズ(例えば、ソルスパース20000、76500など)、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 commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like. In addition, the product described in paragraph number 0129 of JP-A-2012-137564 and the product described in paragraph number 0235 of JP-A-2017-194662 can also be used as a dispersant.
 硬化性化合物の含有量は、組成物の全固形分中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 is preferably 1 to 95% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 94% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and particularly preferably 80% by 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、重合性化合物の含有量は、組成物の全固形分中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 is preferably 1 to 85% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by 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、重合性モノマーの含有量は、組成物の全固形分中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 is preferably 1 to 50% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by 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、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、組成物の全固形分中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 is 1 to 70 mass in the total solid content of the composition. % is preferred. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by 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、樹脂の含有量は、組成物の全固形分中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 is preferably 1 to 85% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 40% by 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、分散剤としての樹脂の含有量は、組成物の全固形分中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、上述した特定化合物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 is preferably 0.1 to 40% by mass based on the total solid content of the composition. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. Moreover, the content of the resin as a dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the above specific compound. The upper limit is preferably 80 parts by mass or less, more preferably 75 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, more preferably 5 parts by mass 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 curable compounds are included, the total amount thereof is preferably within the above range.
<<色素誘導体>>
 本発明の組成物は、上述した特定化合物の他に、更に色素誘導体を含有することができる。色素誘導体は分散助剤として用いられる。色素誘導体としては、色素骨格に酸基または塩基性基が結合した構造を有する化合物が挙げられる。
<<Dye derivative>>
The composition of the present invention can further contain a dye derivative in addition to the specific compounds described above. Dye derivatives are used as dispersing aids. Examples of dye derivatives include compounds having a structure in which an acid group or a basic group is bonded to a dye skeleton.
 色素誘導体を構成する色素骨格としては、スクアリリウム色素骨格、ピロロピロール色素骨格、ジケトピロロピロール色素骨格、キナクリドン色素骨格、アントラキノン色素骨格、ジアントラキノン色素骨格、ベンゾイソインドール色素骨格、チアジンインジゴ色素骨格、アゾ色素骨格、キノフタロン色素骨格、フタロシアニン色素骨格、ナフタロシアニン色素骨格、ジオキサジン色素骨格、ペリレン色素骨格、ペリノン色素骨格、ベンゾイミダゾロン色素骨格、ベンゾチアゾール色素骨格、ベンゾイミダゾール色素骨格およびベンゾオキサゾール色素骨格が挙げられ、スクアリリウム色素骨格、ピロロピロール色素骨格、ジケトピロロピロール色素骨格、フタロシアニン色素骨格、キナクリドン色素骨格およびベンゾイミダゾロン色素骨格が好ましく、スクアリリウム色素骨格およびピロロピロール色素骨格がより好ましい。 Examples of dye skeletons constituting dye derivatives include squarylium dye skeleton, pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, quinacridone dye skeleton, anthraquinone dye skeleton, dianthraquinone dye skeleton, benzoisoindole dye skeleton, and thiazineindigo dye skeleton. , azo dye skeleton, quinophthalone dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, dioxazine dye skeleton, perylene dye skeleton, perinone dye skeleton, benzimidazolone dye skeleton, benzothiazole dye skeleton, benzimidazole dye skeleton and benzoxazole dye skeleton A squarylium dye skeleton, a pyrrolopyrrole dye skeleton, a diketopyrrolopyrrole dye skeleton, a phthalocyanine dye skeleton, a quinacridone dye skeleton and a benzimidazolone dye skeleton are preferred, and a squarylium dye skeleton and a pyrrolopyrrole dye skeleton are more preferred.
 酸基としては、カルボキシル基、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、-NHCORA1で表される基が好ましい。スルホンアミド基としては、-NHSOA2で表される基が好ましい。イミド酸基としては、-SONHSOA3、-CONHSOA4、-CONHCORA5または-SONHCORA6で表される基が好ましく、-SONHSOA3がより好ましい。RA1~RA6は、それぞれ独立してアルキル基またはアリール基を表す。RA1~RA6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。 The acid group includes a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imidic acid group and salts thereof. Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ion and the like. As the carboxylic acid amide group, a group represented by —NHCOR A1 is preferable. As the sulfonamide group, a group represented by —NHSO 2 R A2 is preferable. The imidic acid group is preferably a group represented by -SO 2 NHSO 2 R A3 , -CONHSO 2 R A4 , -CONHCOR A5 or -SO 2 NHCOR A6 , more preferably -SO 2 NHSO 2 R A3 . R A1 to R A6 each independently represent an alkyl group or an aryl group. The alkyl groups and aryl groups represented by R A1 to R A6 may have substituents. The substituent is preferably a halogen atom, more preferably a fluorine atom.
 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 include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups. Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
 色素誘導体の具体例としては、後述する実施例に記載の化合物が挙げられる。また、特開昭56-118462号公報、特開昭63-264674号公報、特開平01-217077号公報、特開平03-009961号公報、特開平03-026767号公報、特開平03-153780号公報、特開平03-045662号公報、特開平04-285669号公報、特開平06-145546号公報、特開平06-212088号公報、特開平06-240158号公報、特開平10-030063号公報、特開平10-195326号公報、国際公開第2011/024896号の段落番号0086~0098、国際公開第2012/102399号の段落番号0063~0094に記載の化合物も挙げられ、これらの内容は本明細書に組み込まれる。 Specific examples of the dye derivative include the compounds described in Examples described later. In addition, JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-009961, JP-A-03-026767, JP-A-03-153780 Publications, JP-A-03-045662, JP-A-04-285669, JP-A-06-145546, JP-A-06-212088, JP-A-06-240158, JP-A-10-030063, JP-A-10-195326, paragraph numbers 0086 to 0098 of International Publication No. 2011/024896, and compounds described in paragraph numbers 0063 to 0094 of International Publication No. 2012/102399, the contents of which are herein incorporated into.
 色素誘導体の含有量は、近赤外線吸収顔料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。
 また、色素誘導体の含有量は、上述した特定化合物100質量部に対し、1~50質量部が好ましい。下限値は、2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。
 本発明の組成物は色素誘導体を1種のみ含んでいてもよく、2種以上含んでいてもよい。色素誘導体を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 content of the dye derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.
Also, the content of the dye derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the above specific compound. The lower limit is preferably 2 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.
The composition of the present invention may contain only one dye derivative, or may contain two or more dye derivatives. When two or more dye derivatives are included, the total amount thereof is preferably 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 invention preferably contains a solvent. Examples of the solvent include water and organic solvents, and organic solvents are preferred. Organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For these details, reference can be made to paragraph 0223 of WO2015/166779, the content of which is incorporated herein. Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups 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, ethylcarbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxy butanol, 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 diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropyl alcohol and the like. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be better reduced for environmental reasons (e.g., 50 mass ppm (parts per million), 10 mass ppm or less, or 1 mass ppm or less).
 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 ppt (parts per trillion) mass level may be used, and such an organic solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).
 有機溶剤から金属等の不純物を除去する方法としては、例えば、蒸留(分子蒸留や薄膜蒸留等)やフィルタを用いたろ過を挙げることができる。ろ過に用いるフィルタのフィルタ孔径としては、10μm以下が好ましく、5μm以下がより好ましく、3μm以下が更に好ましい。フィルタの材質は、ポリテトラフルオロエチレン、ポリエチレンまたはナイロンが好ましい。 Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter 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). Moreover, only one isomer may be contained, or a plurality of isomers may be contained.
 有機溶剤中の過酸化物の含有率が0.8mmol/L以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。 The content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.
 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。本発明の組成物は溶剤を1種のみ含んでいてもよく、2種以上含んでいてもよい。溶剤を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 content of the solvent in the composition is preferably 10-97% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, even more preferably 60% by mass or more, and 70% by mass. It is particularly preferable that it is above. The upper limit is preferably 96% by mass or less, more preferably 95% by mass or less. The composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are included, the total amount thereof is preferably 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。
<<Photoinitiator>>
When the composition of the invention contains a polymerizable compound, the composition of the invention preferably further contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet region to the visible region are preferred. 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。 Examples of 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 and the like. From the viewpoint of exposure sensitivity, photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbi imidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl-substituted coumarin compounds, oxime compounds, α-hydroxyketones compounds, α-aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds. Further, as the photopolymerization initiator, compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3, the peroxide photopolymerization initiator described in 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiator described in JP-A-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, the peroxide-based initiator described in JP-A-2020-055992. An aminoacetophenone-based initiator having an oxazolidine group described, an oxime-based photopolymerization initiator described in JP-A-2013-190459, a polymer described in JP-A-2020-172619, and International Publication No. 2020/152120. and the compounds of Formula 1 described, the contents of which are incorporated herein.
 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, etc. is mentioned.
 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 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above company) and the like. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by Irgacure 369E, Irgacure 379EG). made), etc. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).
 オキシム化合物としては、特開2001-233842号公報に記載の化合物、特開2000-080068号公報に記載の化合物、特開2006-342166号公報に記載の化合物、J.C.S.Perkin II(1979年、pp.1653-1660)に記載の化合物、J.C.S.Perkin II(1979年、pp.156-162)に記載の化合物、Journal of Photopolymer Science and Technology(1995年、pp.202-232)に記載の化合物、特開2000-066385号公報に記載の化合物、特表2004-534797号公報に記載の化合物、特開2017-019766号公報に記載の化合物、特許第6065596号公報に記載の化合物、国際公開第2015/152153号に記載の化合物、国際公開第2017/051680号に記載の化合物、特開2017-198865号公報に記載の化合物、国際公開第2017/164127号の段落番号0025~0038に記載の化合物、国際公開第2013/167515号に記載の化合物、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、及び2-エトキシカルボニルオキシイミノ-1-フェニルプロパン-1-オンなどが挙げられる。市販品としては、Irgacure OXE01、Irgacure OXE02、Irgacure OXE03、Irgacure OXE04(以上、BASF社製)、TR-PBG-304(常州強力電子新材料有限公司製)、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 compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, compounds described in WO 2015/152153, WO 2017 / 051680, the compound described in JP-A-2017-198865, the compound described in paragraphs 0025 to 0038 of WO 2017/164127, the compound described in WO 2013/167515, Compounds described in Japanese Patent No. 5430746, compounds described in Japanese Patent No. 5647738, and the like. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy and imino-1-phenylpropan-1-one. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), and Adeka Optomer N-1919 (manufactured by Co., Ltd. Photopolymerization initiator 2) described in JP-A-2012-014052 manufactured by ADEKA. As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (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を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開2014-137466号公報に記載の化合物、特許6636081号公報に記載の化合物、韓国公開特許第10-2016-0109444号公報に記載の化合物が挙げられる。 An oxime compound having a fluorene ring can also be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466, compounds described in Japanese Patent No. 6636081, and compounds described in Korean Patent Publication No. 10-2016-0109444. be done.
 光重合開始剤としては、カルバゾール環の少なくとも1つのベンゼン環がナフタレン環となった骨格を有するオキシム化合物を用いることもできる。そのようなオキシム化合物の具体例としては、国際公開第2013/083505号に記載の化合物が挙げられる。 As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in WO2013/083505.
