WO2020196394A1 - Composition de résine, film, filtre à coupure en proche infrarouge, filtre passant en proche infrarouge, dispositif d'imagerie semi-conducteur, appareil d'affichage d'images et capteur infrarouge - Google Patents

Composition de résine, film, filtre à coupure en proche infrarouge, filtre passant en proche infrarouge, dispositif d'imagerie semi-conducteur, appareil d'affichage d'images et capteur infrarouge Download PDF

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WO2020196394A1
WO2020196394A1 PCT/JP2020/012685 JP2020012685W WO2020196394A1 WO 2020196394 A1 WO2020196394 A1 WO 2020196394A1 JP 2020012685 W JP2020012685 W JP 2020012685W WO 2020196394 A1 WO2020196394 A1 WO 2020196394A1
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group
resin composition
ring
resin
atom
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PCT/JP2020/012685
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English (en)
Japanese (ja)
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峻輔 北島
季彦 松村
賢 鮫島
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富士フイルム株式会社
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Priority to JP2021509387A priority Critical patent/JP7112592B2/ja
Publication of WO2020196394A1 publication Critical patent/WO2020196394A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C08K5/3447—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters

Definitions

  • the present invention relates to a resin composition containing a squarylium compound.
  • the present invention also relates to a film using a composition containing a squarylium compound, a near-infrared cut filter, a near-infrared transmission filter, a solid-state image sensor, an image display device, and an infrared sensor.
  • CCD charge coupling element
  • CMOS complementary metal oxide semiconductor
  • the near-infrared cut filter is manufactured by using a resin composition containing a near-infrared absorbing dye.
  • a squarylium compound is known as one of the near-infrared absorbing dyes.
  • Patent Documents 1 and 2 describe a squarylium compound having a specific structure, which is a near-infrared absorbing dye.
  • Patent Document 3 describes an invention relating to a composition for an optical filter containing a dye having a maximum absorption wavelength at a wavelength of 500 to 1200 nm and a predetermined metal complex.
  • a dye having a maximum absorption wavelength at a wavelength of 500 to 1200 nm has a function of imparting a predetermined absorption characteristic to the obtained optical filter.
  • the metal complex has a function of imparting light resistance to a dye having a maximum absorption wavelength at a wavelength of 500 to 1200 nm in the state of a composition or in the state of an optical filter obtained by using the composition. There is.
  • Patent Document 3 the metal complex according to Patent Document 3 is used for the purpose of improving the light resistance of the dye.
  • the present invention provides: ⁇ 1> Near-infrared absorbing dye represented by the following formula (SQ1) and With the metal complex represented by the following formula (MC1), With resin Resin composition containing;
  • Rs 119 and Rs 120 each independently represent a substituent and represent a substituent.
  • a 1 and A 2 independently represent an oxygen atom or -N (Rs 125 )-, respectively.
  • Rs 121 to Rs 125 independently represent a hydrogen atom or a substituent, respectively.
  • E 1 is a carbon atom
  • E 2 is a carbon atom
  • ns30 and ns31 independently represent integers from 0 to 5, respectively.
  • ns30 is 2 or more, plural Rs 119, which may be the same or different and may form a ring two Rs 119 between among the plurality of Rs 119 is coupled to, If ns31 is 2 or more, plural Rs 120, which may be the same or different and may form a ring by bonding two Rs 120 between among the plurality of Rs 120, If ns32 is 2, the two Rs 121 may be the same or different and may form a ring together two Rs 121 is coupled to, If ns33 is 2, the two Rs 122 may be the same or different and may form a ring together two Rs 122 is coupled to, Ar 100 represents an arylene group or a heteroarylene group, ns100 represents an integer of 0 to 2.
  • ring Z mc1 and ring Z mc2 each independently represent a nitrogen-containing heterocycle.
  • R mc1 and R mc2 single bond or -CR are each independently Y1
  • R Y2 - represents represents a hydrogen atom or a substituent
  • R Y1 and R Y2 are each independently M mc1 represents a monovalent to trivalent transition metal.
  • 2- A 41 and A 42 independently represent an oxygen atom or -N ( RN2 )-, respectively.
  • RN1 and RN2 independently represent a hydrogen atom, an alkyl group, or an aryl group, respectively.
  • Rs 141 and Rs 142 each independently represent a substituent and represent a substituent.
  • ns41 and ns42 independently represent integers from 0 to 5, respectively.
  • ns41 is 2 or more
  • plural Rs 141 may be the same or different and be two Rs 141 are bonded to each other among the plurality of Rs 141 to form a ring
  • ns42 is 2 or more
  • plural Rs 142 which may be the same or different and may form a ring by bonding two Rs 142 between among the plurality of Rs 142;
  • L 41 ⁇ L 44 is an alkylene group
  • Z 41 and Z 42 is a single bond
  • a 41 and A 42 is -N (R N2) - in the case, Ns41 and ns42 of at least one of an integer from 1 to 5 Is.
  • M 2 represents inorganic or organic cation
  • RX1 ⁇ RX3 independently represents a hydrogen atom, an alkyl group, an aryl group, an acyl group or a heterocyclic group, and RX1 and RX2 may be bonded to each other to form a ring
  • Rs 21 to Rs 28 Of Rs 31 to Rs 38 , adjacent groups may be bonded to each other to form a ring; If Q 1 is a nitrogen atom, Rs 21 does not exist, if Q 4 is a nitrogen atom, Rs 24 does not exist, if Q 5 is a nitrogen atom, Rs 25 does not exist, and Q 8 is a nitrogen atom.
  • ⁇ 7> In any one of ⁇ 1> to ⁇ 6>, which further contains a surfactant and the content of the surfactant is 0.001 to 0.2% by mass in the total solid content of the resin composition.
  • ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, further comprising a polymerizable compound and a photopolymerization initiator.
  • ⁇ 9> The resin composition according to any one of ⁇ 1> to ⁇ 8>, further comprising a coloring material that transmits near infrared rays to block visible light.
  • ⁇ 11> A near-infrared cut filter having the film according to ⁇ 10>.
  • ⁇ 12> A near-infrared ray transmitting filter having the film according to ⁇ 10>.
  • ⁇ 13> A solid-state image sensor having the film according to ⁇ 10>.
  • ⁇ 14> An image display device having the film according to ⁇ 10>.
  • ⁇ 15> An infrared sensor having the film according to ⁇ 10>.
  • a resin composition a film, a near infrared cut filter, a near infrared transmission filter, a solid-state image sensor, an image display device, and an infrared sensor capable of forming a film having excellent spectral characteristics in the near infrared region.
  • the contents of the present invention will be described in detail below.
  • "-" is used in the meaning of including the numerical values before and after it as the lower limit value and the upper limit value.
  • the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified.
  • the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excima laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
  • EUV light extreme ultraviolet rays
  • (meth) acrylate represents both acrylate and methacrylate, or either
  • (meth) acrylic represents both acrylic and methacrylic, or either.
  • Acryloyl "represents both acryloyl and / or methacryloyl.
  • the weight average molecular weight and the number average molecular weight are defined as polystyrene-equivalent values in gel permeation chromatography (GPC) measurements.
  • GPC gel permeation chromatography
  • Me in the chemical formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the near infrared ray means light (electromagnetic wave) having a wavelength of 700 to 2500 nm.
  • the total solid content means the total mass of all the components of the composition excluding the solvent.
  • the term pigment means a compound that is difficult to dissolve in a solvent.
  • the solubility of the pigment in 100 g of water at 23 ° C. and the solubility in 100 g of propylene glycol monomethyl ether acetate at 23 ° C. are preferably less than 0.1 g, more preferably 0.01 g or less.
  • the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
  • the resin composition of the present invention is characterized by containing a near-infrared absorbing dye represented by the formula (SQ1), a metal complex represented by the formula (MC1), and a resin.
  • the resin composition of the present invention By using the resin composition of the present invention, it is possible to form a film having excellent spectral characteristics in the near infrared region.
  • the detailed reason for obtaining such an effect is unknown, but it is presumed to be due to the following.
  • the present inventor diligently studied a film obtained by using a resin composition containing a near-infrared absorbing dye represented by (SQ1), and found that this film has an absorption spectrum in the near-infrared region in the absorption band. It was found that splitting is likely to occur, and the shielding property of near-infrared rays, particularly the shielding property of longer-wave near-infrared rays, is likely to decrease.
  • the near-infrared absorbing dye represented by (SQ1) has a structure in which a bulky substituent is bonded to quaric acid, so that the molecules are diagonally staggered in the membrane. It is presumed that it is easy to form a state. Therefore, the near-infrared absorbing dye represented by (SQ1) is likely to form H-association and J-association in the film, respectively, and as a result, the absorption spectrum in the near-infrared region is divided into absorption bands. It is presumed that the absorption of light on the long wavelength side is reduced, and the shielding property of near infrared rays, particularly the shielding property of near infrared rays of longer waves, is likely to be lowered.
  • the resin composition of the present invention further contains a metal complex represented by the formula (MC1) in addition to the near-infrared absorbing dye represented by the formula (SQ1), it is represented by the formula (MC1) at the time of film formation. It is presumed that the metal complex facilitates the formation of J-association between the near-infrared absorbing dyes represented by the formula (SQ1), and as a result, the decrease in light absorption on the longer wavelength side can be suppressed. Therefore, it is presumed that by using the resin composition of the present invention, a film having excellent spectral characteristics in the near infrared region could be formed.
  • MC1 metal complex represented by the formula (MC1) in addition to the near-infrared absorbing dye represented by the formula (SQ1)
  • the resin composition of the present invention preferably contains two or more types of metal complexes represented by the formula (MC1).
  • the metal complex represented by the formula (MC1) By containing the metal complex represented by the formula (MC1) in the resin composition containing the near-infrared absorbing dye represented by the formula (SQ1), the resin composition is represented by the formula (MC1) during storage. Aggregates derived from metal complexes may precipitate, which may reduce the storage stability of the resin composition.
  • the formula ( The crystallinity of the metal complex represented by MC1) can be reduced to suppress the precipitation of aggregates derived from the metal complex represented by the formula (MC1) during storage of the resin composition, and the storage stability of the resin composition can be suppressed. Can improve sex.
  • the resin composition of the present invention further contains a surfactant, and the content of the surfactant is preferably 0.001 to 0.2% by mass in the total solid content of the resin composition.
  • the coatability of the resin composition can be further improved, and even when the resin composition is applied to a surface having steps such as irregularities, the generation of radial streaks called striations can be suppressed.
  • the storage stability of the resin composition can be improved. In particular, when two or more kinds of metal complexes represented by the formula (MC1) are blended, striations tend to occur, but by blending the surfactant in the above ratio, striations occur. Can be effectively suppressed. Therefore, a particularly remarkable effect can be obtained when the resin composition contains two or more kinds of metal complexes represented by the formula (MC1).
  • the resin composition of the present invention contains a near-infrared absorbing dye represented by the formula (SQ1).
  • the near-infrared absorbing dye represented by the formula (SQ1) is preferably a pigment.
  • Rs 119 and Rs 120 each independently represent a substituent and represent a substituent.
  • a 1 and A 2 independently represent an oxygen atom or -N (Rs 125 )-, respectively.
  • Rs 121 to Rs 125 independently represent a hydrogen atom or a substituent, respectively.
  • ns30 and ns31 independently represent integers from 0 to 5, respectively.
  • ns30 is 2 or more, plural Rs 119, which may be the same or different and may form a ring two Rs 119 between among the plurality of Rs 119 is coupled to, If ns31 is 2 or more, plural Rs 120, which may be the same or different and may form a ring by bonding two Rs 120 between among the plurality of Rs 120, If ns32 is 2, the two Rs 121 may be the same or different and may form a ring together two Rs 121 is coupled to, If ns33 is 2, the two Rs 122 may be the same or different and may form a ring together two Rs 122 is coupled to, Ar 100 represents an arylene group or a heteroarylene group, ns100 represents an integer of 0 to 2.
  • Examples of the substituent represented by Rs 119 and Rs 120 include the group described in Substituent T described later as the substituent, and a halogen atom, an alkyl group, a sulfo group and -SO 3 M are preferable.
