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WO2015005448A1 - Method for producing near infrared cutoff filter, and solid-state imaging element - Google Patents

Method for producing near infrared cutoff filter, and solid-state imaging element Download PDF

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Publication number
WO2015005448A1
WO2015005448A1 PCT/JP2014/068491 JP2014068491W WO2015005448A1 WO 2015005448 A1 WO2015005448 A1 WO 2015005448A1 JP 2014068491 W JP2014068491 W JP 2014068491W WO 2015005448 A1 WO2015005448 A1 WO 2015005448A1
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WO
WIPO (PCT)
Prior art keywords
group
copper
cut filter
infrared
infrared cut
Prior art date
Application number
PCT/JP2014/068491
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French (fr)
Japanese (ja)
Inventor
裕樹 奈良
星戊 朴
Original Assignee
富士フイルム株式会社
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Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to KR1020157036530A priority Critical patent/KR20160013991A/en
Publication of WO2015005448A1 publication Critical patent/WO2015005448A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation

Definitions

  • the present invention relates to a method for manufacturing a near-infrared cut filter and a solid-state imaging device.
  • CCDs and CMOS image sensors which are solid-state imaging devices for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. Since the solid-state imaging device uses a silicon photodiode having sensitivity to near infrared rays in the light receiving portion thereof, it is necessary to perform visibility correction, and a near-infrared cut filter (hereinafter also referred to as IR cut filter). Is often used.
  • IR cut filter a near-infrared cut filter
  • Patent Document 1 discloses that a near-infrared absorbing composition is formed into a layer by vapor deposition or the like.
  • a method for producing a near-infrared cut filter a method in which a near-infrared absorbing composition is applied on a substrate (for example, dip coating, slit coating, screen printing, spray coating, spin coating, etc.) is also conceivable.
  • a substrate for example, dip coating, slit coating, screen printing, spray coating, spin coating, etc.
  • This invention solves the said subject, Comprising: It aims at providing the manufacturing method of the near-infrared cut filter which can form a uniform film
  • the near-infrared absorbing composition is formed on the surface of the hydrophilic region formed on the substrate and / or in the region surrounded by the hydrophobic region. It has been found that the above-mentioned problems can be solved by applying. Specifically, the above problem has been solved by the following means ⁇ 1>, preferably ⁇ 2> to ⁇ 13>.
  • ⁇ 1> a step of forming a hydrophilic region and / or a hydrophobic region on a substrate, and Applying a near-infrared absorbing composition comprising a near-infrared absorbing material to the surface of the hydrophilic region and / or within the region surrounded by the hydrophobic region;
  • the manufacturing method of the near-infrared cut filter which has NO. ⁇ 2>
  • ⁇ 3> The method for producing a near-infrared cut filter according to ⁇ 1> or ⁇ 2>, wherein the contact angle of the surface of the hydrophilic region or the surface of the substrate with the near-infrared absorbing composition is 0 to 45 °. . ⁇ 4>
  • the contact angle of the surface of the hydrophilic region with the near-infrared absorbing composition is in the range of 0 to 45 °, any one of ⁇ 1> to ⁇ 3>
  • a hydrophobic region surrounding the hydrophilic region and the hydrophilic region is formed on the base material.
  • the step of forming a hydrophobic region includes patterning a resist composition applied on a substrate by lithography, and applying a tape having a hydrophobic surface on the substrate.
  • ⁇ 1> to ⁇ 5> The manufacturing method of the near-infrared cut filter in any one of. ⁇ 7>
  • ⁇ 8> The method for producing a near-infrared cut filter according to ⁇ 7>, wherein the application method is drop casting.
  • ⁇ 9> The method for producing a near-infrared cut filter according to any one of ⁇ 1> to ⁇ 8>, wherein the near-infrared absorbing substance contains a compound obtained by a reaction between a polymer containing a coordination site and a copper component.
  • the polymer has at least one selected from a sulfonic acid group or a salt thereof.
  • the near-infrared absorbing material contains a copper complex.
  • the content of the copper complex in the near-infrared absorbing composition is 30% by mass or less
  • FIG. 1 It is a schematic sectional drawing which shows an example of the near-infrared cut filter periphery part in a camera module. It is the schematic which shows an example of the manufacturing process of the near-infrared cut off filter of this invention, (A) is a top view of the base material in which the hydrophilic region and the hydrophobic region were formed, (B) is the above-mentioned base material It is a front view.
  • a weight average molecular weight is defined as a polystyrene conversion value by GPC measurement.
  • the weight average molecular weight (Mw) is, for example, HLC-8120 (manufactured by Tosoh Corporation), TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID ⁇ 30.0 cm) as an eluent. It can be determined by using THF (tetrahydrofuran).
  • the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer.
  • the polymerizable functional group refers to a group that participates in a polymerization reaction.
  • the description which does not describe substitution and unsubstituted includes what has a substituent with what does not have a substituent.
  • the near infrared ray in the present invention refers to one having a maximum absorption wavelength ( ⁇ max) region of 700 to 1000 nm.
  • the boiling point in this invention means the boiling point in 25 degreeC and 1 atmosphere.
  • the liquid in this invention says the state in 25 degreeC and 1 atmosphere.
  • the method for producing a near-infrared cut filter of the present invention includes a step of forming a hydrophilic region and / or a hydrophobic region on a substrate, a surface of the hydrophilic region, and / or a region surrounded by the hydrophobic region. And a step of applying a near-infrared absorbing composition containing a near-infrared absorbing material.
  • a near-infrared absorbing composition containing a near-infrared absorbing material.
  • the film formed on the substrate Thickness can be controlled.
  • a uniform film can be formed on the substrate by applying the near-infrared absorbing composition on the surface of the hydrophilic region and / or in the region surrounded by the hydrophobic region. it is conceivable that.
  • a thick film for example, a film having a thickness of 50 ⁇ m or more
  • a uniform film can be formed more effectively.
  • the hydrophobic region is formed so as to surround a certain range on the substrate, usually a certain range of the surface of the substrate or the surface of the hydrophilic region provided on the substrate.
  • a hydrophobic region so as to enclose a certain range on the substrate, it is possible to control the range to which the near-infrared absorbing composition is applied, and as a result, the thickness of the near-infrared cut filter Can be controlled.
  • the method of forming the hydrophobic region is not particularly limited, and a known method can be adopted.
  • the coordinating atom coordinated by the lone pair with respect to the copper component is synonymous with the coordinating atom coordinated by the lone pair described above, and the preferred range is also the same.
  • Specific examples of the coordination site include those described above for the compound serving as a ligand.
  • Specific examples of the coordination site include those described above for the low-molecular copper compound, and the preferred ranges are also the same.
  • Y 21 represents a ring containing a coordination atom coordinated by an unshared electron pair or a partial structure represented by the group (UE) described above. When q and r represent an integer of 2 or more, the plurality of Y 21 may be the same or different.
  • Y 21a represents at least one selected from a ring containing a coordinating atom coordinated by an unshared electron pair, or the group (UE-1) described above. When q and r represent an integer of 2 or more, the plurality of Y 21a may be the same or different.
  • Y 22 represents a partial structure represented by the group (AN) described above. When q and r represent an integer of 2 or more, the plurality of Y 22 may be the same or different.
  • Examples of the divalent linking group has the same meaning as L 12 in the formula (1a2), and preferred ranges are also the same.
  • Y 31 represents a coordination site coordinated by the anion described above. When p represents an integer of 2 or more, the plurality of Y 31 may be the same or different.
  • Y 31a represents at least one selected from the group (AN-1) described above. When p represents an integer of 2 or more, the plurality of Y 31a may be the same or different.
  • p represents an integer of 1 or more, and preferably 2 or more.
  • the upper limit is preferably 5 or less, and more preferably 3 or less.
  • FIG. 3 is an image diagram showing an example of a polymer-type copper complex having an acid group ion site as a ligand, wherein 6 is a copper ion, 7 is a polymer main chain, and 8 is a polymer side chain.
  • 9 represents an acid group ion site derived from an acid group or a salt thereof.
  • the acid group ion site 9 is bonded to copper (for example, coordinate bond), and a crosslinked structure is formed between the side chains 8 of the polymer starting from copper.
  • the main chain is a polymer having a carbon-carbon bond, and preferably contains a structural unit represented by the following formula (A6).
  • R 1 represents a hydrogen atom or a methyl group
  • L 1 represents a single bond or a divalent linking group
  • X 1 is a coordination site coordinated with an anion to a copper component, and This represents a group having one or more selected from coordinating atoms coordinated with an unshared electron pair to the copper component.
  • R 1 is preferably a hydrogen atom.
  • L 1 has the same meaning as L 1 in formula (1) above, and preferred ranges are also the same.
  • X 1 has the same meaning as Y 1 in the above equation (1), acid group or a salt thereof.
  • first embodiment of the polymer (A0) include the following compounds and salts of the following compounds, but are not limited thereto.
  • the second embodiment of the polymer (A0) includes a structural unit represented by at least one of the following formulas (A7-1), (A7-2) and (A7-3).
  • R 1 represents an aliphatic hydrocarbon group
  • Y 1 represents a single bond or a divalent linking group
  • X 1 represents a coordination site that coordinates with an anion to the copper component
  • R 2 represents an aliphatic hydrocarbon group
  • R 3 represents a hydrocarbon group
  • Y 2 represents a single bond or a divalent linking group
  • R 2 , R 3 and Y 2 At least one of is substituted with a fluorine atom.
  • R 1 and R 2 each independently represents an aliphatic hydrocarbon group, and examples thereof include a linear, branched or cyclic alkyl group.
  • the number of carbon atoms of the linear alkyl group is preferably 1-20, more preferably 1-10, and even more preferably 1-6.
  • the carbon number of the branched alkyl group is preferably 3 to 20, more preferably 3 to 10, and further preferably 3 to 6.
  • the cyclic alkyl group may be monocyclic or polycyclic.
  • the number of carbon atoms in the cyclic alkyl group is preferably 3 to 20, more preferably 4 to 10, and still more preferably 6 to 10.
  • R 1 and R 2 have a substituent, for example, a polymerizable group (preferably a polymerizable group containing a carbon-carbon double bond), a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine) Atom), alkyl group, carboxylic acid ester group, halogenated alkyl group, alkoxy group, methacryloyloxy group, acryloyloxy group, ether group, sulfonyl group, sulfide group, amide group, acyl group, hydroxy group, carboxylic acid group, aralkyl Group, —Si— (OR N22 ) 3 and the like are exemplified, and a fluorine atom is particularly preferred.
  • R N22 represents an alkyl group, preferably having 1 to 3 carbon atoms.
  • the divalent linking group is represented by 2 in the above formula (A6).
  • the hydrocarbon group include a linear, branched or cyclic alkylene group and an arylene group.
  • the number of carbon atoms in the linear alkylene group is preferably 1-20, more preferably 1-10, and even more preferably 1-6.
  • the carbon number of the branched alkylene group is preferably 3 to 20, more preferably 3 to 10, and further preferably 3 to 6.
  • the cyclic alkylene group may be monocyclic or polycyclic.
  • the number of carbon atoms of the cyclic alkylene group is preferably 3 to 20, more preferably 4 to 10, and still more preferably 6 to 10.
  • arylene group and heteroarylene group it is synonymous with the case where the bivalent coupling group in Formula (A6) mentioned above is an arylene group, and its preferable range is also synonymous.
  • Y 1 represents a divalent linking group, —COO—, —CO—, —O—, —NX— (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom)
  • a hydrocarbon group preferably an alkylene group or arylene group having 1 to 30 carbon atoms
  • a combination thereof is preferable.
  • X 1 and X 2 are each independently a coordination site that coordinates with a copper component with an anion, and a copper component with a lone pair.
  • at least one of R 1 and Y 1 is is substituted with a fluorine atom, of R 1 and Y 1, it is preferable that at least Y 1 is substituted with a fluorine atom.
  • R 1 is substituted with a fluorine atom means that at least one hydrogen atom constituting R 1 is substituted with a fluorine atom.
  • At least one of R 1 and Y 1 is preferably a perfluoro group.
  • R 4 is an alkylene group, an alkyl group having 1 carbon atom is preferable, and a group represented by —C (R 4A ) (R 4B ) — is more preferable.
  • R 4A and R 4B each independently represent a fluorine atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms), and the alkyl group may be substituted with a fluorine atom.
  • R 4 contains —C (R 4A ) (R 4B ) —, R 4A and R 4B may be bonded to each other to form a ring.
  • R 4 is a cycloalkylene group
  • a cycloalkylene group having 4 carbon atoms is preferable, and a perfluorocyclobutylene group is particularly preferable.
  • R 4 include —C (R 4A ) (R 4B ) —, —O—, —CO—, —SO 2 —.
  • (A7-3) has at least one fluorine atom of Ar 1, R 4 and Y 3, Ar 1, it is preferred that at least one of R 4 and Y 3 is a perfluoroalkyl group.
  • the structural unit represented by the formula (A7-3) may have one or more of Ar 1 and R 4 in the structural unit, and may have two or more.
  • the third embodiment of the polymer (A0) is a copper complex of an aromatic group-containing polymer.
  • an aryl group is preferable.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the aromatic hydrocarbon group may be monocyclic or polycyclic, but is preferably monocyclic.
  • the aryl group is preferably a phenyl group, a naphthyl group, or a biphenyl group.
  • an aromatic heterocyclic group having 2 to 30 carbon atoms is preferable.
  • halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom
  • carboxylic acid ester group halogenated alkyl group, alkoxy group, methacryloyloxy group, acryloyloxy group, ether group, sulfonyl group, sulfide group
  • Examples include an amide group, an acyl group, a hydroxy group, a carboxylic acid group, and an aralkyl group (hereinafter, these substituents are referred to as a substituent T), and an alkyl group (particularly an alkyl group having 1 to 3 carbon atoms) is preferable.
  • aromatic group-containing polymers are polyethersulfone polymers, polysulfone polymers, polyetherketone polymers, polyphenylene ether polymers, polyimide polymers, polybenzimidazole polymers, polyphenylene polymers. It is preferably at least one polymer selected from a polymer, a phenol resin polymer, a polycarbonate polymer, a polyamide polymer, and a polyester polymer. Examples of each polymer are shown below.
  • Polyethersulfone polymer a polymer having a main chain structure represented by (—O—Ph—SO 2 —Ph—) (Ph represents a phenylene group, the same shall apply hereinafter)
  • Polysulfone polymer (—O— Polymer having a main chain structure represented by Ph—Ph—O—Ph—SO 2 —Ph—)
  • Polyetherketone polymer (—O—Ph—O—Ph—C ( ⁇ O) —Ph— )
  • Polyphenylene polymer (-Ph Polymer having main chain structure represented by-)
  • Phenol resin polymer Polymer having main chain structure represented by (-Ph (OH) -CH 2- )
  • Polycarbonate polymer (-Ph- Having a main chain structure represented by O—C ( ⁇ O) —O
  • Y 1 is preferably a single bond.
  • examples of the divalent linking group include a hydrocarbon group, an aromatic heterocyclic group, —O—, —S—, —SO 2 —, —CO—, — C ( ⁇ O) O—, —O—C ( ⁇ O) —, —SO 2 —, —NX— (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), —C (R Y1 ) ( R Y2 ) —, or a group consisting of a combination thereof.
  • R Y1 and R Y2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group.
  • the hydrocarbon group include a linear, branched or cyclic alkylene group and an arylene group.
  • the number of carbon atoms in the linear alkylene group is preferably 1-20, more preferably 1-10, and even more preferably 1-6.
  • the carbon number of the branched alkylene group is preferably 3 to 20, more preferably 3 to 10, and further preferably 3 to 6.
  • the cyclic alkylene group may be monocyclic or polycyclic.
  • the number of carbon atoms of the cyclic alkylene group is preferably 3 to 20, more preferably 4 to 10, and still more preferably 6 to 10.
  • a hydrogen atom in the alkylene group may be substituted with a fluorine atom.
  • the arylene group has the same meaning as the case where the divalent linking group in the above formulas (A7-1) to (A7-3) is an arylene group.
  • the aromatic heterocyclic group a 5-membered ring or a 6-membered ring is preferable.
  • the aromatic heterocyclic group may be a single ring or a condensed ring, and is preferably a single ring or a condensed ring having 2 to 8 condensations, more preferably a single ring or a condensed ring having 2 to 4 condensations. .
  • Specific examples of the third embodiment of the polymer (A0) include the following compounds and compounds of the following acid group salts, but are not limited thereto.
  • pyrrolopyrrole dye for example, paragraphs 0024 to 0052 of JP 2011-68731 A (corresponding US Patent Application Publication No. 2011/0070407, [0043] to [0074]) can be referred to. Incorporated in the description. Further, as the phthalocyanine compound, naphthalocyanine compound, immonium compound, cyanine dye, squalium dye, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP2010-11750A may be used. This content is incorporated herein.
  • cyanine dye for example, “functional dye, Nobu Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein.
  • the near-infrared absorbing substance compounds disclosed in paragraphs 0004 to 0016 of JP 07-164729 A, compounds disclosed in paragraphs 0027 to 0062 of JP 2002-146254 A, JP 2011 Near infrared-absorbing particles comprising crystallites of oxides containing Cu and / or P disclosed in paragraphs 0034 to 0067 of JP-A-166483 and having a number average aggregated particle diameter of 5 to 200 nm may be used.
  • e-ex color IR-10 “e-ex color IR-12”, “e-ex color IR-14”, “e-ex color HA-1”, “e-ex color HA-14”.
  • SIR-128 “SIR-130”, “SIR-132”, “SIR-152”, “SIR-159”, “SIR-162” (all (Trade name, manufactured by Mitsui Chemicals), “Kayasorb IRG-022”, “Kayasorb IRG-023”, “Kayasorb IRG-040” (all trade names, manufactured by Nippon Kayaku Co., Ltd.), “CIR-1081” (trade name, Nippon Carlit Co., Ltd.), "NIR-IM1”, “NIR-AM1” (all trade names, manufactured by Nagase ChemteX), cesium tungsten oxide compound (YMF-02A, YMF-01A-2
  • the content of the near-infrared absorbing substance in the near-infrared absorbing composition is the total solid content in the composition.
  • 30 mass% or more of a minute is preferable, and 50 mass% or more is more preferable. In particular, it is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass.
  • content of the near-infrared absorbing substance in a near-infrared absorptive composition is composition 0.01 mass% or more of the total solid content in the product is preferable, and 0.1 mass% or more is more preferable.
  • the content is preferably 0.01 to 50% by mass, and more preferably 0.1 to 30% by mass.
  • the composition used in the present invention further contains water.
  • the content of water in the composition is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more.
  • the content is preferably 1 to 90% by mass, and more preferably 10 to 80% by mass.
  • the polar liquid having a boiling point higher than 100 ° C. that can be used in the present invention may be used alone or in combination of two or more.
  • the upper limit of the boiling point of the polar liquid is not particularly limited, but is preferably 250 ° C. or lower, more preferably 230 ° C. or lower, and further preferably 200 ° C. or lower.
  • the difference in boiling point between the polar liquid and water is preferably 10 ° C or higher, more preferably 20 ° C or higher, further preferably 30 ° C or higher, and further preferably 50 ° C or higher.
  • the polar liquid preferably has a hydrophilic functional group, for example, at least one functional group selected from an amino group, a sulfonyl group, an ether group, an epoxy group, a hydroxy group, a carbonyl group, a carboxylic acid group, and a cyano group. It preferably has a group, and more preferably has at least one functional group selected from an amino group, a sulfonyl group, an ether group, and an epoxy group.
  • an aprotic polar liquid and a polar liquid other than the polar liquid having a polymerizable group can be used.
  • an alcohol liquid having a boiling point higher than 100 ° C. can be mentioned.
  • aprotic polar liquid ether liquid, amide liquid, ketone liquid, amine liquid, nitrile liquid, nitrogen atom-containing ring compound, sulfoxide, glyme and the like can be used.
  • the aprotic polar liquid may have a polymerizable group.
  • dimethylformamide (153 ° C), dimethylsulfoxide (189 ° C), dimethylacetamide, N-methylpyrrolidone (202 ° C), 2-pyrrolidone (245 ° C), sulfolane (285 ° C), methyldiglyme (162 ° C) and It is preferably at least one selected from methyltriglyme (216 ° C.), more preferably at least one selected from dimethylformamide, dimethylsulfoxide, methyldiglyme and methyltriglyme.
  • the polar liquid When the polar liquid has a polymerizable group, it is a liquid at least at 1 atm and in the temperature range of 80 to 100 ° C., and is a polar liquid having a thermally polymerizable group that starts and cures at a temperature higher than 100 ° C. It is preferable.
  • the polar liquid having a polymerizable group may be monofunctional or polyfunctional, but polyfunctional is preferable.
  • the number of functional groups is not particularly defined, but 2 to 8 functional groups are preferable.
  • the polymerizable group (meth) acryloyl group, epoxy group, cyanate group, isocyanate group, oxetane and the like are preferable.
  • a polar liquid having a polymerizable group having a boiling point higher than 100 ° C. is a monomer having a polymerizable group (polymerizable monomer) or an oligomer having a polymerizable group (polymerizable oligomer) (hereinafter, the polymerizable monomer and the polymerizable oligomer are combined). And may be referred to as “polymerizable monomer etc.”) or a polymerizable polymer.
  • polar liquids that are polymerizable monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • the polymerizable monomer or the like preferably has at least one addition-polymerizable ethylene group and has an ethylenically unsaturated group having a boiling point higher than 100 ° C. under normal pressure, and a monofunctional (meth) acrylate, Bifunctional (meth) acrylates and trifunctional or higher functional (meth) acrylates (for example, 3 to 6 functional (meth) acrylates) are preferred.
  • Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; Polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Ethylene with polyfunctional alcohols such as dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate,
  • pentaerythritol tetraacrylate (commercially available product is A-TMMT; manufactured by Shin-Nakamura Chemical), dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) Dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, manufactured as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and a structure in which these (meth) acryloyl groups are mediated by ethylene glyco
  • the polar liquid is a polymerizable monomer
  • the water-soluble epoxy resin has at least one hydrophilic portion and two or more epoxy groups in one molecule. In particular, those having an ether bond or a hydroxyl group as the hydrophilic site are preferred.
  • water-soluble epoxy resins examples include 4-hydroxybutyl acrylate glycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, ethylene glycol diglycidyl ether Preferred examples include ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, phenoxypentaethyleneoxyglycidyl ether, and lauryloxypentadecaethyleneoxyglycidyl ether.
  • 4-hydroxybutyl acrylate glycidyl ether is preferred.
  • water-soluble epoxy resins include "Denacol (registered trademark)" series EX-313, EX-421, EX-614B, EX-810, EX-811, EX-851, manufactured by Nagase ChemteX Corporation.
  • 40E, 100E, 200E, 400E, 70P, 200P, and 400P of “Epolite” series manufactured by Kyoeisha Chemical Co., Ltd. may be mentioned.
  • diglycidyl ether of ethylene glycol or polyethylene glycol such as 212, 214 of “Epolide (registered trademark) NT” series manufactured by Daicel Chemical Industries, Ltd. And diglycidyl ether.
  • the content of the polar liquid having a boiling point higher than 100 ° C. in the composition used in the present invention is preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and 30% by mass or less. Particularly preferred. In particular, it is preferably 2 to 80% by mass, more preferably 5 to 60% by mass, and more preferably 15 to 30% by mass.
  • the mass ratio of the polar liquid having a boiling point higher than 100 ° C. and water is preferably 20:80 to 80:20, and more preferably 25:75 to 50:50.
  • the composition used in the present invention may contain a liquid other than the polar liquid and water.
  • Another liquid may be used individually by 1 type and may use 2 or more types together.
  • other liquids include polar liquids having a boiling point of 100 ° C. or lower, specifically, alcoholic liquids having a boiling point of 100 ° C. or lower (eg, methanol, ethanol, propanol), ethers having a boiling point of 100 ° C. or lower. And liquids such as dimethyl ether, ethyl methyl ether, and diethyl ether.
  • the other solution (polar liquid having a boiling point higher than 100 ° C .: other liquid) is: It is preferably 50:50 to 99: 1, more preferably 70:30 to 90:10. As for the composition used by this invention, it is preferable that 99 mass% or more of the liquid component in 25 degreeC is comprised with water and a polar liquid.
  • the composition used by this invention may contain other components other than the component mentioned above as needed.
  • a polymerization initiator, a binder polymer, a surfactant and the like may be included.
  • a polymerization initiator may be blended in the composition used in the present invention.
  • the polymerization initiator may be used alone or in combination of two or more.
  • the polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound by either or both of light and heat, and can be appropriately selected according to the purpose.
  • polymerization initiator that decomposes at 150 to 250 ° C. is preferable.
  • the polymerization initiator that can be used in the present invention include acylphosphine compounds, acetophenone compounds, ⁇ -aminoketone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime compounds, hexaarylbiimidazole compounds.
  • the polymerization initiator is preferably an azo compound, and specific examples include a water-soluble azo compound, an oil-soluble azo compound, and a polymer azo compound.
  • Examples of water-soluble azo compounds include commercially available products VA-044, VA-046B, V-50, VA-057, VA-061, VA-067, VA-086 (trade names: all Wako Pure Chemical Industries, Ltd.) Kogyo Co., Ltd.) can be used.
  • Examples of oil-soluble azo compounds include commercially available products such as V-60, V-70, V-65, V-601, V-59, V-40, VF-096, VAm-110, etc. (trade names: any Also, Wako Pure Chemical Industries, Ltd.) can be used.
  • As the polymer azo compound for example, commercially available products such as VPS-1001 and VPE-0201 (trade names: all manufactured by Wako Pure Chemical Industries, Ltd.) can be used.
  • the content of the polymerization initiator is preferably 0.01 to 25% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition used in the present invention.
  • Binder polymer An alkali-soluble resin can be used as the binder polymer. Only 1 type may be used for a binder polymer and it may combine 2 or more types.
  • the alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable.
  • acrylic resins and acrylamide resins are preferable.
  • Resins and acrylic / acrylamide copolymer resins are preferred.
  • Examples of the group that promotes alkali solubility include a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. What can be developed is preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.
  • Examples of the monomer capable of imparting an acid group after the polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (methacrylate). ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types.
  • a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
  • a treatment for imparting an acid group as described later is required after the polymerization.
  • linear organic polymer used as the alkali-soluble resin a polymer having a carboxylic acid in the side chain is preferable, and as such a polymer, paragraph 0561 of JP 2012-208494 A (corresponding US Patent Application Publication) The description of [0691]) etc. of 2012/0235099 specification can be referred to, The content of these is incorporated in this specification.
  • the following general formula (ED) (In formula (ED), R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms) (hereinafter sometimes referred to as “ether dimer”)
  • ether dimer a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms
  • the polymer (a) obtained by polymerizing the monomer component having the essential component (.) Is included as the essential polymer component (A).
  • the composition used by this invention can form the cured coating film which was extremely excellent also in heat resistance and transparency.
  • the hydrocarbon group having 1 to 25 carbon atoms represented by R 1 and R 2 is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, Linear or branched alkyl groups such as isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butylcyclohexyl, dicyclo Alicyclic groups such as pentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl; aryls such as benzyl An alkyl group substituted with a group; and
  • the ether dimer description in paragraph 0565 of JP2012-208494A (corresponding to [0694] of US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof are described in the present specification. Embedded in the book.
  • the structural unit derived from the ether dimer is preferably 1 to 50% by mole, more preferably 1 to 20% by mole.
  • an alkali-soluble phenol resin can also be preferably used.
  • the alkali-soluble phenol resin include novolak resins and vinyl polymers.
  • the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst.
  • the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
  • the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and the like.
  • the said phenols and aldehydes can be used individually or in combination of 2 or more types.
  • Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol, or a mixture thereof and formalin.
  • the novolak resin may be adjusted in molecular weight distribution by means of fractionation or the like. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.
  • alkali-soluble resin in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are suitable.
  • ком ⁇ онент that can be used in combination include, for example, a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, and the like.
  • Adhesion promoters and other auxiliaries for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.
  • the near-infrared cut filter obtained by the above-described method for producing a near-infrared cut filter of the present invention preferably has a film thickness of 300 ⁇ m or less, more preferably 250 ⁇ m or less, and even more preferably 200 ⁇ m or less.
  • the film thickness is preferably 20 ⁇ m or more, more preferably 50 ⁇ m or more, and further preferably 100 ⁇ m or more.
  • the film thickness is preferably 50 to 300 ⁇ m, more preferably 100 to 250 ⁇ m.
  • the near-infrared cut filter preferably has a surface roughness Ra measured by an atomic force microscope (AFM, Nano-R manufactured by Pacific Nanotechnology) of 0 to 20 nm, and more preferably 0 to 10 nm.
  • AFM atomic force microscope
  • the near-infrared cut filter preferably has a water content of 20% by mass or less, more preferably 0 to 10% by mass.
  • the content of the polar liquid is preferably 0 to 20% by mass, and more preferably 0 to 10% by mass.
  • the near-infrared cut filter preferably has a light transmittance that satisfies at least one of the following conditions (1) to (9), and more preferably satisfies all the following conditions (1) to (8): It is more preferable that all the conditions (1) to (9) are satisfied.
  • the light transmittance at a wavelength of 400 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
  • the light transmittance at a wavelength of 450 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
  • the light transmittance at a wavelength of 500 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
  • the light transmittance at a wavelength of 550 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
  • the light transmittance at a wavelength of 700 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
  • the light transmittance at a wavelength of 750 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
  • the light transmittance at a wavelength of 800 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
  • the light transmittance at a wavelength of 850 nm is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, and particularly preferably 5% or less.
  • the light transmittance at a wavelength of 900 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
  • the near-infrared cut filter preferably has a film thickness of 50 to 300 ⁇ m and a light transmittance of 90% or more in any range of wavelengths from 400 to 575 nm, and in all ranges of wavelengths from 400 to 575 nm.
  • the light transmittance is preferably 90% or more.
  • the near-infrared cut filter has a film thickness of 50 to 300 ⁇ m and has a transmittance of 20% or less in a wavelength range of 700 to 1100 nm, and a transmittance in the entire wavelength range of 700 to 1100 nm. Is more preferably 20% or less.
  • a near-infrared cut filter is good also as a laminated body which has the near-infrared cut layer which hardened the near-infrared absorptive composition, and the dielectric multilayer.
  • a transparent support, a near-infrared cut layer, and a dielectric multilayer film are provided in the above order;
  • a near-infrared cut layer, a transparent support, and a dielectric multilayer film are provided in the above order.
  • the transparent support may be a glass substrate or a transparent resin substrate.
  • the dielectric multilayer film is a film having an ability to reflect and / or absorb near infrared rays.
  • the dielectric multilayer film for example, ceramic can be used.
  • a noble metal film having absorption in the near infrared region may be used in consideration of the thickness and the number of layers so as not to affect the visible light transmittance of the near infrared cut filter.
  • a configuration in which high refractive index material layers and low refractive index material layers are alternately stacked can be suitably used as the dielectric multilayer film.
  • a material constituting the high refractive index material layer a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of 1.7 to 2.5 is usually selected.
  • a material constituting the low refractive index material layer a material having a refractive index of 1.6 or less can be used, and a material having a refractive index range of 1.2 to 1.6 is usually selected.
  • the thicknesses of the high-refractive index material layer and the low-refractive index material layer are usually 0.1 ⁇ to 0.5 ⁇ of the infrared wavelength ⁇ (nm) to be blocked.
  • ⁇ infrared wavelength
  • the thickness is out of the above range, the product (n ⁇ d) of the refractive index (n) and the film thickness (d) is significantly different from the optical film thickness calculated by ⁇ / 4, and the optical characteristics of reflection and refraction are different. The relationship is broken, and it tends to be difficult to control blocking / transmission of a specific wavelength.
  • the number of laminated layers in the dielectric multilayer film is preferably 5 to 50 layers, more preferably 10 to 45 layers.
  • a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately stacked is formed by CVD, sputtering, vacuum deposition, or the like.
  • a method for forming a film can be given.
  • the substrate is warped when the dielectric multilayer film is deposited, in order to eliminate this, the dielectric multilayer film is deposited on both sides of the substrate.
  • the near-infrared cut filter is for lenses that absorb and cut near-infrared rays (camera lenses such as digital cameras, mobile phones, and in-vehicle cameras, optical lenses such as f- ⁇ lenses and pickup lenses) and semiconductor light-receiving elements.
  • Optical filters, near-infrared absorbing films and near-infrared absorbing plates that block heat rays for energy saving, agricultural coatings for selective use of sunlight, recording media that use near-infrared absorbing heat, and electronic equipment It is used for near infrared filters for photography and photography, protective glasses, sunglasses, heat ray blocking films, optical character reading recording, confidential document copy prevention, electrophotographic photoreceptors, laser welding, and the like. It is also useful as a noise cut filter for CCD cameras and a filter for CMOS image sensors.
  • the present invention also relates to a camera module having a solid-state imaging device and the above-described near-infrared cut filter.
  • the near infrared cut filter is the near infrared cut filter of the present invention described above.
  • FIGS. 4 and 5 common portions are denoted by common reference numerals.
  • “upper”, “upper”, and “upper” refer to the side far from the silicon substrate 10, and “lower”, “lower”, and “lower” are closer to the silicon substrate 10. Point to. FIG.
  • FIG. 4 is a schematic cross-sectional view illustrating a configuration of a camera module including a solid-state image sensor.
  • a camera module 200 shown in FIG. 4 is connected to a circuit board 70 that is a mounting board via solder balls 60 that are connection members.
  • the camera module 200 includes a solid-state imaging device (solid-state imaging device substrate) 100 including a photodiode on a first main surface of a silicon substrate, and a first main surface side (light-receiving side) of the solid-state imaging device 100.
  • the near-infrared cut filter 42 provided on the planarizing layer (not shown in FIG. 4), and the near-infrared cut filter 42 disposed above the near-infrared cut filter 42 and the imaging lens 40 in the internal space.
  • the present invention is a method of manufacturing a camera module having a solid-state image sensor 100 and a near-infrared cut filter 42 disposed on the light-receiving side of the solid-state image sensor, and the near-infrared absorption on the light-receiving side of the solid-state image sensor. It is also preferable to have the process of forming the near-infrared cut filter 42 by applying a composition.
  • the near-infrared cut filter 42 can be formed by forming a film by applying a near-infrared absorbing composition on the planarizing layer.
  • the method for applying the near-infrared absorbing composition is as described above.
  • incident light h ⁇ from outside passes through the imaging lens 40, the near-infrared cut filter 42, the glass substrate 30, and the planarization layer in order, and then reaches the imaging device portion of the solid-state imaging device 100. ing.
  • the near infrared cut filter is directly provided on the flattening layer, but the flat layer may be omitted and the near infrared cut filter may be provided directly on the microlens, or on the glass substrate 30.
  • a near-infrared cut filter may be provided, or a glass substrate 30 provided with a near-infrared cut filter may be bonded.
  • FIG. 5 is an enlarged cross-sectional view of the solid-state imaging device 100 in FIG.
  • the solid-state imaging device 100 includes an imaging device unit 12, an interlayer insulating film 13, a base layer 14, a color filter 15, an overcoat 16, and a microlens 17 in this order on the first main surface of a silicon substrate 10 that is a base. Yes.
  • the red color filter 15R, the green color filter 15G, the blue color filter 15B (hereinafter, these may be collectively referred to as “color filter 15”), and the microlens 17 so as to correspond to the imaging element unit 12, Each is arranged.
  • the second main surface opposite to the first main surface of the silicon substrate 10 includes a light shielding film 18, an insulating film 22, a metal electrode 23, a solder resist layer 24, an internal electrode 26, and an element surface electrode 27. Yes. Each member is bonded by an adhesive 20.
  • a planarizing layer 46 and a near infrared cut filter 42 are provided on the microlens 17. Instead of providing the near-infrared cut filter 42 on the flattening layer 46, the near-infrared cut filter 42 is provided on the microlens 17, between the base layer 14 and the color filter 15, or between the color filter 15 and the overcoat 16. The form in which an infrared cut filter is provided may be sufficient.