 光重合開始剤としては、フッ素原子を有するオキシム化合物を用いることもできる。フッ素原子を有するオキシム化合物の具体例としては、特開2010-262028号公報に記載の化合物、特表2014-500852号公報に記載の化合物24、36~40、特開2013-164471号公報に記載の化合物(C-3)などが挙げられる。 An oxime compound having a fluorine atom can also be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of.
 光重合開始剤としては、ニトロ基を有するオキシム化合物を用いることができる。ニトロ基を有するオキシム化合物は、二量体とすることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開2013-114249号公報の段落番号0031~0047、特開2014-137466号公報の段落番号0008~0012、0070~0079に記載されている化合物、特許4223071号公報の段落番号0007~0025に記載されている化合物、アデカアークルズNCI-831((株)ADEKA製)が挙げられる。 An oxime compound having a nitro group can be used as the photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.
 光重合開始剤としては、ベンゾフラン骨格を有するオキシム化合物を用いることもできる。具体例としては、国際公開第2015/036910号に記載されているOE-01~OE-75が挙げられる。 An oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator. Specific examples include OE-01 to OE-75 described in WO 2015/036910.
 光重合開始剤としては、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を用いることもできる。このような光重合開始剤としては国際公開第2019/088055号に記載された化合物などが挙げられる。 As the photopolymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to the carbazole skeleton can also be used. Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
 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 preferably used in the present invention are shown below, but the present invention is not limited to these.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
 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. Further, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1000 to 300000, further preferably 2000 to 300000, even more preferably 5000 to 200000. It is particularly preferred to have The molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
 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、特表2010-527339号公報、特表2011-524436号公報、国際公開第2015/004565号、特表2016-532675号公報の段落番号0407~0412、国際公開第2017/033680号の段落番号0039~0055に記載されているオキシム化合物の2量体、特表2013-522445号公報に記載されている化合物(E)および化合物(G)、国際公開第2016/034963号に記載されているCmpd1~7、特表2017-523465号公報の段落番号0007に記載されているオキシムエステル系光開始剤、特開2017-167399号公報の段落番号0020~0033に記載されている光開始剤、特開2017-151342号公報の段落番号0017~0026に記載されている光重合開始剤(A)、特許第6469669号公報に記載されているオキシムエステル系光開始剤などが挙げられる。 As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation becomes difficult over time, and the stability over time of the composition can be improved. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Paragraph numbers 0407 to 0412, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compounds described in JP-A-2013-522445 ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, an oxime ester photoinitiator described in paragraph number 0007 of JP 2017-523465, JP 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, described in Japanese Patent No. 6469669 Examples include oxime ester photoinitiators.
 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。本発明の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。光重合開始剤を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 content of the photopolymerization initiator is preferably 0.1 to 40% by mass, more preferably 0.5 to 35% by mass, even more preferably 1 to 30% by mass, based on the total solid content of the composition. The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more photopolymerization initiators are included, the total amount thereof preferably falls 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、例えばアミン化合物、酸無水物、アミド化合物、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。本発明の組成物は硬化剤を1種のみ含んでいてもよく、2種以上含んでいてもよい。硬化剤を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。
<<Curing agent>>
When the composition of the present invention contains a compound having a cyclic ether group, it preferably further contains a curing agent. Examples of curing agents include amine compounds, acid anhydrides, amide compounds, phenol compounds, polyvalent carboxylic acids, and thiol compounds. Specific examples of curing agents include succinic acid, trimellitic acid, pyromellitic acid, N,N-dimethyl-4-aminopyridine, pentaerythritol tetrakis(3-mercaptopropionate) and the like. As the curing agent, compounds described in paragraphs 0072 to 0078 of JP-A-2016-075720 and compounds described in JP-A-2017-036379 can also be used. 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 0.1 to 6.0 parts by mass with respect to 100 parts by mass of the compound having a cyclic ether group. is more preferred. The composition of the present invention may contain only one curing agent, or may contain two or more curing agents. When two or more curing agents are included, the total amount thereof is preferably within the above range.
<<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。本発明において、有彩色着色剤とは、白色着色剤および黒色着色剤以外の着色剤を意味する。有彩色着色剤は、波長400nm以上650nm未満の範囲に吸収を有する着色剤が好ましい。
<<Chromatic coloring agent>>
The composition of the invention may contain chromatic colorants. In the present invention, a chromatic colorant means a colorant other than a white colorant and a black colorant. The chromatic colorant is preferably a colorant that absorbs in a wavelength range of 400 nm or more and less than 650 nm.
 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。 The chromatic colorants include red colorants, green colorants, blue colorants, yellow colorants, purple colorants and orange colorants. A chromatic colorant may be a pigment or a dye. A pigment and a dye may be used in combination. Moreover, the pigment may be either an inorganic pigment or an organic pigment. As the pigment, an inorganic pigment or a material in which a part of an organic-inorganic pigment is replaced with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be facilitated.
 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。顔料の平均一次粒子径が上記範囲であれば、組成物中における顔料の分散安定性が良好である。なお、本発明において、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、本発明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 size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, 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. When the average primary particle size of the pigment is within the above range, the dispersion stability of the pigment in the composition is good. In the present invention, the primary particle diameter of the pigment can be determined from the 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 obtained, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle size in the present invention is the arithmetic mean value of the primary particle sizes of 400 primary particles of the pigment. Further, the primary particles of the pigment refer to independent particles without agglomeration.
 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, still more preferably 80% by mass or more, and 90% by mass or more. is particularly preferred. Examples of pigments include those shown below.
 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, 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 (methine), 233 (quinoline), 234 ( aminoketone-based), 235 (aminoketone-based), 236 (aminoketone-based), etc. (above, yellow pigment),
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. (above, orange pigment),
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-based, Organo Ultramarine, Bluish Red), 295 (monoazo-based), 296 (diazo-based), 297 (aminoketone-based), etc. (above, red pigments),
C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine), 65 (phthalocyanine), 66 (phthalocyanine), etc. (green pigments),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane-based), 61 (xanthene-based), etc. (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), 88 (methine-based), etc. (above, blue pigments);
 また、緑色顔料として、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、緑色顔料として中国特許出願第106909027号明細書に記載の化合物、国際公開第2012/102395号に記載のリン酸エステルを配位子として有するフタロシアニン化合物、特開2019-008014号公報に記載のフタロシアニン化合物、特開2018-180023号公報に記載のフタロシアニン化合物、特開2019-038958号公報に記載の化合物、特開2020-076995号公報に記載のコアシェル型色素などを用いることもできる。 Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 per molecule. can also be used. Specific examples include compounds described in International Publication No. 2015/118720. In addition, as a green pigment, the compound described in Chinese Patent Application No. 106909027, the phthalocyanine compound having a phosphoric acid ester as a ligand described in WO 2012/102395, and the phthalocyanine compound described in JP 2019-008014. A phthalocyanine compound, a phthalocyanine compound described in JP-A-2018-180023, a compound described in JP-A-2019-038958, a core-shell type dye described in JP-A-2020-076995, and the like can also be used.
 また、青色顔料として、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。 An aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue pigment. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A-2012-247591 and paragraph number 0047 of JP-A-2011-157478.
 また、黄色顔料として、特開2017-201003号公報に記載の化合物、特開2017-197719号公報に記載の化合物、特開2017-171912号公報の段落番号0011~0062、0137~0276に記載の化合物、特開2017-171913号公報の段落番号0010~0062、0138~0295に記載の化合物、特開2017-171914号公報の段落番号0011~0062、0139~0190に記載の化合物、特開2017-171915号公報の段落番号0010~0065、0142~0222に記載の化合物、特開2013-054339号公報の段落番号0011~0034に記載のキノフタロン化合物、特開2014-026228号公報の段落番号0013~0058に記載のキノフタロン化合物、特開2018-062644号公報に記載のイソインドリン化合物、特開2018-203798号公報に記載のキノフタロン化合物、特開2018-062578号公報に記載のキノフタロン化合物、特許第6432076号公報に記載のキノフタロン化合物、特開2018-155881号公報に記載のキノフタロン化合物、特開2018-111757号公報に記載のキノフタロン化合物、特開2018-040835号公報に記載のキノフタロン化合物、特開2017-197640号公報に記載のキノフタロン化合物、特開2016-145282号公報に記載のキノフタロン化合物、特開2014-085565号公報に記載のキノフタロン化合物、特開2014-021139号公報に記載のキノフタロン化合物、特開2013-209614号公報に記載のキノフタロン化合物、特開2013-209435号公報に記載のキノフタロン化合物、特開2013-181015号公報に記載のキノフタロン化合物、特開2013-061622号公報に記載のキノフタロン化合物、特開2013-032486号公報に記載のキノフタロン化合物、特開2012-226110号公報に記載のキノフタロン化合物、特開2008-074987号公報に記載のキノフタロン化合物、特開2008-081565号公報に記載のキノフタロン化合物、特開2008-074986号公報に記載のキノフタロン化合物、特開2008-074985号公報に記載のキノフタロン化合物、特開2008-050420号公報に記載のキノフタロン化合物、特開2008-031281号公報に記載のキノフタロン化合物、特公昭48-032765号公報に記載のキノフタロン化合物、特開2019-008014号公報に記載のキノフタロン化合物、特許第6607427号公報に記載のキノフタロン化合物、韓国公開特許第10-2014-0034963号公報に記載の化合物、特開2017-095706号公報に記載の化合物、台湾特許出願公開第201920495号公報に記載の化合物、特許第6607427号公報に記載の化合物、特開2020-033525号公報に記載の化合物、特開2020-033524号公報に記載の化合物、特開2020-033523号公報に記載の化合物、特開2020-033522号公報に記載の化合物、特開2020-033521号公報に記載の化合物、国際公開第2020/045200号に記載の化合物、国際公開第2020/045199号に記載の化合物、国際公開第2020/045197号に記載の化合物を用いることもできる。また、これらの化合物を多量体化したものも、色価向上の観点から好ましく用いられる。 Further, as the yellow pigment, compounds described in JP-A-2017-201003, compounds described in JP-A-2017-197719, paragraph numbers 0011-0062 of JP-A-2017-171912, described in 0137-0276 Compounds, compounds described in paragraph numbers 0010 to 0062, 0138 to 0295 of JP 2017-171913, compounds described in paragraph numbers 0011 to 0062, 0139 to 0190 of JP 2017-171914, JP 2017- Compounds described in paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A-171915, quinophthalone compounds described in paragraph numbers 0011-0034 of JP-A-2013-054339, paragraph numbers 0013-0058 of JP-A-2014-026228 Quinophthalone compounds described in, isoindoline compounds described in JP-A-2018-062644, quinophthalone compounds described in JP-A-2018-203798, quinophthalone compounds described in JP-A-2018-062578, Patent No. 6432076 Quinophthalone compounds described in the publication, quinophthalone compounds described in JP-A-2018-155881, quinophthalone compounds described in JP-A-2018-111757, quinophthalone compounds described in JP-A-2018-040835, JP-A-2017- Quinophthalone compounds described in 197640, quinophthalone compounds described in JP-A-2016-145282, quinophthalone compounds described in JP-A-2014-085565, quinophthalone compounds described in JP-A-2014-021139, JP-A quinophthalone compounds described in JP-A-2013-209614, quinophthalone compounds described in JP-A-2013-209435, quinophthalone compounds described in JP-A-2013-181015, quinophthalone compounds described in JP-A-2013-061622, Quinophthalone compounds described in JP-A-2013-032486, quinophthalone compounds described in JP-A-2012-226110, quinophthalone compounds described in JP-A-2008-074987, quinophthalones described in JP-A-2008-081565 Compounds, quinophthalone compounds described in JP-A-2008-074986, quinophthalone compounds described in JP-A-2008-074985, quinophthalone compounds described in JP-A-2008-050420, JP Quinophthalone compounds described in 2008-031281, quinophthalone compounds described in JP-B-48-032765, quinophthalone compounds described in JP-A-2019-008014, quinophthalone compounds described in Japanese Patent No. 6607427, published in Korea Compounds described in Patent No. 10-2014-0034963, compounds described in JP 2017-095706, compounds described in Taiwan Patent Application Publication No. 201920495, compounds described in Patent No. 6607427, Compounds described in JP-A-2020-033525, compounds described in JP-A-2020-033524, compounds described in JP-A-2020-033523, compounds described in JP-A-2020-033522, JP-A-2020 -033521, compounds described in WO2020/045200, compounds described in WO2020/045199, compounds described in WO2020/045197 can also be used. Moreover, those obtained by polymerizing these compounds are also preferably used from the viewpoint of improving the color value.