  • M represents an inorganic or organic cation.
  • the inorganic or organic cation represented by M known ones can be adopted without limitation. For example, alkali metal ions (Li + , Na + , K +, etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ions and the like can be mentioned.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 8, further preferably 1 to 5, and particularly preferably 1 to 3.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • a 1 and A 2 independently represent an oxygen atom or -N (Rs 125 )-, preferably -N (Rs 125 )-.
  • Examples of the substituent represented by Rs 121 to Rs 125 include the group described in Substituent T described later.
  • Rs 123 to Rs 125 are preferably hydrogen atoms, alkyl groups, or aryl groups, and more preferably hydrogen atoms. Further, it is preferable that Rs 121 to Rs 125 are independent substituents.
  • the ring formed by bonding Rs 121 to each other and the ring formed by bonding Rs 122 to each other may be a hydrocarbon ring or a heterocycle. Further, the hydrocarbon ring and the heterocycle may be an aromatic ring or a non-aromatic ring.
  • the hydrocarbon ring and the heterocycle may be a monocyclic ring or a condensed ring.
  • the ring formed by bonding Rs 121 to each other and the ring formed by bonding Rs 122 to each other are preferably fused rings, and more preferably three or more fused rings.
  • the ring formed by bonding Rs 121 to each other and the ring formed by bonding Rs 122 to each other may further have a substituent. Examples of the substituent include the group described in Substituent T described later.
  • ns30 and ns31 each independently represent an integer of 0 to 5, preferably 0 to 4, more preferably 0 to 3, even more preferably 0 to 2, and even more preferably 0 or 1. If ns30 is 2 or more, plural Rs 119, which may be the same or different and may form a ring two Rs 119 between among the plurality of Rs 119 is coupled to, NS31 for but 2 or more, plural Rs 120, which may be the same or different and may form a ring two Rs 120 between among the plurality of Rs 120 is bonded to.
  • the ring formed by bonding Rs 119 to each other and the ring formed by bonding Rs 120 to each other may be a hydrocarbon ring or a heterocycle.
  • the hydrocarbon ring and the heterocycle may be an aromatic ring or a non-aromatic ring. Further, the hydrocarbon ring and the heterocycle may be a monocyclic ring or a condensed ring.
  • the ring formed by bonding Rs 119 to each other and the ring formed by bonding Rs 120 to each other are preferably a 5-membered ring or a 6-membered ring hydrocarbon ring or a heterocyclic ring. Alternatively, it is more preferably a 6-membered hydrocarbon ring.
  • Ar 100 represents an arylene group or a heteroarylene group.
  • the arylene group and the heteroarylene group may be a monocyclic ring or a condensed ring.
  • the arylene group and the heteroarylene group are preferably groups represented by any of the following formulas (Ar-1) to (Ar-7).
  • Xa 1 to Xa 8 independently represent a sulfur atom, an oxygen atom or an NRx a
  • Rx a represents a hydrogen atom or a substituent
  • * represents a bond. Examples of the substituent represented by Rx a include the group described in Substituent T described later.
  • Ns100 represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
  • the near-infrared absorbing dye represented by the formula (SQ1) is preferably a near-infrared absorbing dye represented by the formula (SQ2).
  • L 41 to L 44 independently represent an alkylene group, an alkynylene group, an arylene group, a heterocyclic group, or a divalent group in which two or more of these are bonded.
  • a 41 and A 42 independently represent an oxygen atom or -N ( RN2 )-, respectively.
  • RN1 and RN2 independently represent a hydrogen atom, an alkyl group, or an aryl group, respectively.
  • Rs 141 and Rs 142 each independently represent a substituent and represent a substituent.
  • ns41 and ns42 independently represent integers from 0 to 5, respectively.
  • ns41 is 2 or more
  • plural Rs 141 may be the same or different and be two Rs 141 are bonded to each other among the plurality of Rs 141 to form a ring
  • ns42 is 2 or more
  • plural Rs 142 which may be the same or different and may form a ring by bonding two Rs 142 between among the plurality of Rs 142;
  • L 41 ⁇ L 44 is an alkylene group
  • Z 41 and Z 42 is a single bond
  • a 41 and A 42 is -N (R N2) - in the case, Ns41 and ns42 of at least one of an integer from 1 to 5 Is.
  • L 41 to L 44 each independently represent an alkylene group, an alkynylene group, an arylene group, a heterocyclic group, or a divalent group in which two or more of these are bonded.
  • the number of carbon atoms of the alkylene group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 8, further preferably 1 to 5, and particularly preferably 1 to 3.
  • the alkylene group may be linear, branched or cyclic.
  • the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • the number of carbon atoms of the alkynylene group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8.
  • the alkynylene group may be either linear or branched.
  • the alkynylene group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • the number of carbon atoms of the arylene group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
  • the arylene group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • the heterocyclic group is preferably a monocyclic heterocyclic group or a condensed ring heterocyclic group having a condensation number of 2 to 8, and a monocyclic heterocyclic group or a condensed ring heterocyclic group having a condensation number of 2 to 4 is more preferable.
  • a monocyclic heterocyclic group is more preferred.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3.
  • the hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom.
  • the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
  • the heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • Each of L 41 to L 44 is preferably an arylene group or a heterocyclic group independently, and more preferably an arylene group.
  • a 41 and A 42 independently represent an oxygen atom or ⁇ N ( RN2 ) ⁇ , and are preferably ⁇ N ( RN2 ) ⁇ .
  • RN2 is preferably a hydrogen atom.
  • the number of carbon atoms of the alkyl group represented by RN1 and RN2 is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 8, further preferably 1 to 5, and particularly preferably 1 to 3.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • the aryl group represented by RN1 and RN2 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
  • the aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • Examples of the substituent represented by Rs 141 and Rs 142 include the group described in Substituent T described later, and halogen atoms, alkyl groups, sulfo groups and -SO 3 M are preferable.
  • M represents an inorganic or organic cation.
  • the inorganic or organic cation represented by M known ones can be adopted without limitation.
  • alkali metal ions Li + , Na + , K +, etc.
  • ammonium ions imidazolium ions, pyridinium ions, phosphonium ions and the like can be mentioned.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 8, further preferably 1 to 5, and particularly preferably 1 to 3.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • ns41 and ns42 each independently represent an integer of 0 to 5, preferably 0 to 4, more preferably 0 to 3, even more preferably 0 to 2, and even more preferably 0 or 1. If ns41 is 2 or more, plural Rs 141 may be the same or different and be two Rs 141 are bonded to each other among the plurality of Rs 141 to form a ring, Ns42 for but 2 or more, plural Rs 142, which may be the same or different and each other two Rs 142 may be bonded to form a ring out of a plurality of Rs 142.
  • the ring formed by bonding Rs 141 to each other and the ring formed by bonding Rs 142 to each other may be a hydrocarbon ring or a heterocycle.
  • the hydrocarbon ring and the heterocycle may be an aromatic ring or a non-aromatic ring. Further, the hydrocarbon ring and the heterocycle may be a monocyclic ring or a condensed ring.
  • the ring formed by bonding Rs 141 to each other and the ring formed by bonding Rs 142 to each other are preferably a 5- or 6-membered hydrocarbon ring or a heterocycle, and are preferably 5-membered rings. Alternatively, it is more preferably a 6-membered hydrocarbon ring.
  • the near-infrared absorbing dye represented by the formula (SQ1) is preferably a near-infrared absorbing dye represented by the formula (SQ3).
  • Q 1 , Q 4 , Q 5 , Q 8 , Q 11 , Q 14 , Q 15 and Q 18 each independently represent a carbon or nitrogen atom
  • Rs 1 to Rs 5 and Rs 11 to Rs 15 independently represent a hydrogen atom, an alkyl group, a sulfo group, -SO 3 M 1 or a halogen atom
  • M 1 represents an inorganic or organic cation
  • Rs 2 And Rs 3 , Rs 12 and Rs 13 may combine with each other to form a ring
  • Rs 21 to Rs 28 and Rs 31 to Rs 38 are independently hydrogen atoms, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, hydroxy groups, -NR X1 RX2 , and sulfo groups.
  • M 2 represents inorganic or organic cation
  • RX1 ⁇ RX3 independently represents a hydrogen atom, an alkyl group, an aryl group, an acyl group or a heterocyclic group, and RX1 and RX2 may be bonded to each other to form a ring
  • Rs 21 to Rs 28 Of Rs 31 to Rs 38 , adjacent groups may be bonded to each other to form a ring; If Q 1 is a nitrogen atom, Rs 21 does not exist, if Q 4 is a nitrogen atom, Rs 24 does not exist, if Q 5 is a nitrogen atom, Rs 25 does not exist, and Q 8 is a nitrogen atom.
  • Q 1 , Q 4 , Q 5 , Q 8 , Q 11 , Q 14 , Q 15 and Q 18 are carbon atoms from the viewpoint of various resistances such as heat resistance and light resistance.
  • the number of carbon atoms of the alkyl group represented by Rs 1 to Rs 5 and Rs 11 to Rs 15 is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 8, further preferably 1 to 5, and 1 to 1. 3 is particularly preferable.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • M 1 represented by Rs 1 to Rs 5 and Rs 11 to Rs 15
  • known inorganic or organic cations of M 1 can be adopted without limitation.
  • alkali metal ions Li + , Na + , K +, etc.
  • ammonium ions imidazolium ions, pyridinium ions, phosphonium ions and the like can be mentioned.
  • Examples of the halogen atom represented by Rs 1 to Rs 5 and Rs 11 to Rs 15 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the ring formed may be a hydrocarbon ring or a heterocycle.
  • the hydrocarbon ring and the heterocycle may be an aromatic ring or a non-aromatic ring.
  • the hydrocarbon ring and the heterocycle may be a monocyclic ring or a condensed ring.
  • the ring formed is preferably a 5- or 6-membered hydrocarbon ring or a heterocycle, and more preferably a 5- or 6-membered hydrocarbon ring.
  • Rs 1 to Rs 5 are hydrogen atoms, or four of Rs 1 to Rs 5 are hydrogen atoms, one is a sulfo group, and -SO 3 M 1. Alternatively, it is preferably a halogen atom. Among these, it is particularly preferable that Rs 1 to Rs 5 are hydrogen atoms, or four of Rs 1 to Rs 5 are hydrogen atoms and one is a sulfo group or a halogen atom. Further, in Rs 11 to Rs 15 , from the viewpoint of imparting resistance, Rs 11 to Rs 15 are hydrogen atoms, or four of Rs 11 to Rs 15 are hydrogen atoms and one is a sulfo group, -SO 3.
  • Rs 11 to Rs 15 are hydrogen atoms, or four of Rs 11 to Rs 15 are hydrogen atoms and one is a sulfo group or a halogen atom.
  • the alkyl and alkoxy groups represented by Rs 21 to Rs 28 and Rs 31 to Rs 38 have preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. 1 to 3 are particularly preferable.
  • the alkyl group and the alkoxy group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
  • the alkyl group and the alkoxy group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • the carbon number of the alkenyl group represented by Rs 21 to Rs 28 and Rs 31 to Rs 38 is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8.
  • the alkenyl group may be either a straight chain or a branched chain, and a straight chain is preferable.
  • the alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • the aryl group and aryloxy group represented by Rs 21 to Rs 28 and Rs 31 to Rs 38 preferably have 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
  • the aryl group and the aryloxy group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • the carbon number of the aralkyl group represented by Rs 21 to Rs 28 and Rs 31 to Rs 38 is preferably 7 to 40, more preferably 7 to 30, and even more preferably 7 to 25.
  • M 2 represented by Rs 21 to Rs 28 and Rs 31 to Rs 38
  • known inorganic or organic cations of M 2 can be adopted without limitation.
  • alkali metal ions Li + , Na + , K +, etc.
  • ammonium ions imidazolium ions, pyridinium ions, phosphonium ions and the like can be mentioned.