  • the near infrared cut filter is preferably provided at a position within 2 mm (more preferably within 1 mm) from the surface of the microlens 17. If it is provided at this position, the process of forming the near infrared cut filter can be simplified, and unnecessary near infrared rays to the microlens can be sufficiently cut, so that the near infrared blocking property can be further improved.
  • the description after paragraph 0245 of JP 2012-068418 A (corresponding US Patent Application Publication No. 2012/068292 [0407]) can be referred to, and the contents thereof are described in this specification. Incorporated.
  • the near-infrared cut filter can be subjected to a solder reflow process.
  • a solder reflow process By manufacturing the camera module through the solder reflow process, it is possible to automatically mount electronic component mounting boards, etc. that need to be soldered, making the productivity significantly higher than when not using the solder reflow process. Can be improved. Furthermore, since it can be performed automatically, the cost can be reduced.
  • the infrared cut filter is exposed to a temperature of about 250 to 270 ° C., so that the infrared cut filter can withstand the solder reflow process (hereinafter also referred to as “solder reflow resistance”). It is preferable to have.
  • the ultraviolet / infrared light reflecting film 80 has the effect of imparting or enhancing the function of a near-infrared cut filter.
  • paragraphs 0033 to 0039 of JP2013-68688A can be referred to. Incorporated in the description.
  • the transparent substrate 81 transmits light having a wavelength in the visible region.
  • paragraphs 0026 to 0032 of JP2013-68688A can be referred to, and the contents thereof are incorporated herein.
  • the near-infrared absorbing layer 82 is a layer formed by applying the above-described near-infrared absorbing composition of the present invention.
  • the contact angle of the hydrophilic region or the hydrophobic region with respect to the near-infrared absorbing composition was measured in accordance with JIS R 3257 “Test method for wettability of substrate glass surface”.
  • the variation in film thickness means that the average value of the film thickness was calculated for each of the five types of films prepared in each Example and Comparative Example, and the film thickness between the samples was compared. It represents the difference between the maximum value (film with the average film thickness) and the minimum value (film with the average film thickness).
  • the film thickness was measured with a stylus type surface shape measuring instrument (DektakXT: manufactured by Bruker Ax).
  • the following symbols represent the following compounds, respectively.
  • the obtained solid was dried under reduced pressure to obtain 4.9 g of the following polymer (A-1).
  • the sulfonic acid group content (meq / g) in the polymer (A-1) calculated by neutralization titration was 3.0 meq / g.
  • the weight average molecular weight (Mw) measured by gel permeation chromatography was 53,000.
  • ⁇ Preparation of near-infrared absorbing composition Pure water (2.80 g) and dimethylformamide (1.20 g) were added to copper sulfonate complex polymer X (1.00 g) to obtain a near-infrared absorbing composition A.
  • the prepared near-infrared absorbing composition A was a blue transparent liquid having a solid content concentration of 20% by mass.
  • the near-infrared absorptive composition B which added the pure water to the near-infrared absorptive composition A, and adjusted solid content concentration to 10 mass% was obtained.
  • Glass substrate B on which hydrophilic region ( ⁇ ) is formed >> Further, on the glass substrate A, a resin film (a cyclohexanone solution of benzyl methacrylate (70 wt%) / methacrylic acid (30 wt%) copolymer (weight average molecular weight 25,000) (solid content weight 20 parts by weight)) is formed. 3 ml of the glass substrate B was applied and subjected to oxygen plasma ashing to prepare a glass substrate B on which a hydrophilic region ( ⁇ ) was formed. When the contact angle with respect to the said near-infrared absorptive composition A of the surface of a hydrophilic region ((beta)) was measured, the contact angle was 17.3 degrees.
  • FIG. 9 is a schematic view showing an example of the manufacturing process of the near-infrared cut filter of the present invention, (A) is a plan view of a substrate on which a hydrophilic region and a hydrophobic region are formed, and (B) is It is a front view of the said base material. In the example shown in FIG.
  • a hydrophilic region 2 (hydrophilic region ( ⁇ )) and a hydrophobic region 3 (hydrophobic region ( ⁇ )) surrounding the hydrophilic region 2 were formed on the surface of the glass substrate 1A.
  • the contact angle of the surface of the hydrophobic region ( ⁇ ) to the near-infrared absorbing composition A was measured, the contact angle was 83.4 °.
  • Glass substrate E on which a hydrophobic region ( ⁇ ) surrounding the hydrophilic region ( ⁇ ) is formed >>
  • a photoresist for forming the hydrophobic region is applied on the glass substrate B on which the hydrophilic region ( ⁇ ) is formed, and patterned by lithography to form the hydrophilic region ( ⁇ ).
  • a glass substrate E on which a surrounding hydrophobic region ( ⁇ ) was formed was produced.
  • ⁇ Glass Substrate F with Hydrophobic Region ⁇ >> A substrate F in which a hydrophobic region ⁇ was formed without forming the hydrophilic region ⁇ on the glass substrate (that is, without washing) was produced.
  • the contact angle of the infrared absorbing composition A on the glass substrate F was 39.8 °.
  • Example 1 ⁇ Production of near-infrared cut filter> ⁇ Example 1 >> When 3 ml of the near-infrared absorbing composition A was dropped on the hydrophilic region ⁇ of the glass substrate D, the near-infrared absorbing composition A spreads in the hydrophilic region ⁇ , and on the hydrophobic region ⁇ . No film was formed. The substrate with the coating film was dried at room temperature for 24 hours, and then the coating film thickness was evaluated. The film thickness was 192 ⁇ m. When the same experiment was conducted five times, the film thickness variation was ⁇ 7 ⁇ m, and the reproducibility was good. ⁇ Examples 2 to 4 and Comparative Examples 1 and 2 >> Except as described below, coating films were formed in Examples 2 to 4 and Comparative Examples 1 and 2 in the same manner as in Example 1, and the variation in film thickness was evaluated.
  • Example 2 it was confirmed from the comparison with Example 1 that the film thickness can be adjusted by adjusting the solid content concentration.
  • the near-infrared absorbing compositions used in Examples 1 to 4 when the sulfonic acid copper complex polymer X is replaced with the sulfonic acid copper complex polymer Y, the same effects as these can be obtained.
  • the near-infrared absorbing composition A wets and spreads on the glass substrate, and a part of the near-infrared absorbing composition A leaks out of the substrate.
  • the coating composition did not spread and film formation was not possible.
  • a dielectric multilayer film that reflects near infrared rays at a deposition temperature of 200 ° C. As a dielectric multilayer film that reflects near infrared rays at a deposition temperature of 200 ° C., a silica (SiO 2 : film thickness 20 to 250 nm) layer and titania (TiO 2 : film thickness 70 to 130 nm). A layer in which layers were alternately stacked was formed.
  • a specific layer structure is a total of 41 layers of alternating laminated films of a silica layer (film thickness of 80 nm) on the near infrared cut filter and a titania layer (film thickness of 103 nm) and a silica layer (film thickness of 159 nm).
  • a silica layer (film thickness 80 nm) was used.
  • Example 20 In the near-infrared absorbing composition of Example 1, the low-molecular copper complex A shown below is further added, and the ratio of the sulfonic acid copper complex polymer X and the low-molecular copper complex A is 7: 3 on a solid basis.
  • a near-infrared absorbing composition of Example 20 was obtained in the same manner as Example 1 except for the above. (Examples 21 to 24) In the near-infrared absorbing composition of Example 20, Examples 21 to 24 were carried out in the same manner as in Example 20 except that the low molecular copper complex A was changed to low molecular copper complexes B, C, D, or E, respectively. A near infrared ray absorbing composition was obtained.
  • Examples 25 to 27 In the near-infrared absorbing composition of Example 20, except that the ratio of the sulfonic acid copper complex polymer X to the low molecular copper complex A was changed to 5: 5, 6: 4, and 8: 2, respectively, based on the solid content. Were the same as in Example 20 to obtain near-infrared absorbing compositions of Examples 25 to 27. It was confirmed that the mixed type of the sulfonic acid copper complex polymer X and the low-molecular copper complex can achieve higher near-infrared shielding properties.
  • Low molecular copper complex A Low molecular copper complex A: a copper complex having the following (M-1) as a ligand. The synthesis method will be described later.
  • Low molecular copper complex B a copper complex having the following compound (A1-21) as a ligand. The synthesis method will be described later.
  • Low molecular copper complex C Monobutyl copper phthalate, Tokyo Chemical Industry Co., Ltd.
  • Low molecular copper complex D Copper complex having the following compound (A2-1) as a ligand. The synthesis method will be described later.
  • Low molecular copper complex E a copper complex having the following compound (a-0) as a ligand. The synthesis method will be described later.

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Abstract

Provided are: a method for producing a near infrared cutoff filter with which it is possible to uniformly form a film on a substrate; and a solid-state imaging element. This method for producing a near infrared cutoff filter comprises: a step in which a hydrophilic region and/or a hydrophobic region are formed on a substrate; and a step in which a near infrared absorbent composition containing a near infrared absorbent substance is applied to the surface of a hydrophilic region and/or within a region surrounded by a hydrophobic region.

Description

近赤外線カットフィルタの製造方法および固体撮像素子Manufacturing method of near-infrared cut filter and solid-state imaging device
　本発明は、近赤外線カットフィルタの製造方法および固体撮像素子に関する。 The present invention relates to a method for manufacturing a near-infrared cut filter and a solid-state imaging device.
　近年、ビデオカメラ、デジタルスチルカメラ、カメラ機能付き携帯電話などにはカラー画像の固体撮像素子であるＣＣＤやＣＭＯＳイメージセンサが用いられている。固体撮像素子は、その受光部において近赤外線に感度を有するシリコンフォトダイオードを使用しているために、視感度補正を行うことが必要であり、近赤外線カットフィルタ（以下、ＩＲカットフィルタともいう）を用いることが多い。
　近赤外線カットフィルタの製造方法として、例えば特許文献１には、近赤外線吸収性組成物を蒸着等により層状にして形成することが開示されている。 In recent years, CCDs and CMOS image sensors, which are solid-state imaging devices for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. Since the solid-state imaging device uses a silicon photodiode having sensitivity to near infrared rays in the light receiving portion thereof, it is necessary to perform visibility correction, and a near-infrared cut filter (hereinafter also referred to as IR cut filter). Is often used.
As a method for producing a near-infrared cut filter, for example, Patent Document 1 discloses that a near-infrared absorbing composition is formed into a layer by vapor deposition or the like.
国際公開ＷＯ９９／２６９５２号パンフレットInternational Publication WO99 / 26952 Pamphlet
　近赤外線カットフィルタの製造方法としては、基材上に近赤外線吸収性組成物を適用（例えば、ディップコート、スリットコート、スクリーン印刷、スプレーコート、スピンコート等の塗布）する方法も考えられる。
　ここで、本発明者が検討したところ、上記のような適用方法によって、基材上に膜を形成すると、均一な膜を形成することが困難である場合があることがわかった。
　本発明は、上記課題を解決するものであって、基材上に均一な膜を形成することができる近赤外線カットフィルタの製造方法を提供することを目的とする。 As a method for producing a near-infrared cut filter, a method in which a near-infrared absorbing composition is applied on a substrate (for example, dip coating, slit coating, screen printing, spray coating, spin coating, etc.) is also conceivable.
Here, when this inventor examined, when the film | membrane was formed on a base material with the above application methods, it turned out that it may be difficult to form a uniform film | membrane.
This invention solves the said subject, Comprising: It aims at providing the manufacturing method of the near-infrared cut filter which can form a uniform film | membrane on a base material.
　かかる状況のもと、本発明者が鋭意検討した結果、基材上に形成された親水性領域の表面に、および／または、疎水性領域で囲まれた領域内に、近赤外線吸収性組成物を適用することにより、上記課題を解決しうることを見出した。
　具体的には、以下の手段＜１＞により、好ましくは、＜２＞～＜１３＞により、上記課題は解決された。
＜１＞基材上に親水性領域および／または疎水性領域を形成する工程、および、
親水性領域の表面に、および／または、疎水性領域で囲まれた領域内に、近赤外線吸収物質を含む近赤外線吸収性組成物を適用する工程、
を有する近赤外線カットフィルタの製造方法。
＜２＞近赤外線吸収性組成物がさらに水を含み、固形分が５～３０質量％である、＜１＞に記載の近赤外線カットフィルタの製造方法。
＜３＞親水性領域の表面、または、基材の表面の近赤外線吸収性組成物に対する接触角が０～４５°である、＜１＞または＜２＞に記載の近赤外線カットフィルタの製造方法。
＜４＞基材の表面を親水化処理することによって、親水性領域の表面の近赤外線吸収性組成物に対する接触角を０～４５°の範囲にする、＜１＞～＜３＞のいずれかに記載の近赤外線カットフィルタの製造方法。
＜５＞基材上に親水性領域および／または疎水性領域を形成する工程では、基材上に親水性領域および親水性領域を囲む疎水性領域を形成し、
近赤外線吸収性組成物を適用する工程では、近赤外線吸収性組成物を親水性領域の表面に適用する、＜１＞～＜４＞のいずれかに記載の近赤外線カットフィルタの製造方法。
＜６＞疎水性領域を形成する工程は、基材上に適用されたレジスト組成物をリソグラフィーによりパターニングすること、表面が疎水性のテープを基材上に貼ることを含む、＜１＞～＜５＞のいずれかに記載の近赤外線カットフィルタの製造方法。
＜７＞適用の方法が、ドロップキャスト、ディップコート、スリットコート、スクリーン印刷、スプレーコートおよびスピンコートから選択される少なくとも１つである、＜１＞～＜６＞のいずれかに記載の近赤外線カットフィルタの製造方法。
＜８＞適用の方法がドロップキャストである、＜７＞に記載の近赤外線カットフィルタの製造方法。
＜９＞近赤外線吸収物質が、配位部位を含む重合体と銅成分との反応で得られる化合物を含む、＜１＞～＜８＞のいずれかに記載の近赤外線カットフィルタの製造方法。
＜１０＞重合体が、スルホン酸基またはその塩から選択される少なくとも１種を有する、＜９＞に記載の近赤外線カットフィルタの製造方法。
＜１１＞近赤外線吸収物質が銅錯体を含む、＜１＞～＜１０＞のいずれかに記載の近赤外線カットフィルタの製造方法。
＜１２＞近赤外線吸収性組成物中の銅錯体の含有量が３０質量％以下であり、
銅錯体が、酸基イオンを含む重合体中の酸基イオン部位を配位子とする銅錯体である、＜１１＞に記載の近赤外線カットフィルタの製造方法。
＜１３＞＜１＞～＜１２＞のいずれかに記載の近赤外線カットフィルタの製造方法で得られた近赤外線カットフィルタを有する固体撮像素子。 Under such circumstances, as a result of intensive studies by the present inventors, the near-infrared absorbing composition is formed on the surface of the hydrophilic region formed on the substrate and / or in the region surrounded by the hydrophobic region. It has been found that the above-mentioned problems can be solved by applying.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <13>.
<1> a step of forming a hydrophilic region and / or a hydrophobic region on a substrate, and
Applying a near-infrared absorbing composition comprising a near-infrared absorbing material to the surface of the hydrophilic region and / or within the region surrounded by the hydrophobic region;
The manufacturing method of the near-infrared cut filter which has NO.
<2> The method for producing a near-infrared cut filter according to <1>, wherein the near-infrared absorbing composition further contains water and has a solid content of 5 to 30% by mass.
<3> The method for producing a near-infrared cut filter according to <1> or <2>, wherein the contact angle of the surface of the hydrophilic region or the surface of the substrate with the near-infrared absorbing composition is 0 to 45 °. .
<4> By making the surface of the substrate hydrophilic, the contact angle of the surface of the hydrophilic region with the near-infrared absorbing composition is in the range of 0 to 45 °, any one of <1> to <3> The manufacturing method of the near-infrared cut off filter as described in 2.
<5> In the step of forming the hydrophilic region and / or the hydrophobic region on the base material, a hydrophobic region surrounding the hydrophilic region and the hydrophilic region is formed on the base material,
The method for producing a near-infrared cut filter according to any one of <1> to <4>, wherein in the step of applying the near-infrared absorbing composition, the near-infrared absorbing composition is applied to the surface of the hydrophilic region.
<6> The step of forming a hydrophobic region includes patterning a resist composition applied on a substrate by lithography, and applying a tape having a hydrophobic surface on the substrate. <1> to <5> The manufacturing method of the near-infrared cut filter in any one of.
<7> The near infrared ray according to any one of <1> to <6>, wherein the application method is at least one selected from drop casting, dip coating, slit coating, screen printing, spray coating, and spin coating. Cut filter manufacturing method.
<8> The method for producing a near-infrared cut filter according to <7>, wherein the application method is drop casting.
<9> The method for producing a near-infrared cut filter according to any one of <1> to <8>, wherein the near-infrared absorbing substance contains a compound obtained by a reaction between a polymer containing a coordination site and a copper component.
<10> The method for producing a near-infrared cut filter according to <9>, wherein the polymer has at least one selected from a sulfonic acid group or a salt thereof.
<11> The method for producing a near-infrared cut filter according to any one of <1> to <10>, wherein the near-infrared absorbing material contains a copper complex.
<12> The content of the copper complex in the near-infrared absorbing composition is 30% by mass or less,
The method for producing a near-infrared cut filter according to <11>, wherein the copper complex is a copper complex having an acid group ion site in a polymer containing acid group ions as a ligand.
<13> A solid-state imaging device having a near-infrared cut filter obtained by the method for producing a near-infrared cut filter according to any one of <1> to <12>.
　本発明によれば、基材上に均一な膜を形成することができる近赤外線カットフィルタの製造方法を提供することが可能となった。 According to the present invention, it is possible to provide a method for producing a near-infrared cut filter capable of forming a uniform film on a substrate.
本発明の近赤外線カットフィルタの製造工程の一例を示す概略図である。It is the schematic which shows an example of the manufacturing process of the near-infrared cut off filter of this invention. 本発明の近赤外線カットフィルタの製造工程の一例を示す概略図である。It is the schematic which shows an example of the manufacturing process of the near-infrared cut off filter of this invention. 本発明に用いられる近赤外線吸収物質の一例を示すイメージ図である。It is an image figure which shows an example of the near-infrared absorption material used for this invention. 固体撮像素子を備えたカメラモジュールの構成を示す概略断面図である。It is a schematic sectional drawing which shows the structure of the camera module provided with the solid-state image sensor. 固体撮像素子の概略断面図である。It is a schematic sectional drawing of a solid-state image sensor. カメラモジュールにおける近赤外線カットフィルタ周辺部分の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the near-infrared cut filter periphery part in a camera module. カメラモジュールにおける近赤外線カットフィルタ周辺部分の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the near-infrared cut filter periphery part in a camera module. カメラモジュールにおける近赤外線カットフィルタ周辺部分の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the near-infrared cut filter periphery part in a camera module. 本発明の近赤外線カットフィルタの製造工程の一例を示す概略図であり、（Ａ）は親水性領域および疎水性領域が形成された基材の平面図であり、（Ｂ）は上記基材の正面図である。It is the schematic which shows an example of the manufacturing process of the near-infrared cut off filter of this invention, (A) is a top view of the base material in which the hydrophilic region and the hydrophobic region were formed, (B) is the above-mentioned base material It is a front view.
　以下において、本発明の内容について詳細に説明する。尚、本願明細書において「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
　本明細書中において、“（メタ）アクリレート”はアクリレートおよびメタクリレートを表し、“（メタ）アクリル”はアクリルおよびメタクリルを表し、“（メタ）アクリロイル”はアクリロイルおよびメタクリロイルを表す。
　また、本明細書中において、“単量体”と“モノマー”とは同義である。本発明における単量体は、オリゴマーおよびポリマーと区別され、重量平均分子量が２，０００以下の化合物をいう。
　重量平均分子量は、ＧＰＣ測定によるポリスチレン換算値として定義される。重量平均分子量（Ｍｗ）は、例えば、ＨＬＣ－８１２０（東ソー（株）製）を用い、カラムとしてＴＳＫ ｇｅｌ Ｍｕｌｔｉｐｏｒｅ ＨＸＬ－Ｍ（東ソー（株）製、７．８ｍｍＩＤ×３０．０ｃｍを、溶離液としてＴＨＦ(テトラヒドロフラン)を用いることによって求めることができる。
　本明細書中において、重合性化合物とは、重合性官能基を有する化合物のことをいい、単量体であっても、ポリマーであってもよい。重合性官能基とは、重合反応に関与する基をいう。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は置換基を有さないものと共に置換基を有するものをも包含するものである。
　本発明における近赤外線とは、極大吸収波長（λｍａｘ）領域が７００～１０００ｎｍであるものをいう。
　本発明における沸点とは、２５℃、１気圧における沸点をいう。また、本発明における液体は、２５℃、１気圧における状態をいう。 Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less.
A weight average molecular weight is defined as a polystyrene conversion value by GPC measurement. The weight average molecular weight (Mw) is, for example, HLC-8120 (manufactured by Tosoh Corporation), TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm) as an eluent. It can be determined by using THF (tetrahydrofuran).
In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes what has a substituent with what does not have a substituent.
The near infrared ray in the present invention refers to one having a maximum absorption wavelength (λmax) region of 700 to 1000 nm.
The boiling point in this invention means the boiling point in 25 degreeC and 1 atmosphere. Moreover, the liquid in this invention says the state in 25 degreeC and 1 atmosphere.
＜近赤外線カットフィルタの製造方法＞
　本発明の近赤外線カットフィルタの製造方法は、基材上に親水性領域および／または疎水性領域を形成する工程、親水性領域の表面に、および／または、疎水性領域で囲まれた領域内に、近赤外線吸収物質を含む近赤外線吸収性組成物を適用する工程、を有する。
　このメカニズムは推定であるが、基材上に親水性領域を形成することにより、基材表面の濡れ性を制御することができ、親水性領域の表面に近赤外線吸収性組成物を適用すると、組成物が均一に広がり、均一な膜を製造することができる。また、基材上に疎水性領域を形成し、疎水性領域で囲まれた領域内に近赤外線吸収性組成物を適用し、適用量を調整することにより、基材上に形成される膜の厚さを制御することができる。結果として、親水性領域の表面に、および／または、疎水性領域で囲まれた領域内に、近赤外線吸収性組成物を適用することにより、基材上に均一な膜を形成することができると考えられる。特に厚い膜（例えば５０μｍ以上の厚さの膜）を形成する場合に、より効果的に均一な膜を形成することができる。 <Method for manufacturing near-infrared cut filter>
The method for producing a near-infrared cut filter of the present invention includes a step of forming a hydrophilic region and / or a hydrophobic region on a substrate, a surface of the hydrophilic region, and / or a region surrounded by the hydrophobic region. And a step of applying a near-infrared absorbing composition containing a near-infrared absorbing material.
Although this mechanism is presumed, the wettability of the substrate surface can be controlled by forming a hydrophilic region on the substrate, and when a near-infrared absorbing composition is applied to the surface of the hydrophilic region, The composition spreads uniformly and a uniform film can be produced. Further, by forming a hydrophobic region on the substrate, applying a near-infrared absorbing composition in the region surrounded by the hydrophobic region, and adjusting the amount of application, the film formed on the substrate Thickness can be controlled. As a result, a uniform film can be formed on the substrate by applying the near-infrared absorbing composition on the surface of the hydrophilic region and / or in the region surrounded by the hydrophobic region. it is conceivable that. In particular, when a thick film (for example, a film having a thickness of 50 μm or more) is formed, a uniform film can be formed more effectively.
＜基材上に親水性領域を形成する工程＞
　本発明における親水性領域は、通常、近赤外線吸収性組成物が基材の表面に広がりやすくするために設ける。従って、親水性領域は、基材上を親水化処理して形成することが好ましい。親水化処理の方法としては、特に限定されず公知の方法を採用できるが、例えば、基材の表面を湿式洗浄する方法、基材の表面を光洗浄する方法、基材の表面に親水性化合物を塗布する方法、基材の表面に親水性化合物を塗布し、酸素プラズマアッシング処理を行う方法、またはこれらを組み合わせた方法が挙げられる。 <The process of forming a hydrophilic area | region on a base material>
The hydrophilic region in the present invention is usually provided so that the near-infrared absorbing composition can easily spread on the surface of the substrate. Therefore, the hydrophilic region is preferably formed by subjecting the substrate to a hydrophilic treatment. The method for the hydrophilization treatment is not particularly limited, and a known method can be adopted. For example, a method of wet cleaning the surface of the substrate, a method of photo-cleaning the surface of the substrate, a hydrophilic compound on the surface of the substrate The method of apply | coating, the method of apply | coating a hydrophilic compound to the surface of a base material, performing an oxygen plasma ashing process, or the method of combining these is mentioned.
　基材は、特に限定されず、例えば、ガラスなどからなる透明基板（ガラス基板やプラスチック基板）が挙げられる。また、固体撮像素子用途に用いる場合、基材は、固体撮像素子、固体撮像素子の受光側に設けられた別の基板または平坦化層等の層であってもよい。 The base material is not particularly limited, and examples thereof include a transparent substrate (glass substrate or plastic substrate) made of glass or the like. Moreover, when using for a solid-state image sensor use, a base material may be layers, such as another board | substrate provided in the light-receiving side of a solid-state image sensor, a solid-state image sensor, or a planarization layer.
　基材の湿式洗浄には、水、水系洗浄剤および非水系洗浄剤（例えば、アセトン、エタノール等）から選択される少なくとも１種を用いることができる。
　基材の湿式洗浄方法としては、水系洗浄剤または有機溶剤で基材を浸漬洗浄した後、基材を純水ですすいで乾燥する方法が好ましい。基材を浸漬洗浄する際には、超音波処理による洗浄を併用してもよい。
　浸漬洗浄する時間は、特に限定されないが、１分以上が好ましく、５分以上がより好ましく、８分以上がさらに好ましい。また浸漬洗浄する時間は、３０分以下が好ましい。
　基材を純水ですすぐ方法としては、例えば、基材を純水に浸漬させる方法、基材を流水洗浄する方法等が挙げられる。基材を純水ですすぐ時間は、１分以上が好ましく、２分以上がより好ましく、４分以上がさらに好ましい。すすぐ時間は、３０分以下が好ましい。
　基材を乾燥する方法としては、例えば、自然乾燥する方法や、窒素ガス等でブローする方法、スピンドライヤーで乾燥する方法、オーブン中で加熱乾燥する方法、真空乾燥する方法が挙げられる。
　基材を光洗浄する方法としては、例えば、紫外光、オゾン、または両者の組み合わせによる光洗浄の方法が挙げられる。 For the wet cleaning of the substrate, at least one selected from water, an aqueous cleaning agent and a non-aqueous cleaning agent (for example, acetone, ethanol, etc.) can be used.
As a wet cleaning method for the substrate, a method in which the substrate is immersed and washed with an aqueous cleaning agent or an organic solvent, and then the substrate is rinsed with pure water and dried. When the substrate is immersed and cleaned, cleaning by ultrasonic treatment may be used in combination.
The time for immersion cleaning is not particularly limited, but is preferably 1 minute or more, more preferably 5 minutes or more, and further preferably 8 minutes or more. The time for immersion cleaning is preferably 30 minutes or less.
Examples of the method of rinsing the substrate with pure water include a method of immersing the substrate in pure water and a method of washing the substrate with running water. The time for rinsing the substrate with pure water is preferably 1 minute or longer, more preferably 2 minutes or longer, and even more preferably 4 minutes or longer. The rinsing time is preferably 30 minutes or less.
Examples of the method for drying the substrate include a method for natural drying, a method for blowing with nitrogen gas, a method for drying with a spin dryer, a method for drying by heating in an oven, and a method for vacuum drying.
Examples of the method for photocleaning the substrate include a photocleaning method using ultraviolet light, ozone, or a combination of both.
　上記親水性化合物としては、ポリ（ビニルアルコール）、ポリ（ビニルピロリドン）、ポリ（エチレングリコール）等の親水性ポリマー；グリセリン、ペンタエリスリトール、ソルビトール等の多価アルコール；Ｈ－Ｓｉ（ＯＣＨ2ＣＨ3）3、ＮＨ2ＣＨ2ＣＨ2ＣＨ2－Ｓｉ（ＯＣＨ2ＣＨ3）3等のシラン化合物、または上記化合物の一部または全部が加水分解物された化合物、または上記化合物の加水分解縮合物が挙げられる。
　親水性化合物は、溶剤に溶解させた溶液として基材に適用することが好ましい。親水性ポリマーや多価アルコールは、水に溶解させることが好ましい。シラン化合物は、イソプロピルアルコール等のアルコール系溶剤に溶解させることが好ましい。溶液中の親水性化合物の濃度は、０．０１～１０質量％が好ましく、０．１～１質量％がより好ましい。
　親水性化合物の適用方法は特に限定されず、スピンコート法、ディップコート法、スプレー法、ロールコート法、メニスカスコート法、スクリーン印刷法等が採用できる。 Examples of the hydrophilic compound include hydrophilic polymers such as poly (vinyl alcohol), poly (vinyl pyrrolidone), and poly (ethylene glycol); polyhydric alcohols such as glycerin, pentaerythritol, and sorbitol; H—Si (OCH 2 CH 3 ) 3, NH 2 CH 2 CH 2 CH 2 -Si (OCH 2 CH 3) silane compounds such as 3, or a compound partially or wholly hydrolyzed product of the compound, or a hydrolyzed condensate of said compound Can be mentioned.
The hydrophilic compound is preferably applied to the substrate as a solution dissolved in a solvent. The hydrophilic polymer and polyhydric alcohol are preferably dissolved in water. The silane compound is preferably dissolved in an alcohol solvent such as isopropyl alcohol. The concentration of the hydrophilic compound in the solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 1% by mass.
The application method of the hydrophilic compound is not particularly limited, and spin coating, dip coating, spraying, roll coating, meniscus coating, screen printing, and the like can be employed.
　酸素プラズマアッシング処理を行う方法は、例えば、ドライエッチャー装置（Ｕ－６２１：日立ハイテクノロジーズ社製）を用いて、１Ｐａの圧力でＡｒガス（１０００ｍｌ／ｍｉｎ）、Ｏ2ガス（１０ｍｌ／ｍｉｎ）を流しながら、８００Ｗで１０分間処理することが好ましい。
　基材の表面を親水化処理することによって、親水性領域の表面の近赤外線吸収性組成物に対する接触角が０～４５°の範囲となるように調整することが好ましく、０～４０°の範囲となるように調整することがより好ましい。 A method for performing oxygen plasma ashing treatment is, for example, using a dry etcher (U-621: manufactured by Hitachi High-Technologies Corporation) to supply Ar gas (1000 ml / min) and O 2 gas (10 ml / min) at a pressure of 1 Pa. It is preferable to treat at 800 W for 10 minutes while flowing.
It is preferable to adjust the contact angle of the surface of the hydrophilic region with the near-infrared absorbing composition to be in the range of 0 to 45 ° by hydrophilizing the surface of the substrate, and in the range of 0 to 40 °. It is more preferable to adjust so that.
＜基材上に疎水性領域を形成する工程＞
　疎水性領域は、基材上の一定の範囲、通常は、基材表面または基材上に設けられた親水性領域の表面の一定の範囲を囲むように形成する。このように基材上の一定の範囲を囲むように疎水性領域で囲むことによって、近赤外線吸収性組成物が適用される範囲を制御することができ、結果として、近赤外線カットフィルタの厚さを制御することができる。
　疎水性領域を形成する方法としては、特に限定されず公知の方法を採用できるが、パターニングにより形成する方法、表面が疎水性のテープを貼る方法、表面処理を行う方法が例示される。
　パターニングにより形成する方法は、基材上にレジスト組成物を適用しフォトリソグラフィーにより行うことが好ましい。より具体的には、基材上にレジスト組成物を適用し乾燥させてレジスト層を形成する工程と、上記レジスト層を露光、現像することにより、レジストパターン（パターニングされたレジスト層）を形成する工程を含むことが好ましい。
　レジスト組成物としては、公知のレジスト組成物を用いることができる。
　レジスト組成物を基材上に適用する量としては、レジスト層の厚さが１～１００μｍとなる量が好ましく、５～５０μｍとなる量がより好ましい。
　レジストパターンの形成は、特に制限なく、従来公知のフォトリソグラフィーの技術を用いることができる。レジスト層の露光は、所定のマスクパターンを介して、レジスト層に露光を施すことにより行なうことができる。露光は、例えば放射線の照射により行うことができる。露光に用いることができる放射線としては、特に、電子線、ＫｒＦ、ＡｒＦ、ｇ線、ｈ線、ｉ線等の紫外線や可視光が用いられる。露光方式としては。ステッパー露光、アライナー露光、高圧水銀灯による露光などが挙げられる。露光量は、１００～２０００ｍＪ／ｃｍ2が好ましく２００～１０００ｍＪ／ｃｍ2がより好ましい。
　現像に用いる現像液としては、例えば、種々の有機溶剤の組み合わせやアルカリ性の水溶液を用いることができる。 <Process for forming a hydrophobic region on a substrate>
The hydrophobic region is formed so as to surround a certain range on the substrate, usually a certain range of the surface of the substrate or the surface of the hydrophilic region provided on the substrate. Thus, by enclosing with a hydrophobic region so as to enclose a certain range on the substrate, it is possible to control the range to which the near-infrared absorbing composition is applied, and as a result, the thickness of the near-infrared cut filter Can be controlled.
The method of forming the hydrophobic region is not particularly limited, and a known method can be adopted. Examples of the method include a method of forming by patterning, a method of applying a tape having a hydrophobic surface, and a method of performing a surface treatment.
The method of forming by patterning is preferably performed by applying a resist composition on a substrate and performing photolithography. More specifically, a resist composition is applied onto a substrate and dried to form a resist layer, and the resist layer is exposed and developed to form a resist pattern (patterned resist layer). It is preferable to include a process.
A known resist composition can be used as the resist composition.
The amount of the resist composition to be applied on the substrate is preferably such that the thickness of the resist layer is 1 to 100 μm, more preferably 5 to 50 μm.
The formation of the resist pattern is not particularly limited, and a conventionally known photolithography technique can be used. The resist layer can be exposed by exposing the resist layer through a predetermined mask pattern. The exposure can be performed, for example, by irradiation with radiation. As the radiation that can be used for exposure, ultraviolet rays such as electron beams, KrF, ArF, g rays, h rays, i rays, and visible light are used. As an exposure method. Stepper exposure, aligner exposure, exposure with a high pressure mercury lamp, etc. are mentioned. Exposure is more preferably preferably 100 ~ 2000mJ / cm 2 200 ~ 1000mJ / cm 2.
As a developer used for development, for example, a combination of various organic solvents or an alkaline aqueous solution can be used.
　表面が疎水性のテープを貼る方法としては、例えば、基材上に高耐熱性樹脂からなるテープを用いる方法が挙げられる。耐熱性樹脂は、例えば、ポリアミド樹脂、エポキシ樹脂、ポリイミド樹脂およびポリエチレン樹脂から選択される少なくとも１種を含むことが好ましく、ポリイミド樹脂を含むことがより好ましい。表面が疎水性のテープの市販品としては、例えば、カプトンテープ（登録商標、寺岡製作所製）が挙げられる。
　また、表面処理の方法としては、ヘキサメチルジシラザン（ＨＭＤＳ）等のシリル化剤で表面処理を行う方法が挙げられる。
　本発明では、疎水性領域の表面の近赤外線吸収性組成物に対する接触角が６０°以上となるように調整することが好ましく、７０°以上に調整することがより好ましい。また、上記接触角が１８０°以下となるように調整することが好ましく、１５０°以下に調整することがより好ましい。特に、上記接触角が６０～１８０°の範囲となるように調整することが好ましく、７０～１５０°の範囲となるように調整することがより好ましい。 Examples of the method for applying a tape having a hydrophobic surface include a method using a tape made of a high heat resistant resin on a substrate. The heat resistant resin preferably includes, for example, at least one selected from a polyamide resin, an epoxy resin, a polyimide resin, and a polyethylene resin, and more preferably includes a polyimide resin. Examples of commercially available tapes having a hydrophobic surface include Kapton tape (registered trademark, manufactured by Teraoka Seisakusho).