 赤色顔料として、特開2017-201384号公報に記載の構造中に少なくとも1つの臭素原子が置換したジケトピロロピロール化合物、特許第6248838号の段落番号0016~0022に記載のジケトピロロピロール化合物、国際公開第2012/102399号に記載のジケトピロロピロール化合物、国際公開第2012/117965号に記載のジケトピロロピロール化合物、特開2012-229344号公報に記載のナフトールアゾ化合物、特許第6516119号公報に記載の赤色顔料、特許第6525101号公報に記載の赤色顔料、特開2020-090632号公報の段落番号0229に記載の臭素化ジケトピロロピロール化合物、韓国公開特許第10-2019-0140741号公報に記載のアントラキノン化合物、韓国公開特許第10-2019-0140744号公報に記載のアントラキノン化合物、特開2020-079396号公報に記載のペリレン化合物などを用いることもできる。また、赤色顔料として、芳香族環に対して、酸素原子、硫黄原子または窒素原子が結合した基が導入された芳香族環基がジケトピロロピロール骨格に結合した構造を有する化合物を用いることもできる。 As red pigments, diketopyrrolopyrrole compounds in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, diketopyrrolopyrrole compounds described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, Diketopyrrolopyrrole compounds described in WO 2012/102399, diketopyrrolopyrrole compounds described in WO 2012/117965, naphthol azo compounds described in JP 2012-229344, Patent No. 6516119 Red pigment described in the publication, red pigment described in Patent No. 6525101, brominated diketopyrrolopyrrole compounds described in paragraph number 0229 of JP 2020-090632, Korean Patent No. 10-2019-0140741 Anthraquinone compounds described in publications, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140744, perylene compounds described in JP-A-2020-079396, and the like can also be used. Also, as a red pigment, a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton may be used. can.
 各種顔料が有していることが好ましい回折角については、特許第6561862号公報、特許第6413872号公報、特許第6281345号公報、特開2020-026503号公報の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、ピロロピロール系顔料としては、結晶格子面のうち(±1±1±1)の8個の面の中でX線回折パターンにおける最大ピークに対応する面方向の結晶子サイズが140Å以下であるものを用いることも好ましい。また、ピロロピロール系顔料の物性については、特開2020-097744号公報の段落番号0028~0073に記載の通り設定することも好ましい。 Regarding the diffraction angle that various pigments preferably have, the descriptions of Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, and Japanese Patent Application Laid-Open No. 2020-026503 can be considered, and the contents of these are incorporated herein. Further, the pyrrolopyrrole-based pigment has a crystallite size of 140 Å or less in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes of (±1±1±1) among the crystal lattice planes. It is also preferred to use one. Further, the physical properties of the pyrrolopyrrole pigment are preferably set as described in paragraphs 0028 to 0073 of JP-A-2020-097744.
 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。 Dyes can also be used as chromatic colorants. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo dyes, anilinoazo 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.
 有彩色着色剤には色素多量体を用いることもできる。色素多量体は、溶剤に溶解して用いられる染料であることが好ましい。また、色素多量体は、粒子を形成していてもよい。色素多量体が粒子である場合は通常溶剤に分散した状態で用いられる。粒子状態の色素多量体は、例えば乳化重合によって得ることができ、特開2015-214682号公報に記載されている化合物および製造方法が具体例として挙げられる。色素多量体は、一分子中に、色素構造を2以上有するものであり、色素構造を3以上有することが好ましい。上限は、特に限定はないが、100以下とすることもできる。一分子中に有する複数の色素構造は、同一の色素構造であってもよく、異なる色素構造であってもよい。色素多量体の重量平均分子量(Mw)は、2000~50000が好ましい。下限は、3000以上がより好ましく、6000以上がさらに好ましい。上限は、30000以下がより好ましく、20000以下がさらに好ましい。色素多量体は、特開2011-213925号公報、特開2013-041097号公報、特開2015-028144号公報、特開2015-030742号公報、国際公開第2016/031442号等に記載されている化合物を用いることもできる。 A pigment multimer can also be used as a chromatic colorant. The dye multimer is preferably a dye dissolved in a solvent and used. Further, the dye multimer may form particles. When the dye multimer is particles, it is usually used in a state of being dispersed in a solvent. The particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in JP-A-2015-214682. A dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. A plurality of dye structures in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016/031442, etc. Compounds can also be used.
 また、有彩色着色剤には、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、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を用いることができる。 Further, the chromatic colorant, the thiazole compound described in JP-A-2012-158649, the azo compound described in JP-A-2011-184493, the azo compound described in JP-A-2011-145540, published in Korea Triarylmethane dye polymer described in Patent No. 10-2020-0028160, xanthene compound described in JP-A-2020-117638, phthalocyanine compound described in WO2020/174991, JP-A-2020-160279 An isoindoline compound or a salt thereof described in the publication can be used.
 本発明の組成物が、有彩色着色剤を含有する場合、有彩色着色剤の含有量は、本発明の組成物の全固形分中1~50質量%が好ましい。本発明の組成物は有彩色着色剤を1種のみ含んでいてもよく、2種以上含んでいてもよい。有彩色着色剤を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。 When the composition of the present invention contains a chromatic colorant, the content of the chromatic colorant is preferably 1 to 50% by mass based on the total solid content of the composition of the present invention. The composition of the present invention may contain only one type of chromatic colorant, or may contain two or more types. When two or more chromatic colorants are included, the total amount thereof is preferably within the above range.
<<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 and blocks visible light>>
The composition of the present invention can also contain a coloring material that transmits infrared rays 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 colorant that blocks visible light is preferably a colorant that absorbs light in the wavelength range from violet to red. Further, the coloring material that blocks visible light is preferably a coloring material that blocks light in the wavelength range of 450 to 650 nm. Further, the coloring material that blocks visible light is preferably a coloring material that transmits light with a wavelength of 900 to 1500 nm. The colorant that blocks visible light preferably satisfies at least one of the following requirements (A) and (B).
(A): Two or more chromatic colorants are included, and a combination of two or more chromatic colorants forms a black color.
(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。 As the chromatic coloring agent, those mentioned above can be mentioned. 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 Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, Japanese Patent Application Publication No. 2012-515234, etc. For example, "Irgaphor Black" manufactured by BASF Corporation. Available. Examples of perylene compounds include compounds described in paragraphs 0016 to 0020 of JP-A-2017-226821, C.I. I. Pigment Black 31, 32 and the like. Examples of the azomethine compound include compounds described in JP-A-01-170601, JP-A-02-034664, and the like.
 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 two or more chromatic colorants are combined to form a black color, the combination of chromatic colorants includes, for example, the following aspects (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、可視光を遮光する色材の含有量は、組成物の全固形分中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 is preferably 1 to 50 mass% of the total solid content of the composition. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass or more.
<<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好ましい。界面活性剤としては、フッ素系界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、アニオン性界面活性剤、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が挙げられ、この内容は本明細書に組み込まれる。
<<Surfactant>>
The composition of the invention preferably contains a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants can be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant. Surfactants include those described in paragraphs 0238-0245 of WO2015/166779, the contents of which are incorporated herein.
 フッ素系界面活性剤としては、特開2014-041318号公報の段落番号0060~0064(対応する国際公開第2014/017669号の段落番号0060~0064)等に記載の界面活性剤、特開2011-132503号公報の段落番号0117~0132に記載の界面活性剤、特開2020-008634号公報に記載の界面活性剤が挙げられ、これらの内容は本明細書に組み込まれる。フッ素系界面活性剤の市販品としては、例えば、メガファックF-171、F-172、F-173、F-176、F-177、F-141、F-142、F-143、F-144、F-437、F-475、F-477、F-479、F-482、F-554、F-555-A、F-556、F-557、F-558、F-559、F-560、F-561、F-563、F-565、F-568、F-575、F-780、EXP、MFS-330、R-01、R-40、R-40-LM、R-41、R-41-LM、RS-43、TF-1956、RS-90、R-94、RS-72-K、DS-21(以上、DIC(株)製)、フロラードFC430、FC431、FC171(以上、住友スリーエム(株)製)、サーフロンS-382、SC-101、SC-103、SC-104、SC-105、SC-1068、SC-381、SC-383、S-393、KH-40(以上、AGC(株)製)、PolyFox PF636、PF656、PF6320、PF6520、PF7002(以上、OMNOVA社製)、フタージェント208G、215M、245F、601AD、601ADH2、602A、610FM、710FL、710FM、710FS、FTX-218(以上、(株)NEOS製)等が挙げられる。 As the fluorine-based surfactant, JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-132503 and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein. Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 and F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560 , F-561, F-563, F-565, F-568, F-575, F-780, EXP, MFS-330, R-01, R-40, R-40-LM, R-41, R -41-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, AGC Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), Futergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, FTX-218 (above, manufactured by NEOS Co., Ltd.) and the like.
 また、フッ素系界面活性剤として、フッ素原子を含有する官能基を持つ分子構造を有し、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、DIC(株)製のメガファックDSシリーズ(化学工業日報(2016年2月22日)、日経産業新聞(2016年2月23日))、例えばメガファックDS-21が挙げられる。 In addition, as a fluorine-based surfactant, there is also an acrylic compound that has a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes. It can be used preferably. Examples of such fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafac and DS-21.
 また、フッ素系界面活性剤として、フッ素化アルキル基またはフッ素化アルキレンエーテル基を有するフッ素原子含有ビニルエーテル化合物と、親水性のビニルエーテル化合物との重合体を用いることも好ましい。このようなフッ素系界面活性剤は、特開2016-216602号公報に記載されたフッ素系界面活性剤が挙げられ、この内容は本明細書に組み込まれる。 It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant. Such fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.