  • Examples of the halogen atom represented by Rs 21 to Rs 28 and Rs 31 to Rs 38 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Rs 21 ⁇ Rs 28, Rs 31 ⁇ Rs 38 is represented, -NR X1 R X2, -SO 2 NR X1 R X2, in -COOR X3 and -CONR X1 R X2, R X1 ⁇ R X3 each independently, Represents a hydrogen atom, an alkyl group, an aryl group, an acyl group or a heterocyclic group.
  • the alkyl group represented by RX1 to RX3 has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 8 carbon atoms, further preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • the aryl group represented by RX1 to RX3 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
  • the aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • Heterocyclic group R X1 ⁇ R X3 represents the heterocyclic group is preferably a condensed heterocyclic group or the number of fused monocyclic 2-8, monocyclic heterocyclic group or fused number of 2 to 4 condensed
  • a ring heterocyclic group is more preferred, and a monocyclic heterocyclic group is even more preferred.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3.
  • the hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom.
  • the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
  • the heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later. Specific examples of the heterocyclic group include a pyridinyl group and the like. The pyridinyl group may have a substituent.
  • Examples of the acyl group represented by RX1 to RX3 include a formyl group, an alkylcarbonyl group, and an arylcarbonyl group.
  • the alkylcarbonyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and even more preferably 2 to 8 carbon atoms.
  • the arylcarbonyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and even more preferably 7 to 12 carbon atoms.
  • the alkyl moiety of the alkylcarbonyl group and the aryl moiety of the arylcarbonyl group may have a substituent or may be unsubstituted. Examples of the substituent include the group described in Substituent T described later.
  • R X1 and R X2 may be bonded to each other to form a ring.
  • the ring formed is preferably a 5-membered ring or a 6-membered ring.
  • adjacent groups may be bonded to each other to form a ring.
  • the ring formed may be a hydrocarbon ring or a heterocycle.
  • the hydrocarbon ring and the heterocycle may be an aromatic ring or a non-aromatic ring.
  • the hydrocarbon ring and the heterocycle may be a monocyclic ring or a condensed ring.
  • the ring formed is preferably a 5- or 6-membered hydrocarbon ring or a heterocycle, and more preferably a 5- or 6-membered hydrocarbon ring.
  • Rs 21 ⁇ Rs 28, Rs 31 ⁇ Rs 38 are each independently a hydrogen atom, an alkyl group, hydroxy group, -NR X1 R X2, a sulfo group, -SO 3 M 2, -COOR X3 , a nitro group or a halogen atom Is preferable, and a hydrogen atom is more preferable.
  • Substituents T include halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, -ORt 1 , -CORt 1 , -COORt 1 , -OCORt 1 , -NRt 1 Rt 2 , -NHCORt 1 , -CONRt 1 Rt 2 , -NHCONRT 1 Rt 2 , -NHCOORt 1 , -SRt 1 , -SO 2 Rt 1 , -SO 2 ORt 1 , -NHSO 2 Rt 1 , -SO 2 NRt 1 Included are Rt 2 and -SO 3 Mt 1 .
  • Rt 1 and Rt 2 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, respectively. Rt 1 and Rt 2 may be combined to form a ring. Mt 1 represents an inorganic or organic cation.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched.
  • the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
  • the alkenyl group may be either linear or branched.
  • the alkynyl group preferably has 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and particularly preferably 2 to 25 carbon atoms.
  • the alkynyl group can be either linear or branched.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
  • the heterocyclic group is preferably a monocyclic heterocyclic group or a condensed ring heterocyclic group having a condensation number of 2 to 8, and a monocyclic heterocyclic group or a condensed ring heterocyclic group having a condensation number of 2 to 4 is more preferable. preferable.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3.
  • the hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
  • the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituent described in the above-mentioned Substituent T.
  • Examples of the inorganic or organic cation represented by Mt 1 include alkali metal ions (Li + , Na + , K +, etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ions, and the like.
  • the cation is delocalized and exists.
  • the cation exists delocalized as follows.
  • the near-infrared absorbing dye represented by the formula (SQ1) is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1300 nm, and preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1000 nm. More preferred.
  • the near-infrared absorbing dye represented by the formula (SQ1) include a compound having the following structure, a compound described in paragraph Nos. 0224 to 0341 of JP-A-2019-011455, paragraph of International Publication No. 2018/230486. Examples thereof include the compounds described in Nos. 0221 to 0377.
  • the content of the near-infrared absorbing dye represented by the formula (SQ1) is preferably 1% by mass or more, preferably 3% by mass or more, and 5% by mass in the total solid content of the resin composition of the present invention. % Or more is more preferable, and 10% by mass or more is particularly preferable. Further, the upper limit of the content of the near-infrared absorbing dye represented by the formula (SQ1) is preferably 50% by mass or less, more preferably 45% by mass or less, and preferably 40% by mass or less. More preferred.
  • the resin composition may contain only one type of near-infrared absorbing dye represented by the formula (SQ1), or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention contains a metal complex represented by the formula (MC1).
  • ring Z mc1 and ring Z mc2 each independently represent a nitrogen-containing heterocycle.
  • R mc1 and R mc2 single bond or -CR are each independently Y1
  • R Y2 - represents represents a hydrogen atom or a substituent
  • R Y1 and R Y2 are each independently M mc1 represents a monovalent to trivalent transition metal.
  • the nitrogen-containing heterocycle represented by ring Z mc1 and ring Z mc2 is preferably a 5-membered ring or a 6-membered ring.
  • the nitrogen-containing heterocycle represented by the ring Z mc1 and the ring Z mc2 may be either an aromatic ring or a non-aromatic ring, but is preferably an aromatic ring. It is particularly preferable that the ring Z mc1 and the ring Z mc2 are independently 5- or 6-membered nitrogen-containing aromatic heterocycles, respectively.
  • the nitrogen-containing heterocycle represented by the ring Z mc1 and the ring Z mc2 may have a substituent.
  • substituents examples include a halogen atom, an alkyl group having 1 to 15 carbon atoms (preferably 1 to 8 carbon atoms), an aryl group having 6 to 21 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, and 1 to 15 carbon atoms (preferably 1 to 15 carbon atoms).
  • R 100 to R 102 are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms.
  • a part of hydrogen atom may be substituted with a halogen atom (preferably a fluorine atom).
  • R mc1 and R mc2 single bond or -CR are each independently Y1 R Y2 - represents, each represent R Y1 and R Y2 independently represents a hydrogen atom or a substituent.
  • the substituents R Y1 and R Y2 are represented, which ring Z mc1 and ring Z mc2 described above has been described as an example of the substituent which may have can be mentioned an alkyl group and a halogen atom are preferred. It is preferable that RY1 and RY2 are hydrogen atoms.
  • R mc1 and R mc2 are preferably single bonds.
  • M mc1 represents a monovalent to trivalent transition metal.
  • the transition metal represented by M mc1 include Co, Ni, Cu, Rh, Ag, Ir, Pt and Au, with Cu, Ni and Co being preferred, Ni or Cu being preferred, and Cu being more preferred.
  • the metal complex represented by the formula (MC1) preferably has a molar extinction coefficient ( ⁇ ) of 100 L / (mol ⁇ cm) or less, preferably 50 L / (mol ⁇ cm) or less, in light having a wavelength of 430 to 480 nm. More preferably, it is more preferably 20 L / (mol ⁇ cm) or less, and particularly preferably 10 L / (mol ⁇ cm) or less.
  • the two ligands of the metal complex represented by the formula (MC1) may be the same or different.
  • the metal complex represented by the formula (MC1) is dissolved by adding, for example, a salt of Mcc1 , a compound represented by the formula (L1), and a compound represented by the formula (L2) to a solvent. , Can be produced by adding an equivalent amount of base.
  • the two ligands are the same in the metal complex represented by the formula (MC1), the compound represented by the formula (L1) and the compound represented by the formula (L2) are the same compound.
  • the ring Z mc1 represents a nitrogen-containing heterocyclic ring
  • R mc1 is a single bond or -CR Y1 R Y2 - represents, each represent R Y1 and R Y2 independently represents a hydrogen atom or a substituent.
  • the ring Z mc2 represents a nitrogen-containing heterocyclic ring
  • R mc2 is a single bond or -CR Y1 R Y2 - represents, each represent R Y1 and R Y2 independently represents a hydrogen atom or a substituent.
  • the metal complex represented by the formula (MC1) preferably has a structure represented by the following formula (MC2).
  • R mc11 to R mc18 independently represent a hydrogen atom or a substituent, and M mc1 represents a monovalent to trivalent transition metal.
  • M mc1 of formula (MC2) has the same meaning as M mc1 of formula (MC1), and preferred ranges are also the same.
  • Examples of the substituent represented by R mc11 to R mc18 include those described above as examples of the substituents that the rings Z mc1 and the ring Z mc2 may have.
  • R mc11 to R mc18 is substituted with an alkyl group or halogen atom having 1 to 15 carbon atoms (preferably 1 to 8 carbon atoms) which may be substituted with a halogen atom.
  • An alkoxy group having 1 to 15 carbon atoms (preferably 1 to 8 carbon atoms) may be used.
  • a fluorine atom is preferable as the halogen atom.
  • At least one of R mc1 to R mc18 is preferably CF 3 group or methoxy group, and CF 3 group is particularly preferable.
  • R mc11 to R mc14 and at least one of R mc15 to R mc18 are the above-mentioned substituents, respectively, and R mc14 and R mc18 are the above-mentioned substituents, respectively, and the rest is hydrogen. It is more preferably an atom.
  • metal complex represented by the formula (MC1) include compounds having the following structures, compounds described in paragraphs 0995 and 0906 of JP-A-2018-028605, compounds described in Examples described later, and the like. Can be mentioned.
  • the resin composition of the present invention preferably contains two or more types of metal complexes represented by the formula (MC1). According to this aspect, the storage stability of the resin composition can be improved.
  • the content of the metal complex represented by the formula (MC1) is preferably 10 to 150 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye represented by the formula (SQ1).
  • the lower limit is preferably 15 parts by mass or more.
  • the upper limit is preferably 100 parts by mass or less, and more preferably 80 parts by mass or less.
  • the resin composition of the present invention contains a resin.
  • the resin is blended, for example, for the purpose of dispersing particles such as pigments in the resin composition and for the purpose of a binder.
  • a resin mainly used for dispersing particles such as pigments is also referred to as a dispersant.
  • such an application of the resin is an example, and the resin can be used for a purpose other than such an application.
  • the weight average molecular weight (Mw) of the resin is preferably 2000 to 2000000.
  • the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
  • the lower limit is preferably 3000 or more, and more preferably 5000 or more.
  • the resin examples include (meth) acrylic resin, epoxy resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, and polyimide resin.
  • examples thereof include polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, and styrene resin. One of these resins may be used alone, or two or more thereof may be mixed and used.
  • the cyclic olefin resin a norbornene resin is preferable from the viewpoint of improving heat resistance.
  • Examples of commercially available norbornene resins include the ARTON series manufactured by JSR Corporation (for example, ARTON F4520).
  • Examples of the epoxy resin include an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester type.
  • Epoxy resin glycidylamine-based epoxy resin, epoxy resin obtained by glycidylizing halogenated phenols, condensate of silicon compound having an epoxy group and other silicon compounds, polymerizable unsaturated compound having an epoxy group and other Examples thereof include a copolymer with another polymerizable unsaturated compound.
  • the epoxy resins are Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (NOF). Epoxy group-containing polymer manufactured by Co., Ltd.) can also be used. Further, as the resin, the resin described in the examples of International Publication No.
  • the resin has an ethylenically unsaturated bond-containing group in the side chain, particularly a (meth) acryloyl group
  • the main chain and the ethylenically unsaturated bond-containing group are via a divalent linking group having an alicyclic structure. It is also preferable that they are bonded.
  • the resin composition of the present invention preferably contains an alkali-soluble resin.
  • the resin composition of the present invention contains an alkali-soluble resin
  • the developability of the resin composition is improved, and when a pattern is formed by a photolithography method using the resin composition of the present invention, development residue is generated. Can be effectively suppressed.
  • the alkali-soluble resin include resins having an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferable.
  • the alkali-soluble resin may have only one type of acid group or two or more types.
  • the alkali-soluble resin can also be used as a dispersant.