Examples of the surface treatment method include a surface treatment method using a silylating agent such as hexamethyldisilazane (HMDS).
In this invention, it is preferable to adjust so that the contact angle with respect to the near-infrared absorptive composition of the surface of a hydrophobic region may be 60 degrees or more, and it is more preferable to adjust to 70 degrees or more. Moreover, it is preferable to adjust so that the said contact angle may be 180 degrees or less, and it is more preferable to adjust to 150 degrees or less. In particular, the contact angle is preferably adjusted to be in the range of 60 to 180 °, and more preferably adjusted to be in the range of 70 to 150 °.
　本発明では、基材上に親水性領域および疎水性領域を形成することが好ましく、特に、基材表面に親水性領域を形成し、形成した親水性領域を囲む疎水性領域を形成することがより好ましい。これにより、基材表面の濡れ性を制御するとともに、基材上に形成される膜の厚さを制御することができ、結果として、基材上により均一な厚さの膜を形成することができる。
　本発明では、基材上に疎水性領域のみを形成してもよい。この場合、疎水性領域で囲まれた領域、すなわち、基材の表面の近赤外線吸収性組成物に対する接触角が０～４５°の範囲となるような近赤外線吸収性組成物を適用することが好ましい。例えば、組成物中に添加剤として界面活性剤や低級アルコールを、組成物の全固形物に対して０．０１重量部～１０重量部加えることが好ましい。 In the present invention, it is preferable to form a hydrophilic region and a hydrophobic region on the substrate, and in particular, it is possible to form a hydrophilic region on the substrate surface and form a hydrophobic region surrounding the formed hydrophilic region. More preferred. As a result, the wettability of the substrate surface can be controlled and the thickness of the film formed on the substrate can be controlled. As a result, a film having a more uniform thickness can be formed on the substrate. it can.
In the present invention, only the hydrophobic region may be formed on the substrate. In this case, it is possible to apply a near-infrared absorbing composition in which the contact angle with respect to the near-infrared absorbing composition on the surface of the substrate, that is, the surface of the substrate is in the range of 0 to 45 °. preferable. For example, it is preferable to add 0.01 parts by weight to 10 parts by weight of a surfactant or a lower alcohol as an additive in the composition with respect to the total solids of the composition.
＜＜親水性領域の表面に、および／または、疎水性領域で囲まれた領域内に、近赤外線吸収性組成物を適用する工程＞＞
　適用する近赤外線吸収性組成物の量は、特に限定されないが、近赤外線吸収性組成物を乾燥した後の膜厚が５０μｍ以上となる量が好ましく、１５０μｍ以上となる量がより好ましい。また、３００μｍ以下となる量が好ましく、２５０μｍ以下となる量がより好ましい。特に、５０～３００μｍとなる量が好ましく、１５０～２５０μｍとなる量がより好ましい。
　適用する近赤外線吸収性組成物の量は、例えば、４０μｌ／ｃｍ2以上が好ましく、２５０μｌ／ｃｍ2以下が好ましい。特に、４０～２５０μｌ／ｃｍ2であることが好ましい。
　近赤外線吸収性組成物中の固形分濃度は、５０質量％以下が好ましく、３０質量％以下がより好ましい。また、固形分濃度は、２質量％以上が好ましく、５質量％以上がより好ましく、１０質量％以上がさらに好ましい。特に、固形分濃度が２～５０質量％であることが好ましく、５～３０質量％であることがより好ましい。
　適用方法としては、塗布や印刷が挙げられる。具体的には、ドロップキャスト、ディップコート、スリットコート、スクリーン印刷、スプレーコートおよびスピンコートから選択される少なくとも１つであることが好ましく、ドロップキャストがより好ましい。 << The process of applying a near-infrared absorptive composition in the surface of a hydrophilic region and / or in a region surrounded by a hydrophobic region >>
Although the quantity of the near-infrared absorptive composition to apply is not specifically limited, The quantity from which the film thickness after drying a near-infrared absorptive composition becomes 50 micrometers or more is preferable, and the quantity from which it becomes 150 micrometers or more is more preferable. Moreover, the quantity used as 300 micrometers or less is preferable, and the quantity used as 250 micrometers or less is more preferable. In particular, an amount of 50 to 300 μm is preferable, and an amount of 150 to 250 μm is more preferable.
The amount of the near-infrared absorbing composition to be applied is, for example, preferably 40 μl / cm 2 or more, and preferably 250 μl / cm 2 or less. In particular, it is preferably 40 to 250 μl / cm 2 .
The solid content concentration in the near-infrared absorbing composition is preferably 50% by mass or less, and more preferably 30% by mass or less. Moreover, 2 mass% or more is preferable, as for solid content concentration, 5 mass% or more is more preferable, and 10 mass% or more is further more preferable. In particular, the solid content concentration is preferably 2 to 50% by mass, and more preferably 5 to 30% by mass.
Application methods include coating and printing. Specifically, at least one selected from drop casting, dip coating, slit coating, screen printing, spray coating, and spin coating is preferable, and drop casting is more preferable.
　本発明の近赤外線カットフィルタの製造工程の一例について、図１を参照しながら説明する。
　まず、（Ａ）に示すように、基材１の表面に親水性領域２を形成し、さらに、親水性領域２を囲むように疎水性領域３を形成する。次いで、（Ｂ）に示すように、疎水性領域３で囲まれた親水性領域２の表面に、近赤外線吸収性組成物４をドロップキャストする。これにより、（Ｃ）に示すように、基材１上の親水性領域２の表面に均一な膜（近赤外線吸収性組成物４を用いた近赤外線カットフィルタ）を形成することができる。 An example of the manufacturing process of the near infrared cut filter of the present invention will be described with reference to FIG.
First, as shown to (A), the hydrophilic region 2 is formed in the surface of the base material 1, and also the hydrophobic region 3 is formed so that the hydrophilic region 2 may be enclosed. Next, as shown in (B), the near-infrared absorbing composition 4 is drop-cast on the surface of the hydrophilic region 2 surrounded by the hydrophobic region 3. Thereby, as shown to (C), a uniform film | membrane (near-infrared cut filter using the near-infrared absorptive composition 4) can be formed in the surface of the hydrophilic region 2 on the base material 1. FIG.
　また、本発明の近赤外線カットフィルタの製造工程の他の例について、図２を参照しながら説明する。まず、（Ａ）に示すように、基材１の表面に親水性領域を形成し、親水性領域の表面にレジスト組成物５を適用する。次いで、（Ｂ）に示すように、レジスト組成物５をリソグラフィーによりパターニングし、レジストパターン５Ａを形成する。その結果、レジストパターン５Ａ（疎水性領域）で囲まれた親水性領域が形成される。次いで、（Ｃ）に示すように、レジストパターン５Ａで囲まれた親水性領域に、近赤外線吸収性組成物４を適用する。次いで、（Ｄ）に示すように、レジストパターン５Ａを除去することにより、基材１上に均一な膜（近赤外線吸収性組成物４を用いた近赤外線カットフィルタ）を形成することができる。なお、レジストパターン５Ａが存在した領域を切断領域とすることで、近赤外線カットフィルタの剥がれなどを生じさせずに、近赤外線カットフィルタを製造することができる。 Further, another example of the manufacturing process of the near infrared cut filter of the present invention will be described with reference to FIG. First, as shown to (A), a hydrophilic area | region is formed in the surface of the base material 1, and the resist composition 5 is applied to the surface of a hydrophilic area | region. Next, as shown in (B), the resist composition 5 is patterned by lithography to form a resist pattern 5A. As a result, a hydrophilic region surrounded by the resist pattern 5A (hydrophobic region) is formed. Next, as shown in (C), the near-infrared absorbing composition 4 is applied to the hydrophilic region surrounded by the resist pattern 5A. Next, as shown in (D), a uniform film (a near-infrared cut filter using the near-infrared absorbing composition 4) can be formed on the substrate 1 by removing the resist pattern 5A. In addition, the near-infrared cut filter can be manufactured without causing the near-infrared cut filter to peel off by setting the region where the resist pattern 5A is present as the cut region.
＜＜その他の工程＞＞
　本発明の近赤外線カットフィルタの製造方法は、上述した以外の他の工程をさらに有していてもよい。本発明では、基材上に適用した近赤外線吸収性組成物を乾燥する工程を有することが好ましい。
　乾燥方法としては、室温で放置して乾燥する方法や、加熱により乾燥する方法が挙げられる。
　室温で放置して乾燥する場合、乾燥時間は特に限定されないが、例えば６時間以上が好ましく、１２時間以上が好ましく、１８時間以上がさらに好ましい。
　加熱により乾燥する方法は、特に限定されないが、後述するように、近赤外線吸収性組成物が水と上記極性液体を含む場合、基材上に適用した近赤外線吸収性組成物を連続的に加熱する方法や、１００℃以下の温度および１００℃を超える温度の少なくとも２段階の温度で加熱する方法が好ましい。連続的とは、近赤外線吸収性組成物を一定の時間、昇温させ続けることをいう。
　加熱開始時の加熱温度は、４０℃以上が好ましく、５０℃以上がより好ましく、６０℃以上がさらに好ましい。加熱終了時は、２００℃以下が好ましく、１８０℃以下がより好ましく、１４０℃以下がさらに好ましい。加熱する時間は、２０～２００分が好ましく、３０～１００分がより好ましく、４０～８０分がさらに好ましい。加熱は、１～２０℃／分で昇温することが好ましい。
　１００℃以下および１００℃を超える温度の少なくとも２段階で加熱する場合、１００℃以下（好ましくは９５℃以下、より好ましくは９０℃以下、さらに好ましくは８５℃以下）および１００℃を超える温度（好ましくは１０５℃以上、より好ましくは１１０℃以上、さらに好ましくは１１５℃以上）のそれぞれで、少なくとも１段階ずつ加熱すればよく、１００℃以下および１００℃を超える温度のそれぞれで、２段階以上加熱することが好ましい。１００℃以下の温度で２段階加熱する場合、その温度差は、１０℃以上が好ましく、１５℃以上がより好ましく、２０℃以上がさらに好ましい。温度差の上限としては、例えば、４０℃以下とすることができる。１００℃を超える温度で２段階以上で加熱する場合、それぞれの温度差は、１０℃以上が好ましく、１５℃以上がより好ましく、２０℃以上がさらに好ましい。温度差の上限としては、例えば、４０℃以下とすることができる。本発明の加熱条件の一実施形態として、５０～７０℃の範囲で加熱し、次いで、７０～９０℃の範囲で加熱し、次いで、９０～１１０℃の範囲で加熱し、次いで、１１０～１３０℃の範囲で加熱し、次いで、１３０～１５０℃の範囲で加熱することが挙げられる。
　それぞれの温度で加熱する時間は、それぞれ、１～４０分が好ましく、５～３０分がより好ましく、５～１５分がさらに好ましい。
　加熱装置としては、特に制限はなく、公知の装置の中から、目的に応じて適宜選択することができ、例えば、ドライオーブン、ホットプレート、ＩＲヒーターなどが挙げられる。 << Other processes >>
The manufacturing method of the near-infrared cut filter of this invention may have further processes other than having mentioned above. In this invention, it is preferable to have the process of drying the near-infrared absorptive composition applied on the base material.
Examples of the drying method include a method of drying at room temperature and a method of drying by heating.
In the case of drying at room temperature, the drying time is not particularly limited, but is preferably 6 hours or longer, preferably 12 hours or longer, and more preferably 18 hours or longer.
Although the method of drying by heating is not particularly limited, as described later, when the near-infrared absorbing composition contains water and the polar liquid, the near-infrared absorbing composition applied on the substrate is continuously heated. And a method of heating at a temperature of at least two stages of a temperature of 100 ° C. or lower and a temperature exceeding 100 ° C. is preferable. The term “continuous” means that the near-infrared absorbing composition is continuously heated for a certain time.
The heating temperature at the start of heating is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 60 ° C. or higher. At the end of heating, 200 ° C. or lower is preferable, 180 ° C. or lower is more preferable, and 140 ° C. or lower is further preferable. The heating time is preferably 20 to 200 minutes, more preferably 30 to 100 minutes, and further preferably 40 to 80 minutes. The heating is preferably performed at a temperature of 1 to 20 ° C./min.
When heating in at least two stages of 100 ° C. or less and a temperature exceeding 100 ° C., the temperature is preferably 100 ° C. or less (preferably 95 ° C. or less, more preferably 90 ° C. or less, more preferably 85 ° C. or less) and a temperature exceeding 100 ° C. Is at least 105 ° C., more preferably at least 110 ° C., and even more preferably at least 115 ° C., and at least two steps at temperatures of 100 ° C. or less and over 100 ° C. It is preferable. When heating in two steps at a temperature of 100 ° C. or lower, the temperature difference is preferably 10 ° C. or higher, more preferably 15 ° C. or higher, and even more preferably 20 ° C. or higher. As an upper limit of a temperature difference, it can be 40 degrees C or less, for example. When heating at a temperature exceeding 100 ° C. in two or more steps, the temperature difference is preferably 10 ° C. or more, more preferably 15 ° C. or more, and further preferably 20 ° C. or more. As an upper limit of a temperature difference, it can be 40 degrees C or less, for example. As one embodiment of the heating conditions of the present invention, heating is performed in the range of 50 to 70 ° C., then heating is performed in the range of 70 to 90 ° C., heating is performed in the range of 90 to 110 ° C., and then 110 to 130 is performed. Heating in the range of ° C., followed by heating in the range of 130 to 150 ° C. can be mentioned.
The heating time at each temperature is preferably 1 to 40 minutes, more preferably 5 to 30 minutes, and further preferably 5 to 15 minutes.
There is no restriction | limiting in particular as a heating apparatus, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.
　本発明の近赤外線カットフィルタの製造方法は、前加熱工程（プリベーク工程）、硬化処理工程、後加熱工程（ポストベーク工程）等をさらに有していてもよい。
　前加熱工程および後加熱工程における加熱温度は、通常、８０℃～２００℃であり、９０℃～１８０℃であることが好ましい。
　前加熱工程および後加熱工程における加熱時間は、通常、３０秒～４００秒であり、６０秒～３００秒であることが好ましい。
　硬化処理工程は、必要に応じ、形成された上記膜に対して硬化処理を行う工程であり、この処理を行うことにより、近赤外線カットフィルタの機械的強度が向上する。
　上記硬化処理工程としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、全面露光処理、全面加熱処理などが好適に挙げられる。ここで、本発明において「露光」とは、各種波長の光のみならず、電子線、Ｘ線などの放射線照射をも包含する意味で用いられる。
　露光は放射線の照射により行うことが好ましく、露光に際して用いることができる放射線としては、特に、電子線、ＫｒＦ、ＡｒＦ、ｇ線、ｈ線、ｉ線等の紫外線や可視光が好ましく用いられる。好ましくは、ＫｒＦ、ｇ線、ｈ線、ｉ線が好ましい。
　露光方式としては。ステッパー露光、アライナー露光、高圧水銀灯による露光などが挙げられる。
　露光量は５～３０００ｍＪ／ｃｍ2が好ましく１０～２０００ｍＪ／ｃｍ2がより好ましく、１００～１０００ｍＪ／ｃｍ2が特に好ましい。
　全面露光処理の方法としては、例えば、形成された上記膜の全面を露光する方法が挙げられる。硬化性組成物が重合性化合物を含む場合、全面露光により、上記組成物より形成される膜中の重合成分の硬化が促進され、上記膜の硬化が更に進行し、機械的強度、耐久性が改良される。
　上記全面露光を行う装置としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、超高圧水銀灯などのＵＶ露光機が好適に挙げられる。 The manufacturing method of the near-infrared cut filter of this invention may have further a preheating process (prebaking process), a hardening process, a post-heating process (post-baking process), etc.
The heating temperature in the preheating step and the postheating step is usually 80 ° C. to 200 ° C., preferably 90 ° C. to 180 ° C.
The heating time in the preheating step and the postheating step is usually 30 seconds to 400 seconds, and preferably 60 seconds to 300 seconds.
The curing process is a process of curing the formed film as necessary, and the mechanical strength of the near-infrared cut filter is improved by performing this process.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably. Here, in the present invention, “exposure” is used to include not only light of various wavelengths but also irradiation of radiation such as electron beams and X-rays.
The exposure is preferably performed by irradiation of radiation, and as the radiation that can be used for the exposure, ultraviolet rays such as electron beams, KrF, ArF, g rays, h rays, i rays and visible light are particularly preferably used. Preferably, KrF, g line, h line, and i line are preferable.
As an exposure method. Stepper exposure, aligner exposure, exposure with a high pressure mercury lamp, etc. are mentioned.
Exposure is more preferably 5 ~ 3000mJ / cm 2 is preferably 10 ~ 2000mJ / cm 2, particularly preferably 100 ~ 1000mJ / cm 2.
Examples of the entire surface exposure processing method include a method of exposing the entire surface of the formed film. When the curable composition contains a polymerizable compound, the entire surface exposure promotes the curing of the polymerization components in the film formed from the composition, the film is further cured, and the mechanical strength and durability are increased. Improved.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.
＜近赤外線吸収性組成物＞
　本発明に用いられる近赤外線吸収性組成物は、近赤外線吸収物質を少なくとも含み、さらに、水および沸点が１００℃より高い極性液体等を含んでいることが好ましい。
＜＜近赤外線吸収物質＞＞
　本発明に用いられる近赤外線吸収物質は、好ましくは、極大吸収波長領域が７００～１０００ｎｍであり、より好ましくは８００～９００ｎｍの物質であることが好ましい。近赤外線吸収性物質は、１種類のみを含んでいてもよいし、２種類以上を含んでいてもよい。
　近赤外線吸収物質のモル吸光係数εは、好ましくは５０，０００～５００，０００であり、より好ましくは１００，０００～３００，０００である。 <Near-infrared absorbing composition>
The near-infrared absorbing composition used in the present invention preferably contains at least a near-infrared absorbing substance, and further contains water, a polar liquid having a boiling point higher than 100 ° C., and the like.
<< Near-infrared absorbing material >>
The near-infrared absorbing material used in the present invention is preferably a material having a maximum absorption wavelength region of 700 to 1000 nm, more preferably 800 to 900 nm. The near-infrared absorbing material may contain only one type or two or more types.
The molar extinction coefficient ε of the near-infrared absorbing material is preferably 50,000 to 500,000, and more preferably 100,000 to 300,000.
　近赤外線吸収物質としては、例えば、銅化合物、ピロロピロール系色素化合物、シアニン系色素化合物、フタロシアニン系化合物、イモニウム系化合物、チオール錯体系化合物、遷移金属酸化物系化合物、スクアリリウム系色素化合物、ナフタロシアニン系色素化合物、クオタリレン系色素化合物、ジチオール金属錯体系色素化合物、クロコニウム化合物等が挙げられ、銅化合物が好ましく、銅錯体がより好ましい。銅錯体は、低分子であってもよいが、ポリマータイプの銅錯体がより好ましい。 Examples of near-infrared absorbing substances include copper compounds, pyrrolopyrrole dye compounds, cyanine dye compounds, phthalocyanine compounds, imonium compounds, thiol complex compounds, transition metal oxide compounds, squarylium dye compounds, and naphthalocyanine. Dye compounds, quaterrylene dye compounds, dithiol metal complex dye compounds, croconium compounds and the like, copper compounds are preferred, and copper complexes are more preferred. The copper complex may be a low molecule, but a polymer type copper complex is more preferable.
　銅化合物が銅錯体である場合、銅に配位する配位子Ｌとしては、例えば、スルホン酸、カルボン酸、リン酸、リン酸エステル、ホスホン酸、ホスホン酸エステル、ホスフィン酸、置換ホスフィン酸、カルボニル（エステル、ケトン）、アミン、アミド、スルホンアミド、ウレタン、ウレア、アルコール、チオールなどを有する化合物が挙げられる。これらの中でも、カルボン酸及びスルホン酸が好ましく、スルホン酸がより好ましい。
　リン含有銅化合物（好ましくはリン酸銅錯体）として具体的には、例えば、ＷＯ２００５／０３０８９８号公報の第５頁第２７行目～第７頁第２０行目に記載された化合物を参酌することができ、これらの内容は本願明細書に組み込まれる。 When the copper compound is a copper complex, examples of the ligand L coordinated to copper include sulfonic acid, carboxylic acid, phosphoric acid, phosphoric ester, phosphonic acid, phosphonic ester, phosphinic acid, substituted phosphinic acid, Examples include compounds having carbonyl (ester, ketone), amine, amide, sulfonamide, urethane, urea, alcohol, thiol and the like. Among these, carboxylic acid and sulfonic acid are preferable, and sulfonic acid is more preferable.
Specific examples of the phosphorus-containing copper compound (preferably a copper phosphate complex) include, for example, the compounds described on page 27, line 27 to page 7, line 20 of WO2005 / 030898. The contents of which are incorporated herein by reference.
＜＜＜低分子銅化合物＞＞＞
　銅化合物としては、例えば、下記式で表される銅錯体が挙げられる。
　Ｃｕ（Ｌ）n1・（Ｘ）n2
　上記式中、Ｌは、銅に配位する配位子を表し、Ｘは、存在しないか、ハロゲン原子、Ｈ2Ｏ、ＮＯ3、ＣｌＯ4、ＳＯ4、ＣＮ、ＳＣＮ、ＢＦ4、ＰＦ6、ＢＰｈ4（Ｐｈはフェニル基を表す）又はアルコールを表す。ｎ１、ｎ２は、各々独立に１～４の整数を表す。
　配位子Ｌは、銅に対しアニオンで配位する配位部位、および、銅に対し非共有電子対で配位する配位部位から選ばれる１種以上を有する基である。例えば、銅に配位可能な原子としてＣ、Ｎ、Ｏ、Ｓを含む置換基を有するものであり、さらに好ましくはＮやＯ、Ｓなどの孤立電子対を持つ基を有するものである。配位可能な基は分子内に１種類に限定されず、２種以上を含んでも良く、解離しても非解離でも良い。好ましい配位子Ｌとしては、上述した配位子Ｌと同義であり、好ましい範囲も同義である。非解離の場合、Ｘは存在しない。
　銅錯体は、例えば銅成分に対して、配位子となる化合物またはその塩を混合・反応等させることによって得られる。
　銅成分は、銅または銅を含む化合物（銅化合物）を用いることができ、２価の銅を含む化合物が好ましい。銅化合物は、銅錯体を含むものが好ましい。銅の含有量を増やすことで、近赤外線遮蔽性が向上することから、近赤外線吸収性組成物の全固形分に対して、銅を元素基準で１０質量％以上が好ましく、２０質量％以上が好ましく、３０質量％以上がさらに好ましい。上限は特にないが、７０質量％以下が好ましく、６０質量％以下がさらに好ましい。銅成分は、１種のみを用いてもよいし、２種以上を用いてもよい。
　銅成分としては、例えば、酸化銅や銅塩を用いることができる。銅塩は、例えば、カルボン酸銅（例えば、酢酸銅、エチルアセト酢酸銅、ギ酸銅、安息香酸銅、ステアリン酸銅、ナフテン酸銅、クエン酸銅、２－エチルヘキサン酸銅など）、スルホン酸銅（例えば、メタンスルホン酸銅など）、リン酸銅、リン酸エステル銅、ホスホン酸銅、ホスホン酸エステル銅、ホスフィン酸銅、アミド銅、スルホンアミド銅、イミド銅、アシルスルホンイミド銅、ビススルホンイミド銅、メチド銅、アルコキシ銅、フェノキシ銅、水酸化銅、炭酸銅、硫酸銅、硝酸銅、過塩素酸銅、塩化銅、臭化銅、（メタ）アクリル酸銅、塩素酸銅、が好ましく、カルボン酸銅、スルホン酸銅、スルホンアミド銅、イミド銅、アシルスルホンイミド銅、ビススルホンイミド銅、アルコキシ銅、フェノキシ銅、水酸化銅、炭酸銅、塩化銅、硫酸銅がより好ましく、カルボン酸銅、アシルスルホンイミド銅、フェノキシ銅、塩化銅が更に好ましく、カルボン酸銅、アシルスルホンイミド銅が特に好ましい。 <<< Low molecular copper compound >>>
As a copper compound, the copper complex represented by a following formula is mentioned, for example.
Cu (L) n1・ (X) n2
In the above formula, L represents a ligand coordinated to copper, and X does not exist or is a halogen atom, H 2 O, NO 3 , ClO 4 , SO 4 , CN, SCN, BF 4 , or PF 6. , BPh 4 (Ph represents a phenyl group) or alcohol. n1 and n2 each independently represents an integer of 1 to 4.
The ligand L is a group having at least one selected from a coordination site coordinated to copper with an anion and a coordination site coordinated to copper with an unshared electron pair. For example, it has a substituent containing C, N, O, S as an atom capable of coordinating to copper, and more preferably has a group having a lone pair of electrons such as N, O, S. The group capable of coordinating is not limited to one type in the molecule and may include two or more types, and may be dissociated or non-dissociated. The preferred ligand L has the same meaning as the ligand L described above, and the preferred range is also the same. In the case of non-dissociation, X is not present.
A copper complex is obtained by, for example, mixing and reacting a compound serving as a ligand or a salt thereof with a copper component.
As the copper component, copper or a compound containing copper (copper compound) can be used, and a compound containing divalent copper is preferable. The copper compound preferably contains a copper complex. By increasing the copper content, the near-infrared shielding properties are improved, and therefore, copper is preferably 10% by mass or more, and 20% by mass or more based on the elemental basis with respect to the total solid content of the near-infrared absorbing composition. Preferably, 30 mass% or more is more preferable. Although there is no upper limit in particular, 70 mass% or less is preferable and 60 mass% or less is more preferable. A copper component may use only 1 type and may use 2 or more types.
As the copper component, for example, copper oxide or copper salt can be used. Examples of the copper salt include copper carboxylate (eg, copper acetate, copper ethyl acetoacetate, copper formate, copper benzoate, copper stearate, copper naphthenate, copper citrate, copper 2-ethylhexanoate), copper sulfonate (For example, copper methanesulfonate), copper phosphate, phosphate copper, phosphonate copper, phosphonate copper, phosphinate, amide copper, sulfonamido copper, imide copper, acylsulfonimide copper, bissulfonimide Copper, methide copper, alkoxy copper, phenoxy copper, copper hydroxide, copper carbonate, copper sulfate, copper nitrate, copper perchlorate, copper chloride, copper bromide, copper (meth) acrylate, copper chlorate are preferred, Carboxylic acid copper, sulfonic acid copper, sulfonamide copper, imide copper, acylsulfonimide copper, bissulfonimide copper, alkoxy copper, phenoxy copper, copper hydroxide, copper carbonate, chloride , More preferably copper sulfate, copper carboxylate, acyl sulfonimide copper, phenoxy copper, more preferably copper chloride, copper carboxylate, acyl sulfonimide copper is particularly preferred.
　配位子となる化合物またはその塩としては、特に限定されないが、下記一般式（ｉ）で表される化合物が好ましい。
Ｒ100－（Ｘ100）n3　　　・・・（ｉ）
　一般式（ｉ）中、Ｘ100は配位部位を表し、ｎ３は１～６の整数を表し、Ｒ100は単結合またはｎ価の基を表す。
　一般式（ｉ）中、Ｘ100は、アニオンで配位する配位部位（例えば酸基またはその塩）および非共有電子対で配位する部位から選ばれる１種以上であることが好ましく、アニオンで配位する配位部位を１種以上含むことが好ましい。 Although it does not specifically limit as a compound used as a ligand or its salt, The compound represented with the following general formula (i) is preferable.
R 100- (X 100 ) n3 (i)
In the general formula (i), X 100 represents a coordination site, n3 represents an integer of 1 ~ 6, R 100 represents a single bond or n-valent group.
In general formula (i), X 100 is preferably at least one selected from a coordination site coordinated by an anion (for example, an acid group or a salt thereof) and a site coordinated by an unshared electron pair, It is preferable that one or more coordination sites coordinated with each other are included.
　上記アニオンは、銅成分中の銅原子に配位可能なアニオンを含むものであればよく、例えば、酸素アニオン、窒素アニオンまたは硫黄アニオンを含むことが好ましい。
　アニオンで配位する配位部位は、例えば、下記群（ＡＮ）から選択される少なくとも１種であることが好ましい。 The said anion should just contain the anion which can be coordinated to the copper atom in a copper component, for example, it is preferable that an oxygen anion, a nitrogen anion, or a sulfur anion is included.
The coordination site coordinated by an anion is preferably at least one selected from the following group (AN), for example.
群（ＡＮ）
Figure JPOXMLDOC01-appb-C000001
 Group (AN)
Figure JPOXMLDOC01-appb-C000001
　群（ＡＮ）中、Ｘは、ＮまたはＣＲを表し、Ｒは、それぞれ独立して水素原子、アルキル基、アルケニル基、アルキニル基、アリール基またはヘテロアリール基を表す。
　Ｒが表すアルキル基は、直鎖状、分岐状または環状であってもよいが、直鎖状が好ましい。アルキル基の炭素数は、１～１０が好ましく、１～６がより好ましく、１～４がさらに好ましい。アルキル基の例としては、メチル基が挙げられる。アルキル基は置換基を有していてもよく、置換基としてはハロゲン原子、カルボン酸基、ヘテロ環基が挙げられる。置換基としてのヘテロ環基は、単環であっても多環であってもよく、また、芳香族であっても非芳香族であってもよい。ヘテロ環を構成するヘテロ原子の数は１～３が好ましく、１または２が好ましい。ヘテロ環を構成するヘテロ原子は、窒素原子が好ましい。アルキル基が置換基を有している場合、さらに置換基を有していてもよい。
　Ｒが表すアルキニル基の炭素数は、１～１０が好ましく、１～６がより好ましい。
　Ｒが表すアリール基は、単環であっても多環であってもよいが単環が好ましい。アリール基の炭素数は６～１８が好ましく、６～１２がより好ましく、６がさらに好ましい。
　Ｒが表すヘテロアリール基は、単環であっても多環であってもよい。ヘテロアリール基を構成するヘテロ原子の数は１～３が好ましい。ヘテロアリール基を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。ヘテロアリール基の炭素数は６～１８が好ましく、６～１２がより好ましい。 In the group (AN), X represents N or CR, and each R independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
The alkyl group represented by R may be linear, branched or cyclic, but is preferably linear. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group. The alkyl group may have a substituent, and examples of the substituent include a halogen atom, a carboxylic acid group, and a heterocyclic group. The heterocyclic group as a substituent may be monocyclic or polycyclic, and may be aromatic or non-aromatic. The number of heteroatoms constituting the heterocycle is preferably 1 to 3, and preferably 1 or 2. The hetero atom constituting the hetero ring is preferably a nitrogen atom. When the alkyl group has a substituent, it may further have a substituent.
The alkynyl group represented by R preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
The aryl group represented by R may be monocyclic or polycyclic, but is preferably monocyclic. The aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 carbon atoms.
The heteroaryl group represented by R may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms.
　アニオンで配位する配位部位の例として、モノアニオン性配位部位も挙げられる。モノアニオン性配位部位は、１つの負電荷を有する官能基を介して銅原子と配位する部位を表す。例えば、酸解離定数（ｐＫａ）が１２以下の酸基が挙げられる。具体的には、リン原子を含有する酸基（リン酸ジエステル基、ホスホン酸モノエステル基、ホスフィン酸基等）、スルホン酸基、カルボン酸基、イミド酸基等が挙げられ、スルホン酸基、カルボン酸基が好ましく、カルボン酸基がより好ましい。 Examples of coordination sites coordinated by anions also include monoanionic coordination sites. A monoanionic coordination site | part represents the site | part coordinated with a copper atom through the functional group which has one negative charge. For example, an acid group having an acid dissociation constant (pKa) of 12 or less can be mentioned. Specific examples include an acid group containing a phosphorus atom (phosphoric acid diester group, phosphonic acid monoester group, phosphinic acid group, etc.), a sulfonic acid group, a carboxylic acid group, an imido acid group, and the like. Carboxylic acid groups are preferred, and carboxylic acid groups are more preferred.
　非共有電子対で配位する配位原子は、酸素原子、窒素原子、硫黄原子またはリン原子を含むことが好ましく、酸素原子、窒素原子または硫黄原子を含むことがより好ましく、窒素原子を含むことがさらに好ましい。また、非共有電子対で配位する配位原子が窒素原子であり、かかる窒素原子に隣接する原子が炭素原子である態様が好ましく、かかる炭素原子が置換基を有することも好ましい。このような構成とすることにより、銅錯体の構造がより歪みやすくなるため、色価をより向上させることができる。置換基は、炭素数１～１０のアルキル基、炭素数６～１２のアリール基、カルボン酸基、炭素数１～１２のアルコキシ基、炭素数２～１２のアシル基、炭素数１～１２のアルキルチオ基、ハロゲン原子が好ましい。
　非共有電子対で配位する配位原子は、環に含まれていてもよいし、以下の群（ＵＥ）から選択される少なくとも１種の部分構造に含まれていてもよい。 The coordination atom coordinated by the lone pair preferably contains an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, more preferably contains an oxygen atom, a nitrogen atom or a sulfur atom, and contains a nitrogen atom. Is more preferable. Moreover, the aspect in which the coordinating atom coordinated by a lone pair is a nitrogen atom, and the atom adjacent to this nitrogen atom is a carbon atom, and it is also preferable that this carbon atom has a substituent. By setting it as such a structure, since the structure of a copper complex becomes easier to distort, color value can be improved more. The substituent includes an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a carboxylic acid group, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms. An alkylthio group and a halogen atom are preferred.
The coordinating atom coordinated by the lone pair may be contained in the ring, or may be contained in at least one partial structure selected from the following group (UE).
群（ＵＥ）
Figure JPOXMLDOC01-appb-C000002
 Group (UE)
Figure JPOXMLDOC01-appb-C000002
　群（ＵＥ）中、Ｒ1は、それぞれ独立して水素原子、アルキル基、アルケニル基、アルキニル基、アリール基またはヘテロアリール基を表し、Ｒ2は、それぞれ独立して水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオ基、アリールチオ基、ヘテロアリールチオ基、アミノ基またはアシル基を表す。 In the group (UE), each R 1 independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and each R 2 independently represents a hydrogen atom, an alkyl group, or an alkenyl group. Represents a group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, amino group or acyl group.
　Ｒ1が表すアルキル基は、群（ＡＮ）中のＲで説明したアルキル基と同義であり、好ましい範囲も同様である。
　Ｒ1が表すアルケニル基の炭素数は、１～１０が好ましく、１～６がより好ましい。
　Ｒ1が表すアルキニル基の炭素数は、１～１０が好ましく、１～６がより好ましい。
　Ｒ1が表すヘテロアリール基は、群（ＡＮ）中のＲで説明したヘテロアリール基と同義であり、好ましい範囲も同様である。 The alkyl group represented by R 1 has the same meaning as the alkyl group described for R in the group (AN), and the preferred range is also the same.
The alkenyl group represented by R 1 preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
The number of carbon atoms of the alkynyl group represented by R 1 is preferably 1 to 10, 1 to 6 is more preferred.
The heteroaryl group represented by R 1 has the same meaning as the heteroaryl group described for R in the group (AN), and the preferred range is also the same.
　Ｒ2が表すアルキル基は、群（ＵＥ）中のＲ1で説明したアルキル基と同義であり、好ましい範囲も同様である。
　Ｒ2が表すアルケニル基の炭素数は、１～１０が好ましく、１～６がより好ましい。
　Ｒ2が表すアルキニル基の炭素数は、１～１０が好ましく、１～６がより好ましい。
　Ｒ2が表すアリール基は、群（ＵＥ）中のＲ1で説明したアリール基と同義であり、好ましい範囲も同様である。
　Ｒ2が表すヘテロアリール基は、群（ＵＥ）中のＲ1で説明したヘテロアリール基と同義であり、好ましい範囲も同様である。
　Ｒ2が表すアルコキシ基の炭素数は、１～１２が好ましい。
　Ｒ2が表すアリールオキシ基の炭素数は、６～１８が好ましい。
　Ｒ2が表すヘテロアリールオキシ基は、単環であっても多環であってもよい。ヘテロアリールオキシ基を構成するヘテロアリール基は、群（ＵＥ）中のＲ1で説明したヘテロアリール基と同義であり、好ましい範囲も同様である。
　Ｒ2が表すアルキルチオ基の炭素数は、１～１２が好ましい。
　Ｒ2が表すアリールチオ基の炭素数は、６～１８が好ましい。
　Ｒ2が表すヘテロアリールチオ基は、単環であっても多環であってもよい。ヘテロアリールチオ基を構成するヘテロアリール基は、Ｒ1で説明したヘテロアリール基と同義であり、好ましい範囲も同様である。
　Ｒ2が表すアシル基の炭素数は、２～１２が好ましい。 The alkyl group represented by R 2 has the same meaning as the alkyl group described for R 1 in the group (UE), and the preferred range is also the same.