 フッ素系界面活性剤として、ブロックポリマーを用いることもできる。フッ素系界面活性剤として、フッ素原子を有する(メタ)アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基(好ましくはエチレンオキシ基、プロピレンオキシ基)を2以上(好ましくは5以上)有する(メタ)アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができる。また、特開2010-032698号公報の段落番号0016~0037に記載されたフッ素含有界面活性剤や、下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
Figure JPOXMLDOC01-appb-C000024
 上記の化合物の重量平均分子量は、好ましくは3000~50000であり、例えば、14000である。上記の化合物中、繰り返し単位の割合を示す%はモル%である。
A block polymer can also be used as the fluorosurfactant. As a fluorosurfactant, a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. Further, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
Figure JPOXMLDOC01-appb-C000024
The weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol%.
 また、フッ素系界面活性剤として、エチレン性不飽和結合含有基を側鎖に有する含フッ素重合体を用いることもできる。具体例としては、特開2010-164965号公報の段落番号0050~0090および段落番号0289~0295に記載された化合物、DIC(株)製のメガファックRS-101、RS-102、RS-718K、RS-72-K等が挙げられる。また、フッ素系界面活性剤として、特開2015-117327号公報の段落番号0015~0158に記載の化合物を用いることもできる。 A fluorine-containing polymer having an ethylenically unsaturated bond-containing group in a side chain can also be used as the fluorine-based surfactant. Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, MEGAFACE RS-101, RS-102 and RS-718K manufactured by DIC Corporation, and RS-72-K. Further, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used as the fluorosurfactant.
 また、国際公開第2020/084854号に記載の界面活性剤を、炭素数6以上のパーフルオロアルキル基を有する界面活性剤の代替として用いることも、環境規制の観点から好ましい。 It is also preferable from the viewpoint of environmental regulations to use the surfactant described in International Publication No. 2020/084854 as a substitute for the surfactant having a perfluoroalkyl group with 6 or more carbon atoms.
 また、式(fi-1)で表される含フッ素イミド塩化合物を界面活性剤として用いることも好ましい。
Figure JPOXMLDOC01-appb-C000025
 式(fi-1)中、mは1または2を表し、nは1~4の整数を表し、aは1または2を表し、Xa+はa価の金属イオン、第1級アンモニウムイオン、第2級アンモニウムイオン、第3級アンモニウムイオン、第4級アンモニウムイオンまたはNH を表す。
It is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant.
Figure JPOXMLDOC01-appb-C000025
In the formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, a represents 1 or 2, X a+ is an a-valent metal ion, primary ammonium ion, Represents secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH 4 + .
 ノニオン性界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート(例えば、グリセロールプロポキシレート、グリセロールエトキシレート等)、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニックL10、L31、L61、L62、10R5、17R2、25R2(BASF社製)、テトロニック304、701、704、901、904、150R1(BASF社製)、ソルスパース20000(日本ルーブリゾール(株)製)、NCW-101、NCW-1001、NCW-1002(和光純薬工業(株)製)、パイオニンD-6112、D-6112-W、D-6315(竹本油脂(株)製)、オルフィンE1010、サーフィノール104、400、440(日信化学工業(株)製)などが挙げられる。 Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Oil Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.) etc.
 カチオン性界面活性剤としては、テトラアルキルアンモニウム塩、アルキルアミン塩、ベンザルコニウム塩、アルキルピリジウム塩、イミダゾリウム塩等が挙げられる。具体例としては、ジヒドロキシエチルステアリルアミン、2-ヘプタデセニル-ヒドロキシエチルイミダゾリン、ラウリルジメチルベンジルアンモニウムクロライド、セチルピリジニウムクロライド、ステアラミドメチルピリジウムクロライド等が挙げられる。 Cationic surfactants include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridium salts, imidazolium salts, and the like. Specific examples include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, stearamidomethylpyridinium chloride and the like.
 アニオン性界面活性剤としては、ドデシルベンゼンスルホン酸、ドデシルベンゼンスルホン酸ナトリウム、ラウリル硫酸ナトリウム、アルキルジフェニルエーテルジスルホン酸ナトリウム、アルキルナフタレンスルホン酸ナトリウム、ジアルキルスルホコハク酸ナトリウム、ステアリン酸ナトリウム、オレイン酸カリウム、ナトリウムジオクチルスルホサクシネート、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルエーテ硫酸ナトリウム、ポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウム、ジアルキルスルホコハク酸ナトリウム、ステアリン酸ナトリウム、オレイン酸ナトリウム、t-オクチルフェノキシエトキシポリエトキシエチル硫酸ナトリウム塩等が挙げられる。 Anionic surfactants include dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyletherdisulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl Sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, t-octylphenoxyethoxypolyethoxyethyl sodium sulfate and the like.
 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。 Examples of silicone surfactants include SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), TSF-4440, and TSF-4300. , TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (Shin-Etsu Chemical Co., Ltd. Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (manufactured by BYK-Chemie) and the like.
 また、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。
Figure JPOXMLDOC01-appb-C000026
A compound having the following structure can also be used as the silicone-based surfactant.
Figure JPOXMLDOC01-appb-C000026
 界面活性剤の含有量は、組成物の全固形分中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。本発明の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。界面活性剤を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 content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and still more preferably 0.001 to 0.2% by mass of the total solid content of the composition. . The composition of the present invention may contain only one type of surfactant, or may contain two or more types. When two or more surfactants are included, the total amount thereof is preferably 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。重合禁止剤の含有量は、組成物の全固形分中、0.0001~5質量%が好ましい。本発明の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。重合禁止剤を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。
<<polymerization inhibitor>>
The composition of the invention may contain a polymerization inhibitor. Polymerization inhibitors 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), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.), and p-methoxyphenol is preferred. The content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the composition. The composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more polymerization inhibitors are included, the total amount thereof is preferably 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。本明細書において、シランカップリング剤は、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を意味する。また、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。すなわち、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、(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、これらの内容は本明細書に組み込まれる。シランカップリング剤の含有量は、組成物の全固形分中0.01~15.0質量%が好ましく、0.05~10.0質量%がより好ましい。本発明の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。シランカップリング剤を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。
<<Silane coupling agent>>
The composition of the invention can contain a silane coupling agent. As used herein, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction. Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group, isocyanate group, and phenyl group. with (meth)acryloyl groups and epoxy groups being preferred. The silane coupling agent includes compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. incorporated into the specification. The content of the silane coupling agent is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass, based on the total solid content of the composition. The composition of the present invention may contain only one type of silane coupling agent, or may contain two or more types. When two or more silane coupling agents are included, 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、メロシアニン色素などが挙げられる。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。また、紫外線吸収剤は、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。紫外線吸収剤の含有量は、組成物の全固形分中0.01~30質量%が好ましく、0.05~25質量%がより好ましい。本発明の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。紫外線吸収剤を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。
<<Ultraviolet absorber>>
The composition of the invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and merocyanine dyes. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, paragraph numbers 0317-0317 of JP-A-2013-068814. 0334, and compounds described in paragraphs 0061 to 0080 of JP-A-2016-162946, the contents of which are incorporated herein. Commercially available UV absorbers include Tinuvin series and Uvinul series manufactured by BASF. Moreover, as a benzotriazole compound, the MYUA series made from Miyoshi oil and fats (Chemical Daily, February 1, 2016) is mentioned. Further, as the ultraviolet absorber, compounds described in paragraph numbers 0049 to 0059 of Japanese Patent No. 6268967 and paragraph numbers 0059 to 0076 of International Publication No. 2016/181987 can also be used. The content of the ultraviolet absorber is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, based on the total solid content of the composition. The composition of the present invention may contain only one type of ultraviolet absorber, or may contain two or more types. When two or more ultraviolet absorbers are included, the total amount thereof is preferably 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、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、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。また、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。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。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)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(以上、(株)ADEKA製)などが挙げられる。また、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を使用することもできる。酸化防止剤の含有量は、組成物の全固形分中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。本発明の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。酸化防止剤を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。
<<Antioxidant>>
The compositions of the invention may contain antioxidants. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus antioxidant, 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 the like. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like. In addition, antioxidants are compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, and compounds described in WO 2017/164024. can also be used. The content of the antioxidant is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass, based on the total solid content of the composition. The composition of the present invention may contain only one kind of antioxidant, or may contain two or more kinds. When two or more kinds of antioxidants are included, the total amount thereof is preferably 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、硬化促進剤、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、例えば、特開2012-003225号公報の段落番号0183以降(対応する米国特許出願公開第2013/0034812号明細書の段落番号0237)の記載、特開2008-250074号公報の段落番号0101~0104、0107~0109等の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、本発明の組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第2014/021023号、国際公開第2017/030005号、特開2017-008219号公報に記載された化合物が挙げられる。潜在酸化防止剤の市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。
<<Other Ingredients>>
The composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, etc.). agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. The composition of the present invention may also contain latent antioxidants, if desired. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected by a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
<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、原材料や組成物中への不純物混入を抑制することを目的に、容器内壁を6種6層の樹脂で構成する多層ボトルや6種の樹脂を7層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開2015-123351号公報に記載の容器が挙げられる。また、容器内壁は、容器内壁からの金属溶出を防ぎ、組成物の経時安定性を高めたり、成分変質を抑制するなど目的で、ガラス製やステンレス製などにすることも好ましい。
<Container>
The storage container for the composition of the present invention is not particularly limited, and known storage containers can be used. In addition, as a storage container, a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resin and a bottle with a 7-layer structure of 6 types of resin are used for the purpose of suppressing the contamination of raw materials and compositions with impurities. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351. In addition, the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the stability of the composition over time, and suppressing deterioration of components.
<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 for preparing composition>
The compositions of the present invention can be prepared by mixing the aforementioned ingredients. In preparing the composition, the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time, or if necessary, two or more solutions or dispersions in which each component is appropriately blended are prepared in advance. They may be prepared and mixed at the time of use (at the time of application) to prepare a 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、ガラスまたはそれらの組み合わせを使用できる。また、モース硬度が2以上の無機化合物をビーズとして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 of dispersing the pigment. In the process of dispersing pigments, mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like. 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, ultrasonic dispersion, and the like. In pulverizing the pigment in a sand mill (bead mill), it is preferable to use beads with a small diameter or to increase the filling rate of the beads so as to increase the pulverization efficiency. Moreover, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, the process and dispersing machine for dispersing pigments are described in "Dispersion Technology Complete Works, Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial Practical Application General Documents, Published by Management Development Center Publishing Department, October 10, 1978", the process and dispersing machine described in paragraph number 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. Further, in the process of dispersing the pigment, the pigment may be finely divided in the salt milling process. Materials, equipment, processing conditions, etc. used in the salt milling process can be referred to, for example, Japanese Patent Application Laid-Open Nos. 2015-194521 and 2012-046629. Beads used for dispersion can be zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, glass, or combinations thereof. An inorganic compound having a Mohs hardness of 2 or more can also be used as beads. The composition may contain 1 to 10000 ppm of the 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。フィルタとしては、従来からろ過用途等に用いられているフィルタであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン(PTFE)等のフッ素樹脂、ナイロン(例えばナイロン-6、ナイロン-6,6)等のポリアミド樹脂、ポリエチレン、ポリプロピレン(PP)等のポリオレフィン樹脂(高密度、超高分子量のポリオレフィン樹脂を含む)等の素材を用いたフィルタが挙げられる。これら素材の中でもポリプロピレン(高密度ポリプロピレンを含む)およびナイロンが好ましい。 When preparing the composition, it is preferable to filter the composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluorine resin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene, polypropylene (PP) (high density, ultra high molecular weight (including polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.