  • the alkali-soluble resin preferably contains a repeating unit having an acid group in the side chain, and more preferably contains 5 to 70 mol% of the repeating unit having an acid group in the side chain in all the repeating units of the resin.
  • the upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, and more preferably 30 mol% or less.
  • the lower limit of the content of the repeating unit having an acid group in the side chain is preferably 10 mol% or more, more preferably 20 mol% or more.
  • the alkali-soluble resin is also preferably an alkali-soluble resin having a polymerizable group.
  • the polymerizable group include a (meth) allyl group and a (meth) acryloyl group.
  • the alkali-soluble resin having a polymerizable group is preferably a resin containing a repeating unit having a polymerizable group in the side chain and a repeating unit having an acid group in the side chain.
  • the alkali-soluble resin is a monomer component containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer”). It is also preferable to include the derived repeating unit.
  • R 1 and R 2 each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the alkali-soluble resin preferably contains a repeating unit derived from the compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a hydrogen atom or a benzene ring and may contain 1 to 20 carbon atoms.
  • n represents an integer from 1 to 15.
  • the acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g.
  • the lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more.
  • the upper limit is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.
  • alkali-soluble resin examples include resins having the following structures.
  • Me represents a methyl group.
  • the resin composition of the present invention preferably contains a resin having a basic group.
  • the basic group include an amino group and an ammonium base.
  • the resin having a basic group may further have an acid group in addition to the basic group.
  • a resin having a basic group is preferably used as a dispersant for a near-infrared absorbing dye represented by the formula (SQ1).
  • SQ1 near-infrared absorbing dye represented by the formula (SQ1).
  • the resin having a basic group examples include a resin having a tertiary amino group and a quaternary ammonium base.
  • a resin having a tertiary amino group and a quaternary ammonium base is preferably used as a dispersant for a near-infrared absorbing dye represented by the formula (SQ1).
  • the resin having a tertiary amino group and a quaternary ammonium base is preferably a resin having a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium base.
  • the resin having a tertiary amino group and a quaternary ammonium base may further have a repeating unit having an acid group.
  • the resin having a tertiary amino group and a quaternary ammonium base preferably has a block structure.
  • the resin having a tertiary amino group and a quaternary ammonium base preferably has an amine value of 10 to 250 mgKOH / g and a quaternary ammonium salt value of 10 to 90 mgKOH / g, and an amine value of 50 to 200 mgKOH. More preferably, it is / g and the quaternary ammonium salt value is 10 to 50 mgKOH / g.
  • the weight average molecular weight (Mw) of the resin having a tertiary amino group and a quaternary ammonium base is preferably 3000 to 300,000, and more preferably 5000 to 30000.
  • the resin having a tertiary amino group and a quaternary ammonium base is an ethylenically unsaturated monomer having a tertiary amino group, an ethylenically unsaturated monomer having a quaternary ammonium base, and other ethylenically if necessary. It can be produced by copolymerizing an unsaturated monomer.
  • Examples of the ethylenically unsaturated monomer having a tertiary amino group and the ethylenically unsaturated monomer having a quaternary ammonium base are those described in Paragraphs 0150 to 0170 of International Publication No. 2018/230486. This content is incorporated herein by reference.
  • the resin having a basic group it is also preferable that the resin contains a nitrogen atom in the main chain.
  • This resin is also preferably used as a dispersant for the near-infrared absorbing dye represented by the formula (SQ1).
  • Resins containing a nitrogen atom in the main chain are polylower alkyleneimine-based repeating units, polyallylamine-based repeating units, polydialylamine-based repeating units, metaxylene diamine-epichlorohydrin polycondensates It is preferable to include a system repeating unit and a repeating unit having at least one nitrogen atom selected from the polyvinylamine-based repeating unit.
  • the oligoimine-based resin is a resin having a repeating unit having a partial structure X having a functional group of pKa14 or less and a repeating unit having a side chain containing an oligomer chain or a polymer chain Y having 40 to 10,000 atoms. Is preferable.
  • the oligoimine-based resin may further have a repeating unit having an acid group.
  • the description in paragraphs 0102 to 0166 of JP2012-255128A can be referred to, and this content is incorporated in the present specification.
  • the resin composition of the present invention may also contain a resin as a dispersant, and preferably contains a resin as a dispersant.
  • the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
  • the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
  • the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and is substantially an acid. A resin consisting only of groups is more preferable.
  • the acid group contained in the acidic dispersant (acidic resin) is preferably a carboxyl group.
  • the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%.
  • the dispersant is preferably a resin having a basic group, and more preferably a basic dispersant.
  • the resin used as the dispersant examples include the above-mentioned resin having a tertiary amino group and a quaternary ammonium base, an oligoimine resin, and the like. Further, the resin used as the dispersant is preferably a graft resin. Examples of the graft resin include a resin having a repeating unit having a graft chain. The graft resin may further have a repeating unit having an acid group. For details of the graft resin, the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the content thereof is incorporated in the present specification. Further, the resin used as the dispersant is preferably a resin containing a repeating unit having an acid group.
  • the resin used as the dispersant is preferably a resin having a structure in which a plurality of polymer chains are bonded to the core portion.
  • resins include dendrimers (including star-shaped polymers).
  • specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.
  • the above-mentioned alkali-soluble resin can also be used as a dispersant.
  • the dispersant is also available as a commercially available product, and specific examples thereof include Disperbyk-111 (manufactured by BYK Chemie) and Solspers 76500 (manufactured by Nippon Lubrizol Co., Ltd.). Further, the dispersant described in paragraphs 0041 to 0130 of JP2014-130338A can also be used, and the contents thereof are incorporated in the present specification.
  • the resin content is preferably 1 to 50% by mass based on the total solid content of the resin composition.
  • the lower limit is preferably 5% by mass or more, more preferably 7% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the content of the resin having a basic group is based on 100 parts by mass of the near-infrared absorbing dye represented by the formula (SQ1). 1 to 100 parts by mass is preferable.
  • the upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less.
  • the lower limit is preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more.
  • the content of the resin having a basic group in the resin contained in the resin composition is preferably 10 to 70% by mass, more preferably 20 to 65% by mass, and 25 to 60% by mass. Is more preferable.
  • the content of the alkali-soluble resin is preferably 1 to 50% by mass based on the total solid content of the resin composition.
  • the lower limit is preferably 5% by mass or more, more preferably 7% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the content of the alkali-soluble resin in the resin contained in the resin composition is preferably 1 to 100% by mass, more preferably 3 to 100% by mass, and 5 to 100% by mass. Is more preferable.
  • the content of the resin as a dispersant is preferably 0.1 to 40% by mass based on the total solid content of the resin composition.
  • the upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less.
  • the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the content of the resin as the dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye represented by the formula (SQ1).
  • the upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less.
  • the lower limit is preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more.
  • the resin composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention can contain a near-infrared absorbing agent other than the near-infrared absorbing dye represented by the formula (SQ1).
  • Other near-infrared absorbers include pyrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonor compounds, iminium compounds, dithiol compounds, triarylmethane compounds, and pyromethene. Examples thereof include compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, and metal borides.
  • the content of the other near-infrared absorber is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, with respect to 100 parts by mass of the near-infrared absorbing dye represented by the formula (SQ1). It is more preferably parts by mass or less.
  • the total content of the near-infrared absorbing dye represented by the formula (SQ1) and the other near-infrared absorbing agent is preferably 1% by mass or more in the total solid content of the resin composition of the present invention. It is preferably 3% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more.
  • the upper limit of the total content is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less.
  • the near-infrared absorbing layer may contain only one type of other near-infrared absorbing agent, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention does not substantially contain other near-infrared absorbers.
  • the fact that the resin composition is substantially free of other near-infrared absorbers means that the content of the other near-infrared absorbers in the total solid content of the resin composition is preferably 0.5% by mass or less, preferably 0.1% by mass. It is more preferably% or less, more preferably 0.05% by mass or less, and particularly preferably not containing other near-infrared absorbers.
  • the resin composition of the present invention can contain a dye derivative.
  • the dye derivative may be either an acidic dye derivative or a basic dye derivative, but an acidic dye derivative is preferable from the viewpoint of dispersibility of the near-infrared absorbing dye represented by the formula (SQ1).
  • Examples of the acidic dye derivative include compounds in which an acid group is bonded to the dye skeleton.
  • Examples of the acid group include a sulfo group, a carboxyl group, a phosphoric acid group, a boronic acid group, a sulfonimide group, a sulfonamide group and salts thereof.
  • Atoms or groups of atoms 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, etc. Examples include phosphonium ions.
  • a sulfo group, a carboxyl group, a phosphoric acid group, a boronic acid group, a sulfonimide group, a sulfonamide group and salts thereof are preferable, and a sulfo group, a carboxyl group, a phosphate group and a sulfonimide group , Sulfonamide groups and salts thereof are more preferred, sulfo groups, carboxyl groups, and salts thereof are even more preferred, and sulfo groups are particularly preferred.
  • Examples of the basic dye derivative include compounds in which a basic group is bonded to the dye skeleton.
  • Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimide methyl group.
  • Examples of the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion.
  • an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimide methyl group are preferable, an amino group and a phthalimide methyl group are more preferable, and an amino group is further preferable.
  • the dye derivative is preferably a compound represented by the formula (B1).
  • the acidic dye derivative is preferably a compound in which X of the formula (B1) is represented by an acid group.
  • the basic dye derivative is preferably a compound in which X in the formula (B1) is represented by a basic group.
  • P represents the dye skeleton
  • L represents a single bond or linking group
  • X represents an acid group or basicity
  • m represents an integer of 1 or more
  • n represents an integer of 1 or more.
  • the plurality of Ls and Xs may be different from each other, and when n is 2 or more, the plurality of Xs may be different from each other.
  • the pigment skeleton represented by P in the formula (B1) includes squarylium pigment skeleton, pyrolopyrrolop pigment skeleton, diketopyrrolopyrrole pigment skeleton, quinacridone pigment skeleton, anthraquinone pigment skeleton, dianthraquinone pigment skeleton, benzoisoindole pigment skeleton, and thiazine.
  • Indigo pigment skeleton, azo pigment skeleton, quinophthalocyanine pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, dioxazine pigment skeleton, perylene pigment skeleton, perinone pigment skeleton, benzoimidazolone pigment skeleton, benzothiazole pigment skeleton, benzoimidazolone pigment skeleton and benzo Oxazole pigment skeleton is mentioned, and at least one selected from squarylium pigment skeleton, pyrolopyrrolop pigment skeleton, diketopyrrolopyrrole pigment skeleton, phthalocyanine pigment skeleton, quinacridone pigment skeleton, and benzoimidazolone pigment skeleton is preferable, and squarylium pigment skeleton is more preferable. preferable.
  • the linking groups represented by L in the formula (B1) include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 atoms.
  • a group consisting of the sulfur atom of. For example, hydrocarbon group, heterocyclic group, -O-, -S-, -CO-, -COO-, -OCO-, -SO 2- , -NR L- , -NR L CO-, -CONR L- , -NR L SO 2- , -SO 2 NR L- and a group consisting of a combination thereof.
  • RL represents a hydrogen atom, an alkyl group or an aryl group.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • the hydrocarbon group include an alkylene group, an arylene group, or a group obtained by removing one or more hydrogen atoms from these groups.
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms.
  • the alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be either monocyclic or polycyclic.
  • the number of carbon atoms of the arylene group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.
  • the heterocyclic group is preferably a single ring or a condensed ring having 2 to 4 condensation numbers.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3.
  • the hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
  • the hydrocarbon group and the heterocyclic group may have a substituent. Examples of the substituent include the groups listed in the above-mentioned Substituent T.
  • the alkyl group represented by RL preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 8 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the alkyl group represented by RL may further have a substituent. Examples of the substituent include the above-mentioned substituent T.
  • the number of carbon atoms of the aryl group represented by RL is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
  • the aryl group represented by RL may further have a substituent. Examples of the substituent include the above-mentioned substituent T.
  • X represents an acid group or basicity, and preferably represents an acid group.
  • the dye derivative is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1200 nm, preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1100 nm, and is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1000 nm. It is also preferable that the compound has a wavelength.