The alkenyl group represented by R 2 preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
The alkynyl group represented by R 2 preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
The aryl group represented by R 2 has the same meaning as the aryl group described for R 1 in the group (UE), and the preferred range is also the same.
The heteroaryl group represented by R 2 has the same meaning as the heteroaryl group described for R 1 in the group (UE), and the preferred range is also the same.
The number of carbon atoms of the alkoxy group represented by R 2 is preferably 1-12.
The number of carbon atoms of the aryloxy group represented by R 2 is preferably 6-18.
The heteroaryloxy group represented by R 2 may be monocyclic or polycyclic. Heteroaryl group constituting the heteroaryl group has the same meaning as the heteroaryl group described for R 1 in group (UE), a preferred range is also the same.
The number of carbon atoms of the alkylthio group represented by R 2, 1-12 preferable.
The arylthio group represented by R 2 preferably has 6 to 18 carbon atoms.
The heteroarylthio group represented by R 2 may be monocyclic or polycyclic. Heteroaryl group constituting the heteroarylthio group has the same meaning as the heteroaryl group described for R 1, preferred ranges are also the same.
The number of carbon atoms of the acyl group represented by R 2 is preferably 2-12.
　非共有電子対で配位する配位原子が環に含まれる場合、配位原子を含む環は、単環であっても多環であってもよく、また、芳香族であっても非芳香族であってもよい。配位原子を含む環は、５～１２員環が好ましく、５～７員環がより好ましく、５員環または６員環がさらに好ましい。
　非共有電子対で配位する配位原子を含む環は、置換基を有していてもよい。置換基としては、炭素数１～１０の直鎖状、分岐状または環状のアルキル基、炭素数６～１２のアリール基、ハロゲン原子、ケイ素原子、炭素数１～１２のアルコキシ基、炭素数１～１２のアシル基、炭素数１～１２のアルキルチオ基、カルボン酸基等が挙げられる。上記置換基は、さらに置換基を有していてもよい。このような置換基としては、例えば、非共有電子対で配位する配位原子を含む環からなる基、上述した群（ＵＥ）から選択される少なくとも１種の部分構造を含む基、炭素数１～１２のアルキル基、炭素数１～１２のアシル基、ヒドロキシ基などが挙げられる。 When a coordination atom coordinated by a lone pair is included in the ring, the ring containing the coordination atom may be monocyclic or polycyclic, and may be aromatic or non-aromatic. It may be a tribe. The ring containing a coordination atom is preferably a 5- to 12-membered ring, more preferably a 5- to 7-membered ring, and even more preferably a 5-membered ring or a 6-membered ring.
The ring containing a coordinating atom coordinated by a lone pair may have a substituent. Examples of the substituent include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, a silicon atom, an alkoxy group having 1 to 12 carbon atoms, and 1 carbon atom. ˜12 acyl groups, C 1-12 alkylthio groups, carboxylic acid groups, and the like. The above substituent may further have a substituent. Examples of such a substituent include a group comprising a ring containing a coordinating atom coordinated by a lone pair, a group containing at least one partial structure selected from the group (UE) described above, and the number of carbon atoms. Examples thereof include an alkyl group having 1 to 12, an acyl group having 1 to 12 carbon atoms, and a hydroxy group.
　一般式（ｉ）中、ｎ３は１～６の整数を表し、１～３の整数が好ましく、２または３がより好ましい。
　一般式（ｉ）中、Ｒ100は単結合またはｎ価の基を表す。ｎ価の基としては、ｎ価の有機基、または、ｎ価の有機基と、－Ｏ－、－ＳＯ－、－ＳＯ2－、－ＮＲN1－、－ＣＯ－、－ＣＳ－との組み合わせからなる基が好ましい。ｎ価の有機基は、炭化水素基、オキシアルキレン基、ヘテロ環基等が挙げられる。また、ｎ価の基は、以下の群（ＡＮ－１）から選択される少なくとも１種を含む基、非共有電子対で配位する配位原子を含む環、または、以下の群（ＵＥ－１）から選択される少なくとも１種を含む基であってもよい。
　炭化水素基は、脂肪族炭化水素基または芳香族炭化水素基が好ましい。炭化水素基は、置換基を有していてもよく、置換基としては、アルキル基、ハロゲン原子（好ましくはフッ素原子）、重合性基（例えば、ビニル基、（メタ）アクリロイル基、エポキシ基、オキセタン基など）、スルホン酸基、カルボン酸基、リン原子を含有する酸基、カルボン酸エステル基（例えば－ＣＯ2ＣＨ3）、ヒドロキシル基、アルコキシ基（例えばメトキシ基）、アミノ基、カルバモイル基、カルバモイルオキシ基、ハロゲン化アルキル基（例えばフルオロアルキル基、クロロアルキル基）、（メタ）アクリロイルオキシ基等が挙げられる。炭化水素基が置換基を有する場合、さらに置換基を有していてもよく、置換基としてはアルキル基、上記重合性基、ハロゲン原子等が挙げられる。
　上記炭化水素基が１価の場合、アルキル基、アルケニル基またはアリール基が好ましく、アリール基がより好ましい。炭化水素基が２価の場合、アルキレン基、アリーレン基、オキシアルキレン基が好ましく、アリーレン基がより好ましい。炭化水素基が３価以上の場合には、上記１価の炭化水素基または２価の炭化水素基に対応するものが好ましい。
　アルキル基及びアルキレン基は、直鎖状、分岐状または環状のいずれであってもよい。直鎖状のアルキル基及びアルキレン基の炭素数は、１～２０が好ましく、１～１２がより好ましく、１～８がさらに好ましい。分岐状のアルキル基及びアルキレン基の炭素数は、３～２０が好ましく、３～１２がより好ましく、３～８がさらに好ましい。環状のアルキル基及びアルキレン基は、単環、多環のいずれであってもよい。環状のアルキル基及びアルキレン基の炭素数は、３～２０が好ましく、４～１０がより好ましく、６～１０がさらに好ましい。
　アルケニル基及びアルケニレン基の炭素数は、２～１０が好ましく、２～８がより好ましく、２～４がさらに好ましい。
　アリール基及びアリーレン基の炭素数は、６～１８が好ましく、６～１４がより好ましく、６～１０がさらに好ましい。
　ヘテロ環基は、脂環基の中にヘテロ原子があるもの、または、芳香族ヘテロ環基が挙げられる。ヘテロ環基としては、５員環または６員環が好ましい。また、ヘテロ環基は、単環または縮合環であり、単環または縮合数が２～８の縮合環が好ましく、単環または縮合数が２～４の縮合環がより好ましい。ヘテロ環基は、置換基を有していてもよく、置換基としては、上述した炭化水素基が有していてもよい置換基と同義である。
　－ＮＲN1－において、ＲN1は、水素原子、アルキル基、アリール基またはアラルキル基を表す。ＲN1におけるアルキル基としては、鎖状、分枝状、環状のいずれであってもよい。直鎖状または分岐状のアルキル基の炭素数は、１～２０が好ましく、１～１２がより好ましい。環状のアルキル基は、単環、多環のいずれであってもよい。環状のアルキル基の炭素数は、３～２０が好ましく、４～１４がより好ましい。
　ＲN1におけるアリール基の炭素数は、６～１８が好ましく、６～１４がより好ましい。具体的には、フェニル基、ナフチル基などが例示される。ＲN1におけるアラルキル基としては、炭素数７～２０のアラルキル基が好ましく、無置換の炭素数７～１５のアラルキル基がより好ましい。 In general formula (i), n3 represents an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably 2 or 3.
In the general formula (i), R 100 represents a single bond or n-valent group. As an n-valent group, an n-valent organic group or a combination of an n-valent organic group and —O—, —SO—, —SO 2 —, —NR N1 —, —CO—, or —CS— The group consisting of Examples of the n-valent organic group include a hydrocarbon group, an oxyalkylene group, and a heterocyclic group. In addition, the n-valent group includes a group containing at least one selected from the following group (AN-1), a ring containing a coordination atom coordinated by a lone pair, or the following group (UE- It may be a group containing at least one selected from 1).
The hydrocarbon group is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group may have a substituent. Examples of the substituent include an alkyl group, a halogen atom (preferably a fluorine atom), a polymerizable group (for example, a vinyl group, a (meth) acryloyl group, an epoxy group, Oxetane group, etc.), sulfonic acid group, carboxylic acid group, acid group containing phosphorus atom, carboxylic acid ester group (eg —CO 2 CH 3 ), hydroxyl group, alkoxy group (eg methoxy group), amino group, carbamoyl group Carbamoyloxy group, halogenated alkyl group (for example, fluoroalkyl group, chloroalkyl group), (meth) acryloyloxy group and the like. When the hydrocarbon group has a substituent, the hydrocarbon group may further have a substituent, and examples of the substituent include an alkyl group, the polymerizable group, and a halogen atom.
When the hydrocarbon group is monovalent, an alkyl group, an alkenyl group or an aryl group is preferable, and an aryl group is more preferable. When the hydrocarbon group is divalent, an alkylene group, an arylene group, or an oxyalkylene group is preferable, and an arylene group is more preferable. When the hydrocarbon group is trivalent or higher, those corresponding to the monovalent hydrocarbon group or divalent hydrocarbon group are preferred.
The alkyl group and the alkylene group may be linear, branched or cyclic. The carbon number of the linear alkyl group and alkylene group is preferably 1-20, more preferably 1-12, and even more preferably 1-8. The branched alkyl group and alkylene group preferably have 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and still more preferably 3 to 8 carbon atoms. The cyclic alkyl group and alkylene group may be monocyclic or polycyclic. The number of carbon atoms in the cyclic alkyl group and the alkylene group is preferably 3 to 20, more preferably 4 to 10, and still more preferably 6 to 10.
The alkenyl group and alkenylene group preferably have 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 2 to 4 carbon atoms.
The number of carbon atoms in the aryl group and arylene group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10.
Examples of the heterocyclic group include those having a hetero atom in the alicyclic group, and aromatic heterocyclic groups. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group is a single ring or a condensed ring, preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations. The heterocyclic group may have a substituent, and the substituent is synonymous with the substituent that the hydrocarbon group described above may have.
In —NR N1 —, R N1 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. The alkyl group in R N1 may be any of a chain, a branch, and a ring. The linear or branched alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. The cyclic alkyl group may be monocyclic or polycyclic. The cyclic alkyl group preferably has 3 to 20 carbon atoms, and more preferably 4 to 14 carbon atoms.
The carbon number of the aryl group in R N1 is preferably 6 to 18, and more preferably 6 to 14. Specific examples include a phenyl group and a naphthyl group. As the aralkyl group in R N1, an aralkyl group having 7 to 20 carbon atoms is preferable, and an unsubstituted aralkyl group having 7 to 15 carbon atoms is more preferable.
群（ＵＥ－１）
Figure JPOXMLDOC01-appb-C000003
 　群（ＵＥ－１）中のＲ1は、群（ＵＥ）中のＲ1と同義である。 Group (UE-1)
Figure JPOXMLDOC01-appb-C000003
 R 1 in group (UE-1) has the same meaning as R 1 in group (UE).
群（ＡＮ－１）
Figure JPOXMLDOC01-appb-C000004
 　群（ＡＮ－１）中のＸは、ＮまたはＣＲを表し、Ｒは、上述した群（ＡＮ）中のＣＲで説明したＲと同義である。 Group (AN-1)
Figure JPOXMLDOC01-appb-C000004
 X in group (AN-1) represents N or CR, and R has the same meaning as R described above for CR in group (AN).
　配位子となる化合物の具体的な形態としては、少なくとも２箇所の配位部位を有する化合物が好ましい。具体的には、アニオンで配位する配位部位を１つ以上と非共有電子対で配位する配位原子を１つ以上とを含む化合物（以下、化合物（Ａ１）ともいう）、非共有電子対で配位する配位原子を２つ以上有する化合物（以下、化合物（Ａ２）ともいう）、アニオンで配位する配位部位を２つ含む化合物（以下、化合物（Ａ３）ともいう）等が挙げられる。これらの化合物は、それぞれ独立に、１種または２種以上を組み合わせて用いることができる。
　また、配位子となる化合物として、アニオンで配位する配位部位を１つ有する化合物を用いることもできる。 As a specific form of the compound to be a ligand, a compound having at least two coordination sites is preferable. Specifically, a compound containing at least one coordination site coordinated by an anion and at least one coordination atom coordinated by an unshared electron pair (hereinafter also referred to as compound (A1)), non-covalent A compound having two or more coordination atoms coordinated by an electron pair (hereinafter also referred to as compound (A2)), a compound containing two coordination sites coordinated by an anion (hereinafter also referred to as compound (A3)), etc. Is mentioned. These compounds can be used independently or in combination of two or more.
A compound having one coordination site coordinated by an anion can also be used as the ligand compound.
＜＜＜＜化合物（Ａ１）＞＞＞＞
　化合物（Ａ１）は、１分子内中のアニオンで配位する配位部位と非共有電子対で配位する配位原子の合計が２つ以上であればよく、３つであってもよいし、４つであってもよい。
　化合物（Ａ１）としては、例えば、下記式（ｉ－１）で表される化合物が好ましい。
Ｘ11－Ｌ11－Ｙ11　　　・・・（ｉ－１）
　Ｘ11は、上述した群（ＡＮ）で表される配位部位を表す。
　Ｙ11は、上述した非共有電子対で配位する配位原子を含む環、または、群（ＵＥ）で表される部分構造を表す。
　Ｌ11は、単結合または２価の連結基を表す。２価の連結基としては、炭素数１～１２のアルキレン基、炭素数６～１２のアリーレン基、－ＳＯ－、－ＳＯ2－、－Ｏ－、または、これらの組み合わせからなる基が好ましい。 <<<< Compound (A1) >>>>
In the compound (A1), the total number of coordination atoms coordinated by an anion in one molecule and coordination atoms coordinated by a lone pair may be two or more, and may be three. There may be four.
As the compound (A1), for example, a compound represented by the following formula (i-1) is preferable.
X 11 -L 11 -Y 11 (i-1)
X 11 represents a coordination site represented by the group (AN) described above.
Y 11 represents a ring containing a coordination atom coordinated by the above-described lone pair or a partial structure represented by a group (UE).
L 11 represents a single bond or a divalent linking group. As the divalent linking group, an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —SO—, —SO 2 —, —O—, or a group consisting of a combination thereof is preferable.
　化合物（Ａ１）のより詳細な例として、下記一般式（ｉ－２）～（ｉ－９）で表される化合物も挙げられる。
Ｘ12－Ｌ12－Ｙ12－Ｌ13－Ｘ13                          （ｉ－２）
Ｙ13－Ｌ14－Ｙ14－Ｌ15－Ｘ14                          （ｉ－３）
Ｙ15－Ｌ16－Ｘ15－Ｌ17－Ｘ16                          （ｉ－４）
Ｙ16－Ｌ18－Ｘ17－Ｌ19－Ｙ17                          （ｉ－５）
Ｘ18－Ｌ20－Ｙ18－Ｌ21－Ｙ19－Ｌ22－Ｘ19                （ｉ－６）
Ｘ20－Ｌ23－Ｙ20－Ｌ24－Ｙ21－Ｌ25－Ｙ22                （ｉ－７）
Ｙ23－Ｌ26－Ｘ21－Ｌ27－Ｘ22－Ｌ28－Ｙ24                （ｉ－８）
Ｙ25－Ｌ29－Ｘ23－Ｌ30－Ｙ26－Ｌ31－Ｙ27                （ｉ－９）
　一般式（ｉ－２）～（ｉ－９）中、Ｘ12～Ｘ14、Ｘ16、Ｘ18～Ｘ20はそれぞれ独立して、上述した群（ＡＮ）で表される配位部位を表す。また、Ｘ15、Ｘ17、Ｘ21～Ｘ23はそれぞれ独立して、上述した群（ＡＮ－１）で表される配位部位を表す。
　一般式（ｉ－２）～（ｉ－９）中、Ｌ12～Ｌ31はそれぞれ独立して単結合または２価の連結基を表す。２価の連結基は、一般式（ｉ－１）中のＬ1が２価の連結基を表す場合と同義である。 More detailed examples of the compound (A1) include compounds represented by the following general formulas (i-2) to (i-9).
X 12 -L 12 -Y 12 -L 13 -X 13 (i-2)
Y 13 -L 14 -Y 14 -L 15 -X 14 (i-3)
Y 15 -L 16 -X 15 -L 17 -X 16 (i-4)
Y 16 -L 18 -X 17 -L 19 -Y 17 (i-5)
X 18 -L 20 -Y 18 -L 21 -Y 19 -L 22 -X 19 (i-6)
X 20 -L 23 -Y 20 -L 24 -Y 21 -L 25 -Y 22 (i-7)
Y 23 -L 26 -X 21 -L 27 -X 22 -L 28 -Y 24 (i-8)
Y 25 -L 29 -X 23 -L 30 -Y 26 -L 31 -Y 27 (i-9)
In the general formulas (i-2) to (i-9), X 12 to X 14 , X 16 and X 18 to X 20 each independently represent a coordination site represented by the group (AN) described above. . X 15 , X 17 and X 21 to X 23 each independently represent a coordination site represented by the group (AN-1) described above.
In general formulas (i-2) to (i-9), L 12 to L 31 each independently represents a single bond or a divalent linking group. The divalent linking group is synonymous with the case where L 1 in formula (i-1) represents a divalent linking group.
　化合物（Ａ１）としては、式（ｉ－１０）または式（ｉ－１１）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000005
 　式（ｉ－１０）中、Ｘ2は、アニオンで配位する配位部位を含む基を表す。Ｙ2は、酸素原子、窒素原子、硫黄原子またはリン原子を表す。Ａ1およびＡ5は、それぞれ独立して炭素原子、窒素原子またはリン原子を表す。Ａ2～Ａ4は、それぞれ独立して炭素原子、酸素原子、窒素原子、硫黄原子またはリン原子を表す。Ｒ1は、置換基を表す。ＲX2は、置換基を表す。ｎ２は０～３の整数を表す。
　式（ｉ－１０）中、Ｘ2は、上記アニオンで配位する配位部位を含む基のみからなっていてもよいし、上記アニオンで配位する配位部位を含む基が置換基を有していてもよい。アニオンで配位する配位部位を含む基が有していてもよい置換基は、ハロゲン原子、カルボン酸基、ヘテロ環基が挙げられる。置換基としてのヘテロ環基は、単環であっても多環であってもよく、また、芳香族であっても非芳香族であってもよい。ヘテロ環を構成するヘテロ原子の数は１～３が好ましい。ヘテロ環を構成するヘテロ原子は、窒素原子が好ましい。
　式（ｉ－１０）中、Ｙ2は、酸素原子、窒素原子または硫黄原子が好ましく、酸素原子または窒素原子がより好ましく、窒素原子がさらに好ましい。
　式（ｉ－１０）中、Ａ1およびＡ5は、炭素原子が好ましい。
　式（ｉ－１０）中、Ａ2およびＡ3は、炭素原子を表すことが好ましい。Ａ4は、炭素原子または窒素原子を表すことが好ましい。
　式（ｉ－１０）中、Ｒ1は、上述した非共有電子対で配位する配位原子を含む環が有していてもよい置換基と同義である。
　式（ｉ－１０）中、ＲX2は、上述した非共有電子対で配位する配位原子を含む環が有していてもよい置換基と同義であり、好ましい範囲も同様である。
　式（ｉ－１０）中、ｎ２は０～３の整数を表し、０または１が好ましく、０がより好ましい。
　式（ｉ－１０）で表される化合物は、Ｙ2を含むヘテロ環が、単環構造であってもよいし、多環構造であってもよい。Ｙ2を含むヘテロ環が単環構造である場合の具体例としては、ピリジン環、ピリダジン環、ピリミジン環、ピラジン環、トリアジン環、ピラン環等が挙げられる。Ｙ2を含むヘテロ環が多環構造である場合の具体例としては、キノリン環、イソキノリン環、キノキサリン環、アクリジン環等が挙げられる。 As the compound (A1), a compound represented by the formula (i-10) or the formula (i-11) is preferable.
Figure JPOXMLDOC01-appb-C000005
 In formula (i-10), X 2 represents a group containing a coordination site coordinated by an anion. Y 2 represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A 1 and A 5 each independently represent a carbon atom, a nitrogen atom or a phosphorus atom. A 2 to A 4 each independently represents a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. R 1 represents a substituent. R X2 represents a substituent. n2 represents an integer of 0 to 3.
In formula (i-10), X 2 may consist only of a group containing a coordination site coordinated with the anion, or the group containing a coordination site coordinated with the anion may have a substituent. You may do it. Examples of the substituent that the group containing a coordination site coordinated with an anion may have include a halogen atom, a carboxylic acid group, and a heterocyclic group. The heterocyclic group as a substituent may be monocyclic or polycyclic, and may be aromatic or non-aromatic. The number of heteroatoms constituting the heterocycle is preferably 1 to 3. The hetero atom constituting the hetero ring is preferably a nitrogen atom.
In formula (i-10), Y 2 is preferably an oxygen atom, a nitrogen atom or a sulfur atom, more preferably an oxygen atom or a nitrogen atom, and further preferably a nitrogen atom.
In formula (i-10), A 1 and A 5 are preferably carbon atoms.
In formula (i-10), A 2 and A 3 preferably represent carbon atoms. A 4 preferably represents a carbon atom or a nitrogen atom.
In formula (i-10), R 1 has the same meaning as the substituent that the ring containing the coordinating atom coordinated by the above-mentioned lone pair may have.
In formula (i-10), R X2 has the same meaning as the substituent that the ring containing the coordinating atom coordinated by the lone pair described above may have, and the preferred range is also the same.
In formula (i-10), n2 represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
The compound represented by the formula (i-10), can be a hetero ring containing Y 2 is, may be a single ring structure or may be a polycyclic structure. Specific examples when the heterocycle containing Y 2 has a monocyclic structure include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a pyran ring, and the like. Specific examples when the heterocycle containing Y 2 has a polycyclic structure include a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring and the like.
　式（ｉ－１１）中、Ｘ3は、上記アニオンで配位する配位部位を含む基を表す。Ｙ3は、酸素原子、窒素原子、硫黄原子またはリン原子を表す。Ａ6およびＡ9は、それぞれ独立して炭素原子、窒素原子またはリン原子を表す。Ａ7およびＡ8は、それぞれ独立して炭素原子、酸素原子、窒素原子、硫黄原子またはリン原子を表す。Ｒ2は、置換基を表す。ＲX3は、置換基を表す。ｎ３は０～２の整数を表す。
　式（ｉ－１１）中、Ｘ3は、式（ｉ－１０）中のＸ2と同義であり、好ましい範囲も同様である。
　式（ｉ－１１）中、Ｙ3は、酸素原子、窒素原子または硫黄原子が好ましく、酸素原子または窒素原子がより好ましい。
　式（ｉ－１１）中、Ａ6は、炭素原子または窒素原子が好ましい。Ａ9は、炭素原子が好ましい。
　式（ｉ－１１）中、Ａ7は、炭素原子が好ましい。Ａ8は、炭素原子、窒素原子または硫黄原子が好ましい。
　式（ｉ－１１）中、Ｒ2は、疎水的な置換基が好ましく、炭素数１～３０の炭化水素基がより好ましく、炭素数３～３０のアルキル基または炭素数６～３０のアリール基がさらに好ましく、炭素数３～１５のアルキル基が特に好ましい。
　式（ｉ－１１）中、ＲX3は、式（ｉ－１０）中のＲX2と同義であり、好ましい範囲も同様である。
　式（ｉ－１１）中、ｎ３は、０または１が好ましく、０がより好ましい。
　式（ｉ－１１）で表される化合物は、Ｙ3を含むヘテロ環が、単環構造であってもよいし、多環構造であってもよい。Ｙ3を含むヘテロ環が単環構造である場合の具体例としては、ピラゾール環、イミダゾール環、トリアゾール環、オキサゾール環、チアゾール環、イソチアゾール環等が挙げられる。Ｙ3を含むヘテロ環が多環構造である場合の具体例としては、インドール環、イソインドール環、ベンゾフラン環、イソベンゾフラン環等が挙げられる。
　特に、式（ｉ－１１）で表される化合物は、ピラゾール環を含む化合物であってピラゾール環の５位に２級または３級のアルキル基を有することが好ましい。本願明細書において、式（ｉ－１１）で表される化合物が、ピラゾール環を含む化合物である場合のピラゾール環の５位とは、上記（ｉ－１１）中のＹ3およびＡ6が窒素原子を表し、Ａ7～Ａ9が炭素原子を表す場合のＲ2の置換位置をいう。ピラゾール環の５位における２級または３級のアルキル基の炭素数は、３～１５が好ましく、３～１２がより好ましい。
　化合物（Ａ１）の分子量は、１０００以下が好ましく、７５０以下がより好ましく、６００以下がさらに好ましい。また、化合物（Ａ１）の分子量は、５０以上が好ましく、８０以上がより好ましい。 In formula (i-11), X 3 represents a group containing a coordination site coordinated with the anion. Y 3 represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A 6 and A 9 each independently represents a carbon atom, a nitrogen atom or a phosphorus atom. A 7 and A 8 each independently represent a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. R 2 represents a substituent. R X3 represents a substituent. n3 represents an integer of 0-2.
In formula (i-11), X 3 has the same meaning as X 2 in formula (i-10), and the preferred range is also the same.
In formula (i-11), Y 3 is preferably an oxygen atom, a nitrogen atom or a sulfur atom, more preferably an oxygen atom or a nitrogen atom.
In formula (i-11), A 6 is preferably a carbon atom or a nitrogen atom. A 9 is preferably a carbon atom.
In formula (i-11), A 7 is preferably a carbon atom. A 8 is preferably a carbon atom, a nitrogen atom or a sulfur atom.
In formula (i-11), R 2 is preferably a hydrophobic substituent, more preferably a hydrocarbon group having 1 to 30 carbon atoms, an alkyl group having 3 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Is more preferable, and an alkyl group having 3 to 15 carbon atoms is particularly preferable.
In formula (i-11), R X3 has the same meaning as R X2 in formula (i-10), and the preferred range is also the same.
In formula (i-11), n3 is preferably 0 or 1, more preferably 0.
The compound represented by the formula (i-11), can be a hetero ring containing Y 3 is may be a monocyclic structure or may be a polycyclic structure. Specific examples when the heterocycle containing Y 3 has a monocyclic structure include a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, an isothiazole ring, and the like. Specific examples when the heterocycle containing Y 3 has a polycyclic structure include an indole ring, an isoindole ring, a benzofuran ring, an isobenzofuran ring, and the like.
In particular, the compound represented by the formula (i-11) is a compound containing a pyrazole ring, and preferably has a secondary or tertiary alkyl group at the 5-position of the pyrazole ring. In the present specification, when the compound represented by the formula (i-11) is a compound containing a pyrazole ring, the 5-position of the pyrazole ring means that Y 3 and A 6 in the above (i-11) are nitrogen Represents an atom, and the substitution position of R 2 when A 7 to A 9 represent a carbon atom. The carbon number of the secondary or tertiary alkyl group at the 5-position of the pyrazole ring is preferably 3 to 15, more preferably 3 to 12.
The molecular weight of the compound (A1) is preferably 1000 or less, more preferably 750 or less, and still more preferably 600 or less. Moreover, 50 or more are preferable and, as for the molecular weight of a compound (A1), 80 or more are more preferable.
　化合物（Ａ１）の具体例としては、以下が挙げられる。
Figure JPOXMLDOC01-appb-C000006
 Specific examples of the compound (A1) include the following.
Figure JPOXMLDOC01-appb-C000006
＜＜＜＜化合物（Ａ１）の塩＞＞＞＞
　化合物（Ａ１）の塩、すなわち、アニオンで配位する配位部位の塩を含む化合物としては、例えば金属塩が好ましい。金属塩を構成する金属原子は、アルカリ金属原子またはアルカリ土類金属原子が好ましい。アルカリ金属原子としては、ナトリウム、カリウム等が挙げられる。アルカリ土類金属原子としては、カルシウム、マグネシウム等が挙げられる。 <<<<< Salt of Compound (A1) >>>>
As the compound (A1) salt, that is, a compound containing a salt of a coordination site coordinated by an anion, for example, a metal salt is preferable. The metal atom constituting the metal salt is preferably an alkali metal atom or an alkaline earth metal atom. Examples of the alkali metal atom include sodium and potassium. Examples of alkaline earth metal atoms include calcium and magnesium.
＜＜＜＜化合物（Ａ２）＞＞＞＞
　化合物（Ａ２）は、１分子内に、非共有電子対で配位する配位原子を２つ以上有していればよく、３つ以上有していてもよく、２～４つ有していることが好ましい。
　化合物（Ａ２）は、例えば、下記一般式（ｉｉ－１）で表される化合物が好ましい。
Ｙ40－Ｌ40－Ｙ41　・・・（ｉｉ－１）
　一般式（ｉｉ－１）中、Ｙ40およびＹ41はそれぞれ独立して、非共有電子対で配位する配位原子を含む環、または、群（ＵＥ）で表される部分構造を表す。
　一般式（ｉｉ－１）中、Ｌ40は、単結合または２価の連結基を表す。Ｌ40が２価の連結基を表す場合、炭素数１～１２のアルキレン基、炭素数６～１２のアリーレン基、－ＳＯ－、－Ｏ－、－ＳＯ2－または、これらの組み合わせからなる基が好ましく、炭素数１～３のアルキレン基、フェニレン基または－ＳＯ2－が好ましい。 <<<<< Compound (A2) >>>>
The compound (A2) may have two or more coordination atoms coordinated by a lone pair in one molecule, may have three or more, and has two to four. Preferably it is.
The compound (A2) is preferably, for example, a compound represented by the following general formula (ii-1).
Y 40 -L 40 -Y 41 (ii-1)
In general formula (ii-1), Y 40 and Y 41 each independently represent a ring containing a coordination atom coordinated by an unshared electron pair or a partial structure represented by group (UE).
In general formula (ii-1), L 40 represents a single bond or a divalent linking group. When L 40 represents a divalent linking group, an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —SO—, —O—, —SO 2 —, or a combination thereof. An alkylene group having 1 to 3 carbon atoms, a phenylene group, or —SO 2 — is preferable.
　化合物（Ａ２）のより詳細な例として、下記一般式（ｉｉ－２）または（ｉｉ－３）で表される化合物も挙げられる。
Ｙ42－Ｌ41－Ｙ43－Ｌ42－Ｙ44                          （ｉｉ－２）
Ｙ45－Ｌ43－Ｙ46－Ｌ44－Ｙ47－Ｌ45－Ｙ48                （ｉｉ－３）
　一般式（ｉｉ－２）および（ｉｉ－３）中、Ｙ42、Ｙ44、Ｙ45およびＹ48はそれぞれ独立して、非共有電子対で配位する配位原子を含む環、または、群（ＵＥ）で表される部分構造を表す。
　また、Ｙ43、Ｙ46、Ｙ47はそれぞれ独立して、非共有電子対で配位する配位原子を含む環、または、上述した群（ＵＥ－１）で表される部分構造である。
　一般式（ｉｉ－２）および（ｉｉ－３）中、Ｌ41～Ｌ45はそれぞれ独立して単結合または２価の連結基を表す。２価の連結基は、一般式（ｉｉ－１）中のＬ40が２価の連結基を表す場合と同義であり、好ましい範囲も同様である。
　化合物（Ａ２）の分子量は、１０００以下が好ましく、７５０以下がより好ましく、６００以下がさらに好ましい。また、化合物（Ａ２）の分子量は、５０以上が好ましく、８０以上がより好ましい。 As more detailed examples of the compound (A2), compounds represented by the following general formula (ii-2) or (ii-3) may also be mentioned.
Y 42 -L 41 -Y 43 -L 42 -Y 44 (ii-2)
Y 45 -L 43 -Y 46 -L 44 -Y 47 -L 45 -Y 48 (ii-3)
In the general formulas (ii-2) and (ii-3), Y 42 , Y 44 , Y 45 and Y 48 are each independently a ring or group containing a coordinating atom coordinated by a lone pair of electrons. The partial structure represented by (UE) is represented.
Y 43 , Y 46 , and Y 47 are each independently a ring containing a coordinating atom coordinated by an unshared electron pair, or a partial structure represented by the group (UE-1) described above.
In the general formulas (ii-2) and (ii-3), L 41 to L 45 each independently represents a single bond or a divalent linking group. The divalent linking group is synonymous with the case where L 40 in the general formula (ii-1) represents a divalent linking group, and the preferred range is also the same.
The molecular weight of the compound (A2) is preferably 1000 or less, more preferably 750 or less, and even more preferably 600 or less. Moreover, 50 or more are preferable and, as for the molecular weight of a compound (A2), 80 or more are more preferable.
　化合物（Ａ２）の具体例としては、以下が挙げられる。
Figure JPOXMLDOC01-appb-C000007
 Specific examples of the compound (A2) include the following.
Figure JPOXMLDOC01-appb-C000007
＜＜＜＜化合物（Ａ３）＞＞＞＞
　化合物（Ａ３）は、アニオンで配位する配位部位を２つ有する。アニオンで配位する配位部位は、上述したアニオンで配位する配位部位と同義である。
　化合物（Ａ３）としては、下記一般式（ｉｉｉ－１）で表される化合物が好ましい。
Ｘ50－Ｌ50－Ｘ51　　（ｉｉｉ－１）
　一般式（ｉｉｉ－１)中、Ｘ50およびＸ51は、それぞれ独立に、アニオンで配位する配位部位を表し、上述したアニオンで配位する配位部位と同義であり、モノアニオン性配位部位が好ましい。
　一般式（ｉｉｉ－１)中、Ｌ50は、単結合または２価の連結基を表す。２価の連結基としては、炭素数１～２０のアルキレン基、炭素数２～１０のアルケニレン基、炭素数６～１８のアリーレン基、ヘテロ環基、－Ｏ－、－Ｓ－、－ＮＲN1－、－ＣＯ－、－ＣＳ－、－ＳＯ2－、または、これらの組み合わせからなる基が好ましい。ＲN1は、水素原子、炭素数１～１２のアルキル基、炭素数６～１８のアリール基または炭素数７～２０のアラルキル基が好ましい。
　化合物（Ａ３）は、スルホン酸基およびカルボン酸基から選ばれる１種以上を含むことが好ましく、スルホン酸基およびカルボン酸基を含むことが更に好ましい。スルホン酸基およびカルボン酸基から選ばれる少なくとも１種を有する化合物を用いることにより、色価をより向上させることができる。
　化合物（Ａ３）の分子量は、１０００以下が好ましく、７５０以下がより好ましく、６００以下がさらに好ましい。また、化合物（Ａ３）の分子量は、５０以上が好ましく、８０以上がより好ましい。 <<<<< Compound (A3) >>>>
The compound (A3) has two coordination sites coordinated with an anion. The coordination site | part coordinated with an anion is synonymous with the coordination site | part coordinated with the anion mentioned above.
As the compound (A3), a compound represented by the following general formula (iii-1) is preferable.
X 50 -L 50 -X 51 (iii-1)
In the general formula (iii-1), X 50 and X 51 each independently represent a coordination site coordinated with an anion, which is synonymous with the coordination site coordinated with an anion described above, and has a monoanionic configuration. A position site is preferred.