 フィルタの孔径は、0.01~7.0μmが好ましく、0.01~3.0μmがより好ましく、0.05~0.5μmが更に好ましい。フィルタの孔径が上記範囲であれば、微細な異物をより確実に除去できる。フィルタの孔径値については、フィルタメーカーの公称値を参照することができる。フィルタは、日本ポール株式会社(DFA4201NIEY、DFA4201NAEY、DFA4201J006Pなど)、アドバンテック東洋株式会社、日本インテグリス株式会社(旧日本マイクロリス株式会社)および株式会社キッツマイクロフィルタ等が提供する各種フィルタを用いることができる。 The pore size of the filter is preferably 0.01-7.0 μm, more preferably 0.01-3.0 μm, and even more preferably 0.05-0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For the pore size value of the filter, reference can be made to the filter manufacturer's nominal value. Various filters provided by Nihon Pall Co., Ltd. (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used as the filter. .
 また、フィルタとしてファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。市販品としては、ロキテクノ社製のSBPタイプシリーズ(SBP008など)、TPRタイプシリーズ(TPR002、TPR005など)、SHPXタイプシリーズ(SHPX003など)が挙げられる。 It is also preferable to use a fiber-like filter medium as the filter. Examples of fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.
 フィルタを使用する際、異なるフィルタ(例えば、第1のフィルタと第2のフィルタなど)を組み合わせてもよい。その際、各フィルタでのろ過は、1回のみでもよいし、2回以上行ってもよい。また、上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。また、第1のフィルタでのろ過は、分散液のみに対して行い、他の成分を混合した後で、第2のフィルタでろ過を行ってもよい。 When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed.
<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、近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。近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近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近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近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近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 explained. The membrane of the invention is obtained from the composition of the invention described above. The film of the present invention can be preferably used as an optical filter. Applications of the optical filter are not particularly limited, but examples thereof include a near-infrared cut filter and an infrared transmission filter. As a near-infrared cut filter, for example, a near-infrared cut filter on the light receiving side of the solid-state image sensor (for example, a near-infrared cut filter for a wafer level lens, etc.), a back side of the solid-state image sensor (opposite to the light receiving side) Infrared cut filter, near-infrared cut filter for ambient light sensor (e.g., illuminance sensor that detects the illuminance and color tone of the environment in which the information terminal device is placed and adjusts the color tone of the display, color correction sensor that adjusts the color tone ) and the like. In particular, it can be preferably used as a near-infrared cut filter on the light receiving side of a solid-state imaging device. Examples of the infrared transmission filter include a filter capable of blocking visible light and selectively transmitting infrared light having a specific wavelength or longer.
 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). Moreover, the film of the present invention may be used by laminating it on a support, or may be used by peeling the film of the present invention 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, or the like may be formed on the semiconductor substrate used as the support. Also, a black matrix that isolates each pixel may be formed on the semiconductor substrate. Further, if necessary, an undercoat layer may be provided on the semiconductor substrate for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the surface of the substrate.
 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 composed of a material that can transmit at least visible light. Examples thereof include base materials made of materials such as glass and resin. Examples of resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer, acrylic resins such as norbornene resin, polyacrylate, and polymethyl methacrylate, urethane resins, and vinyl chloride resins. , fluororesin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin, and the like. Examples of glass include soda-lime glass, borosilicate glass, alkali-free glass, quartz glass, glass containing copper, and the like. Glass containing copper includes phosphate glass containing copper, fluorophosphate glass containing copper, and the like. A commercially available glass containing copper can also be used. Commercially available glass containing copper includes NF-50 (manufactured by AGC Techno Glass 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20μm以下が好ましく、10μm以下がより好ましく、5μm以下が更に好ましい。膜の厚さの下限は0.1μm以上が好ましく、0.2μm以上がより好ましい。 The thickness of the film of the present invention can be adjusted as appropriate according to the purpose. The thickness of the film is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more.
 本発明の膜を近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420~550nmの光の平均透過率が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く、85%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が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、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)の範囲の少なくとも1点での透過率が15%以下であることが好ましく、10%以下がより好ましく、5%以下が更に好ましい。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 a near-infrared cut filter, 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). preferable. In addition, the average transmittance of light with a wavelength of 420 to 550 nm is preferably 50% or more, more preferably 70% or more, still more preferably 80% or more, and particularly 85% or more. preferable. Also, 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 film of the present invention preferably has a transmittance of 15% or less at at least one point in the wavelength range of 650 to 1500 nm (preferably 660 to 1200 nm, more preferably 660 to 1000 nm). The following is more preferable, and 5% or less is even more preferable. The film of the present invention preferably has an average absorbance of less than 0.030, more preferably less than 0.025 in the wavelength range of 420 to 550 nm when the absorbance at the maximum absorption wavelength is 1.
 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): The maximum transmittance in the wavelength range of 400 to 850 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1000 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the wavelength range of 400 to 850 nm and transmit light in the wavelength range of 950 nm or more.
(i2): The maximum transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1100 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the wavelength range of 400 to 950 nm and transmit light in the wavelength range of 1050 nm or more.
(i3): The maximum transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1200 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the wavelength range of 400 to 1050 nm and transmit light in the wavelength range of 1150 nm or more.
 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。本発明の膜を近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. A color filter can be produced using a coloring composition containing a chromatic colorant. When the film of the present invention is used as a near-infrared cut filter and the film of the present invention is used in combination with a color filter, the color filter is preferably arranged on the optical path of the film of the present invention. For example, it is preferable to laminate the film of the present invention and a color filter and use it as a laminate. In the laminate, the film of the present invention and the color filter may or may not be adjacent in the thickness direction. When the film of the present invention and the color filter are not adjacent 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. Other members (for example, a microlens, a planarization layer, etc.) constituting the solid-state imaging device may be interposed between the film 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。
<Method for producing membrane>
The film of the present invention can be produced through the step 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、公知の方法を用いることができる。例えば、滴下法(ドロップキャスト);スリットコート法;スプレー法;ロールコート法;回転塗布法(スピンコーティング);流延塗布法;スリットアンドスピン法;プリウェット法(たとえば、特開2009-145395号公報に記載されている方法);インクジェット(例えばオンデマンド方式、ピエゾ方式、サーマル方式)、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷法などの各種印刷法;金型等を用いた転写法;ナノインプリント法などが挙げられる。インクジェットでの適用方法としては、特に限定されず、例えば「広がる・使えるインクジェット-特許に見る無限の可能性-、2005年2月発行、住ベテクノリサーチ」に示された方法(特に115ページ~133ページ)や、特開2003-262716号公報、特開2003-185831号公報、特開2003-261827号公報、特開2012-126830号公報、特開2006-169325号公報などに記載の方法が挙げられる。 Examples of the support include those mentioned above. As a method for applying the composition, a known method can be used. For example, drop method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); methods described in publications); inkjet (e.g., on-demand method, piezo method, thermal method), discharge system printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like. The application method for inkjet is not particularly limited. 133 page), and methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. mentioned.
 組成物を塗布して形成した組成物層は、乾燥(プリベーク)してもよい。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 (pre-baked). When pre-baking is performed, the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower. The lower limit can be, for example, 50° C. or higher, and can also be 80° C. or higher. The prebaking time is preferably 10 seconds to 3000 seconds, more preferably 40 seconds to 2500 seconds, and even more preferably 80 seconds to 220 seconds. Drying can be performed using a hot plate, an oven, or the like.
 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 photolithographic method and a pattern forming method using a dry etching method, and the pattern forming method using the photolithographic method is preferable. In addition, when the film of the present invention is used as a flat film, the step of forming a pattern may not be performed. The process of forming the pattern 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 patterning by photolithography)
The pattern formation method by photolithography comprises a step of patternwise exposing the composition layer formed by coating the composition of the present invention (exposure step), and developing and removing the unexposed portion of the composition layer. and a step of forming 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 in a pattern. For example, the composition layer can be exposed in a pattern by exposing through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.
 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, i-line, and the like. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferable. A long-wave light source 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, when exposing, the light may be continuously irradiated and exposed, or may be irradiated and exposed in pulses (pulse exposure). Note that pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and rest in short-time (for example, millisecond level or less) cycles.
 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 at the time of exposure can be selected as appropriate, and in addition to exposure in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free) or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). In addition, the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W/m 2 to 100000 W/m 2 (eg, 5000 W/m 2 , 15000 W/m 2 or 35000 W/m 2 ). can be done. Oxygen concentration and exposure illuminance may be appropriately combined. For example, illuminance of 10000 W/m 2 at oxygen concentration of 10% by volume and illuminance of 20000 W/m 2 at oxygen concentration of 35% by volume.
 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, an unexposed portion of the composition layer after exposure is removed by development to form a pattern. The development and removal of the composition layer in the unexposed area can be carried out using a developer. As a result, the unexposed portion of the composition layer in the exposure step is eluted into the developer, leaving only the photocured portion on the support. The temperature of the developer is preferably 20 to 30° C., for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the step 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。アルカリ現像液としては、アルカリ剤を純水で希釈したアルカリ性水溶液(アルカリ現像液)が好ましい。アルカリ剤としては、例えば、アンモニア、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、ジグリコールアミン、ジエタノールアミン、ヒドロキシアミン、エチレンジアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、ジメチルビス(2-ヒドロキシエチル)アンモニウムヒドロキシド、コリン、ピロール、ピペリジン、1,8-ジアザビシクロ[5.4.0]-7-ウンデセンなどの有機アルカリ性化合物や、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウムなどの無機アルカリ性化合物が挙げられる。アルカリ剤は、分子量が大きい化合物の方が環境面および安全面で好ましい。アルカリ性水溶液のアルカリ剤の濃度は、0.001~10質量%が好ましく、0.01~1質量%がより好ましい。また、現像液は、更に界面活性剤を含有していてもよい。界面活性剤としては、ノニオン系界面活性剤が好ましい。現像液は、移送や保管の便宜などの観点より、一旦濃縮液として製造し、使用時に必要な濃度に希釈してもよい。希釈倍率は特に限定されないが、例えば1.5~100倍の範囲に設定することができる。また、現像後純水で洗浄(リンス)することも好ましい。また、リンスは、現像後の組成物層が形成された支持体を回転させつつ、現像後の組成物層へリンス液を供給して行うことが好ましい。また、リンス液を吐出させるノズルを支持体の中心部から支持体の周縁部に移動させて行うことも好ましい。この際、ノズルの支持体中心部から周縁部へ移動させるにあたり、ノズルの移動速度を徐々に低下させながら移動させてもよい。このようにしてリンスを行うことで、リンスの面内ばらつきを抑制できる。また、ノズルを支持体中心部から周縁部へ移動させつつ、支持体の回転速度を徐々に低下させても同様の効果が得られる。 The developer includes an organic solvent, an alkaline developer, etc., and an alkaline developer is preferably used. As the alkaline developer, an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable. Examples of alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene. Alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate and sodium metasilicate. A compound having a large molecular weight is preferable for the alkaline agent from the standpoint of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Moreover, the developer may further contain a surfactant. A nonionic surfactant is preferable as the surfactant. From the viewpoint of transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse liquid to the composition layer after development while rotating the support on which the composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support. At this time, when moving the nozzle from the center of the support to the periphery, the moving speed of the nozzle may be gradually decreased. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. A similar effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the periphery.