  • a dye derivative having a maximum absorption wavelength in the above wavelength range can easily have a spread of the ⁇ plane close to that of the near-infrared absorbing dye represented by the formula (SQ1), and adsorption of the near-infrared absorbing dye represented by the formula (SQ1). The property is improved, and it is easy to obtain better dispersion stability.
  • the dye derivative is preferably a compound having a ⁇ -conjugated plane having the same structure as the ⁇ -conjugated plane contained in the near-infrared absorbing dye represented by the formula (SQ1). Further, the number of ⁇ electrons contained in the ⁇ -conjugated plane of the pigment derivative is preferably 8 to 100.
  • the upper limit is preferably 90 or less, and more preferably 80 or less.
  • the lower limit is preferably 10 or more, and more preferably 12 or more.
  • the dye derivative has a ⁇ -conjugated plane containing a partial structure represented by the following formula (SQ-a) or a ⁇ -conjugated plane containing a partial structure represented by the following formula (CR-a). It is also preferably a compound, and more preferably a compound having a ⁇ -conjugated plane containing a partial structure represented by the following formula (SQ-a). In the above equation, the wavy line represents the bond.
  • the dye derivative is preferably at least one selected from a compound represented by the following formula (Syn1) and a compound represented by the following formula (Syn2), and is preferably a compound represented by the following formula (Syn1). More preferred.
  • Rsy 1 and Rsy 2 independently represent organic groups
  • L 1 represents a single bond or p1 + 1 valent group
  • a 1 represents an acid group or basicity
  • p1 and q1 represent acid groups or basics, respectively. Independently represents an integer of 1 or more. If p1 is 2 or more, a plurality of A 1 may be the same or different. If q1 is 2 or more, a plurality of L 1 and A 1 may be the same or different.
  • Rsy 3 and Rsy 4 independently represent organic groups
  • L 2 represents a single bond or p2 + 1 valent group
  • a 2 represents an acid group or basicity
  • p2 and q2 represent acid groups or basics, respectively. Independently represents an integer greater than or equal to 1. If p2 is 2 or more, plural A 2 may be the same or different. If q2 is 2 or more, the plurality of L 2 and A 2 may be the same or may be different.
  • the organic groups represented by Rsy 1 and Rsy 2 of the formula (Syn1) and the organic groups represented by Rsy 3 and Rsy 4 of the formula (Syn2) include aryl groups, heteroaryl groups, and the following formulas (R1) to (R7).
  • the group represented by is mentioned.
  • R 1 to R 3 independently represent a hydrogen atom or a substituent
  • As 3 represents a heteroaryl group
  • n r1 represents an integer of 0 or more
  • R 1 and R 2 May be bonded to each other to form a ring
  • R 1 and As 3 may be bonded to each other to form a ring
  • R 2 and R 3 may be bonded to each other to form a ring.
  • n r1 is 2 or more
  • the plurality of R 2 and R 3 may be the same or different
  • * represents a bond.
  • ring Z 1 represents an aromatic heterocycle or a fused ring containing an aromatic heterocycle, which may have one or more substituents
  • ring Z 2 is one or more. It represents a 4- to 9-membered hydrocarbon ring or heterocycle which may have a substituent, and when rings Z 1 and Z 2 have a plurality of substituents, the plurality of substituents may be the same. It may be different, and * represents a bond.
  • R 11 to R 14 independently represent a hydrogen atom or a substituent, and even if two adjacent groups of R 11 to R 14 are bonded to each other to form a ring.
  • R 20 represents an aryl or heteroaryl group
  • R 21 represents a substituent
  • X 10 represents CO or SO 2 .
  • R 22 and R 23 independently represent a hydrogen atom or a substituent, R 22 and R 23 may be bonded to each other to form a ring, and X 20 is an oxygen atom. , Sulfur atom, NR 24 , selenium atom or tellurium atom, R 24 represents a hydrogen atom or a substituent, and when X 20 is NR 24 , R 24 and R 22 bond with each other to form a ring.
  • n r2 represents an integer of 0 to 5, and when n r2 is 2 or more, a plurality of R 22s may be the same or different, and two of the plurality of R 22s may be used.
  • R 22 may be bonded to each other to form a ring, and * represents a bond.
  • R 35 to R 38 independently represent hydrogen atoms or substituents, and R 35 and R 36 , R 36 and R 37 , and R 37 and R 38 combine with each other to form a ring. * May represent a bond.
  • R 39 to R 45 represent hydrogen atoms or substituents independently of each other, R 39 and R 45 , R 40 and R 41 , R 40 and R 42 , R 42 and R 43 , R. 43 and R 44 , R 44 and R 45 may be combined with each other to form a ring, and * represents a bond.
  • X 21 represents a ring structure
  • R 46 to R 50 represent hydrogen atoms or substituents independently of each other
  • R 47 and R 48 can be bonded to each other to form a ring.
  • * represents a bond.
  • Examples of the p1 + 1 valent group represented by L 1 in the formula (Syn 1 ) and the p2 + 1 valent group represented by L 2 in the formula (Syn 2 ) include the group described as the linking group represented by L in the above formula (B1). Be done.
  • Specific examples of the dye derivative include compounds having the following structures. Further, in the following structural formula, Ph is a phenyl group. Specific examples of the dye derivative include Japanese Patent Application Laid-Open No. 56-118462, Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 01-2170777, Japanese Patent Application Laid-Open No. 03-099661, and Japanese Patent Application Laid-Open No. 03-026767. Japanese Patent Application Laid-Open No. 03-153780, Japanese Patent Application Laid-Open No. 03-045662, Japanese Patent Application Laid-Open No. 04-285669, Japanese Patent Application Laid-Open No. 06-145546, Japanese Patent Application Laid-Open No.
  • 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 dye represented by the formula (SQ1).
  • the lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more.
  • the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.
  • the content of the dye derivative is within the above range, the dispersibility of the near-infrared absorbing dye represented by the formula (SQ1) can be enhanced, and the storage stability of the resin composition can be improved. Only one kind of pigment derivative may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably in the above range.
  • the resin composition of the present invention can contain a chromatic colorant.
  • the chromatic colorant means a colorant other than the white colorant and the black colorant.
  • the chromatic colorant is preferably a colorant having absorption in a wavelength range of 400 nm or more and less than 650 nm.
  • the chromatic colorant examples include a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant.
  • the chromatic colorant may be a pigment or a dye. Pigments and dyes may be used in combination. Further, the pigment may be either an inorganic pigment or an organic pigment. Further, as the pigment, an inorganic pigment or a material in which a part of the organic-inorganic pigment is replaced with an organic chromophore can be used. Hue design can be facilitated by replacing inorganic pigments and organic-inorganic pigments with organic chromophores.
  • 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 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 diameter in the present invention is an arithmetic mean value of the primary particle diameter for the primary particles of 400 pigments.
  • the primary particles of the pigment refer to independent particles without aggregation.
  • 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, further preferably 80% by mass or more, and 90% by mass or more. Is particularly preferred. Examples of the pigment include those shown below.
  • a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms in one molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms.
  • Specific examples include the compounds described in International Publication No. 2015/118720.
  • the compound described in Chinese Patent Application No. 106909027, the phthalocyanine compound having a phosphoric acid ester described in International Publication No. 2012/10395 as a ligand, and the like can also be used.
  • an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP2012-247591A and paragraph numbers 0047 of JP2011-157478A.
  • the yellow pigment the pigment described in JP-A-2008-074985, the compound described in JP-A-2008-074987, the quinophthalone compound described in JP-A-2013-061622, and the like.
  • Pigments described in JP-A-2018-203798, pigments described in JP-A-2018-062578, quinophthalone-based yellow pigments described in JP-A-2018-155881, JP-A-2018-0626444 , The quinophthalone compound described in Japanese Patent No. 6432077, and the pigment described in Japanese Patent No. 6443711 can also be used.
  • the compound described in JP-A-2018-062644 can also be used. This compound can also be used as a pigment derivative.
  • the diketopyrrolopyrrole compound described in WO2012 / 102399, the diketopyrrolopyrrole compound described in WO2012 / 117965, the naphtholazo compound described in JP2012-229344 can also be used. it can.
  • red pigment a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom or a nitrogen atom bonded to the aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used. it can.
  • a dye can also be used as the coloring material.
  • the dye is not particularly limited, and a known dye can be used.
  • pyrazole azo system anilino azo system, triarylmethane system, anthraquinone system, anthrapyridone system, benzylidene system, oxonol system, pyrazolotriazole azo system, pyridone azo system, cyanine system, phenothiazine system, pyrrolopyrazole azomethine system, xanthene system
  • Examples thereof include phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes.
  • the thiazole compound described in JP2012-158649A, the azo compound described in JP2011-184493, and the azo compound described in JP2011-145540 can also be preferably used.
  • the yellow dye the quinophthalone compounds described in paragraphs 0011 to 0034 of JP2013-054339A, the quinophthalone compounds described in paragraphs 0013 to 0058 of JP2014-026228, and the like can also be used.
  • the content of the chromatic colorant is preferably 1 to 50% by mass based on the total solid content of the resin composition of the present invention.
  • the total amount thereof is preferably within the above range.
  • the resin composition of the present invention is also referred to as a coloring material that transmits near infrared rays (light having a wavelength in the near infrared region) and blocks visible light (light having a wavelength in the visible region) (hereinafter, also a coloring material that blocks visible light). It can also contain).
  • a resin composition containing a coloring material that blocks visible light is preferably used as a resin composition for forming a near-infrared transmissive filter.
  • the color material that blocks visible light is preferably a color material that absorbs light in the wavelength region of purple to red. Further, in the present invention, the color material that blocks visible light is preferably a color material that blocks light in the wavelength region of 450 to 650 nm. Further, the color material that blocks visible light is preferably a color material that transmits light having a wavelength of 900 to 1300 nm. In the present invention, the coloring material that blocks visible light preferably satisfies at least one of the following requirements (A) and (B).
  • B Contains an organic black colorant.
  • Examples of the chromatic colorant include those described above.
  • Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perillene compounds, and azo compounds, and bisbenzofuranone compounds and perillene compounds are preferable.
  • Examples of the bisbenzofuranone compound include the compounds described in JP-A-2010-534726, JP-A-2012-515233, and JP-A-2012-515234.
  • Examples of the perillene compound include the compounds described in paragraphs 0016 to 0020 of JP-A-2017-226821, C.I. I. Pigment Black 31, 32 and the like can be mentioned.
  • Examples of the azomethine compound include the compounds described in JP-A-01-17601 and JP-A-02-0346664, and are available as, for example, "Chromofine Black A1103" manufactured by Dainichiseika.
  • Examples of the combination of chromatic colorants when black is formed by the combination of two or more kinds of chromatic colorants include the following. (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.
  • the content of the coloring material that blocks visible light is preferably 1 to 50% by mass in the total solid content of the resin composition.
  • the resin composition of the present invention preferably contains a polymerizable compound.
  • a polymerizable compound a compound that can be polymerized by the action of radicals is preferable. That is, the polymerizable compound is preferably a radically polymerizable compound.
  • the polymerizable compound is preferably a compound having one or more ethylenically unsaturated bond-containing groups, more preferably a compound having two or more ethylenically unsaturated bond-containing groups, and contains an ethylenically unsaturated bond. It is more preferable that the compound has three or more groups.
  • the upper limit of the number of ethylenically unsaturated bond-containing groups is, for example, preferably 15 or less, and more preferably 6 or less.
  • the ethylenically unsaturated bond-containing group include a vinyl group, a styrene group, a (meth) allyl group, a (meth) acryloyl group, and the like, and a (meth) acryloyl group is preferable.
  • the polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.
  • polymerizable compound examples include paragraph numbers 0905 to 0108 of JP2009-288705A, paragraphs 0227 of JP2013-209760A, paragraphs 0254 to 0257 of JP2008-292970, and JP-A.
  • Examples include the compounds described in the publication, the contents of which are incorporated herein.
  • the polymerizable compound may be in either a monomer or a polymer form, but a monomer is preferable.
  • the monomer-type polymerizable compound preferably has a molecular weight of 100 to 3000.