In general formula (iii-1), L 50 represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an arylene group having 6 to 18 carbon atoms, a heterocyclic group, —O—, —S—, and —NR N1. A group consisting of —, —CO—, —CS—, —SO 2 —, or a combination thereof is preferred. R N1 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
The compound (A3) preferably contains one or more selected from a sulfonic acid group and a carboxylic acid group, and more preferably contains a sulfonic acid group and a carboxylic acid group. By using a compound having at least one selected from a sulfonic acid group and a carboxylic acid group, the color value can be further improved.
The molecular weight of the compound (A3) is preferably 1000 or less, more preferably 750 or less, and even more preferably 600 or less. Moreover, 50 or more are preferable and, as for the molecular weight of a compound (A3), 80 or more are more preferable.
＜＜＜＜アニオンで配位する配位部位を１つ有する化合物＞＞＞＞
　配位子となる化合物としては、アニオンで配位する配位部位を１つ有する化合物を用いることもできる。
　例えば、有機酸化合物（例えば、スルホン酸基を有する化合物（スルホン酸化合物）、カルボン酸基を有する化合物（カルボン酸化合物））またはその塩なども挙げられる。 <<<<< Compound having one coordination site coordinated by an anion >>>>
As the compound serving as a ligand, a compound having one coordination site coordinated by an anion can also be used.
For example, an organic acid compound (for example, a compound having a sulfonic acid group (sulfonic acid compound), a compound having a carboxylic acid group (carboxylic acid compound)) or a salt thereof may be used.
　スルホン酸化合物としては、下記式（Ａ４）で表される化合物が好ましい。
式（Ａ４）
Figure JPOXMLDOC01-appb-C000008
 （式（Ａ４）中、Ｒ7は１価の有機基を表す。）
　１価の有機基としては、直鎖状、分岐状または環状のアルキル基、直鎖状、分岐状または環状のアルケニル基、および、アリール基、ならびに、これらと、２価の連結基の組み合わせからなる基が好ましい。２価の連結基としては、アルキレン基、シクロアルキレン基、アリーレン基、－Ｏ－、－Ｓ－、－ＣＯ－、－Ｃ（＝Ｏ）Ｏ－、－ＯＣＯ－、－ＳＯ2－、－ＮＲ－（Ｒは水素原子あるいはアルキル基）など）が例示される。また、１価の有機基は置換基を有していてもよい。
　直鎖状または分岐状のアルキル基の炭素数としては、１～２０が好ましく、１～１２がより好ましく、１～８がさらに好ましい。環状のアルキル基は、単環、多環のいずれであってもよい。環状のアルキル基としては、炭素数３～２０のシクロアルキル基が好ましく、炭素数４～１０のシクロアルキル基がより好ましく、炭素数６～１０のシクロアルキル基がさらに好ましい。アルケニル基は直鎖のアルケニル基が好ましい。アルケニル基の炭素数としては、２～１０が好ましく、２～８がより好ましく、２～４がさらに好ましい。アリール基の炭素数としては、６～１８が好ましく、６～１４がより好ましく、６～１０がさらに好ましい。 As the sulfonic acid compound, a compound represented by the following formula (A4) is preferable.
Formula (A4)
Figure JPOXMLDOC01-appb-C000008
 (In the formula (A4), R 7 represents a monovalent organic group.)
Examples of monovalent organic groups include linear, branched or cyclic alkyl groups, linear, branched or cyclic alkenyl groups, and aryl groups, and combinations of these with divalent linking groups. Is preferred. Examples of the divalent linking group include an alkylene group, a cycloalkylene group, an arylene group, —O—, —S—, —CO—, —C (═O) O—, —OCO—, —SO 2 —, —NR. -(R is a hydrogen atom or an alkyl group)). The monovalent organic group may have a substituent.
The carbon number of the linear or branched alkyl group is preferably 1-20, more preferably 1-12, and even more preferably 1-8. The cyclic alkyl group may be monocyclic or polycyclic. As the cyclic alkyl group, a cycloalkyl group having 3 to 20 carbon atoms is preferable, a cycloalkyl group having 4 to 10 carbon atoms is more preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. The alkenyl group is preferably a linear alkenyl group. The number of carbon atoms of the alkenyl group is preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 4. The number of carbon atoms of the aryl group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10.
　２価の連結基であるアルキレン基、シクロアルキレン基、アリーレン基としては、前述のアルキル基、シクロアルキル基、アリール基から水素原子を１個除いて誘導される２価の連結基が挙げられる。
　１価の有機基が有していてもよい置換基としては、アルキル基、重合性基（例えば、ビニル基、（メタ）アクリロイル基、エポキシ基、オキセタン基など）、ハロゲン原子、カルボン酸基、カルボン酸エステル基（例えば、－ＣＯ2ＣＨ3など）水酸基、アミド基、ハロゲン化アルキル基（例えば、フルオロアルキル基、クロロアルキル基）などが例示される。
　式（Ａ４）で表されるスルホン酸化合物あるいはその塩の分子量は、８０以上が好ましく、上限は７５０以下が好ましく、６００以下がより好ましく、４５０以下がさらに好ましい。また、分子量は、８０～７５０が好ましく、８０～６００がより好ましく、８０～４５０がさらに好ましい。 Examples of the alkylene group, cycloalkylene group, and arylene group which are divalent linking groups include divalent linking groups derived by removing one hydrogen atom from the aforementioned alkyl group, cycloalkyl group, and aryl group.
Examples of the substituent that the monovalent organic group may have include an alkyl group, a polymerizable group (for example, a vinyl group, a (meth) acryloyl group, an epoxy group, and an oxetane group), a halogen atom, a carboxylic acid group, Examples include carboxylic acid ester groups (for example, —CO 2 CH 3 and the like), hydroxyl groups, amide groups, halogenated alkyl groups (for example, fluoroalkyl groups and chloroalkyl groups), and the like.
The molecular weight of the sulfonic acid compound represented by the formula (A4) or a salt thereof is preferably 80 or more, the upper limit is preferably 750 or less, more preferably 600 or less, and even more preferably 450 or less. The molecular weight is preferably 80 to 750, more preferably 80 to 600, and still more preferably 80 to 450.
　スルホン酸化合物は、市販のスルホン酸を用いることもできるし、公知の方法を参照して、合成することもできる。スルホン酸化合物の塩としては、例えば金属塩が挙げられる。金属塩を構成する金属原子は、アルカリ金属原子またはアルカリ土類金属原子が好ましい。具体的には、ナトリウム塩、カリウム塩等が挙げられる。 The sulfonic acid compound can be a commercially available sulfonic acid, or can be synthesized by referring to a known method. Examples of the sulfonic acid compound salt include metal salts. The metal atom constituting the metal salt is preferably an alkali metal atom or an alkaline earth metal atom. Specific examples include sodium salts and potassium salts.
　本発明では、カルボン酸を配位子とする銅化合物を用いてもよい。配位子となるカルボン酸としては、下記式（Ａ５）で表される化合物が好ましい。 In the present invention, a copper compound having a carboxylic acid as a ligand may be used. As a carboxylic acid used as a ligand, the compound represented by a following formula (A5) is preferable.
Figure JPOXMLDOC01-appb-C000009
 （式（Ａ５）中、Ｒ1は１価の有機基を表す。）
　式（Ａ５）中、Ｒ1は１価の有機基を表す。１価の有機基としては、例えば、上述した式（Ａ４）中の１価の有機基と同義であり、好ましい範囲も同義である。
Figure JPOXMLDOC01-appb-C000009
 (In formula (A5), R 1 represents a monovalent organic group.)
In formula (A5), R 1 represents a monovalent organic group. As a monovalent organic group, it is synonymous with the monovalent organic group in Formula (A4) mentioned above, for example, and its preferable range is also synonymous.
　化合物（Ａ３）、式（Ａ４）で表される化合物および式（Ａ５）で表される化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of the compound (A3), the compound represented by the formula (A4) and the compound represented by the formula (A5) are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
＜＜＜ポリマータイプの銅化合物＞＞＞
　銅化合物としては、配位部位を含む重合体（以下、重合体（Ａ０）ともいう）と銅成分との反応で得られるポリマータイプの銅化合物を用いることもできる。ポリマータイプの銅化合物は、配位部位が、銅成分の銅と配位することにより、ポリマータイプの銅化合物の構造が歪んで、可視光領域の高い透過性が得られ、近赤外線の吸光能力が向上し、更には、色価も向上すると考えられる。また、ポリマータイプの銅化合物は、銅を起点として、ポリマーの側鎖間に架橋構造が形成されるので、耐熱性に優れた膜が得られる。ポリマータイプの銅化合物としては、主鎖に炭素－炭素結合を有する重合体の銅錯体、主鎖に炭素－炭素結合を有する重合体の銅錯体であって、フッ素原子を含む銅錯体、主鎖に芳香族炭化水素基及び／又は芳香族ヘテロ環基を有する重合体（以下、芳香族基含有重合体という。）の銅錯体等が挙げられる。
　銅成分としては、上述したものが挙げられる。銅成分中の銅含有量は、好ましくは２～４０質量％であり、より好ましくは５～４０質量％である。銅成分は、１種のみを用いてもよいし、２種以上を用いてもよい。
　銅成分の具体例としては、上述した低分子銅化合物で用いられる銅成分と同義であり、水酸化銅、酢酸銅、塩化銅、ギ酸銅、ステアリン酸銅、安息香酸銅、エチルアセト酢酸銅、ピロリン酸銅、ナフテン酸銅、クエン酸銅、硝酸銅、硫酸銅、炭酸銅、塩素酸銅、（メタ）アクリル酸銅、過塩素酸銅が例示され、水酸化銅、酢酸銅、塩化銅、硫酸銅、安息香酸銅、（メタ）アクリル酸銅が好ましく、水酸化銅、酢酸銅および硫酸銅が特に好ましい。
　銅成分の量は、重合体の配位部位（好ましくは酸基またはその塩）１当量に対して、０．０５～１当量が好ましく、０．１～０．８当量がより好ましく、０．２～０．５当量がさらに好ましい。銅成分の量をこのような範囲とすることにより、より高い近赤外線遮蔽性を有する硬化膜が得られる傾向にある。 <<< Polymer type copper compound >>>
As the copper compound, a polymer-type copper compound obtained by a reaction between a polymer containing a coordination site (hereinafter, also referred to as polymer (A0)) and a copper component may be used. Polymer-type copper compounds coordinate with the copper component of the copper component, which distorts the structure of the polymer-type copper compound and provides high transmittance in the visible light region, and the ability to absorb near infrared light It is considered that the color value is improved. In addition, since a polymer-type copper compound has a crosslinked structure formed between side chains of the polymer starting from copper, a film having excellent heat resistance can be obtained. Polymer-type copper compounds include polymer copper complexes having a carbon-carbon bond in the main chain, polymer copper complexes having a carbon-carbon bond in the main chain, and a copper complex containing a fluorine atom, main chain And a copper complex of a polymer having an aromatic hydrocarbon group and / or an aromatic heterocyclic group (hereinafter referred to as an aromatic group-containing polymer).
What was mentioned above is mentioned as a copper component. The copper content in the copper component is preferably 2 to 40% by mass, more preferably 5 to 40% by mass. A copper component may use only 1 type and may use 2 or more types.
Specific examples of the copper component are the same as those used in the low molecular weight copper compound described above, and include copper hydroxide, copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, and pyrroline. Examples include copper oxide, copper naphthenate, copper citrate, copper nitrate, copper sulfate, copper carbonate, copper chlorate, copper (meth) acrylate, copper perchlorate, copper hydroxide, copper acetate, copper chloride, sulfuric acid Copper, copper benzoate and copper (meth) acrylate are preferred, and copper hydroxide, copper acetate and copper sulfate are particularly preferred.
The amount of the copper component is preferably 0.05 to 1 equivalent, more preferably 0.1 to 0.8 equivalent relative to 1 equivalent of the coordination site (preferably an acid group or salt thereof) of the polymer. 2 to 0.5 equivalents are more preferred. By setting the amount of the copper component in such a range, a cured film having higher near-infrared shielding properties tends to be obtained.
　配位部位としては、銅成分に対しアニオンで配位する配位部位、銅成分に対し非共有電子対で配位する配位原子などが挙げられる。
　銅成分に対しアニオンで配位する配位部位は、上述したアニオンで配位する配位部位と同義であり、酸基またはその塩が例示される。酸基は、銅成分と配位結合するものが好ましい。具体的には、酸解離定数（ｐＫａ）が１２以下の酸基が挙げられ、スルホン酸基、カルボン酸基、リン酸基、ホスホン酸基、ホスフィン酸基、イミド酸基、メチド酸基等が好ましい。酸基は、カルボン酸基またはスルホン酸基が好ましく、スルホン酸基がより好ましい。酸基は、１種のみでもよいし、２種以上でもよい。酸基の塩としては、ナトリウム塩等の金属塩（特にアルカリ金属塩）、テトラブチルアンモニウム塩等挙げられる。
　銅成分に対し非共有電子対で配位する配位原子は、上述した非共有電子対で配位する配位原子と同義であり、好ましい範囲も同様である。配位部位の具体例としては、上述した配位子となる化合物で説明したものが挙げられる。
　配位部位の具体例としては、上述した低分子タイプの銅化合物で説明したものが挙げられ、好ましい範囲も同様である。 As a coordination site | part, the coordination site | part coordinated with an anion with respect to a copper component, the coordination atom coordinated with a lone pair with respect to a copper component, etc. are mentioned.
The coordination site | part coordinated with an anion with respect to a copper component is synonymous with the coordination site | part coordinated with the anion mentioned above, and an acid group or its salt is illustrated. The acid group preferably has a coordinate bond with the copper component. Specific examples include acid groups having an acid dissociation constant (pKa) of 12 or less, such as a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, an imidoic acid group, and a methide acid group. preferable. The acid group is preferably a carboxylic acid group or a sulfonic acid group, and more preferably a sulfonic acid group. Only one type of acid group may be used, or two or more types may be used. Examples of the acid group salt include metal salts such as sodium salts (particularly alkali metal salts), tetrabutylammonium salts, and the like.
The coordinating atom coordinated by the lone pair with respect to the copper component is synonymous with the coordinating atom coordinated by the lone pair described above, and the preferred range is also the same. Specific examples of the coordination site include those described above for the compound serving as a ligand.
Specific examples of the coordination site include those described above for the low-molecular copper compound, and the preferred ranges are also the same.
　ポリマータイプの銅化合物は、下記式（１）で表される基を側鎖に含むことが好ましい。
＊－Ｌ1－Ｙ1　　　　　・・・（１）
　一般式（１）において、Ｌは単結合または連結基を表し、Ｙ1は、銅成分に対しアニオンで配位する配位部位、および、銅成分に対し非共有電子対で配位する配位原子から選ばれる１種以上を有する基を表し、＊は、ポリマーの主鎖との連結手を表す。
　一般式（１）において、Ｙ1は、銅成分に対しアニオンで配位する配位部位、および、銅成分に対し非共有電子対で配位する配位原子から選ばれる１種以上を有する基を表す。
　一般式（１）において、Ｌ1が連結基を表す場合、２価の連結基としては、例えば、２価の炭化水素基、ヘテロアリーレン基、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＳＯ2－、－ＮＸ－（Ｘは水素原子あるいはアルキル基を表し、水素原子が好ましい）、または、これらの組み合わせからなる基が挙げられる。
　２価の炭化水素基としては、直鎖状、分岐状または環状のアルキレン基や、アリーレン基が挙げられる。炭化水素基は、置換基を有していてもよいが、無置換であることが好ましい。
　直鎖状のアルキレン基の炭素数としては、１～３０が好ましく、１～１５がより好ましく、１～６がさらに好ましい。また、分岐状のアルキレン基の炭素数としては、３～３０が好ましく、３～１５がより好ましく、３～６がさらに好ましい。環状のアルキレン基は、単環、多環のいずれであってもよい。環状のアルキレン基の炭素数としては、３～２０が好ましく、４～１０がより好ましく、６～１０がさらに好ましい。
　アリーレン基の炭素数としては、６～１８が好ましく、６～１４がより好ましく、６～１０がさらに好ましく、フェニレン基が特に好ましい。
　ヘテロアリーレン基としては、５員環または６員環が好ましい。また、ヘテロアリーレン基は、単環でも縮合環であってもよく、単環または縮合数が２～８の縮合環が好ましく、単環または縮合数が２～４の縮合環がより好ましい。
　Ｌ1が３価以上の連結基を表す場合は、上述した２価の連結基の例として挙げた基のうち、１個以上の水素原子を取り除いた基が挙げられる。 The polymer-type copper compound preferably contains a group represented by the following formula (1) in the side chain.
* -L 1 -Y 1 (1)
In General Formula (1), L represents a single bond or a linking group, and Y 1 is a coordination site that coordinates with a copper component by an anion, and a coordination that coordinates by a lone pair with respect to a copper component. A group having one or more selected from atoms is represented, and * represents a bond to the main chain of the polymer.
In General Formula (1), Y 1 is a group having one or more selected from a coordination site coordinated with an anion to a copper component and a coordination atom coordinated with an unshared electron pair to the copper component. Represents.
In the general formula (1), when L 1 represents a linking group, examples of the divalent linking group include a divalent hydrocarbon group, heteroarylene group, —O—, —S—, —CO—, — COO—, —OCO—, —SO 2 —, —NX— (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a group formed of a combination thereof.
Examples of the divalent hydrocarbon group include a linear, branched or cyclic alkylene group and an arylene group. The hydrocarbon group may have a substituent, but is preferably unsubstituted.
The linear alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 6 carbon atoms. The number of carbon atoms of the branched alkylene group is preferably 3 to 30, more preferably 3 to 15, and still more preferably 3 to 6. The cyclic alkylene group may be monocyclic or polycyclic. The number of carbon atoms of the cyclic alkylene group is preferably 3 to 20, more preferably 4 to 10, and still more preferably 6 to 10.
The number of carbon atoms of the arylene group is preferably 6 to 18, more preferably 6 to 14, still more preferably 6 to 10, and particularly preferably a phenylene group.
The heteroarylene group is preferably a 5-membered ring or a 6-membered ring. The heteroarylene group may be a single ring or a condensed ring, and is preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations.
In the case where L 1 represents a trivalent or higher linking group, a group in which one or more hydrogen atoms have been removed from the above-described examples of the divalent linking group can be given.
＜＜＜＜非共有電子対で配位する配位原子を有する基＞＞＞＞
　上記一般式（１）において、Ｙ1が、非共有電子対で配位する配位原子を有する基を表す場合、Ｙ1としては、例えば下記式（１ａ１）または（１ａ２）で表される基が挙げられる。
＊－Ｌ11－（Ｙ11）p　　　・・・（１ａ１）
＊－Ｌ11－（Ｙ11a－Ｌ12－Ｙ11）p　　　・・・（１ａ２）
　「＊」は式（１）のＬ1との連結手を表す。
　Ｌ11は、単結合または（ｐ＋１）価の連結基を表す。Ｌ11が２価の連結基を表す場合、炭素数１～１２のアルキレン基、炭素数６～１２のアリーレン基、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＳＯ2－、－Ｏ－、－ＮＲ10－（Ｒ10は水素原子あるいはアルキル基を表し、水素原子が好ましい）、または、これらの組み合わせからなる基が好ましい。
　Ｌ11が３価以上の連結基を表す場合は、上述した２価の連結基の例として挙げた基のうち、１個以上の水素原子を取り除いた基が挙げられる。
　Ｌ12は、単結合または２価の連結基を表す。２価の連結基としては、Ｌ11で説明した２価の連結基が好ましく挙げられる。Ｌ12は、単結合、アルキレン基、または、－ＮＨ－と－ＣＯ－との組み合わせからなる基がより好ましい。
　Ｙ11は、非共有電子対で配位する配位原子を含む環、または、上述した群（ＵＥ）で表される部分構造を表す。ｐが２以上の整数を表す場合、複数のＹ11は同一であってもよく、異なっていてもよい。
　Ｙ11aは、非共有電子対で配位する配位原子を含む環、または、上述した群（ＵＥ－１）から選択される少なくとも１種を表す。ｐが２以上の整数を表す場合、複数のＹ11aは同一であってもよく、異なっていてもよい。
　式（１ａ１）および（１ａ２）において、ｐは、１以上の整数を表し、２以上が好ましい。上限は、例えば、５以下が好ましく、３以下がより好ましい。 <<<<< Group having a coordination atom coordinated by an unshared electron pair >>>>
In the general formula (1), when Y 1 represents a group having a coordinating atom coordinated by a lone pair, Y 1 is, for example, a group represented by the following formula (1a1) or (1a2) Is mentioned.
* -L 11 - (Y 11) p ··· (1a1)
* -L 11 - (Y 11a -L 12 -Y 11) p ··· (1a2)
“*” Represents a joint with L 1 in the formula (1).
L 11 represents a single bond or a (p + 1) -valent linking group. When L 11 represents a divalent linking group, an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —CO—, —COO—, —OCO—, —SO 2 —, —O— —NR 10 — (R 10 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a group consisting of a combination thereof.
When L 11 represents a trivalent or higher linking group, a group in which one or more hydrogen atoms have been removed among the groups listed as examples of the divalent linking group described above can be given.
L 12 represents a single bond or a divalent linking group. Preferred examples of the divalent linking group include the divalent linking group described in L 11 . L 12 is more preferably a single bond, an alkylene group, or a group consisting of a combination of —NH— and —CO—.
Y 11 represents a ring containing a coordination atom coordinated by an unshared electron pair or a partial structure represented by the group (UE) described above. When p represents an integer of 2 or more, the plurality of Y 11 may be the same or different.
Y 11a represents at least one selected from a ring containing a coordinating atom coordinated by an unshared electron pair, or the group (UE-1) described above. When p represents an integer of 2 or more, the plurality of Y 11a may be the same or different.
In formulas (1a1) and (1a2), p represents an integer of 1 or more, and preferably 2 or more. For example, the upper limit is preferably 5 or less, and more preferably 3 or less.
＜＜＜＜非共有電子対で配位する配位原子を１個以上とアニオンで配位する配位部位を１個以上有する基＞＞＞＞
　上記一般式（１）において、Ｙ1が、非共有電子対で配位する配位原子を１個以上とアニオンで配位する配位部位を１個以上有する基を表す場合、Ｙ1としては、例えば、下記式で表される基が挙げられる。
＊－Ｌ21－（Ｙ21a－Ｌ23－Ｙ22）q　　　・・・（１ｂ１）
＊－Ｌ21－（Ｙ22a－Ｌ23－Ｙ21）q　　　・・・（１ｂ２）
＊－Ｌ22－（Ｙ21）q（Ｙ22）r　　　・・・（１ｂ３）
＊－Ｌ22－（Ｙ21a－Ｌ23－Ｙ22）q（Ｙ21）r　　　・・・（１ｂ４）
＊－Ｌ22－（Ｙ22a－Ｌ23－Ｙ21）q（Ｙ21）r　　　・・・（１ｂ５）
＊－Ｌ22－（Ｙ21a－Ｌ23－Ｙ22）q（Ｙ22）r　　　・・・（１ｂ６）
＊－Ｌ22－（Ｙ22a－Ｌ23－Ｙ21）q（Ｙ22）r　　　・・・（１ｂ７）
　「＊」は式（１）のＬ1との連結手を表す。
　Ｌ21は、単結合または（ｑ＋１）価の連結基を表す。Ｌ21は、式（１ａ１）のＬ11と同義であり、好ましい範囲も同様である。
　Ｌ22は、単結合または（ｑ＋ｒ＋１）価の連結基を表す。Ｌ22は、式（１ａ１）のＬ11と同義であり、好ましい範囲も同様である。
　Ｌ23は、単結合または２価の連結基を表す。２価の連結基としては、式（１ａ１）のＬ11で説明した２価の連結基が好ましく挙げられる。Ｌ23は、単結合、アルキレン基、または、－ＮＨ－と－ＣＯ－との組み合わせからなる基がより好ましい。
　Ｙ21は、非共有電子対で配位する配位原子を含む環、または、上述した群（ＵＥ）で表される部分構造を表す。ｑ、ｒが、２以上の整数を表す場合、複数のＹ21は同一であってもよく、異なっていてもよい。
　Ｙ21aは、非共有電子対で配位する配位原子を含む環、または、上述した群（ＵＥ－１）から選択される少なくとも１種を表す。ｑ、ｒが、２以上の整数を表す場合、複数のＹ21aは同一であってもよく、異なっていてもよい。
　Ｙ22は、上述した群（ＡＮ）で表される部分構造を表す。ｑ、ｒが、２以上の整数を表す場合、複数のＹ22は同一であってもよく、異なっていてもよい。
　Ｙ22aは、上述した群（ＡＮ－１）から選択される少なくとも１種を表す。
　ｑは、１以上の整数を表し、１～５が好ましく、１～３が特に好ましい。
　ｒは、１以上の整数を表し、１～５が好ましく、１～３が特に好ましい。
　ｑ＋ｒは、２以上を表し、２～５が好ましく、２～３が特に好ましい。 <<<<< Group having at least one coordination atom coordinated by an unshared electron pair and at least one coordination site coordinated by an anion >>>>
In the general formula (1), if Y 1 is represents an unshared electron pair coordinated coordinating atoms of one or more and anion coordinated group having at least one coordination site, as Y 1 is Examples include groups represented by the following formula.
* -L 21 - (Y 21a -L 23 -Y 22) q ··· (1b1)
* -L 21 - (Y 22a -L 23 -Y 21) q ··· (1b2)
* -L 22 - (Y 21) q (Y 22) r ··· (1b3)
* -L 22 - (Y 21a -L 23 -Y 22) q (Y 21) r ··· (1b4)
* -L 22 - (Y 22a -L 23 -Y 21) q (Y 21) r ··· (1b5)
* -L 22 - (Y 21a -L 23 -Y 22) q (Y 22) r ··· (1b6)
* -L 22 - (Y 22a -L 23 -Y 21) q (Y 22) r ··· (1b7)
“*” Represents a joint with L 1 in the formula (1).
L 21 represents a single bond or a (q + 1) -valent linking group. L 21 has the same meaning as L 11 in formula (1a1), and the preferred range is also the same.
L 22 represents a single bond or a (q + r + 1) -valent linking group. L 22 has the same meaning as L 11 in formula (1a1), and the preferred range is also the same.
L 23 represents a single bond or a divalent linking group. Preferred examples of the divalent linking group include the divalent linking groups described for L 11 in formula (1a1). L 23 is more preferably a single bond, an alkylene group, or a group consisting of a combination of —NH— and —CO—.
Y 21 represents a ring containing a coordination atom coordinated by an unshared electron pair or a partial structure represented by the group (UE) described above. When q and r represent an integer of 2 or more, the plurality of Y 21 may be the same or different.
Y 21a represents at least one selected from a ring containing a coordinating atom coordinated by an unshared electron pair, or the group (UE-1) described above. When q and r represent an integer of 2 or more, the plurality of Y 21a may be the same or different.
Y 22 represents a partial structure represented by the group (AN) described above. When q and r represent an integer of 2 or more, the plurality of Y 22 may be the same or different.
Y 22a represents at least one selected from the group (AN-1) described above.
q represents an integer of 1 or more, preferably 1 to 5, and particularly preferably 1 to 3.
r represents an integer of 1 or more, preferably 1 to 5, and particularly preferably 1 to 3.
q + r represents 2 or more, preferably 2 to 5, and particularly preferably 2 to 3.
＜＜＜＜アニオンで配位する配位部位を有する基＞＞＞＞
　上記一般式（１）において、Ｙ1が、アニオンで配位する配位部位を有する基を表す場合、Ｙ1としては、例えば下記式（１ｃ１）または（１ｃ２）で表される基が挙げられる。
＊－Ｌ31－（Ｙ31）p　　　・・・（１ｃ１）
＊－Ｌ31－（Ｙ31a－Ｌ32－Ｙ31）p　　　・・・（１ｃ２）
　「＊」は式（１）のＬ1との連結手を表す。
　Ｌ31は、単結合または（ｐ＋１）価の連結基を表す。Ｌ31は、式（１ａ１）のＬ11と同義であり、好ましい範囲も同様である。
　Ｌ32は、単結合または２価の連結基を表す。２価の連結基としては、式（１ａ２）のＬ12と同義であり、好ましい範囲も同様である。
　Ｙ31は、上述したアニオンで配位する配位部位を表す。ｐが２以上の整数を表す場合、複数のＹ31は同一であってもよく、異なっていてもよい。
　Ｙ31aは、上述した群（ＡＮ－１）から選択される少なくとも１種を表す。ｐが２以上の整数を表す場合、複数のＹ31aは同一であってもよく、異なっていてもよい。
　式（１ｃ１）および（１ｃ２）において、ｐは、１以上の整数を表し、２以上が好ましい。上限は、例えば、５以下が好ましく、３以下がより好ましい。 <<<<< Group having coordination site coordinated by anion >>>>
In the general formula (1), when Y 1 represents a group having a coordination site coordinated by an anion, examples of Y 1 include a group represented by the following formula (1c1) or (1c2). .
* -L 31 - (Y 31) p ··· (1c1)
* -L 31 - (Y 31a -L 32 -Y 31) p ··· (1c2)
“*” Represents a joint with L 1 in the formula (1).
L 31 represents a single bond or a (p + 1) -valent linking group. L 31 has the same meaning as L 11 in formula (1a1), and the preferred range is also the same.
L 32 represents a single bond or a divalent linking group. Examples of the divalent linking group has the same meaning as L 12 in the formula (1a2), and preferred ranges are also the same.
Y 31 represents a coordination site coordinated by the anion described above. When p represents an integer of 2 or more, the plurality of Y 31 may be the same or different.
Y 31a represents at least one selected from the group (AN-1) described above. When p represents an integer of 2 or more, the plurality of Y 31a may be the same or different.
In formulas (1c1) and (1c2), p represents an integer of 1 or more, and preferably 2 or more. For example, the upper limit is preferably 5 or less, and more preferably 3 or less.
　銅化合物は、酸基またはその塩を含む重合体（以下、重合体（Ａ１）ともいう）と銅成分との反応で得られるポリマータイプの銅化合物が好ましい。この銅化合物は、具体的には、重合体が有する酸基イオン部位を配位子とするポリマータイプの銅錯体であることが好ましい。このポリマータイプの銅錯体は、通常、重合体の側鎖に酸基イオン部位を有し、酸基イオン部位が銅に結合（例えば、配位結合）し、銅を起点として、側鎖間に架橋構造を形成している。
　図３は、酸基イオン部位を配位子とするポリマータイプの銅錯体の一例を示すイメージ図であって、６は銅イオンを、７は重合体の主鎖を、８は重合体の側鎖を、９は酸基またはその塩に由来する酸基イオン部位をそれぞれ示している。この場合、酸基イオン部位９が銅に結合（例えば、配位結合）し、銅を起点として、重合体の側鎖８間に架橋構造を形成している。このような構成とすることにより、加熱しても、銅錯体の構造が壊れにくく、耐熱性に優れた硬化膜が得られると推定される。また、重合体が有する酸基イオン部位と、銅成分に由来する銅とを結合させることができるので、銅の含有量をより多くすることができ、結果として、近赤外線遮蔽性がより向上する傾向にあると推定される。また、加熱しても銅が抜け落ちにくいという利点もある。尚、酸基またはその塩は、重合体（Ａ１）の主鎖および側鎖の少なくとも一方に含まれていればよく、少なくとも側鎖に含まれていることが好ましい。 The copper compound is preferably a polymer-type copper compound obtained by a reaction between a polymer containing an acid group or a salt thereof (hereinafter also referred to as polymer (A1)) and a copper component. Specifically, the copper compound is preferably a polymer-type copper complex having an acid group ion site of the polymer as a ligand. This polymer-type copper complex usually has an acid group ion site in the side chain of the polymer, the acid group ion site is bonded to copper (for example, coordinate bond), and copper is the starting point between the side chains. A crosslinked structure is formed.
FIG. 3 is an image diagram showing an example of a polymer-type copper complex having an acid group ion site as a ligand, wherein 6 is a copper ion, 7 is a polymer main chain, and 8 is a polymer side chain. 9 represents an acid group ion site derived from an acid group or a salt thereof. In this case, the acid group ion site 9 is bonded to copper (for example, coordinate bond), and a crosslinked structure is formed between the side chains 8 of the polymer starting from copper. By setting it as such a structure, even if it heats, it is estimated that the structure of a copper complex is hard to break and the cured film excellent in heat resistance is obtained. Moreover, since the acid group ion site | part which a polymer has and the copper originating in a copper component can be combined, copper content can be increased more and, as a result, near-infrared shielding property improves more. It is estimated that there is a tendency. In addition, there is an advantage that copper does not easily fall off even when heated. The acid group or salt thereof may be contained in at least one of the main chain and the side chain of the polymer (A1), and is preferably contained in at least the side chain.
　本発明で用いられる重合体（Ａ０）の第１の実施の形態は、主鎖が炭素－炭素結合を有する重合体であり、下記式（Ａ６）で表される構成単位を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000013
 （式（Ａ６）中、Ｒ1は水素原子またはメチル基を表し、Ｌ1は単結合または２価の連結基を表し、Ｘ1は銅成分に対しアニオンで配位する配位部位、および、銅成分に対し非共有電子対で配位する配位原子から選ばれる１種以上を有する基を表す。）
　上記式（Ａ６）中、Ｒ1は水素原子であることが好ましい。
　上記式（Ａ６）中、Ｌ1は、上述した式（１）のＬ1と同義であり、好ましい範囲も同様である。
　上記式（Ａ６）中、Ｘ1は、上述した式（１）のＹ1と同義であり、酸基またはその塩が好ましい。 In the first embodiment of the polymer (A0) used in the present invention, the main chain is a polymer having a carbon-carbon bond, and preferably contains a structural unit represented by the following formula (A6).
Figure JPOXMLDOC01-appb-C000013
 (In Formula (A6), R 1 represents a hydrogen atom or a methyl group, L 1 represents a single bond or a divalent linking group, X 1 is a coordination site coordinated with an anion to a copper component, and This represents a group having one or more selected from coordinating atoms coordinated with an unshared electron pair to the copper component.)
In the above formula (A6), R 1 is preferably a hydrogen atom.
In the formula (A6), L 1 has the same meaning as L 1 in formula (1) above, and preferred ranges are also the same.
In the formula (A6), X 1 has the same meaning as Y 1 in the above equation (1), acid group or a salt thereof.
　重合体（Ａ０）の第１の実施の形態の具体例としては、下記化合物および下記化合物の塩が挙げられるが、これらに限定されるものではない。
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
 Specific examples of the first embodiment of the polymer (A0) include the following compounds and salts of the following compounds, but are not limited thereto.
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
　重合体（Ａ０）の第２の実施の形態は、下記式（Ａ７－１）、（Ａ７－２）及び（Ａ７－３）のうち少なくともいずれかで表される構成単位を含む。
Figure JPOXMLDOC01-appb-C000017
 （式（Ａ７－１）中、Ｒ1は脂肪族炭化水素基を表し、Ｙ1は単結合又は２価の連結基を表し、Ｘ1は銅成分に対しアニオンで配位する配位部位、および、銅成分に対し非共有電子対で配位する配位原子から選ばれる１種以上を有する基を表し、Ｒ1及びＹ1の少なくとも１つがフッ素原子で置換されている。
　式（Ａ７－２）中、Ｒ2は脂肪族炭化水素基を表し、Ｒ3は炭化水素基を表し、Ｙ2は単結合又は２価の連結基を表し、Ｒ2、Ｒ3及びＹ2の少なくとも１つがフッ素原子で置換されている。
　式（Ａ７－３）中、Ａｒ1は芳香族炭化水素基及び／又は芳香族ヘテロ環基を表し、Ｒ4は有機基を表し、Ｙ3は単結合又は２価の連結基を表し、Ｘ2は銅成分に対しアニオンで配位する配位部位、および、銅成分に対し非共有電子対で配位する配位原子から選ばれる１種以上を有する基を表し、Ａｒ1、Ｒ4及びＹ3の少なくとも１つがフッ素原子で置換されている。） The second embodiment of the polymer (A0) includes a structural unit represented by at least one of the following formulas (A7-1), (A7-2) and (A7-3).