 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, it is preferable to perform additional exposure processing and heat processing (post-baking) after drying. Additional exposure processing and post-baking are post-development curing treatments for complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. . When the additional exposure process is performed, the light used for exposure preferably has a wavelength of 400 nm or less. Also, the additional exposure process 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 patterning by dry etching method)
Pattern formation by a dry etching method includes curing the composition layer formed by coating the composition on a support to form a cured product layer, and then forming a photoresist layer patterned on the cured product layer. is formed, and then dry etching is performed on the cured product layer using an etching gas using the patterned photoresist layer as a mask. In forming the photoresist layer, pre-baking is preferably performed. Regarding pattern formation by a dry etching method, descriptions in paragraphs 0010 to 0067 of JP-A-2013-064993 can be referred to, and the contents thereof are incorporated into this specification.
<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、近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 film of the present invention as described above. Types of optical filters include near-infrared cut filters and infrared transmission filters.
 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 have a layer containing copper, a dielectric multilayer film, an ultraviolet absorbing layer, etc., in addition to the film of the present invention described above. Examples of the ultraviolet absorbing layer include the absorbing layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/099060. Dielectric multilayer films include dielectric multilayer films described in paragraphs 0255 to 0259 of JP-A-2014-041318. As the layer containing copper, a glass substrate made of glass containing copper (copper-containing glass substrate) or a layer containing a copper complex (copper complex-containing layer) can be used. Copper-containing glass substrates include copper-containing phosphate glass, copper-containing fluorophosphate glass, and the like. Commercially available copper-containing glasses include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (manufactured by Schott), CD5000 (manufactured by HOYA Corporation), and the like.
<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含む。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 image sensor>
The solid-state imaging device of the present invention includes the film of the present invention described above. 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 configuration can be mentioned.
 支持体上に、固体撮像素子の受光エリアを構成する複数のフォトダイオード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。 A plurality of photodiodes constituting the light receiving area of the solid-state imaging device and transfer electrodes made of polysilicon or the like are provided on the support, and light shielding made of tungsten or the like with only the light receiving portions of the photodiodes being opened on the photodiodes and the transfer electrodes. A device protective film made of silicon nitride or the like is formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion, and the film of the present invention is provided on the device protective film. be. Furthermore, on the device protective film, a structure having a condensing means (for example, a microlens, etc.; the same applies hereinafter) under the film of the present invention (on the side close to the support), or a condensing means on the film of the present invention A configuration or the like having a means may be used. Moreover, the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. The partition in this case preferably has a lower refractive index than each pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478 and JP-A-2014-179577.
<画像表示装置>
 本発明の画像表示装置は、本発明の膜を含む。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 invention comprises the film of the invention. Examples of image display devices include liquid crystal display devices and organic electroluminescence (organic EL) display devices. For the definition and details of the image display device, see, for example, "Electronic Display Device (written by Akio Sasaki, Industrial Research Institute, 1990)", "Display Device (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd., 1989). issued)”, etc. Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied. The image display device may have a white organic EL element. A white organic EL device preferably has a tandem structure. Regarding the tandem structure of organic EL elements, see Japanese Patent Application Laid-Open No. 2003-045676, supervised by Akiyoshi Mikami, "Forefront of Organic EL Technology Development -High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, 326-328, 2008, and others. The spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430-485 nm), the green region (530-580 nm) and the yellow region (580-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 to 700 nm) are more preferred.
<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含む。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 invention comprises the membrane of the invention as described above. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. An embodiment of the infrared sensor of the present invention will be described below 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、近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、近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 is a solid-state imaging device. A near-infrared cut filter 111 and an infrared transmission filter 114 are arranged on the imaging area of the solid-state imaging device 110 . A color filter 112 is arranged on the near-infrared cut filter 111 . A microlens 115 is arranged on the incident light hν side of the color filter 112 and the infrared transmission filter 114 . A planarization layer 116 is formed to cover the microlens 115 .
 近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 near-infrared cut filter 111 can be formed using the composition of the present invention. The color filter 112 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible region, and is not particularly limited, and conventionally known color filters for forming pixels can be used. For example, a color filter having red (R), green (G), and blue (B) pixels is used. For example, paragraph numbers 0214 to 0263 of JP-A-2014-043556 can be referred to, and the contents thereof are incorporated herein. The characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used. 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、近赤外線カットフィルタ111とは別の近赤外線カットフィルタ(他の近赤外線カットフィルタ)が更に配置されていてもよい。他の近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、他の近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, a near-infrared cut filter different from the near-infrared cut filter 111 (another near-infrared cut filter) may be further arranged on the flattening layer 116 . Other near-infrared cut filters include those having copper-containing layers and/or dielectric multilayer films. These details are given above. A dual bandpass filter may be used as another near-infrared cut filter.
 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。また、構造式中のMeはメチル基を表し、Phはフェニル基を表す。 The present invention will be described more specifically below with reference to examples. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Me in the structural formula represents a methyl group, and Ph represents a phenyl group.
<重量平均分子量及び数平均分子量の測定方法>
 樹脂の重量平均分子量は、測定装置としてHPC-8220GPC(東ソー(株)製)、ガードカラムとしてTSKguardcolumn SuperHZ-L、カラムとしてTSKgel SuperHZM-M、TSKgel SuperHZ4000、TSKgel SuperHZ3000、TSKgel SuperHZ2000を直結したカラムを用い、カラム温度を40℃にして、試料濃度0.1質量%のテトラヒドロフラン溶液をカラムに10μL注入し、溶出溶剤としてテトラヒドロフランを毎分0.35mLの流量でフローさせ、RI(示差屈折率)検出装置にて試料ピークを検出し、標準ポリスチレンを用いて作製した検量線を用いて測定した。
<Method for measuring weight average molecular weight and number average molecular weight>
The weight-average molecular weight of the resin is determined by using HPC-8220GPC (manufactured by Tosoh Corporation) as a measuring device, TSKguardcolumn SuperHZ-L as a guard column, and TSKgel SuperHZM-M, TSKgel SuperHZ4000, TSKgel SuperHZ3000, and TSKgel SuperHZ2000 as columns. , The column temperature is set to 40 ° C., 10 μL of a tetrahydrofuran solution with a sample concentration of 0.1% by mass is injected into the column, tetrahydrofuran is flowed at a flow rate of 0.35 mL per minute as an elution solvent, and an RI (differential refractive index) detector. A sample peak was detected at , and measured using a calibration curve prepared using standard polystyrene.
<顔料分散液の製造>
 下記表に示す素材を下記表に示す割合で配合し、総量10gの混合物を得た。この混合物を0.3mm径のジルコニアビーズを使用して、ビーズミル(減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製))で、3時間、混合および分散して、下記表に示す固形分濃度の顔料分散液を製造した。なお、顔料分散液の固形分濃度は溶剤の配合量で調整した。顔料分散液の固形分濃度および粘度、ならびに、顔料分散液中の顔料の平均粒子径D50値を合わせて記す。
 なお、顔料分散液の粘度は、顔料分散液の温度を25℃に調整し、E型粘度計を用いて、回転数1000rpmの条件で測定して求めた。また、顔料の平均粒子径D50値は、日機装(株)製のMICROTRACUPA150を用いて顔料分散液中の顔料の粒度分布を体積基準で測定し、粒度分布における累積体積が50%となる粒子径を測定して求めた。
<Production of pigment dispersion>
The materials shown in the table below were blended in the proportions shown in the table below to obtain a mixture with a total amount of 10 g. This mixture was mixed and dispersed in a bead mill (high-pressure disperser NANO-3000-10 with decompression mechanism (manufactured by Nippon BEE Co., Ltd.)) for 3 hours using zirconia beads with a diameter of 0.3 mm. A pigment dispersion having a solid content concentration shown in was prepared. The solid content concentration of the pigment dispersion was adjusted by adjusting the blending amount of the solvent. The solid content concentration and viscosity of the pigment dispersion and the average particle diameter D50 value of the pigment in the pigment dispersion are also shown.
The viscosity of the pigment dispersion liquid was obtained by adjusting the temperature of the pigment dispersion liquid to 25° C. and measuring it using an E-type viscometer at a rotation speed of 1000 rpm. In addition, the average particle diameter D50 value of the pigment is obtained by measuring the particle size distribution of the pigment in the pigment dispersion on a volume basis using MICROTRACUPA 150 manufactured by Nikkiso Co., Ltd., and the particle diameter at which the cumulative volume in the particle size distribution becomes 50%. Measured and sought.
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
 上記表に記載の素材の詳細は以下の通りである。 The details of the materials listed in the table above are as follows.