  • the upper limit is preferably 2000 or less, and more preferably 1500 or less.
  • the lower limit is preferably 150 or more, more preferably 250 or more.
  • the polymerizable compound is a compound having substantially no molecular weight distribution.
  • a compound having a degree of dispersion (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.0 to 1.5 is preferable. More preferably 1.0 to 1.3.
  • dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku) NK ester A-DPH-12E manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues.
  • trimethylolpropane tri (meth) acrylate trimethylolpropane propyleneoxy-modified tri (meth) acrylate, trimethylolpropane ethyleneoxy-modified tri (meth) acrylate, and isocyanurate ethyleneoxy-modified tri (meth) acrylate.
  • a trifunctional (meth) acrylate compound such as pentaerythritol trimethylolpropane (meth) acrylate.
  • Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305.
  • M-303, M-452, M-450 manufactured by Toagosei Co., Ltd.
  • a compound having an acid group can also be used.
  • the polymerizable compound in the unexposed portion can be easily removed during development, and the generation of development residue can be suppressed.
  • the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferable.
  • Examples of commercially available products of the polymerizable compound having an acid group include Aronix M-305, M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
  • the acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g.
  • a compound having a caprolactone structure can also be used.
  • Polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.
  • a polymerizable compound having an alkyleneoxy group can also be used.
  • the polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and having 4 to 20 ethyleneoxy groups 3 to 3 to A hexafunctional (meth) acrylate compound is more preferred.
  • Commercially available products of the polymerizable compound having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, and a trifunctional (meth) having three isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330, which is an acrylate.
  • a polymerizable compound having a fluorene skeleton can also be used.
  • examples of commercially available products of the polymerizable compound having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., a (meth) acrylate monomer having a fluorene skeleton).
  • the polymerizable compound it is also preferable to use a compound that does not substantially contain an environmentally regulated substance such as toluene.
  • an environmentally regulated substance such as toluene.
  • commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
  • Examples of the polymerizable compound include urethane acrylates as described in JP-A-48-041708, JP-A-51-0371993, JP-A-02-032293, and JP-A-02-016765.
  • Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
  • a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238.
  • the polymerizable compounds are UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, Commercially available products such as T-600, AI-600, and LINK-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.
  • the content of the polymerizable compound is preferably 0.1 to 40% by mass based on the total solid content of the resin composition.
  • the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less.
  • the resin composition may contain only one type of polymerizable compound, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention contains a polymerizable compound
  • the resin composition of the present invention further contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and thio compounds. , Ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
  • the photopolymerization initiator includes trihalomethyltriazine compound, benzyldimethylketal compound, ⁇ -hydroxyketone compound, ⁇ -aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, and triarylimidazole. It is preferably a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxaziazole compound and a 3-aryl substituted coumarin compound, and an oxime compound and an ⁇ -hydroxyketone compound.
  • ⁇ -Aminoketone compound, and acylphosphine compound are more preferable, and an oxime compound is further preferable.
  • an oxime compound is further preferable.
  • the photopolymerization initiator include compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, the contents of which are incorporated in the present specification.
  • Examples of commercially available ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins BV).
  • Examples of commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV).
  • Examples of commercially available acylphosphine compounds include Omnirad819 and OmniradTPO (all manufactured by IGM Resins BV).
  • Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, the compounds described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385.
  • oxime compound examples include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Examples thereof include imino-1-phenylpropane-1-one.
  • IRGACURE-OXE01 IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Joshu Powerful Electronics New Materials Co., Ltd.), ADEKA PTOMER N-1919.
  • a photopolymerization initiator 2 manufactured by ADEKA Corporation and described in JP2012-014502A.
  • the oxime compound it is also preferable to use a compound having no coloring property or a compound having high transparency and being hard to discolor.
  • Examples of commercially available products include ADEKA ARKULS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).
  • 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 the compounds described in JP-A-2014-137466.
  • 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 an oxime compound include the compounds described in International Publication No. 2013/083505.
  • an oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, the compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like.
  • an oxime compound having a nitro group can be used as the photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation).
  • 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 International Publication No. 2015/036910.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and 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, more preferably 1000 to 300,000, further preferably 2000 to 300,000, and more preferably 5000 to 200,000, from the viewpoint of sensitivity. It is particularly preferable to have.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with 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 photoradical polymerization initiator two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained.
  • the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the resin composition with time can be improved.
  • Specific examples of the bifunctional or trifunctional or higher functional photoradical polymerization initiators include JP-A-2010-527339, JP-A-2011-524436, International Publication No.
  • the photopolymerization initiator contains an oxime compound and an ⁇ -aminoketone compound.
  • the ⁇ -aminoketone compound is preferably 50 to 600 parts by mass, more preferably 150 to 400 parts by mass with respect to 100 parts by mass of the oxime compound.
  • the content of the photopolymerization initiator is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass, based on the total solid content of the resin composition.
  • the resin composition may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • Epoxy compound The resin composition of the present invention can contain a compound having an epoxy group (hereinafter, also referred to as an epoxy compound).
  • the epoxy compound include monofunctional or polyfunctional glycidyl ether compounds, polyfunctional aliphatic glycidyl ether compounds, and compounds having an alicyclic epoxy group.
  • the epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule.
  • the upper limit of the epoxy group may be 10 or less, or 5 or less.
  • the lower limit is preferably two or more.
  • the epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 1000) or a high molecular weight compound (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 epoxy compound is preferably 2000 to 100000.
  • the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and even more preferably 3000 or less.
  • Examples of commercially available epoxy compounds include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), and ADEKA Glycyrrol ED-505 (manufactured by ADEKA Corporation). Further, as the epoxy compound, it is described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraph numbers 0147 to 0156 of JP-A-2014-0435556, and paragraph numbers 0085-0092 of JP-A-2014-089408. It is also possible to use the compound.
  • the content of the epoxy compound is preferably 0.1 to 40% by mass based on the total solid content of the resin composition.
  • the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less.
  • the resin composition may contain only one type of epoxy compound, or may contain two or more types of epoxy compounds. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • Epoxy curing agent When the resin composition of the present invention contains an epoxy compound, it is preferable that the resin composition of the present invention further contains an epoxy curing agent.
  • the epoxy curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, polyvalent carboxylic acids, thiol compounds and the like.
  • a polyvalent carboxylic acid is preferable from the viewpoint of heat resistance and transparency of the cured product, and a compound having two or more carboxylic acid anhydride groups in the molecule is most preferable.
  • Specific examples of the epoxy curing agent include butanedioic acid.
  • the compounds described in paragraphs 0072 to 0078 of JP-A-2016-07720 can also be used, and the contents thereof are incorporated in the present specification.
  • the content of the epoxy curing agent is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, still more preferably 0.1 to 6.0 parts by mass with respect to 100 parts by mass of the epoxy compound. ..
  • the resin composition may contain only one type of epoxy curing agent, or may contain two or more types of epoxy curing agent. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention preferably contains a solvent.
  • a solvent an organic solvent is preferable.
  • the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents and the like.
  • paragraph number 0223 of WO 2015/166779 can be referred to, the contents of which are incorporated herein by reference.
  • an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used.
  • organic solvent examples 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, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like.
  • aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may need to be reduced for environmental reasons (for example, 50 mass ppm (parts) with respect to the total amount of organic solvent. Per million) or less, 10 mass ppm or less, 1 mass ppm or less)
  • an organic solvent having a low metal content it is preferable to use an organic solvent having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, an organic solvent at the mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015).
  • Examples of the method for removing impurities such as metals from the organic solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the organic solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.
  • the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.
  • the content of the solvent is preferably 10 to 97% by mass with respect to the total amount of the resin composition.
  • the lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and 70% by mass. The above is particularly preferable.
  • the upper limit is preferably 96% by mass or less, and more preferably 95% by mass or less.
  • the resin composition may contain only one type of solvent, or may contain two or more types of solvent. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention can contain a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like.
  • examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salt (ammonium salt, primary cerium salt, etc.), and p-methoxyphenol is preferable.
  • the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the resin composition.
  • the resin composition may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention can contain a silane coupling agent.
  • the 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 linked to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
  • the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • Examples of the functional group other than the hydrolyzable group include a vinyl group, a styryl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group and a phenyl group. Etc., and (meth) acryloyl group and epoxy group are preferable.
  • Examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP2009-288703A and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A. 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 resin composition.
  • the resin composition may contain only one type of silane coupling agent, or may contain two or more types of silane coupling agent. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention preferably contains a surfactant. According to this aspect, it is possible to suppress the generation of striations when the resin composition is applied. Furthermore, the storage stability of the resin composition can be improved.
  • surfactant various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicon-based surfactants can be used.
  • the surfactant described in paragraph Nos. 0238 to 0245 of International Publication No. 2015/166779 is mentioned, and the content thereof is incorporated in the present specification.
  • the surfactant is preferably a fluorine-based surfactant. The above effect can be obtained more remarkably by including a fluorine-based surfactant in the resin composition.
  • the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving property, and has good solubility in the composition.
  • fluorine-based surfactant examples include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Application Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of the corresponding International Publication No. 2014/017669) and the like, JP-A-2011- The surfactants described in paragraphs 0117 to 0132 of JP 132503 are mentioned and their contents are incorporated herein by reference.
  • Commercially available products of fluorine-based surfactants include, for example, Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS.
  • the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied.
  • fluorine-based surfactants include Megafvck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafvck. DS-21 can be mentioned.
  • fluorine-based surfactant 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 fluorine-based surfactant.
  • a fluorine-based surfactant include the fluorine-based surfactant described in JP-A-2016-216602, the contents of which are incorporated in the present specification.
  • the fluorine-based surfactant a block polymer can also be used.
  • the fluorine-based surfactant has 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) (meth).
  • 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 the fluorine-based surfactants used in the present invention.
  • the weight average molecular weight of the above compounds is preferably 3000-50000, for example 14000.
  • % indicating the ratio of the repeating unit is mol%.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used.
  • the compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation, RS-72-K and the like can be mentioned.
  • the fluorine-based surfactant the compounds described in paragraphs 0015 to 0158 of JP2015-117327A can also be used.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylates, glycerol ethoxylates, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc.
  • Examples of the silicon-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, (Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by Big Chemie) and the like.
  • the content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and generation of striations when the resin composition is applied, based on the total solid content of the resin composition. Is more preferably 0.001 to 0.2% by mass because it can more effectively suppress.
  • the resin composition may contain only one type of surfactant, or may contain two or more types of surfactants. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the resin composition can contain an ultraviolet absorber.
  • the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indol compounds, and triazine compounds. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraph numbers 0052 to 0072 of JP2012-208374A, and paragraph numbers 0317 to JP2013-068814A. 0334, the compounds described in paragraph numbers 0061 to 0080 of JP2016-162946 are mentioned, and their contents are incorporated in the present specification.
  • Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.).
  • examples of the benzotriazole compound include the MYUA series made by Miyoshi Oil & Fat Co., Ltd. (The Chemical Daily, February 1, 2016).
  • the ultraviolet absorber the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used.
  • the content of the ultraviolet absorber is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the resin composition.
  • the resin composition may contain only one type of ultraviolet absorber, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention can contain an antioxidant.
  • the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like.
  • the phenol compound any phenol compound known as a phenolic antioxidant can be used.
  • Preferred phenolic compounds include hindered phenolic compounds.
  • a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
  • a phosphorus-based antioxidant can also be preferably used.
  • a phosphorus-based antioxidant tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) 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 (above, manufactured by ADEKA Corporation) and the like.
  • the antioxidant includes the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, the compounds described in International Publication No. 2017/006600, and the compounds described in International Publication No. 2017/164024. It 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 resin composition.
  • the resin composition may contain only one type of antioxidant, or may contain two or more types of antioxidants. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention can be used as a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, a filler, a defoaming agent, etc.). It may contain a flame retardant, a leveling agent, a peeling accelerator, a fragrance, a surface tension modifier, a chain transfer agent, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. These components are described in, for example, paragraph No. 0183 and subsequent paragraphs of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No.
  • the resin composition of the present invention may contain a latent antioxidant, if necessary.