Figure JPOXMLDOC01-appb-C000017
 (In Formula (A7-1), R 1 represents an aliphatic hydrocarbon group, Y 1 represents a single bond or a divalent linking group, and X 1 represents a coordination site that coordinates with an anion to the copper component; And a group having one or more selected from a coordinating atom coordinated by a lone pair with respect to the copper component, and at least one of R 1 and Y 1 is substituted with a fluorine atom.
In the formula (A7-2), R 2 represents an aliphatic hydrocarbon group, R 3 represents a hydrocarbon group, Y 2 represents a single bond or a divalent linking group, R 2 , R 3 and Y 2 At least one of is substituted with a fluorine atom.
In formula (A7-3), Ar 1 represents an aromatic hydrocarbon group and / or an aromatic heterocyclic group, R 4 represents an organic group, Y 3 represents a single bond or a divalent linking group, and X 2 represents a group having at least one selected from a coordination site coordinated with an anion to a copper component and a coordination atom coordinated with an unshared electron pair to the copper component, Ar 1 , R 4 and At least one of Y 3 is substituted with a fluorine atom. )
　式（Ａ７－１）および式（Ａ７－２）中、Ｒ1およびＲ2がそれぞれ独立して脂肪族炭化水素基を表し、例えば、直鎖状、分岐状又は環状のアルキル基が挙げられる。直鎖状のアルキル基の炭素数としては、１～２０が好ましく、１～１０がより好ましく、１～６がさらに好ましい。分岐状のアルキル基の炭素数としては、３～２０が好ましく、３～１０がより好ましく、３～６がさらに好ましい。環状のアルキル基は、単環、多環のいずれであってもよい。環状のアルキル基の炭素数としては、３～２０が好ましく、４～１０がより好ましく、６～１０がさらに好ましい。
　Ｒ1およびＲ2が置換基を有している場合、例えば、重合性基（好ましくは、炭素－炭素二重結合を含む重合性基）、ハロゲン原子（フッ素原子、塩素原子、臭素原子、ヨウ素原子）、アルキル基、カルボン酸エステル基、ハロゲン化アルキル基、アルコキシ基、メタクリロイルオキシ基、アクリロイルオキシ基、エーテル基、スルホニル基、スルフィド基、アミド基、アシル基、ヒドロキシ基、カルボン酸基、アラルキル基、－Ｓｉ－（ＯＲN22）3などが例示され、フッ素原子が特に好ましい。(ＲN22はアルキル基を表し、炭素数１～３が好ましい。)  In formula (A7-1) and formula (A7-2), R 1 and R 2 each independently represents an aliphatic hydrocarbon group, and examples thereof include a linear, branched or cyclic alkyl group. The number of carbon atoms of the linear alkyl group is preferably 1-20, more preferably 1-10, and even more preferably 1-6. The carbon number of the branched alkyl group is preferably 3 to 20, more preferably 3 to 10, and further preferably 3 to 6. The cyclic alkyl group may be monocyclic or polycyclic. The number of carbon atoms in the cyclic alkyl group is preferably 3 to 20, more preferably 4 to 10, and still more preferably 6 to 10.
When R 1 and R 2 have a substituent, for example, a polymerizable group (preferably a polymerizable group containing a carbon-carbon double bond), a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine) Atom), alkyl group, carboxylic acid ester group, halogenated alkyl group, alkoxy group, methacryloyloxy group, acryloyloxy group, ether group, sulfonyl group, sulfide group, amide group, acyl group, hydroxy group, carboxylic acid group, aralkyl Group, —Si— (OR N22 ) 3 and the like are exemplified, and a fluorine atom is particularly preferred. (R N22 represents an alkyl group, preferably having 1 to 3 carbon atoms.)
　式（Ａ７－１）～式（Ａ７－３）中、Ｙ1～Ｙ3がそれぞれ独立して２価の連結基を表す場合、２価の連結基は、上述した式（Ａ６）中の２価の連結基と同義である。
　炭化水素基としては、例えば、直鎖状、分岐状又は環状のアルキレン基や、アリーレン基が挙げられる。直鎖状のアルキレン基の炭素数としては、１～２０が好ましく、１～１０がより好ましく、１～６がさらに好ましい。分岐状のアルキレン基の炭素数としては、３～２０が好ましく、３～１０がより好ましく、３～６がさらに好ましい。環状のアルキレン基は、単環、多環のいずれであってもよい。環状のアルキレン基の炭素数としては、３～２０が好ましく、４～１０がより好ましく、６～１０がさらに好ましい。
　アリーレン基およびヘテロアリーレン基としては、上述した式（Ａ６）中の２価の連結基がアリーレン基である場合と同義であり、好ましい範囲も同義である。
　本発明では、特に、Ｙ1が２価の連結基を表す場合、－ＣＯＯ－、－ＣＯ－、－Ｏ－、－ＮＸ－（Ｘは水素原子又はアルキル基を表し、水素原子が好ましい）、炭化水素基（好ましくは、炭素数１～３０のアルキレン基又はアリーレン基）、又は、これらの組み合わせからなる基であることが好ましい。 In the formulas (A7-1) to (A7-3), when Y 1 to Y 3 each independently represents a divalent linking group, the divalent linking group is represented by 2 in the above formula (A6). Synonymous with a valent linking group.
Examples of the hydrocarbon group include a linear, branched or cyclic alkylene group and an arylene group. The number of carbon atoms in the linear alkylene group is preferably 1-20, more preferably 1-10, and even more preferably 1-6. The carbon number of the branched alkylene group is preferably 3 to 20, more preferably 3 to 10, and further preferably 3 to 6. The cyclic alkylene group may be monocyclic or polycyclic. The number of carbon atoms of the cyclic alkylene group is preferably 3 to 20, more preferably 4 to 10, and still more preferably 6 to 10.
As an arylene group and heteroarylene group, it is synonymous with the case where the bivalent coupling group in Formula (A6) mentioned above is an arylene group, and its preferable range is also synonymous.
In the present invention, particularly when Y 1 represents a divalent linking group, —COO—, —CO—, —O—, —NX— (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), A hydrocarbon group (preferably an alkylene group or arylene group having 1 to 30 carbon atoms) or a combination thereof is preferable.
　式（Ａ７－１）および式（Ａ７－３）中、Ｘ1およびＸ2はそれぞれ独立して銅成分に対しアニオンで配位する配位部位、および、銅成分に対し非共有電子対で配位する配位原子から選ばれる１種以上を有する基を表し、上述した銅成分に対しアニオンで配位する配位部位、および、銅成分に対し非共有電子対で配位する配位原子から選ばれる１種以上を有する基と同義であり、酸基またはその塩が好ましい。
　また、式（Ａ７－１）中、Ｒ1及びＹ1の少なくとも１つがフッ素原子で置換されており、Ｒ1及びＹ1のうち、少なくともＹ1がフッ素原子で置換されていることが好ましい。ここで、例えば、Ｒ1がフッ素原子で置換されているとは、Ｒ1を構成する水素原子の少なくとも１つがフッ素原子で置換されていることをいう。Ｒ1及びＹ1は、少なくとも一方がパーフルオロ基であることが好ましい。 In Formula (A7-1) and Formula (A7-3), X 1 and X 2 are each independently a coordination site that coordinates with a copper component with an anion, and a copper component with a lone pair. Represents a group having one or more selected from coordinated coordination atoms, from the coordination site coordinated by the anion to the copper component described above, and from the coordination atom coordinated by an unshared electron pair to the copper component It is synonymous with the group which has 1 or more types chosen, and an acid group or its salt is preferable.
In the formula (A7-1), at least one of R 1 and Y 1 is is substituted with a fluorine atom, of R 1 and Y 1, it is preferable that at least Y 1 is substituted with a fluorine atom. Here, for example, R 1 is substituted with a fluorine atom means that at least one hydrogen atom constituting R 1 is substituted with a fluorine atom. At least one of R 1 and Y 1 is preferably a perfluoro group.
　式（Ａ７－２）中、Ｒ3は炭化水素基を表し、上記式（Ａ７－１）中のＲ1で説明したアルキル基や、アリール基が挙げられる。アルキル基は、上記式（Ａ７－１）中のＲ1で説明したアルキル基と同義であり、好ましい範囲も同様である。アリール基の炭素数は、６～１８が好ましく、６～１４がより好ましく、６～１０がより好ましい。Ｒ3が置換基を有している場合、フッ素原子が好ましい。
　式（Ａ７－２）中、Ｒ2、Ｒ3及びＹ2の少なくとも１つがフッ素原子を有し、Ｒ2、Ｒ3及びＹ2の少なくとも１つがパーフルオロ基であることが好ましい。 In formula (A7-2), R 3 represents a hydrocarbon group, and examples thereof include the alkyl group and aryl group described for R 1 in formula (A7-1). The alkyl group has the same meaning as the alkyl group described for R 1 in the above formula (A7-1), and the preferred range is also the same. The number of carbon atoms in the aryl group is preferably 6 to 18, more preferably 6 to 14, and more preferably 6 to 10. When R 3 has a substituent, a fluorine atom is preferable.
Wherein (A7-2), at least one of R 2, R 3 and Y 2 is a fluorine atom, it is preferred that R 2, R 3 and Y 2 at least one of a perfluoroalkyl group.
　式（Ａ７－３）中、Ａｒ1は芳香族炭化水素基を表すことが好ましい。芳香族炭化水素基としては、炭素数６～２０のアリール基が好ましく、フェニル基又はビフェニル基がより好ましい。芳香族ヘテロ環基としては、例えば、炭素数２～３０の芳香族ヘテロ環基を用いることができる。
　式（Ａ７－３）中、Ｒ4は有機基を表し、炭素数１～６のアルキレン基、炭素数１～６のシクロアルキレン基、－Ｏ－、－ＳＯ2－、－ＣＯ－、－ＮＲN－（ＲNは水素原子又はアルキル基）、及びこれらの組み合わせが例示される。Ｒ4がアルキレン基の場合、炭素数１のアルキル基が好ましく、－Ｃ（Ｒ4A）（Ｒ4B）－で表される基がより好ましい。Ｒ4A及びＲ4Bはそれぞれ独立してフッ素原子、又はアルキル基（好ましくは炭素数１～３のアルキル基）を表し、アルキル基はフッ素原子で置換されてもよい。Ｒ4が－Ｃ（Ｒ4A）（Ｒ4B）－を含む場合、Ｒ4AとＲ4Bが互いに結合して環を形成してもよい。
　Ｒ4がシクロアルキレン基の場、炭素数４のシクロアルキレン基が好ましく、中でもパーフルオロシクロブチレン基が好ましい。
　Ｒ4の好ましい例としては、－Ｃ（Ｒ4A）（Ｒ4B）－、－Ｏ－、－ＣＯ－、－ＳＯ2－が挙げられる。
　式（Ａ７－３）中、Ａｒ1、Ｒ4及びＹ3の少なくとも１つがフッ素原子を有し、Ａｒ1、Ｒ4及びＹ3の少なくとも１つがパーフルオロ基であることが好ましい。
　また、式（Ａ７－３）で表される構成単位は、構成単位中にＡｒ1及びＲ4をそれぞれ１つ以上有していればよく、２以上有していてもよい。 In formula (A7-3), Ar 1 preferably represents an aromatic hydrocarbon group. As the aromatic hydrocarbon group, an aryl group having 6 to 20 carbon atoms is preferable, and a phenyl group or a biphenyl group is more preferable. As the aromatic heterocyclic group, for example, an aromatic heterocyclic group having 2 to 30 carbon atoms can be used.
In the formula (A7-3), R 4 represents an organic group, an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 1 to 6 carbon atoms, —O—, —SO 2 —, —CO—, —NR N- (R N is a hydrogen atom or an alkyl group), and combinations thereof are exemplified. When R 4 is an alkylene group, an alkyl group having 1 carbon atom is preferable, and a group represented by —C (R 4A ) (R 4B ) — is more preferable. R 4A and R 4B each independently represent a fluorine atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms), and the alkyl group may be substituted with a fluorine atom. When R 4 contains —C (R 4A ) (R 4B ) —, R 4A and R 4B may be bonded to each other to form a ring.
When R 4 is a cycloalkylene group, a cycloalkylene group having 4 carbon atoms is preferable, and a perfluorocyclobutylene group is particularly preferable.
Preferable examples of R 4 include —C (R 4A ) (R 4B ) —, —O—, —CO—, —SO 2 —.
Wherein (A7-3), has at least one fluorine atom of Ar 1, R 4 and Y 3, Ar 1, it is preferred that at least one of R 4 and Y 3 is a perfluoroalkyl group.
In addition, the structural unit represented by the formula (A7-3) may have one or more of Ar 1 and R 4 in the structural unit, and may have two or more.
　重合体の重量平均分子量は、２０００以上が好ましく、２０００～２００万がより好ましく、５０００～４００，０００がさらに好ましい。 The weight average molecular weight of the polymer is preferably 2000 or more, more preferably 2000 to 2 million, and still more preferably 5000 to 400,000.
　重合体（Ａ０）の第２の実施の形態の具体例としては、下記化合物及び下記化合物の塩が挙げられるが、これらに限定されるものではない。また、その他、ナフィオン（登録商標）に代表されるパーフルオロカーボンスルホン酸ポリマーを用いることもできる。
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
 Specific examples of the second embodiment of the polymer (A0) include the following compounds and salts of the following compounds, but are not limited thereto. In addition, a perfluorocarbon sulfonic acid polymer represented by Nafion (registered trademark) can also be used.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
　重合体（Ａ０）の第３の実施の形態は、芳香族基含有重合体の銅錯体である。
　芳香族炭化水素基としては、アリール基が好ましい。アリール基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１２がさらに好ましい。芳香族炭化水素基は単環又は多環であってもよいが、単環が好ましい。具体的には、アリール基は、フェニル基、ナフチル基又はビフェニル基が好ましい。
　芳香族ヘテロ環基としては、炭素数２～３０の芳香族ヘテロ環基が好ましい。芳香族ヘテロ環基は、５員環又は６員環の、単環又は縮合環が好ましく、単環又は縮合数が２～８の縮合環がより好ましい。ヘテロ環に含まれるヘテロ原子としては、窒素、酸素、硫黄原子が好ましく、窒素または酸素がより好ましい。
　芳香族炭化水素基及び／又は芳香族ヘテロ環基が置換基を有していている場合、置換基としては、例えば、アルキル基、重合性基（好ましくは、炭素－炭素二重結合を含む重合性基）、ハロゲン原子（フッ素原子、塩素原子、臭素原子、ヨウ素原子）、カルボン酸エステル基、ハロゲン化アルキル基、アルコキシ基、メタクリロイルオキシ基、アクリロイルオキシ基、エーテル基、スルホニル基、スルフィド基、アミド基、アシル基、ヒドロキシ基、カルボン酸基、アラルキル基などが例示され（以下、これらの置換基を置換基Ｔを呼ぶ）、アルキル基（特に炭素数１～３のアルキル基）が好ましい。
　特に、芳香族基含有重合体は、ポリエーテルスルホン系重合体、ポリスルホン系重合体、ポリエーテルケトン系重合体、ポリフェニレンエーテル系重合体、ポリイミド系重合体、ポリベンズイミダゾール系重合体、ポリフェニレン系重合体、フェノール樹脂系重合体、ポリカーボネート系重合体、ポリアミド系重合体及びポリエステル系重合体から選択される少なくとも１種の重合体であることが好ましい。以下に各重合体の例を示す。
　ポリエーテルスルホン系重合体：（－Ｏ－Ｐｈ－ＳＯ2－Ｐｈ－）で表される主鎖構造（Ｐｈはフェニレン基を示す、以下同じ）を有する重合体
　ポリスルホン系重合体：（－Ｏ－Ｐｈ－Ｐｈ－Ｏ－Ｐｈ－ＳＯ2－Ｐｈ－）で表される主鎖構造を有する重合体
　ポリエーテルケトン系重合体：（－Ｏ－Ｐｈ－Ｏ－Ｐｈ－Ｃ（＝Ｏ）－Ｐｈ－）で表される主鎖構造を有する重合体
　ポリフェニレンエーテル系重合体：（－Ｐｈ－Ｏ－、－Ｐｈ－Ｓ－）で表される主鎖構造を有する重合体
　ポリフェニレン系重合体：（－Ｐｈ－）で表される主鎖構造を有する重合体
　フェノール樹脂系重合体：（－Ｐｈ（ＯＨ）－ＣＨ2－）で表される主鎖構造を有する重合体
　ポリカーボネート系重合体：（－Ｐｈ－Ｏ－Ｃ（＝Ｏ）－Ｏ－）で表される主鎖構造を有する重合体
　ポリアミド系重合体としては、例えば、（－Ｐｈ－Ｃ（＝Ｏ）－ＮＨ－）で表される主鎖構造を有する重合体
　ポリエステル系重合体としては、例えば、（－Ｐｈ－Ｃ（＝Ｏ）Ｏ－）で表される主鎖構造を有する重合体
　ポリエーテルスルホン系重合体、ポリスルホン系重合体及びポリエーテルケトン系重合体としては、例えば、特開２００６－３１００６８号公報の段落００２２及び特開２００８－２７８９０号公報の段落００２８に記載の主鎖構造を参酌でき、これらの内容は本願明細書に組み込まれる。
　ポリイミド系重合体としては、特開２００２－３６７６２７号公報の段落００４７～００５８の記載及び特開２００４－３５８９１号公報の００１８～００１９に記載の主鎖構造を参酌でき、これらの内容は本願明細書に組み込まれる。 The third embodiment of the polymer (A0) is a copper complex of an aromatic group-containing polymer.
As the aromatic hydrocarbon group, an aryl group is preferable. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 12 carbon atoms. The aromatic hydrocarbon group may be monocyclic or polycyclic, but is preferably monocyclic. Specifically, the aryl group is preferably a phenyl group, a naphthyl group, or a biphenyl group.
As the aromatic heterocyclic group, an aromatic heterocyclic group having 2 to 30 carbon atoms is preferable. The aromatic heterocyclic group is preferably a 5-membered or 6-membered monocyclic or condensed ring, more preferably a monocyclic ring or a condensed ring having 2 to 8 condensations. As a hetero atom contained in the heterocycle, a nitrogen, oxygen, or sulfur atom is preferable, and nitrogen or oxygen is more preferable.
When the aromatic hydrocarbon group and / or aromatic heterocyclic group has a substituent, examples of the substituent include an alkyl group and a polymerizable group (preferably a polymerization containing a carbon-carbon double bond). Functional group), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxylic acid ester group, halogenated alkyl group, alkoxy group, methacryloyloxy group, acryloyloxy group, ether group, sulfonyl group, sulfide group, Examples include an amide group, an acyl group, a hydroxy group, a carboxylic acid group, and an aralkyl group (hereinafter, these substituents are referred to as a substituent T), and an alkyl group (particularly an alkyl group having 1 to 3 carbon atoms) is preferable.
In particular, aromatic group-containing polymers are polyethersulfone polymers, polysulfone polymers, polyetherketone polymers, polyphenylene ether polymers, polyimide polymers, polybenzimidazole polymers, polyphenylene polymers. It is preferably at least one polymer selected from a polymer, a phenol resin polymer, a polycarbonate polymer, a polyamide polymer, and a polyester polymer. Examples of each polymer are shown below.
Polyethersulfone polymer: a polymer having a main chain structure represented by (—O—Ph—SO 2 —Ph—) (Ph represents a phenylene group, the same shall apply hereinafter) Polysulfone polymer: (—O— Polymer having a main chain structure represented by Ph—Ph—O—Ph—SO 2 —Ph—) Polyetherketone polymer: (—O—Ph—O—Ph—C (═O) —Ph— ) Polymer having main chain structure represented by: Polyphenylene ether polymer: Polymer having main chain structure represented by (-Ph-O-, -Ph-S-) Polyphenylene polymer: (-Ph Polymer having main chain structure represented by-) Phenol resin polymer: Polymer having main chain structure represented by (-Ph (OH) -CH 2- ) Polycarbonate polymer: (-Ph- Having a main chain structure represented by O—C (═O) —O—) Polymer As the polyamide-based polymer, for example, a polymer having a main chain structure represented by (-Ph-C (= O) -NH-) As the polyester-based polymer, for example, (-Ph-C ( = O) Polymer having main chain structure represented by O-) Examples of the polyethersulfone-based polymer, polysulfone-based polymer, and polyetherketone-based polymer include paragraph 0022 of JP-A-2006-310068. And the main chain structure described in paragraph 0028 of JP-A-2008-27890 can be referred to, and the contents thereof are incorporated in the present specification.
As the polyimide polymer, the main chain structures described in paragraphs 0047 to 0058 of JP-A No. 2002-367627 and 0018 to 0019 of JP-A No. 2004-35891 can be taken into consideration. Incorporated into.
　芳香族基含有重合体の好ましい一例は、下記式（Ａ８）で表される構成単位を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000023
 （式（Ａ８）中、Ａｒ1は芳香族炭化水素基及び／又は芳香族ヘテロ環基を表し、Ｙ1は単結合又は２価の連結基を表し、Ｘ1は銅成分に対しアニオンで配位する配位部位、および、銅成分に対し非共有電子対で配位する配位原子から選ばれる１種以上を有する基を表す。） A preferred example of the aromatic group-containing polymer preferably includes a structural unit represented by the following formula (A8).
Figure JPOXMLDOC01-appb-C000023
 (In the formula (A8), Ar 1 represents an aromatic hydrocarbon group and / or an aromatic heterocyclic group, Y 1 represents a single bond or a divalent linking group, and X 1 is an anion with respect to the copper component. Represents a group having at least one selected from a coordination site that coordinates and a coordination atom that coordinates with a copper component by an unshared electron pair.)
　式（Ａ８）中、Ａｒ1が芳香族炭化水素基を表す場合、上述した芳香族炭化水素基と同義であり、好ましい範囲も同様である。Ａｒ1が芳香族ヘテロ環基を表す場合、上述した芳香族ヘテロ環基と同義であり、好ましい範囲も同様である。
　Ａｒ1は、上記式（Ａ８）中の－Ｙ1－Ｘ1の他に置換基を有していてもよい。Ａｒ1が置換基を有する場合、置換基としては上述した置換基Ｔと同義であり、好ましい範囲も同様である。 In formula (A8), when Ar 1 represents an aromatic hydrocarbon group, it is synonymous with the aromatic hydrocarbon group described above, and the preferred range is also the same. When Ar 1 represents an aromatic heterocyclic group, it is synonymous with the aromatic heterocyclic group described above, and the preferred range is also the same.
Ar 1 may have a substituent in addition to —Y 1 —X 1 in the above formula (A8). When Ar 1 has a substituent, the substituent has the same meaning as the substituent T described above, and the preferred range is also the same.
　式（Ａ８）中、Ｙ1は、単結合であることが好ましい。Ｙ1が２価の連結基を表す場合、２価の連結基としては、例えば、炭化水素基、芳香族ヘテロ環基、－Ｏ－、－Ｓ－、－ＳＯ2－、－ＣＯ－、－Ｃ（＝Ｏ）Ｏ－、－Ｏ－Ｃ（＝Ｏ）－、－ＳＯ2－、－ＮＸ－（Ｘは水素原子又はアルキル基を表し、水素原子が好ましい）、－Ｃ（ＲY1）（ＲY2）－、又は、これらの組み合わせからなる基が挙げられる。ここで、ＲY1及びＲY2は、それぞれ独立して水素原子、フッ素原子又はアルキル基を表す。
　炭化水素基としては、例えば、直鎖状、分岐状又は環状のアルキレン基や、アリーレン基が挙げられる。直鎖状のアルキレン基の炭素数としては、１～２０が好ましく、１～１０がより好ましく、１～６がさらに好ましい。分岐状のアルキレン基の炭素数としては、３～２０が好ましく、３～１０がより好ましく、３～６がさらに好ましい。環状のアルキレン基は、単環、多環のいずれであってもよい。環状のアルキレン基の炭素数としては、３～２０が好ましく、４～１０がより好ましく、６～１０がさらに好ましい。これら直鎖状、分岐状又は環状のアルキレン基は、アルキレン基中の水素原子がフッ素原子で置換されていてもよい。
　アリーレン基は、上述した式（Ａ７－１）～式（Ａ７－３）中の２価の連結基がアリーレン基である場合と同義である。
　芳香族ヘテロ環基としては、５員環または６員環が好ましい。また、芳香族ヘテロ環基は、単環でも縮合環であってもよく、単環または縮合数が２～８の縮合環が好ましく、単環または縮合数が２～４の縮合環がより好ましい。
　式（Ａ８）中、Ｘ1で表される銅成分に対しアニオンで配位する配位部位、および、銅成分に対し非共有電子対で配位する配位原子から選ばれる１種以上を有する基としては、上述した銅成分に対しアニオンで配位する配位部位、および、銅成分に対し非共有電子対で配位する配位原子から選ばれる１種以上を有する基と同義であり、酸基またはその塩が好ましい。 In formula (A8), Y 1 is preferably a single bond. When Y 1 represents a divalent linking group, examples of the divalent linking group include a hydrocarbon group, an aromatic heterocyclic group, —O—, —S—, —SO 2 —, —CO—, — C (═O) O—, —O—C (═O) —, —SO 2 —, —NX— (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), —C (R Y1 ) ( R Y2 ) —, or a group consisting of a combination thereof. Here, R Y1 and R Y2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group.
Examples of the hydrocarbon group include a linear, branched or cyclic alkylene group and an arylene group. The number of carbon atoms in the linear alkylene group is preferably 1-20, more preferably 1-10, and even more preferably 1-6. The carbon number of the branched alkylene group is preferably 3 to 20, more preferably 3 to 10, and further preferably 3 to 6. The cyclic alkylene group may be monocyclic or polycyclic. The number of carbon atoms of the cyclic alkylene group is preferably 3 to 20, more preferably 4 to 10, and still more preferably 6 to 10. In these linear, branched or cyclic alkylene groups, a hydrogen atom in the alkylene group may be substituted with a fluorine atom.
The arylene group has the same meaning as the case where the divalent linking group in the above formulas (A7-1) to (A7-3) is an arylene group.
As the aromatic heterocyclic group, a 5-membered ring or a 6-membered ring is preferable. The aromatic heterocyclic group may be a single ring or a condensed ring, and is preferably a single ring or a condensed ring having 2 to 8 condensations, more preferably a single ring or a condensed ring having 2 to 4 condensations. .
Having the formula (A8), coordinated coordination site with an anion to copper component represented by X 1, and, at least one selected from the ligand atoms coordinating with unshared electron pair to the copper component The group is synonymous with the above-described group having at least one selected from the coordination site coordinated with the anion to the copper component and the coordination atom coordinated with the lone pair to the copper component, An acid group or a salt thereof is preferred.
　重合体（Ａ０）の第３の実施の形態の具体例としては、下記化合物及び下記酸基の塩の化合物が挙げられるが、これらに限定されるものではない。
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
 Specific examples of the third embodiment of the polymer (A0) include the following compounds and compounds of the following acid group salts, but are not limited thereto.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
　ピロロピロール色素としては、例えば特開２０１１－６８７３１号公報の段落００２４～００５２（対応する米国特許出願公開第２０１１／００７０４０７号明細書の[００４３]～[００７４]）を参酌でき、この内容は本願明細書に組み込まれる。
　また、フタロシアニン系化合物、ナフタロシアニン化合物、インモニウム系化合物、シアニン系色素、スクアリウム系色素及びクロコニウム化合物は、特開２０１０－１１１７５０号公報の段落００１０～００８１に開示の化合物を使用してもよく、この内容は本明細書に組み込まれる。シアニン系色素は、例えば、「機能性色素、大河原信／松岡賢／北尾悌次郎／平嶋恒亮・著、講談社サイエンティフィック」を参酌することができ、この内容は本願明細書に組み込まれる。
　また、本発明では、近赤外線吸収物質として、特開平０７－１６４７２９号公報の段落０００４～００１６に開示の化合物や、特開２００２－１４６２５４号公報の段落００２７～００６２に開示の化合物、特開２０１１－１６４５８３号公報の段落００３４～００６７に開示のＣｕおよび／またはＰを含む酸化物の結晶子からなり数平均凝集粒子径が５～２００ｎｍである近赤外線吸収粒子を使用してもよく、この内容は本明細書に組み込まれる。
　その他、本発明では、「イーエクスカラーＩＲ－１０」、「イーエクスカラーＩＲ－１２」、「イーエクスカラーＩＲ－１４」、「イーエクスカラーＨＡ－１」、「イーエクスカラーＨＡ－１４」（いずれも商品名、日本触媒社製）、「ＳＩＲ－１２８」、「ＳＩＲ－１３０」、「ＳＩＲ－１３２」、「ＳＩＲ－１５２」、「ＳＩＲ－１５９」、「ＳＩＲ－１６２」（いずれも商品名、三井化学社製）、「Ｋａｙａｓｏｒｂ ＩＲＧ－０２２」、「Ｋａｙａｓｏｒｂ ＩＲＧ－０２３」、「ＫａｙａｓｏｒｂＩＲＧ－０４０」（いずれも商品名、日本化薬社製）、「ＣＩＲ－１０８１」（商品名、日本カーリット社製）、「ＮＩＲ－ＩＭ１」、「ＮＩＲ－ＡＭ１」（いずれも商品名、ナガセケムテックス社製）、セシウム酸化タングステン化合物（住友金属鉱山社製のＹＭＦ－０２Ａ、ＹＭＦ－０１Ａ－２、ＹＭＦ－１０Ａ－1）、「Ｌｕｍｏｇｅｎ ＩＲ７６５」、「Ｌｕｍｏｇｅｎ ＩＲ７８８」（ＢＡＳＦ社製）、「ＡＲＳ６７０Ｔ」、「ＩＲＡ８００」、「ＩＲＡ８５０」、「ＩＲＡ８６８」（Exciton社製）等を用いることができる。 As the pyrrolopyrrole dye, for example, paragraphs 0024 to 0052 of JP 2011-68731 A (corresponding US Patent Application Publication No. 2011/0070407, [0043] to [0074]) can be referred to. Incorporated in the description.
Further, as the phthalocyanine compound, naphthalocyanine compound, immonium compound, cyanine dye, squalium dye, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP2010-11750A may be used. This content is incorporated herein. As the cyanine dye, for example, “functional dye, Nobu Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein.
In the present invention, as the near-infrared absorbing substance, compounds disclosed in paragraphs 0004 to 0016 of JP 07-164729 A, compounds disclosed in paragraphs 0027 to 0062 of JP 2002-146254 A, JP 2011 Near infrared-absorbing particles comprising crystallites of oxides containing Cu and / or P disclosed in paragraphs 0034 to 0067 of JP-A-166483 and having a number average aggregated particle diameter of 5 to 200 nm may be used. Are incorporated herein.
In addition, in the present invention, “e-ex color IR-10”, “e-ex color IR-12”, “e-ex color IR-14”, “e-ex color HA-1”, “e-ex color HA-14”. (All trade names, manufactured by Nippon Shokubai Co., Ltd.), “SIR-128”, “SIR-130”, “SIR-132”, “SIR-152”, “SIR-159”, “SIR-162” (all (Trade name, manufactured by Mitsui Chemicals), “Kayasorb IRG-022”, “Kayasorb IRG-023”, “Kayasorb IRG-040” (all trade names, manufactured by Nippon Kayaku Co., Ltd.), “CIR-1081” (trade name, Nippon Carlit Co., Ltd.), "NIR-IM1", "NIR-AM1" (all trade names, manufactured by Nagase ChemteX), cesium tungsten oxide compound (YMF-02A, YMF-01A-2, YMF-10A-1 manufactured by Sumitomo Metal Mining Co., Ltd.), “Lumogen IR765”, “Lumogen IR788” (manufactured by BASF), “ARS670T”, “IRA800”, “IRA850” "IRA868" (manufactured by Exciton) or the like can be used.
　近赤外線吸収物質として上記ポリマータイプの銅錯体（例えば、重量平均分子量が２０００以上のもの）を用いる場合、近赤外線吸性組成物中における近赤外線吸収物質の含有量は、組成物中の全固形分の３０質量％以上が好ましく、５０質量％以上がより好ましい。特に、３０～１００質量％であることが好ましく、５０～１００質量％であることがより好ましい。
　また、近赤外線吸収物質として上記ポリマータイプの銅錯体以外のもの（例えば、重量平均分子量が２０００未満のもの）を用いる場合、近赤外線吸性組成物中における近赤外線吸収物質の含有量は、組成物中の全固形分の０．０１質量％以上が好ましく、０．１質量％以上がより好ましい。特に、０．０１～５０質量％とすることが好ましく、０．１～３０質量％とすることがより好ましい。 When the polymer type copper complex (for example, having a weight average molecular weight of 2000 or more) is used as the near-infrared absorbing substance, the content of the near-infrared absorbing substance in the near-infrared absorbing composition is the total solid content in the composition. 30 mass% or more of a minute is preferable, and 50 mass% or more is more preferable. In particular, it is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass.
Moreover, when using things other than the said polymer type copper complex as a near-infrared absorbing substance (for example, a weight average molecular weight is less than 2000), content of the near-infrared absorbing substance in a near-infrared absorptive composition is composition 0.01 mass% or more of the total solid content in the product is preferable, and 0.1 mass% or more is more preferable. In particular, the content is preferably 0.01 to 50% by mass, and more preferably 0.1 to 30% by mass.
＜＜水＞＞
　本発明で用いられる組成物は、水をさらに含んでいることが好ましい。組成物中の水の含有量は、１質量％以上が好ましく、１０質量％以上がより好ましく、２０質量％以上がさらに好ましく、３０質量％以上が特に好ましい。特に、１～９０質量％であることが好ましく、１０～８０質量％であることがより好ましい。 << Water >>
It is preferable that the composition used in the present invention further contains water. The content of water in the composition is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more. In particular, the content is preferably 1 to 90% by mass, and more preferably 10 to 80% by mass.
＜＜沸点が１００℃より高い極性液体＞＞
　本発明で用いることができる沸点が１００℃より高い極性液体は、１種単独で用いてもよく、２種以上を併用してもよい。
　極性液体の沸点の上限は、特に限定されないが、２５０℃以下が好ましく、２３０℃以下がより好ましく、２００℃以下がさらに好ましい。
　極性液体と水との沸点の差は、１０℃以上が好ましく２０℃以上がより好ましく、３０℃以上がさらに好ましく、５０℃以上がさらに好ましい。沸点の差がこのような範囲を満たすことにより、本発明で用いられる組成物を基材上に層状に適用して加熱しても、層の表面付近の液体が急激に乾燥してしまうのを抑制でき、膜の表面付近と膜内部の液体成分の乾燥をより均一にすることができる。
　極性液体は、親水性の官能基を有することが好ましく、例えば、アミノ基、スルホニル基、エーテル基、エポキシ基、ヒドロキシ基、カルボニル基、カルボン酸基、シアノ基から選択される少なくとも１種の官能基を有することが好ましく、アミノ基、スルホニル基、エーテル基、エポキシ基から選択される少なくとも１種の官能基を有することがより好ましい。 << Polar liquid with boiling point higher than 100 ° C >>
The polar liquid having a boiling point higher than 100 ° C. that can be used in the present invention may be used alone or in combination of two or more.
The upper limit of the boiling point of the polar liquid is not particularly limited, but is preferably 250 ° C. or lower, more preferably 230 ° C. or lower, and further preferably 200 ° C. or lower.
The difference in boiling point between the polar liquid and water is preferably 10 ° C or higher, more preferably 20 ° C or higher, further preferably 30 ° C or higher, and further preferably 50 ° C or higher. When the difference in boiling points satisfies such a range, even if the composition used in the present invention is applied in layers on a substrate and heated, the liquid near the surface of the layer is dried rapidly. It is possible to suppress the drying of liquid components in the vicinity of the surface of the membrane and in the membrane.
The polar liquid preferably has a hydrophilic functional group, for example, at least one functional group selected from an amino group, a sulfonyl group, an ether group, an epoxy group, a hydroxy group, a carbonyl group, a carboxylic acid group, and a cyano group. It preferably has a group, and more preferably has at least one functional group selected from an amino group, a sulfonyl group, an ether group, and an epoxy group.