(顔料)
 Pig-001~Pig-005:下記構造の化合物(近赤外線吸収顔料、ピロロピロール化合物、Pig-001~Pig-005の25℃のプロピレングリコールメチルエーテルアセテート100gへの溶解度はいずれも0.05g以下である)
 Pig-101:下記構造の化合物(近赤外線吸収顔料、スクアリリウム化合物、25℃のプロピレングリコールメチルエーテルアセテート100gへの溶解度は0.05g以下である)
 Pig-102:下記構造の化合物(近赤外線吸収顔料、ボラジアジン化合物、25℃のプロピレングリコールメチルエーテルアセテート100gへの溶解度は0.1g以下である)
Figure JPOXMLDOC01-appb-C000028
 PB15:6 : C.I.Pigment Blue15:6(青色顔料)
 PY150 : C.I.Pigment Yellow150(黄色顔料)
 PR254 : C.I.Pigment Red254(赤色顔料)
(pigment)
Pig-001 to Pig-005: Compounds having the following structures (near-infrared absorbing pigments, pyrrolopyrrole compounds, and the solubility of Pig-001 to Pig-005 in 100 g of propylene glycol methyl ether acetate at 25° C. are all 0.05 g or less. be)
Pig-101: compound having the following structure (near-infrared absorbing pigment, squarylium compound, solubility in 100 g of propylene glycol methyl ether acetate at 25°C is 0.05 g or less)
Pig-102: compound having the following structure (near-infrared absorbing pigment, boradiazine compound, solubility in 100 g of propylene glycol methyl ether acetate at 25°C is 0.1 g or less)
Figure JPOXMLDOC01-appb-C000028
PB15:6: C.I. I. Pigment Blue 15:6 (blue pigment)
PY150: C.I. I. Pigment Yellow150 (yellow pigment)
PR254: C.I. I. Pigment Red254 (red pigment)
(顔料誘導体)
 Syn-001~Syn-005:下記構造の化合物
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
(pigment derivative)
Syn-001 to Syn-005: compounds having the following structures
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
(分散剤)
 Dis-001:下記構造の樹脂(主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。重量平均分子量25000、分散度2.0)
Figure JPOXMLDOC01-appb-C000031
 Dis-002:下記構造の樹脂(主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。重量平均分子量32000、分散度2.5)
Figure JPOXMLDOC01-appb-C000032
 Dis-003:下記構造の樹脂(主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。重量平均分子量15000、分散度2.8)
Figure JPOXMLDOC01-appb-C000033
(dispersant)
Dis-001: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight 25000, dispersion degree 2.0)
Figure JPOXMLDOC01-appb-C000031
Dis-002: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 32,000, dispersity: 2.5)
Figure JPOXMLDOC01-appb-C000032
Dis-003: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 15,000, dispersity: 2.8)
Figure JPOXMLDOC01-appb-C000033
(溶剤)
 S-001:プロピレングリコールモノメチルエーテルアセテート
(solvent)
S-001: Propylene glycol monomethyl ether acetate
<組成物の調製>
 下記表に示す溶剤以外の素材を下記表に示す割合で混合し、下記表に示す溶剤を加えて固形分濃度が20質量%となるように調整した後、撹拌し、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製)でろ過して、組成物を調製した。表中の配合量の欄の数値は固形分換算値での質量部の値である。また、近赤外線吸収顔料100質量部に対する特定化合物の質量部の値を、「特定化合物の含有量」の欄に記す。
<Preparation of composition>
Materials other than the solvent shown in the table below are mixed in the ratio shown in the table below, and the solvent shown in the table below is added to adjust the solid content concentration to 20% by mass, then stirred and nylon with a pore size of 0.45 μm. filter (manufactured by Nippon Pall Co., Ltd.) to prepare a composition. Numerical values in the columns of compounding amounts in the table are values in parts by mass in terms of solid content. Also, the value of parts by mass of the specific compound with respect to 100 parts by mass of the near-infrared absorbing pigment is shown in the column of "content of specific compound".
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
 上記表に記載の素材の詳細は以下の通りである。 The details of the materials listed in the table above are as follows.
(顔料分散液)
 A001~A005、Bk-1、B-1、Y-1:上述した顔料分散液
(Pigment dispersion)
A001 to A005, Bk-1, B-1, Y-1: the above pigment dispersions
(特定化合物)
 PP-001~PP-010:下記構造の化合物(式(1)で表される化合物、PP-001~PP-010の25℃のプロピレングリコールメチルエーテルアセテート100gへの溶解度はいずれも0.5g以上である)
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
(specific compound)
PP-001 to PP-010: Compounds having the following structures (compounds represented by formula (1), PP-001 to PP-010 have a solubility of 0.5 g or more in 100 g of propylene glycol methyl ether acetate at 25° C.) is)
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
(樹脂)
 B001:アリルメタクリレートとメタクリル酸のランダム共重合体(アリルメタクリレート:メタクリル酸=50/50(モル比)、重量平均分子量20000、分散度2.1))
 B002:ベンジルメタクリレートとメタクリル酸のランダム共重合体(ベンジルメタクリレート:メタクリル酸=60/40(モル比)、重量平均分子量20000、分散度1.9)
 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15000、分散度2.1)
Figure JPOXMLDOC01-appb-C000038
 B004:下記構造の樹脂(主鎖に付記した数値はモル比である。Mw=25000、分散度2.2)
Figure JPOXMLDOC01-appb-C000039
(resin)
B001: Random copolymer of allyl methacrylate and methacrylic acid (allyl methacrylate: methacrylic acid = 50/50 (molar ratio), weight average molecular weight 20000, degree of dispersion 2.1))
B002: Random copolymer of benzyl methacrylate and methacrylic acid (benzyl methacrylate: methacrylic acid = 60/40 (molar ratio), weight average molecular weight 20000, degree of dispersion 1.9)
B003: Resin having the following structure (the numerical values attached to the main chain are the molar ratios of the repeating units, the weight average molecular weight is 15,000, the degree of dispersion is 2.1)
Figure JPOXMLDOC01-appb-C000038
B004: Resin having the following structure (numerical values attached to the main chain are molar ratios, Mw = 25000, dispersity 2.2)
Figure JPOXMLDOC01-appb-C000039
(光重合開始剤)
 C-1:Irgacure OXE01(BASF社製、オキシムエステル系開始剤)
 C-2:Irgacure OXE02(BASF社製、オキシムエステル系開始剤)
(Photoinitiator)
C-1: Irgacure OXE01 (manufactured by BASF, oxime ester initiator)
C-2: Irgacure OXE02 (manufactured by BASF, oxime ester initiator)
(重合性化合物)
 M-1:アロニックスM-305(東亞合成(株)製、ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートとの混合物。ペンタエリスリトールトリアクリレートの含有量が55質量%~63質量%である。)
 M-2:KAYARAD RP-1040(日本化薬(株)製、エチレンオキサイド変性ペンタエリスリトールテトラアクリレート)
 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: Aronix M-305 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate. The content of pentaerythritol triacrylate is 55% by mass to 63% by mass.)
M-2: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd., ethylene oxide-modified pentaerythritol tetraacrylate)
M-3: Aronix M-510 (manufactured by Toagosei Co., Ltd., polybasic acid-modified acrylic oligomer)
(界面活性剤)
 F-1:メガファックRS-72-K(DIC(株)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)
Figure JPOXMLDOC01-appb-C000040
 F-3:KF-6001(信越化学工業(株)製、両末端カルビノール変性ポリジメチルシロキサン、水酸基価62mgKOH/g)
(Surfactant)
F-1: Megafac RS-72-K (manufactured by DIC Corporation, fluorine-based surfactant)
F-2: A compound having the following structure (weight average molecular weight: 14,000, % indicating the ratio of repeating units is mol %)
Figure JPOXMLDOC01-appb-C000040
F-3: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., carbinol-modified polydimethylsiloxane at both ends, hydroxyl value 62 mgKOH/g)
(重合禁止剤)
 G-1:p-メトキシフェノール
(polymerization inhibitor)
G-1: p-methoxyphenol
(その他添加剤)
 U-1:Uvinul3050(BASF社製、紫外線吸収剤)
 U-2:Tinuvin477(BASF社製、ヒドロキシフェニルトリアジン系紫外線吸収剤)
 U-3:Tinuvin326(BASF社製、紫外線吸収剤)
(Other additives)
U-1: Uvinul 3050 (manufactured by BASF, UV absorber)
U-2: Tinuvin477 (manufactured by BASF, hydroxyphenyltriazine-based UV absorber)
U-3: Tinuvin326 (manufactured by BASF, UV absorber)
(溶剤)
 S-001:プロピレングリコールモノメチルエーテルアセテート
 S-002:プロピレングリコールモノメチルエーテル
(solvent)
S-001: Propylene glycol monomethyl ether acetate S-002: Propylene glycol monomethyl ether
<異物欠陥の評価>
 各組成物を保管容器(株式会社マルエム製、バキュームバイアル、褐色瓶、容量30mL)に25mL充填したのち蓋を閉め、蓋と瓶の接続部にシールテープ(日東エルマテリアル製ニトフロンパイプシール No.95S)を巻き付け密閉した。保管容器の充填された組成物を、50℃で3ヵ月間保管した。
 直径15cmのガラス基板上に、前述の保管後の組成物を製膜後の膜厚が1.0μmとなるようにスピンコート塗布し、その後ホットプレートで、100℃で2分間加熱した。次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を用い、1μmのベイヤーパターンを有するマスクを介して1000mJ/cmの露光量で露光した。次いで、水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液を用い、23℃で60秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、さらに純水にて水洗した後に、ホットプレートで、200℃で5分間加熱してパターン(画素)を形成した。画素が形成されたガラス基板について、顕微鏡を用いて10000倍の倍率で観察し、ガラス基板上に形成された画素中に存在するサイズ1μm以上の異物結晶の数を計測し、以下の基準で異物欠陥を評価した。
 A:異物結晶の数が0個
 B:異物結晶の数が1~9個
 C:異物結晶の数が10~99個
 D:異物結晶の数が100~999個
 E:異物結晶の数が1000個以上
<Evaluation of Foreign Matter Defect>
After filling 25 mL of each composition in a storage container (manufactured by Maruem Co., Ltd., vacuum vial, brown bottle, capacity 30 mL), the lid is closed, and a sealing tape (Nitto L Material Nitoflon Pipe Seal No. 1) is applied to the connection between the lid and the bottle. 95S) was wrapped and sealed. The filled composition in the storage container was stored at 50°C for 3 months.
A glass substrate having a diameter of 15 cm was spin-coated with the composition after storage so that the film thickness after film formation was 1.0 μm, and then heated at 100° C. for 2 minutes with a hot plate. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at an exposure amount of 1000 mJ/cm 2 through a mask having a Bayer pattern of 1 μm. Then, using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH), puddle development was performed at 23° C. for 60 seconds. Thereafter, the substrate was rinsed with a spin shower, washed with pure water, and then heated at 200° C. for 5 minutes on a hot plate to form a pattern (pixels). The glass substrate on which the pixels are formed is observed with a microscope at a magnification of 10,000 times, and the number of foreign crystals having a size of 1 μm or more present in the pixels formed on the glass substrate is counted. Defects were evaluated.
A: The number of foreign crystals is 0 B: The number of foreign crystals is 1 to 9 C: The number of foreign crystals is 10 to 99 D: The number of foreign crystals is 100 to 999 E: The number of foreign crystals is 1000 more than one
<粘度変化率の評価>
 製造直後および50℃で3ヵ月間保管後の組成物の粘度をそれぞれ測定し、保管前後の粘度変化率を測定した。なお、各組成物の粘度は、組成物の温度を25℃に調整し、E型粘度計を用いて、回転数1000rpmの条件で測定して求めた。
 粘度変化率(%)=((50℃で3ヵ月間保管後の組成物-製造直後の組成物の粘度)/製造直後の組成物の粘度)×100
<Evaluation of viscosity change rate>
The viscosities of the compositions were measured immediately after production and after storage at 50° C. for 3 months, and the rate of change in viscosity before and after storage was measured. The viscosity of each composition was obtained by adjusting the temperature of the composition to 25° C. and measuring with an E-type viscometer at a rotation speed of 1000 rpm.
Viscosity change rate (%) = ((composition after storage at 50°C for 3 months - viscosity of composition immediately after production)/viscosity of composition immediately after production) x 100
<耐光性の評価>
 製造直後の組成物を、ガラス基板上に製膜後の膜厚が1.0μmとなるようにスピンコート塗布し、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、200℃で2分間加熱し、膜を製造した。
 上記の膜を製膜したガラス基板について、紫外可視近赤外分光光度計U-4100((株)日立ハイテクノロジーズ製)を用いて、波長400~2000nmの範囲の透過率を測定した。
 次に、上記の膜を製膜したガラス基板を、キセノンランプを用い10万luxで20時間照射(200万lux・h相当)し、キセノンランプ照射後の膜の透過率を測定した。
 キセノンランプ照射前後での波長600~800nmの範囲での透過率平均値変化(ΔT)を測定した。測定波長域全体で、透過率変化(ΔT)が最も大きい値に基づき、以下の基準で耐光性を評価した。ΔTの値が小さいほうが耐光性が良好である。
 透過率変化(ΔT)=|キセノンランプ照射前の膜の透過率-キセノンランプ照射後の膜の透過率|
 A:ΔTが1%未満である
 B:ΔTが1%以上である
Figure JPOXMLDOC01-appb-T000041
<Evaluation of light resistance>
The composition immediately after production was spin-coated on a glass substrate so that the film thickness after film formation was 1.0 μm, and an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used to apply 1000 mJ/ The entire surface was exposed with an exposure amount of cm 2 . Then, using a hot plate, it was heated at 200° C. for 2 minutes to produce a film.