  • the latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst.
  • Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
  • Commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like.
  • the viscosity (23 ° C.) of the resin composition of the present invention is preferably 1 to 100 mPa ⁇ s, for example, when a film is formed by coating.
  • the lower limit is more preferably 2 mPa ⁇ s or more, and further preferably 3 mPa ⁇ s or more.
  • the upper limit is more preferably 50 mPa ⁇ s or less, further preferably 30 mPa ⁇ s or less, and particularly preferably 15 mPa ⁇ s or less.
  • the storage container for the resin composition of the present invention is not particularly limited, and a known storage container can be used.
  • a storage container a multi-layer bottle in which the inner wall of the container is composed of 6 types and 6 layers of resin and a bottle in which 6 types of resin are composed of 7 layers are used for the purpose of suppressing impurities from being mixed into raw materials and resin compositions. It is also preferable 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, improving the storage stability of the resin composition, and suppressing deterioration of the components.
  • the resin composition of the present invention can be preferably used as a resin composition for forming a near-infrared cut filter or a near-infrared transmissive filter.
  • the resin composition of the present invention preferably further contains a coloring material that blocks visible light.
  • the resin composition of the present invention can also be used for heat ray cutting material applications, photothermal conversion material applications, laser welding and wearing material applications, and the like.
  • the resin composition of the present invention can be prepared by mixing the above-mentioned components.
  • all the components may be dissolved or dispersed in a solvent at the same time to prepare the resin composition, or if necessary, two or more solutions or dispersions in which each component is appropriately blended. May be prepared in advance and mixed at the time of use (at the time of application) to prepare a composition.
  • the near-infrared absorbing dye represented by the formula (SQ1) is a pigment
  • the mechanical force used for dispersing the pigment includes 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.
  • the process and disperser for dispersing pigments are "Dispersion Technology Taizen, published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology and industrial application centered on suspension (solid / liquid dispersion system)". The process and disperser described in Paragraph No. 0022 of Japanese Patent Application Laid-Open No.
  • the particles may be miniaturized in the salt milling step.
  • the materials, equipment, processing conditions, etc. used in the salt milling step for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.
  • Preferred aspects of the method for preparing the resin composition include the following aspects 1 and 2, and the following aspect 2 is preferable from the viewpoint of storage stability.
  • a dispersion liquid is prepared by mixing and dispersing a near-infrared absorbing dye represented by the formula (SQ1), a metal complex represented by the formula (MC1), a resin, and a solvent, and the dispersion liquid is used. An embodiment of preparing a resin composition by further mixing with other components such as a resin and a solvent, if necessary.
  • a dispersion liquid is prepared by mixing and dispersing a near-infrared absorbing dye represented by the formula (SQ1), a resin, and a solvent, and the dispersion liquid and a metal complex represented by the formula (MC1) are used. An embodiment of preparing a resin composition by further mixing with other components such as a resin and a solvent, if necessary.
  • any filter conventionally used for filtration or the like can be used without particular limitation.
  • fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight).
  • PTFE polytetrafluoroethylene
  • nylon eg, nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight).
  • PP polypropylene
  • nylon high-density polypropylene
  • the pore size of the filter is preferably 0.01 to 7.0 ⁇ m, more preferably 0.01 to 3.0 ⁇ m, and even more preferably 0.05 to 0.5 ⁇ m. If the pore size of the filter is within the above range, fine foreign matter can be removed more reliably.
  • the nominal value of the filter manufacturer can be referred to.
  • various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc. can be used.
  • fibrous filter medium examples include polypropylene fiber, nylon fiber, glass fiber and the like.
  • examples of commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Loki Techno Co., Ltd.
  • filters for example, a first filter and a second filter
  • the filtration with each filter may be performed only once or twice or more.
  • filters having different pore diameters may be combined within the above-mentioned range.
  • the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration with the second filter may be performed.
  • the film of the present invention is obtained from the above-mentioned resin composition of the present invention.
  • the film of the present invention can be preferably used as a near-infrared cut filter or a near-infrared transmissive filter.
  • the film of the present invention can also be used as a heat ray shielding filter.
  • the film of the present invention may have a pattern or may be a film having no pattern (flat film). Further, the film of the present invention may be used by being laminated on a support, or the film of the present invention may be peeled off from the support and used. Examples of the support include a semiconductor base material such as a silicon substrate and a transparent base material.
  • a charge coupling element (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the semiconductor base material used as the support. Further, a black matrix that separates each pixel may be formed on the semiconductor base material. Further, if necessary, an undercoat layer may be provided on the semiconductor base material in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the substrate surface.
  • CCD charge coupling element
  • CMOS complementary metal oxide semiconductor
  • a transparent conductive film or the like
  • an undercoat layer may be provided on the semiconductor base material in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the substrate surface.
  • the transparent base material used as the support is not particularly limited as long as it is made of at least a material capable of transmitting visible light.
  • a base material made of a material such as glass or resin can be mentioned.
  • the resin include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene and ethylene vinyl acetate copolymers, acrylic resins such as norbornene resin, polyacrylate and polymethylmethacrylate, urethane resins and vinyl chloride resins. , Fluorine resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin and the like.
  • Examples of the glass include soda lime glass, borosilicate glass, non-alkali glass, quartz glass, and glass containing copper.
  • Examples of the copper-containing glass include copper-containing phosphate glass and copper-containing fluoride glass.
  • As the glass containing copper a commercially available product can also be used. Examples of commercially available copper-containing glass include NF-50 (manufactured by AGC Techno Glass Co., Ltd.) and the like.
  • the thickness of the film of the present invention can be appropriately adjusted according to the purpose.
  • the thickness of the film is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more.
  • 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 preferably has a maximum absorption wavelength in the wavelength range of 700 to 1800 nm (preferably a wavelength of 700 to 1300 nm, more preferably a wavelength of 700 to 1000 nm). .. Further, the average transmittance of light having a wavelength of 400 to 600 nm is preferably 50% or more, more preferably 70% or more, further preferably 80% or more, and particularly preferably 85% or more. preferable. Further, the transmittance in the entire range of the wavelength of 400 to 600 nm is preferably 50% or more, more preferably 70% or more, and further 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 700 to 1800 nm (preferably a wavelength of 700 to 1300 nm, more preferably a wavelength of 700 to 1000 nm) of 10%. The following is more preferable, and 5% or less is further preferable. Further, the film of the present invention preferably has A 1 / A 2, which is the ratio of the maximum absorbance A 1 in the wavelength range of 400 to 600 nm to the absorbance A 2 in the maximum absorption wavelength, of 0.30 or less. , 0.20 or less, more preferably 0.15 or less, and particularly preferably 0.10 or less.
  • the film of the present invention When the film of the present invention is used as a near-infrared transmissive filter, the film of the present invention has a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 830 nm. It is preferable that the minimum value of the transmittance in the wavelength range of 1100 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the film of the present invention used as a near-infrared transmissive filter preferably satisfies any of the following spectral characteristics (1) or (2).
  • the maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1000 to 1300 nm is. It is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of the 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 value of the transmittance in the wavelength range of 1100 to 1300 nm is. It is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the film of the present invention can also be used in combination with a color filter containing a chromatic colorant.
  • the color filter can be produced by using a coloring composition containing a chromatic colorant.
  • the chromatic colorant include the chromatic colorants mentioned as those which may be contained in the resin composition of the present invention.
  • the film of the present invention may contain a chromatic colorant to form a filter having a function as a near-infrared cut filter and a color filter.
  • the color filter is arranged on the optical path of the film of the present invention.
  • the film of the present invention and a color filter may or may not be adjacent to each other in the thickness direction.
  • the film of the present invention may be formed on a support different from the support on which the color filter is formed.
  • Other members for example, a microlens, a flattening layer, etc. constituting the solid-state image sensor may be interposed between the film and the color filter.
  • the film of the present invention can be used for solid-state imaging devices such as CCD (charge coupling element) and CMOS (complementary metal oxide semiconductor), and various devices such as infrared sensors and image display devices.
  • CCD charge coupling element
  • CMOS complementary metal oxide semiconductor
  • the film of the present invention can be produced through a step of applying the resin composition of the present invention.
  • Examples of the support include those described above.
  • a method for applying the resin composition a known method can be used. For example, a drop method (drop cast); a slit coating method; a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395). Methods described in the publication); Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Various printing methods; transfer method using a mold or the like; nanoimprint method and the like can be mentioned.
  • the application method for inkjet is not particularly limited, and for example, the method shown in "Expandable / Usable Inkjet-Infinite Possibilities Seen in Patents-, Published in February 2005, Sumi Betechno Research" (especially from page 115). (Page 133), and the methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned.
  • the resin composition layer formed by applying the resin composition may be dried (prebaked).
  • the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower.
  • the lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher.
  • the prebaking time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. Drying can be performed on 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 photolithography method and a pattern forming method using a dry etching method, and a pattern forming method using a photolithography method is preferable.
  • the film of the present invention is used as a flat film, it is not necessary to perform the step of forming the pattern.
  • the process of forming the pattern will be described in detail.
  • the pattern forming method in the photolithography method includes a step of exposing the resin composition layer formed by applying the resin composition of the present invention in a pattern (exposure step) and developing the resin composition layer of the unexposed portion. It is preferable to include a step of removing and forming a pattern (development step). If necessary, a step of baking the developed pattern (post-baking step) may be provided. Hereinafter, each step will be described.
  • the resin composition layer is exposed in a pattern.
  • the resin composition layer can be exposed in a pattern by exposing the resin composition layer through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. As a result, the exposed portion can be cured.
  • Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm), and KrF line (wavelength 248 nm) is preferable. Further, a long wave light source having a diameter of 300 nm or more can also be used.
  • pulse exposure is an exposure method of a method in which light irradiation and pause are repeated in a short cycle (for example, millisecond level or less).
  • the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less.
  • the lower limit of the pulse width is not particularly limited, but may be 1 femtosecond (fs) or more, and may be 10 femtoseconds or more.
  • the frequency is preferably 1 kHz or higher, more preferably 2 kHz or higher, and even more preferably 4 kHz or higher.
  • the upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and further preferably 10 kHz or less.
  • Maximum instantaneous intensity is preferably at 50000000W / m 2 or more, more preferably 100000000W / m 2 or more, more preferably 200000000W / m 2 or more.
  • the upper limit of the maximum instantaneous intensity is preferably at 1000000000W / m 2 or less, more preferably 800000000W / m 2 or less, further preferably 500000000W / m 2 or less.
  • the pulse width is the time during which light is irradiated in the pulse period.
  • the frequency is the number of pulse cycles per second.
  • the maximum instantaneous illuminance is the average illuminance within the time during which the light is irradiated in the pulse period.
  • the pulse cycle is a cycle in which light irradiation and pause in pulse exposure are one cycle.
  • Irradiation dose for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2.
  • the oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment) or in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, or 50% by volume) in which the oxygen concentration exceeds 21% by volume.
  • the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15,000 W / m 2 , or 35,000 W / m 2 ). Can be done. Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
  • the resin composition layer in the unexposed portion of the exposed resin composition layer is developed and removed to form a pattern.
  • the development and removal of the resin composition layer in the unexposed portion can be performed using a developing solution.
  • the resin composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains on the support.
  • the temperature of the developing solution is preferably, for example, 20 to 30 ° C.
  • the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.
  • Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used.
  • the alkaline developer an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable.
  • the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
  • Ethyltrimethylammonium hydroxide Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and other organic substances.
  • alkaline compounds examples include alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate.
  • the alkaline agent a compound having a large molecular weight is preferable in terms 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.
  • the developer may further contain a surfactant.
  • a surfactant a nonionic surfactant is preferable.
  • the developer may be once produced as a concentrated solution and diluted to a concentration required for use.
  • the dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development.
  • the rinsing is performed by supplying the rinsing liquid to the developed composition layer while rotating the support on which the developed composition layer is formed. It is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral edge of the support. At this time, when moving the nozzle from the central portion of the support to the peripheral portion, the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the central portion to the peripheral portion of the support.
  • Additional exposure treatment and post-baking are post-development curing treatments to complete the curing.