　極性液体として、非プロトン性の極性液体および／または重合性基を有する極性液体から選択される少なくとも１種を用いることが好ましい。このような極性液体を用いることにより、得られる硬化膜の透明性をより向上させることができる。この理由は、例えば、近赤外線吸収性物質として銅化合物を用いる場合、銅の還元を効果的に抑制し、透明性をより向上させることができるためと推定される。 As the polar liquid, it is preferable to use at least one selected from an aprotic polar liquid and / or a polar liquid having a polymerizable group. By using such a polar liquid, the transparency of the obtained cured film can be further improved. The reason for this is presumed that, for example, when a copper compound is used as the near-infrared absorbing substance, reduction of copper can be effectively suppressed and transparency can be further improved.
　極性液体としては、非プロトン性の極性液体および重合性基を有する極性液体以外の他の極性液体を用いることができる。例えば、沸点が１００℃より高いアルコール系液体が挙げられる。具体的には、ジプロピレングリコールモノメチルエーテル、エチレングリコール、ブトキシプロパノール、テトラヒドロフルフリルアルコ－ル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル（２－フェノキシエタノール）、トリエチレングリコールモノメチルエーテル、ポリエチレングリコールモノメチルエーテル、３－メトキシブタノール、１，３ブチレングリコール、プロピレングリコールｎ－プロピルエーテル、プロピレングリコールｎ－ブチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロピレングリコールｎ－プロピルエーテル、ジプロピレングリコールｎ－ブチルエーテル、トリプロピレングリコールメチルエーテル、トリプロピレングリコールｎ－ブチルエーテル、プロピレングリコールモノメチルエーテル等が挙げられる。 As the polar liquid, an aprotic polar liquid and a polar liquid other than the polar liquid having a polymerizable group can be used. For example, an alcohol liquid having a boiling point higher than 100 ° C. can be mentioned. Specifically, dipropylene glycol monomethyl ether, ethylene glycol, butoxypropanol, tetrahydrofurfuryl alcohol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether (2-phenoxyethanol), triethylene glycol monomethyl ether, polyethylene Glycol monomethyl ether, 3-methoxybutanol, 1,3 butylene glycol, propylene glycol n-propyl ether, propylene glycol n-butyl ether, diethylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene Glycol methyl ether, trip Propylene glycol n- butyl ether, propylene glycol monomethyl ether, and the like.
　非プロトン性の極性液体としては、エーテル系液体、アミド系液体、ケトン系液体、アミン系液体、ニトリル系液体、窒素原子含有環化合物、スルホキシド、グライム等を用いることができる。また、非プロトン性の極性液体は、重合性基を有していてもよい。
　例えば、プロピレングリコールジアセテート、１，３－ブチレングリコールジアセテート、１，４－ブタンジオールジアセテート、１，６－ヘキサンジオールジアセテート、シクロヘキサノールアセテート、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、１－エトキシ－２－プロピルアセタート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジプロピレングリコールメチルエーテルアセテート、エチル３－エトキシプロピオナート、プロピレングリコールモノメチルエーテルプロピオネート、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、トリプロピレングリコールジメチルエーテル、ジプロピレングリコールメチル-ｎ-プロピルエーテル、1,2-ビス(2-メトキシメチルエトキシ)プロパン、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールイソプロピルメチルエーテル、1-[2-(2-メトキシエトキシ)エトキシ]ブタン、トリエチレングリコールブチルメチルエーテル、ポリエチレングリコールジメチルエーテル、エチレングリコールジメチルエーテル、トリアセチン、シクロヘキサノン、シクロペンタノン、メチルアミルケトン、ジメチルホルムアミド、ジメチルスルホキシド、ジメチルアセトアミド、Ｎ－メチルピロリドン、２－ピロリドン、スルホラン、メチルジグライムおよびメチルトリグライムから選択される少なくとも１種であることが好ましい。
　特に、ジメチルホルムアミド（１５３℃）、ジメチルスルホキシド（１８９℃）、ジメチルアセトアミド、Ｎ－メチルピロリドン（２０２℃）、２－ピロリドン（２４５℃）、スルホラン（２８５℃）、メチルジグライム（１６２℃）およびメチルトリグライム（２１６℃）から選択される少なくとも１種であることが好ましく、ジメチルホルムアミド、ジメチルスルホキシド、メチルジグライムおよびメチルトリグライムから選択される少なくとも１種であることがより好ましい。 As the aprotic polar liquid, ether liquid, amide liquid, ketone liquid, amine liquid, nitrile liquid, nitrogen atom-containing ring compound, sulfoxide, glyme and the like can be used. Moreover, the aprotic polar liquid may have a polymerizable group.
For example, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, cyclohexanol acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, 1-ethoxy-2-propyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether propionate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Triethylene glycol dimethyl ether Ter, tetraethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, 1,2-bis (2-methoxymethylethoxy) propane, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, 1- [2 -(2-methoxyethoxy) ethoxy] butane, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, ethylene glycol dimethyl ether, triacetin, cyclohexanone, cyclopentanone, methyl amyl ketone, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methyl Selected from pyrrolidone, 2-pyrrolidone, sulfolane, methyldiglyme and methyltriglyme It is preferable that it is at least one kind.
In particular, dimethylformamide (153 ° C), dimethylsulfoxide (189 ° C), dimethylacetamide, N-methylpyrrolidone (202 ° C), 2-pyrrolidone (245 ° C), sulfolane (285 ° C), methyldiglyme (162 ° C) and It is preferably at least one selected from methyltriglyme (216 ° C.), more preferably at least one selected from dimethylformamide, dimethylsulfoxide, methyldiglyme and methyltriglyme.
　極性液体が重合性基を有する場合、少なくとも１気圧、８０～１００℃の温度範囲で液体であり、１００℃より高い温度で熱重合を開始して硬化する熱重合性基を有する極性液体であることが好ましい。また、重合性基を有する極性液体は、単官能であっても多官能であってもよいが、多官能が好ましい。官能基の数は特に定めるものではないが、２～８官能が好ましい。重合性基としては、（メタ）アクリロイル基、エポキシ基、シアネート基、イソシアネート基、オキセタン等が好ましい。
　重合性基を有する沸点が１００℃より高い極性液体は、重合性基を有するモノマー（重合性モノマー）または重合性基を有するオリゴマー（重合性オリゴマー）（以下、重合性モノマーと重合性オリゴマーを合わせて「重合性モノマー等」ということがある。）および重合性ポリマーのいずれであってもよい。 When the polar liquid has a polymerizable group, it is a liquid at least at 1 atm and in the temperature range of 80 to 100 ° C., and is a polar liquid having a thermally polymerizable group that starts and cures at a temperature higher than 100 ° C. It is preferable. The polar liquid having a polymerizable group may be monofunctional or polyfunctional, but polyfunctional is preferable. The number of functional groups is not particularly defined, but 2 to 8 functional groups are preferable. As the polymerizable group, (meth) acryloyl group, epoxy group, cyanate group, isocyanate group, oxetane and the like are preferable.
A polar liquid having a polymerizable group having a boiling point higher than 100 ° C. is a monomer having a polymerizable group (polymerizable monomer) or an oligomer having a polymerizable group (polymerizable oligomer) (hereinafter, the polymerizable monomer and the polymerizable oligomer are combined). And may be referred to as “polymerizable monomer etc.”) or a polymerizable polymer.
　極性液体が重合性モノマー等である場合の例としては、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など）やそのエステル類、アミド類が挙げられ、好ましくは、不飽和カルボン酸と脂肪族多価アルコール化合物とのエステル、及び不飽和カルボン酸と脂肪族多価アミン化合物とのアミド類である。また、ヒドロキシル基やアミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能イソシアネート類或いはエポキシ類との付加反応物や、単官能若しくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基やエポキシ基等の親電子性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との付加反応物、更に、ハロゲン基やトシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との置換反応物も好適である。また、別の例として、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン等のビニルベンゼン誘導体、ビニルエーテル、アリルエーテル等に置き換えた化合物群を使用することも可能である。 Examples of polar liquids that are polymerizable monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
　また、上記重合性モノマー等は、少なくとも１個の付加重合可能なエチレン基を有する、常圧下で１００℃より高い沸点を持つエチレン性不飽和基を持つものも好ましく、単官能（メタ）アクリレート、２官能（メタ）アクリレート、３官能以上の（メタ）アクリレート（例えば、３～６官能の（メタ）アクリレート）が好ましい。
　その例としては、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、等の単官能のアクリレートやメタアクリレート；
　ポリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイロキシエチル）イソシアヌレート、グリセリンやトリメチロールエタン等の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後（メタ）アクリレート化したもの、
　特公昭４８－４１７０８号、特公昭５０－６０３４号、特開昭５１－３７１９３号各公報に記載されているようなウレタン（メタ）アクリレート類、特開昭４８－６４１８３号、特公昭４９－４３１９１号、特公昭５２－３０４９０号各公報に記載されているポリエステルアクリレート類、エポキシポリマーと（メタ）アクリル酸との反応生成物であるエポキシアクリレート類等の多官能のアクリレートやメタアクリレートおよびこれらの混合物を挙げることができる。 In addition, the polymerizable monomer or the like preferably has at least one addition-polymerizable ethylene group and has an ethylenically unsaturated group having a boiling point higher than 100 ° C. under normal pressure, and a monofunctional (meth) acrylate, Bifunctional (meth) acrylates and trifunctional or higher functional (meth) acrylates (for example, 3 to 6 functional (meth) acrylates) are preferred.
Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate;
Polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Ethylene with polyfunctional alcohols such as dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane (Meth) acrylated after adding oxide or propylene oxide,
Urethane (meth) acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy polymers and (meth) acrylic acid, and mixtures thereof described in JP-B No. 52-30490 Can be mentioned.
　中でも、重合性モノマー等としては、ペンタエリスリトールテトラアクリレート（市販品としては　Ａ－ＴＭＭＴ；新中村化学製）、ジペンタエリスリトールトリアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬株式会社製）、ジペンタエリスリトールテトラアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬株式会社製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬株式会社製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　ＤＰＨＡ　；日本化薬株式会社製）、及びこれらの（メタ）アクリロイル基がエチレングリコール、プロピレングリコール残基を介している構造や、ジグリセリンＥＯ（エチレンオキシド）変性（メタ）アクリレート（市販品としては　アロニックスＭ－４６０；東亜合成製）が好ましい。これらのオリゴマータイプも使用できる。 Among them, as the polymerizable monomer, pentaerythritol tetraacrylate (commercially available product is A-TMMT; manufactured by Shin-Nakamura Chemical), dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) Dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, manufactured as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues Diglycerol EO (ethylene oxide) modified (meth) acrylate (Aronix M-460 is commercially; manufactured by Toagosei) are preferred. These oligomer types can also be used.
　極性液体が重合性モノマー等である場合の別の例としては、水溶性エポキシ樹脂が挙げられる。水溶性エポキシ樹脂は、１分子中に少なくとも１個の親水性部位と２個以上のエポキシ基を有するものである。特に、親水性部位として、エーテル結合、水酸基を有するものが好ましい。
　水溶性エポキシ樹脂としては、例えば、４－ヒドロキシブチルアクリレートグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、フェノキシペンタエチレンオキシグリシジルエーテル、ラウリロキシペンタデカエチレンオキシグリシジルエーテルを好ましく挙げることができる。これらのうち、４－ヒドロキシブチルアクリレートグリシジルエーテルが好ましい。
　水溶性エポキシ樹脂の市販品の例としては、ナガセケムテックス社製「デナコール（登録商標）」シリーズのＥＸ－３１３、ＥＸ－４２１、ＥＸ－６１４Ｂ、ＥＸ－８１０、ＥＸ－８１１、ＥＸ－８５１、ＥＸ－８２１、ＥＸ－８３０、ＥＸ－８３２、ＥＸ－８４１、ＥＸ－８６１、ＥＸ－９１１、ＥＸ－９４１、ＥＸ－９２０、ＥＸ－９２１、ＥＸ－９３１が挙げられる。
　また、共栄社化学社製「エポライト」シリーズの４０Ｅ、１００Ｅ、２００Ｅ、４００Ｅ、７０Ｐ、２００Ｐ、４００Ｐが挙げられる。
　また、ダイセル化学社製「エポリード（登録商標）ＮＴ」シリーズの２１２、２１４等のエチレングリコールまたはポリエチレングリコールのジグリシジルエーテル、「エポリード（登録商標）ＮＴ」シリーズの２２８等のプロピレングリコールまたはポリプロピレングリコールのジグリシジルエーテル等が挙げられる。 Another example of the case where the polar liquid is a polymerizable monomer is a water-soluble epoxy resin. The water-soluble epoxy resin has at least one hydrophilic portion and two or more epoxy groups in one molecule. In particular, those having an ether bond or a hydroxyl group as the hydrophilic site are preferred.
Examples of water-soluble epoxy resins include 4-hydroxybutyl acrylate glycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, ethylene glycol diglycidyl ether Preferred examples include ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, phenoxypentaethyleneoxyglycidyl ether, and lauryloxypentadecaethyleneoxyglycidyl ether. Of these, 4-hydroxybutyl acrylate glycidyl ether is preferred.
Examples of commercially available water-soluble epoxy resins include "Denacol (registered trademark)" series EX-313, EX-421, EX-614B, EX-810, EX-811, EX-851, manufactured by Nagase ChemteX Corporation. EX-821, EX-830, EX-832, EX-841, EX-861, EX-911, EX-941, EX-920, EX-921 and EX-931.
Further, 40E, 100E, 200E, 400E, 70P, 200P, and 400P of “Epolite” series manufactured by Kyoeisha Chemical Co., Ltd. may be mentioned.
In addition, diglycidyl ether of ethylene glycol or polyethylene glycol such as 212, 214 of “Epolide (registered trademark) NT” series manufactured by Daicel Chemical Industries, Ltd. And diglycidyl ether.
　本発明で用いられる組成物中の沸点が１００℃より高い極性液体の含有量は、８０質量％以下が好ましく、６０質量％以下がより好ましく、５０質量％以下がさらに好ましく、３０質量％以下が特に好ましい。特に、２～８０質量％が好ましく、５～６０質量％がより好ましく、１５～３０質量％がより好ましい。
　また、沸点が１００℃より高い極性液体と、水との質量比は、２０：８０～８０：２０とすることが好ましく、２５：７５～５０：５０とすることがより好ましい。 The content of the polar liquid having a boiling point higher than 100 ° C. in the composition used in the present invention is preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and 30% by mass or less. Particularly preferred. In particular, it is preferably 2 to 80% by mass, more preferably 5 to 60% by mass, and more preferably 15 to 30% by mass.
The mass ratio of the polar liquid having a boiling point higher than 100 ° C. and water is preferably 20:80 to 80:20, and more preferably 25:75 to 50:50.
　本発明で用いられる組成物は、上記極性液体および水以外の他の液体を含んでいてもよい。他の液体は、１種単独で用いてもよく、２種以上を併用してもよい。他の液体の例としては、沸点が１００℃以下の極性液体が挙げられ、具体的には、沸点が１００℃以下のアルコール系液体（例えばメタノール、エタノール、プロパノール）、沸点が１００℃以下のエーテル系液体（例えばジメチルエーテル、エチルメチルエーテル、ジエチルエーテル）等が挙げられる。
　沸点が１００℃より高い極性液体とともに、上記その他の液体を併用する場合、沸点が１００℃より高い極性液体とその他の溶液の質量比（沸点が１００℃より高い極性液体：その他の液体）は、５０：５０～９９：１とすることが好ましく、７０：３０～９０：１０とすることがより好ましい。
　本発明で用いられる組成物は、２５℃における液体成分の９９質量％以上が、水および極性液体で構成されることが好ましい。 The composition used in the present invention may contain a liquid other than the polar liquid and water. Another liquid may be used individually by 1 type and may use 2 or more types together. Examples of other liquids include polar liquids having a boiling point of 100 ° C. or lower, specifically, alcoholic liquids having a boiling point of 100 ° C. or lower (eg, methanol, ethanol, propanol), ethers having a boiling point of 100 ° C. or lower. And liquids such as dimethyl ether, ethyl methyl ether, and diethyl ether.
When the other liquid is used together with the polar liquid having a boiling point higher than 100 ° C., the mass ratio of the polar liquid having a boiling point higher than 100 ° C. and the other solution (polar liquid having a boiling point higher than 100 ° C .: other liquid) is: It is preferably 50:50 to 99: 1, more preferably 70:30 to 90:10.
As for the composition used by this invention, it is preferable that 99 mass% or more of the liquid component in 25 degreeC is comprised with water and a polar liquid.
＜＜その他の成分＞＞
　本発明で用いられる組成物は、必要に応じて、上述した成分以外の他の成分を含んでいてもよい。例えば、重合開始剤、バインダーポリマー、界面活性剤等を含んでもよい。
＜＜＜重合開始剤＞＞＞
　極性液体として重合性基を有する沸点が１００℃より高い極性液体を用いる場合、本発明で用いられる組成物中に重合開始剤を配合してもよい。重合開始剤は、１種単独でも、２種以上を併用してもよい。
　重合開始剤としては、光、熱のいずれかあるいはその双方により重合性化合物の重合を開始する能力を有する限り、特に制限はなく、目的に応じて適宜選択することができる。光で重合を開始させる場合、紫外線領域から可視の光線に対して感光性を有するものが好ましい。また、熱で重合を開始させる場合には、１５０～２５０℃で分解する重合開始剤が好ましい。
　本発明に用いうる重合開始剤としては、例えば、アシルホスフィン化合物、アセトフェノン系化合物、α－アミノケトン化合物、ベンゾフェノン系化合物、ベンゾインエーテル系化合物、ケタール誘導体化合物、チオキサントン化合物、オキシム化合物、ヘキサアリールビイミダゾール化合物、トリハロメチル化合物、アゾ化合物、有機過酸化物、ジアゾニウム化合物、ヨードニウム化合物、スルホニウム化合物、アジニウム化合物、ベンゾインエーテル系化合物、ケタール誘導体化合物、メタロセン化合物等のオニウム塩化合物、有機硼素塩化合物、ジスルホン化合物などが挙げられる。
　特に、重合開始剤としては、アゾ化合物が好ましく、具体的には、水溶性アゾ化合物、油溶性アゾ化合物、高分子アゾ化合物等が挙げられる。
　水溶性アゾ化合物としては、例えば、市販品であるＶＡ－０４４、ＶＡ－０４６Ｂ、Ｖ－５０、ＶＡ－０５７、ＶＡ－０６１、ＶＡ－０６７、ＶＡ－０８６等（商品名：いずれも和光純薬工業株式会社製）を用いることができる。油溶性アゾ化合物としては、例えば、市販品であるＶ－６０、Ｖ－７０、Ｖ－６５、Ｖ－６０１、Ｖ－５９、Ｖ－４０、ＶＦ－０９６、ＶＡｍ－１１０等（商品名：いずれも和光純薬工業株式会社製）を用いることができる。高分子アゾ化合物としては、例えば、市販品であるＶＰＳ－１００１、ＶＰＥ－０２０１等（商品名：いずれも和光純薬工業株式会社製）を用いることができる。
　重合開始剤の含有量は、本発明で用いられる組成物の全固形分中に対して、０．０１～２５質量％が好ましく、０．１～２０質量％がより好ましい。 << Other ingredients >>
The composition used by this invention may contain other components other than the component mentioned above as needed. For example, a polymerization initiator, a binder polymer, a surfactant and the like may be included.
<<< Polymerization initiator >>>
When a polar liquid having a polymerizable group having a boiling point higher than 100 ° C. is used as the polar liquid, a polymerization initiator may be blended in the composition used in the present invention. The polymerization initiator may be used alone or in combination of two or more.
The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound by either or both of light and heat, and can be appropriately selected according to the purpose. When polymerization is initiated by light, those having photosensitivity to visible light from the ultraviolet region are preferred. In addition, when the polymerization is initiated by heat, a polymerization initiator that decomposes at 150 to 250 ° C. is preferable.
Examples of the polymerization initiator that can be used in the present invention include acylphosphine compounds, acetophenone compounds, α-aminoketone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime compounds, hexaarylbiimidazole compounds. , Trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, benzoin ether compounds, ketal derivative compounds, onium salt compounds such as metallocene compounds, organic boron salt compounds, disulfone compounds, etc. Is mentioned.
In particular, the polymerization initiator is preferably an azo compound, and specific examples include a water-soluble azo compound, an oil-soluble azo compound, and a polymer azo compound.
Examples of water-soluble azo compounds include commercially available products VA-044, VA-046B, V-50, VA-057, VA-061, VA-067, VA-086 (trade names: all Wako Pure Chemical Industries, Ltd.) Kogyo Co., Ltd.) can be used. Examples of oil-soluble azo compounds include commercially available products such as V-60, V-70, V-65, V-601, V-59, V-40, VF-096, VAm-110, etc. (trade names: any Also, Wako Pure Chemical Industries, Ltd.) can be used. As the polymer azo compound, for example, commercially available products such as VPS-1001 and VPE-0201 (trade names: all manufactured by Wako Pure Chemical Industries, Ltd.) can be used.
The content of the polymerization initiator is preferably 0.01 to 25% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition used in the present invention.
＜＜＜バインダーポリマー＞＞＞
　バインダーポリマーとしては、アルカリ可溶性樹脂を用いることができる。バインダーポリマーは、１種のみを用いてもよいし、２種類以上を組み合わせてもよい。
　アルカリ可溶性樹脂としては、線状有機高分子重合体であって、分子（好ましくは、アクリル系共重合体、スチレン系共重合体を主鎖とする分子）中に少なくとも１つのアルカリ可溶性を促進する基を有するアルカリ可溶性樹脂の中から適宜選択することができる。耐熱性の観点からは、ポリヒドロキシスチレン系樹脂、ポリシロキサン系樹脂、アクリル系樹脂、アクリルアミド系樹脂、アクリル／アクリルアミド共重合体樹脂が好ましく、現像性制御の観点からは、アクリル系樹脂、アクリルアミド系樹脂、アクリル／アクリルアミド共重合体樹脂が好ましい。
　アルカリ可溶性を促進する基（以下、酸基ともいう）としては、例えば、カルボン酸基、リン酸基、スルホン酸基、フェノール性水酸基などが挙げられるが、有機溶剤に可溶で弱アルカリ水溶液により現像可能なものが好ましく、（メタ）アクリル酸が特に好ましいものとして挙げられる。これら酸基は、１種のみであってもよいし、２種以上であってもよい。
　上記重合後に酸基を付与しうるモノマーとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート等の水酸基を有するモノマー、グリシジル（メタ）アクリレート等のエポキシ基を有するモノマー、２－イソシアナートエチル（メタ）アクリレート等のイソシアネート基を有するモノマー等が挙げられる。これら酸基を導入するための単量体は、１種のみであってもよいし、２種以上であってもよい。アルカリ可溶性バインダーに酸基を導入するには、例えば、酸基を有するモノマーおよび／または重合後に酸基を付与しうるモノマー（以下「酸基を導入するための単量体」と称することもある。）を、単量体成分として重合するようにすればよい。　なお、重合後に酸基を付与しうるモノマーを単量体成分として酸基を導入する場合には、重合後に例えば後述するような酸基を付与するための処理が必要となる。 <<< Binder polymer >>>
An alkali-soluble resin can be used as the binder polymer. Only 1 type may be used for a binder polymer and it may combine 2 or more types.
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. What can be developed is preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.
Examples of the monomer capable of imparting an acid group after the polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (methacrylate). ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble binder, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component. In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.
　アルカリ可溶性樹脂として用いられる線状有機高分子重合体としては、側鎖にカルボン酸を有するポリマーが好ましく、このようなポリマーとしては、特開２０１２－２０８４９４号公報段落０５６１（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の[０６９１]）等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。 As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, and as such a polymer, paragraph 0561 of JP 2012-208494 A (corresponding US Patent Application Publication) The description of [0691]) etc. of 2012/0235099 specification can be referred to, The content of these is incorporated in this specification.
　アルカリ可溶性樹脂としては、下記一般式（ＥＤ）
Figure JPOXMLDOC01-appb-C000031
 （式（ＥＤ）中、Ｒ1およびＲ2は、それぞれ独立して、水素原子または炭素数１～２５の炭化水素基を表す。）で示される化合物（以下「エーテルダイマー」と称することもある。）を必須とする単量体成分を重合してなるポリマー（ａ）を、必須成分であるポリマー成分（Ａ）として含むことも好ましい。これにより、本発明で用いられる組成物は、耐熱性とともに透明性にも極めて優れた硬化塗膜を形成しうる。上記エーテルダイマーを示す上記一般式（ＥＤ）中、Ｒ1およびＲ2で表される炭素数１～２５の炭化水素基としては、特に制限はないが、例えば、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ｔ－アミル、ステアリル、ラウリル、２－エチルヘキシル等の直鎖状または分岐状のアルキル基；フェニル等のアリール基；シクロヘキシル、ｔ－ブチルシクロヘキシル、ジシクロペンタジエニル、トリシクロデカニル、イソボルニル、アダマンチル、２－メチル－２－アダマンチル等の脂環式基；１－メトキシエチル、１－エトキシエチル等のアルコキシで置換されたアルキル基；ベンジル等のアリール基で置換されたアルキル基；等が挙げられる。これらの中でも特に、メチル、エチル、シクロヘキシル、ベンジル等のような酸や熱で脱離しにくい１級または２級炭素の置換基が耐熱性の点で好ましい。
　上記エーテルダイマーの具体例としては、特開２０１２－２０８４９４号公報段落０５６５（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の[０６９４]）等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
　本発明では、エーテルダイマー由来の構成単位が全体の１～５０モル％であることが好ましく、１～２０モル％であることがより好ましい。 As an alkali-soluble resin, the following general formula (ED)
Figure JPOXMLDOC01-appb-C000031
 (In formula (ED), R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms) (hereinafter sometimes referred to as “ether dimer”) It is also preferable that the polymer (a) obtained by polymerizing the monomer component having the essential component (.) Is included as the essential polymer component (A). Thereby, the composition used by this invention can form the cured coating film which was extremely excellent also in heat resistance and transparency. In the general formula (ED) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms represented by R 1 and R 2 is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, Linear or branched alkyl groups such as isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butylcyclohexyl, dicyclo Alicyclic groups such as pentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl; aryls such as benzyl An alkyl group substituted with a group; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.
As specific examples of the ether dimer, description in paragraph 0565 of JP2012-208494A (corresponding to [0694] of US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof are described in the present specification. Embedded in the book.
In the present invention, the structural unit derived from the ether dimer is preferably 1 to 50% by mole, more preferably 1 to 20% by mole.
　本発明では、アルカリ可溶性フェノール樹脂も好ましく用いることができる。アルカリ可溶性フェノール樹脂としては、例えば、ノボラック樹脂、またはビニル重合体等が挙げられる。
　上記ノボラック樹脂としては、例えば、フェノール類とアルデヒド類とを酸触媒の存在下に縮合させて得られるものが挙げられる。上記フェノール類としては、例えば、フェノール、クレゾール、エチルフェノール、ブチルフェノール、キシレノール、フェニルフェノール、カテコール、レゾルシノール、ピロガロール、ナフトール、又はビスフェノールＡ等が挙げられる。
　上記アルデヒド類としては、例えば、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、またはベンズアルデヒド等が挙げられる。
　上記フェノール類およびアルデヒド類は、単独若しくは２種以上を組み合わせて用いることができる。
　上記ノボラック樹脂の具体例としては、例えば、メタクレゾール、パラクレゾールまたはこれらの混合物とホルマリンとの縮合生成物が挙げられる。
　上記ノボラック樹脂は分別等の手段を用いて分子量分布を調節してもよい。又、ビスフェノールＣやビスフェノールＡ等のフェノール系水酸基を有する低分子量成分を上記ノボラック樹脂に混合してもよい。 In the present invention, an alkali-soluble phenol resin can also be preferably used. Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.
Examples of the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and the like.
The said phenols and aldehydes can be used individually or in combination of 2 or more types.
Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol, or a mixture thereof and formalin.
The novolak resin may be adjusted in molecular weight distribution by means of fractionation or the like. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.
　アルカリ可溶性樹脂としては、特に、ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体やベンジル（メタ）アクリレート／（メタ）アクリル酸／他のモノマーからなる多元共重合体が好適である。この他、２－ヒドロキシエチルメタクリレートを共重合したもの、特開平７－１４０６５４号公報に記載の、２－ヒドロキシプロピル（メタ）アクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシ－３－フェノキシプロピルアクリレート／ポリメチルメタクリレートマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／メチルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／ベンジルメタクレート／メタクリル酸共重合体などが挙げられる。 As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are suitable. In addition, 2-hydroxyethyl methacrylate copolymerized, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy -3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / Benzyl methacrylate / methacrylic acid copolymer.
　アルカリ可溶性樹脂の酸価としては好ましくは３０ｍｇＫＯＨ／ｇ～２００ｍｇＫＯＨ／ｇ、より好ましくは５０ｍｇＫＯＨ／ｇ～１５０ｍｇＫＯＨ／ｇであることが好ましく、７０～１２０ｍｇＫＯＨ／ｇであることが最も好ましい。
　また、アルカリ可溶性樹脂の重量平均分子量（Ｍｗ）としては、２，０００～５０，０００が好ましく、５，０００～３０，０００がさらに好ましく、７，０００～２０，０００が最も好ましい。
　また、アルカリ可溶性樹脂としては、特開２０１２－２０８４９４号公報段落０５５８～０５７１（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の[０６８５]～[０７００]）以降の記載を参酌でき、これらの内容は本願明細書に組み込まれる。 The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 to 120 mgKOH / g.
The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000.
Further, as the alkali-soluble resin, paragraphs 0558 to 0571 of JP2012-208494A (corresponding to [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be taken into consideration. Is incorporated herein by reference.
　本発明では、近赤外線吸収物質として、上述したポリマータイプの銅化合物以外の銅化合物（例えば分子量１０００以下のスルホン酸銅化合物）を用いる場合、バインダーポリマーとして、水溶性バインダーを用いることが好ましい。水溶性バインダーは、１種類のみでも、２種類以上でもよい。
　水溶性バインダーとしては、アクリルアミドと、上述した水溶性エポキシ樹脂との共重合体を用いることが好ましく、特に、Ｎ，Ｎ－ジメチルアクリルアミドと４－ヒドロキシブチルアクリレートグリシジルエーテルの共重合体であることが好ましい。
　アクリルアミドの具体例としては、アクリルアミド、Ｎ－メチルアクリルアミド、Ｎ－エチルアクリルアミド、Ｎ－プロピルアクリルアミド、Ｎ－ブチルアクリルアミド、Ｎ－ベンジルアクリルアミド、Ｎ－ヒドロキシエチルアクリルアミド、Ｎ－フェニルアクリルアミド、Ｎ－トリルアクリルアミド、Ｎ－（ヒドロキシフェニル）アクリルアミド、Ｎ－（スルファモイルフェニル）アクリルアミド、Ｎ－（フェニルスルホニル）アクリルアミド、Ｎ－（トリルスルホニル）アクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ－メチル－Ｎ－フェニルアクリルアミド、Ｎ－ヒドロキシエチル－Ｎ－メチルアクリルアミド等が挙げられる。また、これらに対応するメタクリルアミドも同様に使用できる。
　ジメチルアクリルアミド／４－ヒドロキシブチルアクリレートグリシジルエーテルの比率は、１０／９０～９０／１０であることが好ましく、３０／７０～７０／３０であることがより好ましい。上記共重合体の重量平均分子量は、１０,０００～５０,０００であることが好ましく、２０,０００～３０,０００であることがより好ましい。 In the present invention, when a copper compound other than the polymer type copper compound described above (for example, a sulfonic acid copper compound having a molecular weight of 1000 or less) is used as the near-infrared absorbing substance, a water-soluble binder is preferably used as the binder polymer. Only one type of water-soluble binder may be used, or two or more types may be used.
As the water-soluble binder, a copolymer of acrylamide and the above-mentioned water-soluble epoxy resin is preferably used, and in particular, it is a copolymer of N, N-dimethylacrylamide and 4-hydroxybutyl acrylate glycidyl ether. preferable.
Specific examples of acrylamide include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-phenylacrylamide, And N-hydroxyethyl-N-methylacrylamide. Moreover, methacrylamide corresponding to these can be used similarly.
The ratio of dimethylacrylamide / 4-hydroxybutyl acrylate glycidyl ether is preferably 10/90 to 90/10, and more preferably 30/70 to 70/30. The weight average molecular weight of the copolymer is preferably 10,000 to 50,000, and more preferably 20,000 to 30,000.
　バインダーポリマーの含有量は、本発明で用いられる組成物の全固形分中に対して、８０質量％以下とすることができ、５０質量％以下とすることもでき、３０質量％以下とすることもできる。 The content of the binder polymer can be 80% by mass or less, can be 50% by mass or less, and can be 30% by mass or less, based on the total solid content of the composition used in the present invention. You can also.
＜＜＜界面活性剤＞＞＞
　本発明で用いられる組成物は、界面活性剤を含んでいてもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。界面活性剤は、１種のみを用いてもよいし、２種類以上を組み合わせてもよい。 <<< surfactant >>>
The composition used in the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Only one type of surfactant may be used, or two or more types may be combined.
　特に、本発明で用いられる組成物は、フッ素系界面活性剤、およびシリコーン系界面活性剤の少なくともいずれかを含有することで、塗布液として調製したときの液特性（特に、流動性）がより向上することから、塗布厚の均一性や省液性をより改善することができる。
　即ち、フッ素系界面活性剤およびシリコーン系界面活性剤の少なくともいずれかを含有する組成物を適用した塗布液を用いて膜形成する場合においては、被塗布面と塗布液との界面張力を低下させることにより、被塗布面への濡れ性が改善され、被塗布面への塗布性が向上する。このため、少量の液量で数μｍ程度の薄膜を形成した場合であっても、厚みムラの小さい均一厚の膜形成をより好適に行える点で有効である。 In particular, the composition used in the present invention contains at least one of a fluorine-based surfactant and a silicone-based surfactant, so that the liquid properties (particularly, fluidity) when prepared as a coating solution are further improved. Since it improves, the uniformity of application | coating thickness and liquid-saving property can be improved more.
That is, when a film is formed using a coating liquid to which a composition containing at least one of a fluorosurfactant and a silicone surfactant is applied, the interfacial tension between the coated surface and the coating liquid is reduced. Thereby, the wettability to the coated surface is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
　フッ素系界面活性剤中のフッ素含有率は、例えば、３～４０質量％とすることができる。
　フッ素系界面活性剤としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０、同Ｒ０８（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、同Ｓ－１４１、同Ｓ－１４５、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ３９３、同ＫＨ－４０（以上、旭硝子（株）製）、エフトップＥＦ３０１、同ＥＦ３０３、同ＥＦ３５１、同ＥＦ３５２（以上、ジェムコ（株）製）、ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（ＯＭＮＯＶＡ社製）等が挙げられる。 The fluorine content in the fluorosurfactant can be, for example, 3 to 40% by mass.
Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F479, F482, F554, F780, R08 (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, S-141, S- 145, SC-101, SC-103, SC-104, SC-105, SC-106, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) ), EFtop EF301, EF303, EF351, EF352 (above, manufactured by Gemco), PF636, PF656, F6320, PF6520, PF7002 (OMNOVA Co., Ltd.), and the like.
　フッ素系界面活性剤としては、フルオロ脂肪族基を有する重合体を用いることができる。フルオロ脂肪族基を有する重合体としては、フルオロ脂肪族基を有し、このフルオロ脂肪族基が、テロメリゼーション法（テロマー法ともいわれる）、またはオリゴメリゼーション法（オリゴマー法ともいわれる）によって製造されたフルオロ脂肪族化合物から得られたフッ素系界面活性剤が例示される。
　ここで、「テロメリゼーション法」とは、低分子量の物質を重合させて分子内に１～２個の活性基を有する化合物の合成方法を意味する。また、「オリゴメゼーション法」とは、単量体または単量体類の混合物をオリゴマーに転化する方法を意味する。
　本発明におけるフルオロ脂肪族基としては、例えば、－ＣＦ3基、－Ｃ2Ｆ5基、－Ｃ3Ｆ7基、－Ｃ4Ｆ9基、－Ｃ5Ｆ11基、－Ｃ6Ｆ13基、－Ｃ7Ｆ15基、－Ｃ8Ｆ17基、Ｃ9Ｆ19基、Ｃ10Ｆ21基が挙げられ、相溶性・塗布性の点から、－Ｃ2Ｆ5基、－Ｃ3Ｆ7基、－Ｃ4Ｆ9基、－Ｃ5Ｆ11基、－Ｃ6Ｆ13基、－Ｃ7Ｆ15基、－Ｃ8Ｆ17基を用いることができる。 As the fluorosurfactant, a polymer having a fluoroaliphatic group can be used. The polymer having a fluoroaliphatic group has a fluoroaliphatic group, and this fluoroaliphatic group is produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). Examples thereof include fluorine-based surfactants obtained from the obtained fluoroaliphatic compounds.