Transmittance in the wavelength range of 400 to 2000 nm was measured for the glass substrate on which the above film was formed using an ultraviolet-visible-near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation).
Next, the glass substrate on which the film was formed was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2,000,000 lux·h), and the transmittance of the film after irradiation with the xenon lamp was measured.
The change in average transmittance (ΔT) in the wavelength range of 600 to 800 nm before and after irradiation with the xenon lamp was measured. Based on the largest change in transmittance (ΔT) in the entire measurement wavelength range, the light resistance was evaluated according to the following criteria. The smaller the value of ΔT, the better the light resistance.
Change in transmittance (ΔT)=|Transmittance of film before irradiation with xenon lamp−Transmittance of film after irradiation with xenon lamp|
A: ΔT is less than 1% B: ΔT is 1% or more
Figure JPOXMLDOC01-appb-T000041
 上記表に示すように、実施例の組成物は異物欠陥の抑制された膜を形成することができた。また、実施例の組成物について、製造直後の組成物を用いてガラス基板上に上記と同様の画素を形成して顕微鏡観察を行ったところ、異物は観測されなかった。また、実施例22の組成物は、他の実施例の組成物よりも組成物調製時におけるフィルタろ過において通液速度高くが、通液性に優れていた。 As shown in the table above, the compositions of the examples were able to form films in which foreign matter defects were suppressed. In addition, regarding the composition of the example, when the same pixel as described above was formed on a glass substrate using the composition immediately after production and microscopic observation was performed, no foreign matter was observed. In addition, the composition of Example 22 had a higher liquid permeation rate in filter filtration during preparation of the composition than the compositions of other Examples, but was superior in liquid permeation.
110:固体撮像素子、111:近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 imaging device, 111: near-infrared cut filter, 112: color filter, 114: infrared transmission filter, 115: microlens, 116: flattening layer

Claims (13)

  1.  式(1)で表される化合物と、近赤外線吸収顔料と、硬化性化合物と、を含有し、
     前記式(1)で表される化合物の含有量が前記近赤外線吸収顔料の100質量部に対して、0.01~10質量部である、組成物;
    Figure JPOXMLDOC01-appb-C000001
     式(1)中、R~Rは、それぞれ独立して置換基を表し、RおよびRのいずれか一方はヘテロアリール基で、RおよびRのいずれか一方はヘテロアリール基であり、
     RおよびRは、それぞれ独立してアルキル基、アリール基またはヘテロアリール基を表す。
    containing a compound represented by formula (1), a near-infrared absorbing pigment, and a curable compound,
    A composition in which the content of the compound represented by formula (1) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment;
    Figure JPOXMLDOC01-appb-C000001
    In formula (1), R 1 to R 4 each independently represent a substituent, one of R 1 and R 2 is a heteroaryl group, and one of R 3 and R 4 is a heteroaryl group and
    R5 and R6 each independently represent an alkyl group, an aryl group or a heteroaryl group.
  2.  前記式(1)のRおよびRのいずれか一方はヘテロアリール基で、他方はシアノ基であり、
     前記式(1)のRおよびRのいずれか一方はヘテロアリール基で、他方はシアノ基である、請求項1に記載の組成物。
    one of R 1 and R 2 in the formula (1) is a heteroaryl group and the other is a cyano group;
    2. The composition of claim 1, wherein one of R3 and R4 in formula (1) is a heteroaryl group and the other is a cyano group.
  3.  前記式(1)のRおよびRのいずれか一方が表すヘテロアリール基、ならびに、前記式(1)のRおよびRのいずれか一方が表すヘテロアリール基が、それぞれ独立して、式(A-1)で表される基または式(A-2)で表される基である、請求項1または2に記載の組成物;
    Figure JPOXMLDOC01-appb-C000002
     式(A-1)中、XA1はO、S、NRX1またはCRX2X3を表し、RX1~RX3は、それぞれ独立して水素原子または置換基を表し、
     RA1およびRA2は、それぞれ独立して水素原子または置換基を表し、
     RA1とRA2は互いに結合して環を形成してよく、
     *は結合手を表す;
     式(A-2)中、YA1~YA4は、それぞれ独立してNまたはCRY1を表し、RY1は水素原子または置換基を表し、
     YA1~YA4の少なくとも2つはCRY1であり、
     YA1~YA4のうち隣接する2つがCRY1である場合、隣接する2つのCRY1におけるRY1同士は互いに結合して環を形成してよく、
     *は結合手を表す。
    The heteroaryl group represented by either one of R 1 and R 2 in formula (1) and the heteroaryl group represented by either one of R 3 and R 4 in formula (1) are each independently The composition according to claim 1 or 2, which is a group represented by formula (A-1) or a group represented by formula (A-2);
    Figure JPOXMLDOC01-appb-C000002
    In formula (A-1), X A1 represents O, S, NR X1 or CR X2 R X3 , and R X1 to R X3 each independently represent a hydrogen atom or a substituent,
    R A1 and R A2 each independently represent a hydrogen atom or a substituent,
    R A1 and R A2 may combine with each other to form a ring,
    * represents a bond;
    In formula (A-2), Y A1 to Y A4 each independently represent N or CR Y1 , R Y1 represents a hydrogen atom or a substituent,
    at least two of Y A1 to Y A4 are CR Y1 ;
    When adjacent two of Y A1 to Y A4 are CR Y1 , the R Y1s in the two adjacent CR Y1 may be bonded to each other to form a ring,
    * represents a bond.
  4.  前記式(1)で表される化合物が、式(1-1)または式(1-2)で表される化合物である、請求項1~3のいずれか1項に記載の組成物;
    Figure JPOXMLDOC01-appb-C000003
     式(1-1)中、R11およびR12は、それぞれ独立して置換基を表し、
     R13およびR14は、それぞれ独立してアルキル基、アリール基またはヘテロアリール基を表し、
     X11およびX12は、それぞれ独立してO、S、NRX11またはCRX12X13を表し、RX11~RX13は、それぞれ独立して水素原子または置換基を表し、
     R15~R18は、それぞれ独立して水素原子または置換基を表し、
     R15とR16は互いに結合して環を形成してよく、
     R17とR18は互いに結合して環を形成してよい;
     式(1-2)中、R11およびR12は、それぞれ独立して置換基を表し、
     R13およびR14は、それぞれ独立してアルキル基、アリール基またはヘテロアリール基を表し、
     Y11~Y18は、それぞれ独立してNまたはCRY11を表し、RY11は水素原子または置換基を表し、
     Y11~Y14の少なくとも2つと、Y15~Y18の少なくとも2つは、CRY11であり、
     Y11~Y14のうち隣接する2つがCRY11である場合、隣接する2つのCRY11におけるRY11同士は互いに結合して環を形成してよく、
     Y15~Y18のうち隣接する2つがCRY11である場合、隣接する2つのCRY11におけるRY11同士は互いに結合して環を形成してよい。
    The composition according to any one of claims 1 to 3, wherein the compound represented by formula (1) is a compound represented by formula (1-1) or formula (1-2);
    Figure JPOXMLDOC01-appb-C000003
    In formula (1-1), R 11 and R 12 each independently represent a substituent,
    R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group;
    X 11 and X 12 each independently represent O, S, NR X11 or CR X12 R X13 , R X11 to R X13 each independently represent a hydrogen atom or a substituent,
    R 15 to R 18 each independently represent a hydrogen atom or a substituent,
    R 15 and R 16 may combine with each other to form a ring,
    R 17 and R 18 may combine with each other to form a ring;
    In formula (1-2), R 11 and R 12 each independently represent a substituent,
    R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group;
    Y 11 to Y 18 each independently represent N or CR Y11 , R Y11 represents a hydrogen atom or a substituent,
    at least two of Y 11 to Y 14 and at least two of Y 15 to Y 18 are CR Y11 ;
    When adjacent two of Y 11 to Y 14 are CR Y11 , R Y11 in the two adjacent CR Y11 may combine with each other to form a ring,
    When adjacent two of Y 15 to Y 18 are CR Y11 , R Y11 in the two adjacent CR Y11 may combine with each other to form a ring.
  5.  前記近赤外線吸収顔料がピロロピロール化合物である、請求項1~4のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 4, wherein the near-infrared absorbing pigment is a pyrrolopyrrole compound.
  6.  前記近赤外線吸収顔料が、式(P-1)で表される化合物である、請求項1~5のいずれか1項に記載の組成物;
    Figure JPOXMLDOC01-appb-C000004
     式(P-1)中、Rp~Rpはそれぞれ独立して置換基を表し、かつ、RpおよびRpのいずれか一方はヘテロアリール基で、RpおよびRpのいずれか一方はヘテロアリール基であり、
     RpおよびRpは、それぞれ独立してアルキル基、アリール基またはヘテロアリール基を表し、
     BおよびBは、それぞれ独立してBRp11Rp12を表し、Rp11およびRp12は、それぞれ独立して置換基を表し、
     Rp11とRp12は互いに結合して環を形成してよい。
    The composition according to any one of claims 1 to 5, wherein the near-infrared absorbing pigment is a compound represented by formula (P-1);
    Figure JPOXMLDOC01-appb-C000004
    In formula (P-1), Rp 1 to Rp 4 each independently represent a substituent, one of Rp 1 and Rp 2 is a heteroaryl group, and one of Rp 3 and Rp 4 is a heteroaryl group,
    Rp 5 and Rp 6 each independently represent an alkyl group, an aryl group or a heteroaryl group;
    B 1 and B 2 each independently represent BRp 11 Rp 12 , Rp 11 and Rp 12 each independently represent a substituent,
    Rp 11 and Rp 12 may combine with each other to form a ring.
  7.  前記硬化性化合物は、重合性化合物を含有する、請求項1~6のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 6, wherein the curable compound contains a polymerizable compound.
  8.  前記硬化性化合物は、酸基を有する樹脂を含有する、請求項1~7のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 7, wherein the curable compound contains a resin having an acid group.
  9.  請求項1~8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 8.
  10.  請求項9に記載の膜を含む光学フィルタ。 An optical filter comprising the film according to claim 9.
  11.  請求項9に記載の膜を含む固体撮像素子。 A solid-state imaging device comprising the film according to claim 9.
  12.  請求項9に記載の膜を含む画像表示装置。 An image display device comprising the film according to claim 9.
  13.  請求項9に記載の膜を含む赤外線センサ。 An infrared sensor comprising the film according to claim 9.
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