  • the heating temperature in the post-baking is, for example, preferably 100 to 240 ° C, more preferably 200 to 240 ° C.
  • Post-baking can be performed on the developed film in a continuous or batch manner by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high frequency heater so as to meet the above conditions. ..
  • the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
  • the resin composition layer formed by applying the above resin composition on a support is cured to form a cured product layer, and then a patterned photoresist is formed on the cured product layer.
  • a resist layer is formed, and then the cured photoresist layer is dry-etched with an etching gas using the patterned photoresist layer as a mask.
  • the description in paragraphs 0010 to 0067 of JP2013-064993A can be referred to, and this content is incorporated in the present specification.
  • the near-infrared cut filter of the present invention has the above-mentioned film of the present invention.
  • the near-infrared cut filter of the present invention preferably has an average transmittance of light having a wavelength of 400 to 600 nm of 70% or more, more preferably 80% or more, further preferably 85% or more, and 90%. % Or more is particularly preferable. Further, the transmittance in the entire range of the wavelength of 400 to 600 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.
  • the preferred range of near-infrared shielding property of the near-infrared cut filter varies depending on the application, but the transmittance at at least one point in the wavelength range of 700 to 1800 nm (preferably wavelength 700 to 1300 nm, more preferably wavelength 700 to 1000 nm). Is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less.
  • the near-infrared cut filter of the present invention may further have a copper-containing layer, a dielectric multilayer film, an ultraviolet absorbing layer, and the like, 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. 2015/09960.
  • the dielectric multilayer film include the dielectric multilayer films described in paragraphs 0255 to 0259 of JP-A-2014-041318.
  • the copper-containing layer a glass substrate made of copper-containing glass (copper-containing glass substrate) or a layer containing a copper complex (copper complex-containing layer) can also be used.
  • Examples of the copper-containing glass substrate include copper-containing phosphate glass and copper-containing fluoride glass.
  • Examples of commercially available copper-containing glass products include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (all manufactured by Schott AG), CD5000 (manufactured by HOYA Corporation), and the like.
  • the near-infrared transmission filter of the present invention has the above-mentioned film of the present invention.
  • the near-infrared transmissive filter of the present invention has a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 830 nm, and transmits in the wavelength range of 1100 to 1300 nm.
  • the minimum value of the rate is preferably 70% or more (preferably 75% or more, more preferably 80% or more).
  • the near-infrared transmission filter of the present invention preferably satisfies any of the following spectral characteristics (1) or (2).
  • the maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1000 to 1300 nm is. It is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of the 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 value of the transmittance in the wavelength range of 1100 to 1300 nm is. It is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the solid-state image sensor of the present invention includes the film of the present invention described above.
  • the configuration of the solid-state image sensor is not particularly limited as long as it has the film of the present invention and functions as a solid-state image sensor. For example, the following configuration can be mentioned.
  • a transfer electrode made of a plurality of photodiodes and polysilicon or the like constituting the light receiving area of the solid-state image sensor is provided, and light shielding made of tungsten or the like in which only the light receiving portion of the photodiode is opened on the photodiode and the transfer electrode.
  • It has a film, has a device protective film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part on the light-shielding film, and has the film of the present invention on the device protective film. is there.
  • a configuration having a condensing means for example, a microlens or the like; the same applies hereinafter) on the device protective film under the film of the present invention (the side closer to the support), or condensing on the film of the present invention.
  • the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
  • the partition wall in this case preferably has a lower refractive index than each pixel. Examples of the imaging device having such a structure include the devices described in JP-A-2012-227478 and JP-A-2014-179757.
  • the image display device of the present invention includes the film of the present invention.
  • Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device.
  • organic EL organic electroluminescence
  • the image display device for example, “Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)", “Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd., 1989)” Issuance) ”and so on.
  • the liquid crystal display device is described in, for example, “Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".
  • the image display device may have a white organic EL element.
  • the white organic EL element preferably has a tandem structure.
  • Japanese Patent Application Laid-Open No. 2003-045676 supervised by Akiyoshi Mikami, "Frontiers of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, It is described on pages 326 to 328, 2008 and the like.
  • the spectrum of white light emitted by the organic EL element preferably has a strong maximum emission peak in the blue region (430 to 485 nm), the green region (530 to 580 nm), and the yellow region (580 to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 to 700 nm) are more preferable.
  • the infrared sensor of the present invention includes the film of the present invention 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 with reference to the drawings.
  • reference numeral 110 is a solid-state image sensor.
  • a near-infrared cut filter 111 and a near-infrared transmission filter 114 are arranged on the image pickup region of the solid-state image sensor 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 near infrared transmission filter 114.
  • the flattening layer 116 is formed so as to cover the microlens 115.
  • the near-infrared cut filter 111 can be formed by using the resin composition of the present invention.
  • the spectral characteristics of the near-infrared cut filter 111 are selected according to the emission wavelength of the infrared light emitting diode (infrared LED) used.
  • the color filter 112 is a color filter on which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used.
  • R red
  • G green
  • B blue
  • the characteristics of the near-infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used.
  • a near-infrared cut filter (another 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 a copper-containing layer and / or a dielectric multilayer film. These details include those described above. Further, as another near-infrared cut filter, a dual bandpass filter may be used.
  • IR dispersions 1-26 The mixed solution having the following composition is mixed for 2 hours with a bead mill (high pressure disperser NANO-3000-10 with decompression mechanism (manufactured by Nippon BEE Co., Ltd.)) using zirconia beads having a diameter of 0.3 mm. Each dispersion was prepared. The values shown in the table below are parts by mass.
  • IR dyes 1 to 16 Compounds IR-1 to IR-16 having the following structures
  • (Dye derivative) Derivative 1 Compound with the following structure (acid dye derivative)
  • Derivative 2 A compound having the following structure (basic dye derivative)
  • Derivative 3 A compound having the following structure (acid dye derivative)
  • Derivative 4 Compound with the following structure (acid dye derivative)
  • Derivative 5 Compound with the following structure (acid dye derivative)
  • Dispersant 2 Solsperse 36000 (manufactured by Nippon Lubrizol Co., Ltd.)
  • Metal complex 1 Compound with the following structure
  • Metal complex 2 A compound having the following structure
  • ⁇ Preparation of resin composition The raw materials shown in the table below are mixed and stirred at the ratio (parts by mass) shown in the table below, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m to obtain a resin composition. Prepared. The values shown in the table below are parts by mass. The mass ratio of the metal complex contained in the resin composition to the near-infrared absorbing dye (metal complex / near-infrared absorbing dye (IR dye)) is also described.
  • Resin 1 Resin having the following structure (weight average molecular weight 41400, the numerical value added to the repeating unit of the main chain is the molar ratio).
  • Polymerizable compound Polymerizable Compound 1: NK Ester A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
  • Photopolymerization initiator 1 Photopolymerization Initiator 1: IRGACURE-OXE01 (manufactured by BASF)
  • UV absorber 1 UV-503 (manufactured by Daito Kagaku Co., Ltd.)
  • Antioxidant Antioxidant 1: Neo Heliopan 357 (manufactured by Symrise)
  • Metal complex Metal complex 1
  • Metal complex 2 Compound of the above structure
  • Metal complex 3 Compound of the following structure
  • Metal complex 4 A compound having the following structure
  • Polymerization inhibitor 1 Polymerization inhibitor 1: p-methoxyphenol
  • the resin composition was applied onto an 8-inch (20.32 cm) glass wafer by a spin coating method so that the film thickness after film formation was 1.0 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at an exposure amount of 1000 mJ / cm 2 , and then heating was performed at 200 ° C. for 5 minutes to form a film (near infrared cut filter). did.
  • FPA-3000i5 + manufactured by Canon Inc.
  • the obtained film was measured for absorbance in the wavelength range of 400 to 1300 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Co., Ltd.).
  • the indicated ODL (absorbance) and ODS (absorbance) were obtained, the ratio of ODS to ODL (ODS / ODL) was calculated, and the spectral characteristics in the near infrared region were evaluated according to the following criteria.
  • the smaller the ODS / ODL value the better the near-infrared shading property, and the better the spectral characteristics in the near-infrared region.
  • the absorbance at the maximum absorption wavelength ⁇ 1 on the longest wave side is set to ODL, which is on the short wave side of the maximum absorption wavelength ⁇ 1 and is closest to the maximum absorption wavelength ⁇ 1.
  • the absorbance at the maximum absorption wavelength is set to ODL, and among the wavelengths indicating the variation points of the absorption spectrum in the wavelength range of 600 to 1300 nm, the maximum absorption wavelength is higher than the maximum absorption wavelength. Is also on the short wave side, and the absorbance at the wavelength closest to the maximum absorption wavelength is defined as ODS.
  • the evaluation criteria for the spectral characteristics in the near infrared region are as follows. A: ODS / ODL ⁇ 0.9 B: 0.9 ⁇ ODS / ODL ⁇ 1.1 C: 1.1 ⁇ ODS / ODL
  • the transmittance of the obtained film was measured in the wavelength range of 700 to 1300 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). Then, the resin composition immediately after production was left in a constant temperature bath at 23 ° C. for 2 months. A film was formed in the same manner as above using the resin composition after being left to stand, and the obtained film was subjected to an ultraviolet-visible near-infrared spectrophotometer (U-4100, Hitachi High-Technologies Corporation). Was used to measure the transmittance in the wavelength range of 700 to 1300 nm.
  • the change in transmittance ( ⁇ T%) at the wavelength where the change in transmittance in the wavelength range of 700 to 1300 nm is the largest in the film obtained by using the resin composition before and after being left in a constant temperature bath is measured and stored according to the following criteria. Stability was evaluated. The smaller the value of ⁇ T%, the better the storage stability. A: ⁇ T ⁇ 2% B: 2% ⁇ ⁇ T% ⁇ 5% C: 5% ⁇ ⁇ T%
  • a step (recess) pattern having a size of 3000 ⁇ m ⁇ 4000 ⁇ m and a depth of 1.5 ⁇ m was formed in a grid pattern on the entire surface of an 8-inch (20.32 cm) silicon wafer.
  • the distance between the steps was 100 ⁇ m.
  • the resin composition was applied to the silicon wafer on which the step pattern was formed by a spin coating method, and heated at 100 ° C. for 120 seconds using a hot plate. Then, it was further heated at 200 ° C. for 300 seconds using a hot plate. Steps located at points 1 to 28 shown in FIG. 2 were selected, and the corners of the steps were observed with an optical microscope (50 times).
  • the corners of the step the corners of the four corners farthest from the center of the silicon wafer were observed, and the striation was evaluated according to the following criteria.
  • Example 2 the examples had good spectral characteristics in the near infrared region.
  • the photopolymerization initiator 1 was replaced with IRGACURE-OXE02 (manufactured by BASF) and evaluated in the same manner. As a result, the same result was obtained.
  • the photopolymerization initiator 1 was replaced with Omnirad907 (manufactured by IGM Resins VV) and evaluated in the same manner. As a result, the same result was obtained.
  • Example 2 except for the polymerization inhibitor 1, the same result was obtained.
  • the near-infrared cut filter, the near-infrared transmission filter, the solid-state image sensor, the image display device, and the infrared sensor using the film obtained by using the resin composition described in the examples of the present invention had good performance. ..
  • 110 Solid-state image sensor
  • 111 Near-infrared cut filter
  • 112 Color filter
  • 114 Near-infrared transmission filter
  • 115 Microlens
  • 116 Flattening layer

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Abstract

L'invention concerne : une composition de résine qui comprend un pigment d'absorption dans l'infrarouge proche prédéterminé, un complexe métallique représenté par la formule (MC1) et une résine ; un film ; un filtre à coupure en proche infrarouge ; un filtre passant en proche infrarouge ; un dispositif d'imagerie semi-conducteur ; un appareil d'affichage d'image ; et un capteur infrarouge.
PCT/JP2020/012685 2019-03-28 2020-03-23 Composition de résine, film, filtre à coupure en proche infrarouge, filtre passant en proche infrarouge, dispositif d'imagerie semi-conducteur, appareil d'affichage d'images et capteur infrarouge WO2020196394A1 (fr)

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