Here, the “telomerization method” means a method for synthesizing a compound having 1 to 2 active groups in a molecule by polymerizing a low molecular weight substance. The “oligomerization method” means a method of converting a monomer or a mixture of monomers into an oligomer.
Examples of the fluoroaliphatic group in the present invention include —CF 3 group, —C 2 F 5 group, —C 3 F 7 group, —C 4 F 9 group, —C 5 F 11 group, —C 6 F 13 Group, -C 7 F 15 group, -C 8 F 17 group, C 9 F 19 group, C 10 F 21 group. From the viewpoint of compatibility and coatability, -C 2 F 5 group, -C 3 F 7 group, -C 4 F 9 groups, -C 5 F 11 group, -C 6 F 13 group, -C 7 F 15 group, it is possible to use -C 8 F 17 group.
　本発明におけるフルオロ脂肪族化合物は、特開２００２－９０９９１号公報に記載された方法によって合成することが出来る。
　本発明におけるフルオロ脂肪族基を有する重合体としては、本発明におけるフルオロ脂肪族基を有するモノマーと（ポリ（オキシアルキレン））アクリレートおよび／または（ポリ（オキシアルキレン））メタクリレートとの共重合体を用いることができる。この共重合体は、不規則に分布しているものでも、ブロック共重合していてもよい。また、上記ポリ（オキシアルキレン）基としては、ポリ（オキシエチレン）基、ポリ（オキシプロピレン）基、ポリ（オキシブチレン）基などが挙げられ、ポリ（オキシエチレンとオキシプロピレンとオキシエチレンとのブロック連結体）基やポリ（オキシエチレンとオキシプロピレンとのブロック連結体）基など同じ鎖長内に異なる鎖長のアルキレンを有するようなユニットでもよい。さらに、フルオロ脂肪族基を有するモノマーと（ポリ（オキシアルキレン））アクリレート（またはメタクリレート）との共重合体は２元共重合体ばかりでなく、異なる２種以上のフルオロ脂肪族基を有するモノマーや、異なる２種以上の（ポリ（オキシアルキレン））アクリレート（またはメタクリレート）などを同時に共重合した３元系以上の共重合体でもよい。 The fluoroaliphatic compound in the present invention can be synthesized by the method described in JP-A-2002-90991.
The polymer having a fluoroaliphatic group in the present invention includes a copolymer of a monomer having a fluoroaliphatic group in the present invention and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate. Can be used. The copolymer may be randomly distributed or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a block of poly (oxyethylene, oxypropylene, and oxyethylene). It may be a unit having different chain lengths in the same chain length, such as a (linkage) group or a poly (block connection body of oxyethylene and oxypropylene) group. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates) at the same time.
　本発明におけるフルオロ脂肪族基を有する重合体を含む市販の界面活性剤としては、例えば、特開２０１２－２０８４９４号公報段落０５５２（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の[０６７８]）等に記載の界面活性剤が挙げられ、これらの内容は本願明細書に組み込まれる。また、メガファックＦ－７８１、（大日本インキ化学工業（株）製）、Ｃ6Ｆ13基を有するアクリレート（またはメタクリレート）と（ポリ（オキシエチレン））アクリレート（またはメタクリレート）と（ポリ（オキシプロピレン））アクリレート（またはメタクリレート）との共重合体、Ｃ8Ｆ17基を有するアクリレート（またはメタクリレート）と（ポリ（オキシアルキレン））アクリレート（またはメタクリレート）との共重合体、Ｃ8Ｆ17基を有するアクリレート（またはメタクリレート）と（ポリ（オキシエチレン））アクリレート（またはメタクリレート）と（ポリ（オキシプロピレン））アクリレート（またはメタクリレート）との共重合体、などを使用することができる。 Examples of commercially available surfactants containing a polymer having a fluoroaliphatic group in the present invention include, for example, paragraph 0552 of JP2012-208494A (corresponding to [0678] of the corresponding US Patent Application Publication No. 2012/0235099). ) And the like, the contents of which are incorporated herein. In addition, MegaFuck F-781 (manufactured by Dainippon Ink & Chemicals, Inc.), acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate) and (poly (oxy) having a C 6 F 13 group Copolymer of propylene)) acrylate (or methacrylate), copolymer of acrylate (or methacrylate) having C 8 F 17 group and (poly (oxyalkylene)) acrylate (or methacrylate), C 8 F 17 group A copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate), and the like can be used.
　ノニオン系界面活性剤として具体的には、特開２０１２－２０８４９４号公報段落０５５３（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の[０６７９]）等に記載のノニオン系界面活性剤が挙げられ、これらの内容は本願明細書に組み込まれる。
　カチオン系界面活性剤として具体的には、特開２０１２－２０８４９４号公報段落０５５４（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の[０６８０]）に記載のカチオン系界面活性剤が挙げられ、これらの内容は本願明細書に組み込まれる。
　アニオン系界面活性剤として具体的には、Ｗ００４、Ｗ００５、Ｗ０１７（裕商（株）社製）等が挙げられる。 Specific examples of the nonionic surfactant include nonionic surfactants described in paragraph 0553 of JP2012-208494A (corresponding to [0679] of the corresponding US Patent Application Publication No. 2012/0235099). The contents of which are incorporated herein by reference.
Specific examples of the cationic surfactant include a cationic surfactant described in paragraph 0554 of JP2012-208494A (corresponding to [0680] of the corresponding US Patent Application Publication No. 2012/0235099). The contents of which are incorporated herein by reference.
Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
　シリコーン系界面活性剤としては、例えば、特開２０１２－２０８４９４号公報段落０５５６（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の[０６８２]）等に記載のシリコーン系界面活性剤が挙げられ、これらの内容は本願明細書に組み込まれる。また、東レ・ダウコーニング（株）製「トーレシリコーンＳＦ８４１０」、「同ＳＦ８４２７」、「同ＳＨ８４００」、「ＳＴ８０ＰＡ」、「ＳＴ８３ＰＡ」、「ＳＴ８６ＰＡ」、モメンティブ・パフォーマンス・マテリアルズ社製「ＴＳＦ－４００」、「ＴＳＦ－４０１」、「ＴＳＦ－４１０」、「ＴＳＦ－４４４６」信越シリコーン株式会社製「ＫＰ３２１」、「ＫＰ３２３」、「ＫＰ３２４」、「ＫＰ３４０」等も例示される。 Examples of the silicone surfactant include silicone surfactants described in paragraph 0556 of JP2012-208494A (corresponding to [0682] of the corresponding US Patent Application Publication No. 2012/0235099). The contents of which are incorporated herein by reference. Also, “Toray Silicone SF8410”, “Same SF8427”, “Shi8400”, “ST80PA”, “ST83PA”, “ST86PA” manufactured by Toray Dow Corning Co., Ltd. “TSF-400” manufactured by Momentive Performance Materials, Inc. "TSF-401", "TSF-410", "TSF-4446" "KP321", "KP323", "KP324", "KP340", etc. manufactured by Shin-Etsu Silicone Co., Ltd. are also exemplified.
　界面活性剤の添加量は、本発明で用いられる組成物の全固形分に対して、０．０００１～２質量％とすることができ、０．００５～１．０質量％とすることもできる。 The addition amount of the surfactant can be 0.0001 to 2% by mass with respect to the total solid content of the composition used in the present invention, and can also be 0.005 to 1.0% by mass. .
　その他、併用可能な成分としては、例えば、分散剤、増感剤、架橋剤、硬化促進剤、フィラー、熱硬化促進剤、熱重合禁止剤、可塑剤などが挙げられ、更に基材表面への密着促進剤およびその他の助剤類（例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、酸化防止剤、香料、表面張力調整剤、連鎖移動剤など）を併用してもよい。これらの成分は、例えば、特開２０１２－００３２２５号公報の段落番号０１８３以降（対応する米国特許出願公開第２０１３／００３４８１２号明細書の[０２３７]以降）の記載、特開２００８－２５００７４号公報の段落番号０１０１～０１０２、段落番号０１０３～０１０４および段落番号０１０７～０１０９等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。 Other components that can be used in combination include, for example, a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, and the like. Adhesion promoters and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) You may use together. These components are described, for example, in paragraph No. 0183 and later of JP2012-003225A (corresponding to [0237] and later of US Patent Application Publication No. 2013/0034812), JP2008-250074A, and the like. The description of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and the like can be taken into consideration, and the contents thereof are incorporated in the present specification.
　上述した本発明の近赤外線カットフィルタの製造方法で得られた近赤外線カットフィルタは、膜厚が３００μｍ以下であることが好ましく、２５０μｍ以下がより好ましく、２００μｍ以下がさらに好ましい。また、膜厚が２０μｍ以上であることが好ましく、５０μｍ以上がより好ましく、１００μｍ以上がさらに好ましい。特に、膜厚が５０～３００μｍであることが好ましく、１００～２５０μｍであることがより好ましい。
　近赤外線カットフィルタは、原子間力顕微鏡（ＡＦＭ、Ｐａｃｉｆｉｃ　Ｎａｎｏｔｅｃｈｎｏｌｏｇｙ社製　Ｎａｎｏ－Ｒ）で測定した表面粗さＲａが０～２０ｎｍであることが好ましく、０～１０ｎｍであることがより好ましい。
　近赤外線カットフィルタは、水の含有量が２０質量％以下であることが好ましく、０～１０質量％であることがより好ましい。
　近赤外線カットフィルタは、上記極性液体の含有量が０～２０質量％であることが好ましく、０～１０質量％であることがより好ましい。
　近赤外線カットフィルタは、光透過率が以下の（１）～（９）のうちの少なくとも１つの条件を満たすことが好ましく、以下の（１）～（８）のすべての条件を満たすことがより好ましく、（１）～（９）のすべての条件を満たすことがさらに好ましい。
（１）波長４００ｎｍでの光透過率は８０％以上が好ましく、９０％以上がより好ましく、９２％以上がさらに好ましく、９５％以上が特に好ましい。
（２）波長４５０ｎｍでの光透過率は８０％以上が好ましく、９０％以上がより好ましく、９２％以上がさらに好ましく、９５％以上が特に好ましい。
（３）波長５００ｎｍでの光透過率は８０％以上が好ましく、９０％以上がより好ましく、９２％以上がさらに好ましく、９５％以上が特に好ましい。
（４）波長５５０ｎｍでの光透過率は８０％以上が好ましく、９０％以上がより好ましく、９２％以上がさらに好ましく、９５％以上が特に好ましい。
（５）波長７００ｎｍでの光透過率は２０％以下が好ましく、１５％以下がより好ましく、１０％以下がさらに好ましく、５％以下が特に好ましい。
（６）波長７５０ｎｍでの光透過率は２０％以下が好ましく、１５％以下がより好ましく、１０％以下がさらに好ましく、５％以下が特に好ましい。
（７）波長８００ｎｍでの光透過率は２０％以下が好ましく、１５％以下がより好ましく、１０％以下がさらに好ましく、５％以下が特に好ましい。
（８）波長８５０ｎｍでの光透過率は２０％以下が好ましく、１５％以下がより好ましく、１０％以下がさらに好ましく、５％以下が特に好ましい。
（９）波長９００ｎｍでの光透過率は２０％以下が好ましく、１５％以下がより好ましく、１０％以下がさらに好ましく、５％以下が特に好ましい。
　近赤外線カットフィルタは、膜厚５０～３００μｍのいずれかで、波長４００～５７５ｎｍのいずれかの範囲での光透過率が９０％以上であることが好ましく、波長４００～５７５ｎｍの全ての範囲での光透過率が９０％以上であることが好ましい。
　また、近赤外線カットフィルタは、膜厚５０～３００μｍのいずれかで、波長７００～１１００ｎｍのいずれかの範囲での透過率が２０％以下であり、波長７００～１１００ｎｍの全ての範囲での透過率が２０％以下であることがさらに好ましい。 The near-infrared cut filter obtained by the above-described method for producing a near-infrared cut filter of the present invention preferably has a film thickness of 300 μm or less, more preferably 250 μm or less, and even more preferably 200 μm or less. The film thickness is preferably 20 μm or more, more preferably 50 μm or more, and further preferably 100 μm or more. In particular, the film thickness is preferably 50 to 300 μm, more preferably 100 to 250 μm.
The near-infrared cut filter preferably has a surface roughness Ra measured by an atomic force microscope (AFM, Nano-R manufactured by Pacific Nanotechnology) of 0 to 20 nm, and more preferably 0 to 10 nm.
The near-infrared cut filter preferably has a water content of 20% by mass or less, more preferably 0 to 10% by mass.
In the near-infrared cut filter, the content of the polar liquid is preferably 0 to 20% by mass, and more preferably 0 to 10% by mass.
The near-infrared cut filter preferably has a light transmittance that satisfies at least one of the following conditions (1) to (9), and more preferably satisfies all the following conditions (1) to (8): It is more preferable that all the conditions (1) to (9) are satisfied.
(1) The light transmittance at a wavelength of 400 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(2) The light transmittance at a wavelength of 450 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(3) The light transmittance at a wavelength of 500 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(4) The light transmittance at a wavelength of 550 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(5) The light transmittance at a wavelength of 700 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(6) The light transmittance at a wavelength of 750 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(7) The light transmittance at a wavelength of 800 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(8) The light transmittance at a wavelength of 850 nm is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, and particularly preferably 5% or less.
(9) The light transmittance at a wavelength of 900 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
The near-infrared cut filter preferably has a film thickness of 50 to 300 μm and a light transmittance of 90% or more in any range of wavelengths from 400 to 575 nm, and in all ranges of wavelengths from 400 to 575 nm. The light transmittance is preferably 90% or more.
The near-infrared cut filter has a film thickness of 50 to 300 μm and has a transmittance of 20% or less in a wavelength range of 700 to 1100 nm, and a transmittance in the entire wavelength range of 700 to 1100 nm. Is more preferably 20% or less.
　近赤外線カットフィルタは、近赤外線吸収性組成物を硬化させた近赤外線カット層と誘電体多層膜を有する積層体としてもよい。例えば、（ｉ）透明支持体、近赤外線カット層、誘電体多層膜が上記順に設けられた態様、（ｉｉ） 近赤外線カット層、透明支持体、誘電体多層膜が上記順に設けられた態様がある。上記透明支持体は、ガラス基板でも、透明樹脂基板が挙げられる。
　上記誘電体多層膜は、近赤外線を反射および／または吸収する能力を有する膜である。
　誘電体多層膜の材料としては、例えばセラミックを用いることができる。また、近赤外域に吸収を有する貴金属膜を近赤外線カットフィルタの可視光の透過率に影響のないよう、厚みと層数を考慮して用いてもよい。
　誘電体多層膜としては具体的には、高屈折率材料層と低屈折率材料層とを交互に積層した構成を好適に用いることができる。
　高屈折率材料層を構成する材料としては、屈折率が１．７以上の材料を用いることができ、屈折率の範囲が通常は１．７～２．５の材料が選択される。
　この材料としては、例えば、酸化チタン（チタニア）、酸化ジルコニウム、五酸化タンタル、五酸化ニオブ、酸化ランタン、酸化イットリウム、酸化亜鉛、硫化亜鉛、酸化インジウムや、これら酸化物を主成分とし酸化チタン、酸化錫および／または酸化セリウムなどを少量含有させたものが挙げられる。これらの中でも、酸化チタン（チタニア）が好ましい。
　低屈折率材料層を構成する材料としては、屈折率が１．６以下の材料を用いることができ、屈折率の範囲が通常は１．２～１．６の材料が選択される。
　この材料としては、例えば、シリカ、アルミナ、フッ化ランタン、フッ化マグネシウムおよび六フッ化アルミニウムナトリウムが挙げられる。これらの中でも、シリカが好ましい。
　これら高屈折率材料層および低屈折率材料層の各層の厚みは、通常、遮断しようとする赤外線波長λ（ｎｍ）の０．１λ～０．５λの厚みである。厚みが上記範囲外になると、屈折率（ｎ）と膜厚（ｄ）との積（ｎ×ｄ）がλ／４で算出される光学的膜厚と大きく異なって反射・屈折の光学的特性の関係が崩れてしまい、特定波長の遮断・透過をコントロールしにくい傾向にある。
　また、誘電体多層膜における積層数は、好ましくは５～５０層であり、より好ましくは１０～４５層である。 A near-infrared cut filter is good also as a laminated body which has the near-infrared cut layer which hardened the near-infrared absorptive composition, and the dielectric multilayer. For example, (i) an embodiment in which a transparent support, a near-infrared cut layer, and a dielectric multilayer film are provided in the above order; (ii) an embodiment in which a near-infrared cut layer, a transparent support, and a dielectric multilayer film are provided in the above order. is there. The transparent support may be a glass substrate or a transparent resin substrate.
The dielectric multilayer film is a film having an ability to reflect and / or absorb near infrared rays.
As a material of the dielectric multilayer film, for example, ceramic can be used. In addition, a noble metal film having absorption in the near infrared region may be used in consideration of the thickness and the number of layers so as not to affect the visible light transmittance of the near infrared cut filter.
Specifically, a configuration in which high refractive index material layers and low refractive index material layers are alternately stacked can be suitably used as the dielectric multilayer film.
As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of 1.7 to 2.5 is usually selected.
As this material, for example, titanium oxide (titania), zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, titanium oxide mainly composed of these oxides, Examples thereof include those containing a small amount of tin oxide and / or cerium oxide. Among these, titanium oxide (titania) is preferable.
As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index range of 1.2 to 1.6 is usually selected.
Examples of this material include silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride. Among these, silica is preferable.
The thicknesses of the high-refractive index material layer and the low-refractive index material layer are usually 0.1λ to 0.5λ of the infrared wavelength λ (nm) to be blocked. When the thickness is out of the above range, the product (n × d) of the refractive index (n) and the film thickness (d) is significantly different from the optical film thickness calculated by λ / 4, and the optical characteristics of reflection and refraction are different. The relationship is broken, and it tends to be difficult to control blocking / transmission of a specific wavelength.
The number of laminated layers in the dielectric multilayer film is preferably 5 to 50 layers, more preferably 10 to 45 layers.
　誘電体多層膜の形成方法としては、例えば、ＣＶＤ法、スパッタ法、真空蒸着法などにより、高屈折率材料層と低屈折率材料層とを交互に積層した誘電体多層膜を形成し、これを上記膜に接着剤で張り合わせる方法、上記膜上に、直接、ＣＶＤ法、スパッタ法、真空蒸着法などにより、高屈折率材料層と低屈折率材料層とを交互に積層した誘電体多層膜を形成する方法を挙げることができる。
　さらに、誘電体多層膜を蒸着した際に基板にソリが生じてしまう場合には、これを解消するために、基板両面へ誘電体多層膜を蒸着する、基板の誘電多層膜を蒸着した面に紫外線等の放射線を照射する等の方法をとる事ができる。なお、放射線を照射する場合、誘電体多層膜の蒸着を行いながら照射してもよいし、蒸着後別途照射してもよい。
　上記近赤外線カットフィルタは、近赤外線を吸収・カットする機能を有するレンズ（デジタルカメラや携帯電話や車載カメラ等のカメラ用レンズ、ｆ－θレンズ、ピックアップレンズ等の光学レンズ）および半導体受光素子用の光学フィルター、省エネルギー用に熱線を遮断する近赤外線吸収フィルムや近赤外線吸収板、太陽光の選択的な利用を目的とする農業用コーティング剤、近赤外線の吸収熱を利用する記録媒体、電子機器用や写真用近赤外線フィルター、保護めがね、サングラス、熱線遮断フィルム、光学文字読み取り記録、機密文書複写防止用、電子写真感光体、レーザー溶着、などに用いられる。またＣＣＤカメラ用ノイズカットフィルター、ＣＭＯＳイメージセンサ用フィルターとしても有用である。 As a method for forming the dielectric multilayer film, for example, a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately stacked is formed by CVD, sputtering, vacuum deposition, or the like. A dielectric multilayer in which a high refractive index material layer and a low refractive index material layer are alternately laminated directly on the film by a CVD method, a sputtering method, a vacuum deposition method, or the like. A method for forming a film can be given.
In addition, if the substrate is warped when the dielectric multilayer film is deposited, in order to eliminate this, the dielectric multilayer film is deposited on both sides of the substrate. A method of irradiating with radiation such as ultraviolet rays can be taken. In addition, when irradiating a radiation, you may irradiate while performing the vapor deposition of a dielectric multilayer, and you may irradiate separately after vapor deposition.
The near-infrared cut filter is for lenses that absorb and cut near-infrared rays (camera lenses such as digital cameras, mobile phones, and in-vehicle cameras, optical lenses such as f-θ lenses and pickup lenses) and semiconductor light-receiving elements. Optical filters, near-infrared absorbing films and near-infrared absorbing plates that block heat rays for energy saving, agricultural coatings for selective use of sunlight, recording media that use near-infrared absorbing heat, and electronic equipment It is used for near infrared filters for photography and photography, protective glasses, sunglasses, heat ray blocking films, optical character reading recording, confidential document copy prevention, electrophotographic photoreceptors, laser welding, and the like. It is also useful as a noise cut filter for CCD cameras and a filter for CMOS image sensors.
＜カメラモジュール、カメラモジュールの製造方法＞
　本発明は、固体撮像素子と、上述した近赤外線カットフィルタとを有するカメラモジュールにも関する。このカメラモジュールは、近赤外線カットフィルタが、上述した本発明の近赤外線カットフィルタである。
　以下、カメラモジュールを、図４および図５を参照しながら説明するが、本発明は以下の具体例によって限定されることはない。
　なお、図４および図５にわたり、共通する部分には共通する符号を付す。
　また、説明に際し、「上」、「上方」および「上側」は、シリコン基板１０から見て遠い側を指し、「下」、「下方」および「下側」は、はシリコン基板１０に近い側を指す。
　図４は、固体撮像素子を備えたカメラモジュールの構成を示す概略断面図である。
　図４に示すカメラモジュール２００は、実装基板である回路基板７０に接続部材であるハンダボール６０を介して接続されている。
　詳細には、カメラモジュール２００は、シリコン基板の第１の主面にフォトダイオードを備えた固体撮像素子（固体撮像素子基板）１００と、固体撮像素子１００の第１の主面側（受光側）に設けられた平坦化層（図４には不図示）と、平坦化層の上に設けられた近赤外線カットフィルタ４２と、近赤外線カットフィルタ４２の上方に配置され内部空間に撮像レンズ４０を有するレンズホルダー５０と、固体撮像素子１００およびガラス基板３０の周囲を囲うように配置された遮光兼電磁シールド４４と、を備えて構成されている。なお、平坦化層の上には、ガラス基板３０（光透過性基板）を設けてもよい。各部材は、接着剤４５により接着されている。
　本発明は、固体撮像素子１００と、上記固体撮像素子の受光側に配置された近赤外線カットフィルタ４２とを有するカメラモジュールの製造方法であって、固体撮像素子の受光側において、上記近赤外線吸収性組成物を適用することにより近赤外線カットフィルタ４２を形成する工程を有することも好ましい。本実施形態に係るカメラモジュールにおいては、例えば、平坦化層の上に、近赤外線吸収性組成物を塗布することにより膜を形成して、近赤外線カットフィルタ４２を形成できる。近赤外線吸収性組成物を適用する方法は上記した通りである。
　カメラモジュール２００では、外部からの入射光ｈνが、撮像レンズ４０、近赤外線カットフィルタ４２、ガラス基板３０、平坦化層を順次透過した後、固体撮像素子１００の撮像素子部に到達するようになっている。
　カメラモジュール２００は、平坦化層上に直接近赤外線カットフィルタを設けているが、平坦化層を省略しマイクロレンズ上に直接近赤外線カットフィルタを設けるようにしてもよいし、ガラス基板３０上に近赤外線カットフィルタを設けたり、近赤外線カットフィルタを設けたガラス基板３０を貼り合せてもよい。 <Camera module and camera module manufacturing method>
The present invention also relates to a camera module having a solid-state imaging device and the above-described near-infrared cut filter. In this camera module, the near infrared cut filter is the near infrared cut filter of the present invention described above.
Hereinafter, the camera module will be described with reference to FIGS. 4 and 5, but the present invention is not limited to the following specific examples.
In FIG. 4 and FIG. 5, common portions are denoted by common reference numerals.
In the description, “upper”, “upper”, and “upper” refer to the side far from the silicon substrate 10, and “lower”, “lower”, and “lower” are closer to the silicon substrate 10. Point to.
FIG. 4 is a schematic cross-sectional view illustrating a configuration of a camera module including a solid-state image sensor.
A camera module 200 shown in FIG. 4 is connected to a circuit board 70 that is a mounting board via solder balls 60 that are connection members.
Specifically, the camera module 200 includes a solid-state imaging device (solid-state imaging device substrate) 100 including a photodiode on a first main surface of a silicon substrate, and a first main surface side (light-receiving side) of the solid-state imaging device 100. The near-infrared cut filter 42 provided on the planarizing layer (not shown in FIG. 4), and the near-infrared cut filter 42 disposed above the near-infrared cut filter 42 and the imaging lens 40 in the internal space. And a light shielding / electromagnetic shield 44 disposed so as to surround the solid-state imaging device 100 and the glass substrate 30. Note that a glass substrate 30 (light transmissive substrate) may be provided on the planarization layer. Each member is bonded by an adhesive 45.
The present invention is a method of manufacturing a camera module having a solid-state image sensor 100 and a near-infrared cut filter 42 disposed on the light-receiving side of the solid-state image sensor, and the near-infrared absorption on the light-receiving side of the solid-state image sensor. It is also preferable to have the process of forming the near-infrared cut filter 42 by applying a composition. In the camera module according to the present embodiment, for example, the near-infrared cut filter 42 can be formed by forming a film by applying a near-infrared absorbing composition on the planarizing layer. The method for applying the near-infrared absorbing composition is as described above.
In the camera module 200, incident light hν from outside passes through the imaging lens 40, the near-infrared cut filter 42, the glass substrate 30, and the planarization layer in order, and then reaches the imaging device portion of the solid-state imaging device 100. ing.
In the camera module 200, the near infrared cut filter is directly provided on the flattening layer, but the flat layer may be omitted and the near infrared cut filter may be provided directly on the microlens, or on the glass substrate 30. A near-infrared cut filter may be provided, or a glass substrate 30 provided with a near-infrared cut filter may be bonded.
　図５は、図４中の固体撮像素子１００を拡大した断面図である。
　固体撮像素子１００は、基体であるシリコン基板１０の第１の主面に、撮像素子部１２、層間絶縁膜１３、ベース層１４、カラーフィルタ１５、オーバーコート１６、マイクロレンズ１７をこの順に備えている。撮像素子部１２に対応するように、赤色のカラーフィルタ１５Ｒ、緑色のカラーフィルタ１５Ｇ、青色のカラーフィルタ１５Ｂ（以下、これらをまとめて「カラーフィルタ１５」ということがある）やマイクロレンズ１７は、それぞれ配置されている。シリコン基板１０の第１の主面と反対側の第２の主面には、遮光膜１８、絶縁膜２２、金属電極２３、ソルダレジスト層２４、内部電極２６、および素子面電極２７を備えている。各部材は、接着剤２０により接着されている。
　マイクロレンズ１７上には、平坦化層４６、近赤外線カットフィルタ４２を備えている。平坦化層４６の上に近赤外線カットフィルタ４２が設けられる代わりに、マイクロレンズ１７の上、ベース層１４とカラーフィルタ１５との間、または、カラーフィルタ１５とオーバーコート１６との間に、近赤外線カットフィルタが設けられる形態であってもよい。特に、マイクロレンズ１７表面から２ｍｍ以内（より好ましくは１ｍｍ以内）の位置に設けられることが好ましい。この位置に設けると、近赤外線カットフィルタを形成する工程が簡略化でき、マイクロレンズへの不要な近赤外線を十分にカットすることができるので、近赤外線遮断性をより高めることができる。
　固体撮像素子１００については、特開２０１２－０６８４１８号公報段落０２４５（対応する米国特許出願公開第２０１２／０６８２９２号明細書の[０４０７]）以降の説明を参酌でき、これらの内容は本願明細書に組み込まれる。 FIG. 5 is an enlarged cross-sectional view of the solid-state imaging device 100 in FIG.
The solid-state imaging device 100 includes an imaging device unit 12, an interlayer insulating film 13, a base layer 14, a color filter 15, an overcoat 16, and a microlens 17 in this order on the first main surface of a silicon substrate 10 that is a base. Yes. The red color filter 15R, the green color filter 15G, the blue color filter 15B (hereinafter, these may be collectively referred to as “color filter 15”), and the microlens 17 so as to correspond to the imaging element unit 12, Each is arranged. The second main surface opposite to the first main surface of the silicon substrate 10 includes a light shielding film 18, an insulating film 22, a metal electrode 23, a solder resist layer 24, an internal electrode 26, and an element surface electrode 27. Yes. Each member is bonded by an adhesive 20.
A planarizing layer 46 and a near infrared cut filter 42 are provided on the microlens 17. Instead of providing the near-infrared cut filter 42 on the flattening layer 46, the near-infrared cut filter 42 is provided on the microlens 17, between the base layer 14 and the color filter 15, or between the color filter 15 and the overcoat 16. The form in which an infrared cut filter is provided may be sufficient. In particular, it is preferably provided at a position within 2 mm (more preferably within 1 mm) from the surface of the microlens 17. If it is provided at this position, the process of forming the near infrared cut filter can be simplified, and unnecessary near infrared rays to the microlens can be sufficiently cut, so that the near infrared blocking property can be further improved.
Regarding the solid-state imaging device 100, the description after paragraph 0245 of JP 2012-068418 A (corresponding US Patent Application Publication No. 2012/068292 [0407]) can be referred to, and the contents thereof are described in this specification. Incorporated.
　近赤外線カットフィルタは、半田リフロー工程に供することができる。半田リフロー工程によりカメラモジュールを製造することによって、半田付けを行うことが必要な電子部品実装基板等の自動実装化が可能となり、半田リフロー工程を用いない場合と比較して、生産性を格段に向上することができる。更に、自動で行うことができるため、低コスト化を図ることもできる。半田リフロー工程に供される場合、２５０～２７０℃程度の温度にさらされることとなるため、赤外線カットフィルタは、半田リフロー工程に耐え得る耐熱性（以下、「耐半田リフロー性」ともいう。）を有することが好ましい。
　本願明細書中で、「耐半田リフロー性を有する」とは、２００℃で１０分間の加熱を行う前後で赤外線カットフィルタとしての特性を保持することをいう。より好ましくは、２３０℃で１０分間の加熱を行う前後で特性を保持することである。更に好ましくは、２５０℃で３分間の加熱を行う前後で特性を保持することである。耐半田リフロー性を有しない場合には、上記条件で保持した場合に、近赤外線カットフィルタの近赤外線吸収能が低下したり、膜としての機能が不十分となる場合がある。
　また本発明は、リフロー処理する工程を含む、カメラモジュールの製造方法にも関する。近赤外線カットフィルタは、リフロー工程があっても、近赤外線吸収能が維持されるので、小型軽量・高性能化されたカメラモジュールの特性を損なうことがない。
　図６～８は、カメラモジュールにおける近赤外線カットフィルタ周辺部分の一例を示す概略断面図である。
　図６に示すように、カメラモジュールは、固体撮像素子１００と、平坦化層４６と、紫外・赤外光反射膜８０と、透明基材８１と、近赤外線吸収層８２と、反射防止層８３とをこの順に有していてもよい。
　紫外・赤外光反射膜８０は、近赤外線カットフィルタの機能を付与または高める効果を有し、例えば、特開２０１３－６８６８８号公報の段落００３３～００３９を参酌することができ、この内容は本願明細書に組み込まれる。
　透明基材８１は、可視領域の波長の光を透過するものであり、例えば、特開２０１３－６８６８８号公報の段落００２６～００３２を参酌することができ、この内容は本願明細書に組み込まれる。
　近赤外線吸収層８２は、上述した本発明の近赤外線吸収性組成物を塗布して形成される層である。
　反射防止層８３は、近赤外線カットフィルタに入射する光の反射を防止することにより透過率を向上させ、効率よく入射光を利用する機能を有するものであり、例えば、特開２０１３－６８６８８号公報の段落００４０を参酌することができ、この内容は本願明細書に組み込まれる。
　図７に示すように、カメラモジュールは、固体撮像素子１００と、近赤外線吸収層８２と、反射防止層８３と、平坦化層４６と、反射防止層８３と、透明基材８１と、紫外・赤外光反射膜８０とをこの順に有していてもよい。
　図８に示すように、カメラモジュールは、固体撮像素子１００と、近赤外線吸収層８２と、紫外・赤外光反射膜８０と、平坦化層４６と、反射防止層８３と、透明基材８１と、反射防止層８３とをこの順に有していてもよい。

　以上、カメラモジュールの一実施形態について図４～図８を参照して説明したが、上記一実施形態は図４～図８の形態に限られるものではない。 The near-infrared cut filter can be subjected to a solder reflow process. By manufacturing the camera module through the solder reflow process, it is possible to automatically mount electronic component mounting boards, etc. that need to be soldered, making the productivity significantly higher than when not using the solder reflow process. Can be improved. Furthermore, since it can be performed automatically, the cost can be reduced. When subjected to the solder reflow process, the infrared cut filter is exposed to a temperature of about 250 to 270 ° C., so that the infrared cut filter can withstand the solder reflow process (hereinafter also referred to as “solder reflow resistance”). It is preferable to have.
In the specification of the present application, “having solder reflow resistance” refers to retaining characteristics as an infrared cut filter before and after heating at 200 ° C. for 10 minutes. More preferably, the characteristics are maintained before and after heating at 230 ° C. for 10 minutes. More preferably, the characteristics are maintained before and after heating at 250 ° C. for 3 minutes. When it does not have solder reflow resistance, the near-infrared absorptivity of the near-infrared cut filter may be lowered or the function as a film may be insufficient when held under the above conditions.
The present invention also relates to a method for manufacturing a camera module, including a reflow process. The near-infrared cut filter maintains the near-infrared absorptivity even if there is a reflow process, and does not impair the characteristics of a small, lightweight and high-performance camera module.
6 to 8 are schematic sectional views showing an example of the vicinity of the near infrared cut filter in the camera module.
As shown in FIG. 6, the camera module includes a solid-state imaging device 100, a planarization layer 46, an ultraviolet / infrared light reflection film 80, a transparent substrate 81, a near infrared absorption layer 82, and an antireflection layer 83. May be included in this order.
The ultraviolet / infrared light reflecting film 80 has the effect of imparting or enhancing the function of a near-infrared cut filter. For example, paragraphs 0033 to 0039 of JP2013-68688A can be referred to. Incorporated in the description.
The transparent substrate 81 transmits light having a wavelength in the visible region. For example, paragraphs 0026 to 0032 of JP2013-68688A can be referred to, and the contents thereof are incorporated herein.
The near-infrared absorbing layer 82 is a layer formed by applying the above-described near-infrared absorbing composition of the present invention.
The antireflection layer 83 has a function of improving the transmittance by preventing the reflection of light incident on the near-infrared cut filter and using the incident light efficiently. For example, JP 2013-68688 A Paragraph 0040, which is incorporated herein by reference.
As shown in FIG. 7, the camera module includes a solid-state imaging device 100, a near-infrared absorbing layer 82, an antireflection layer 83, a planarization layer 46, an antireflection layer 83, a transparent substrate 81, an ultraviolet The infrared light reflecting film 80 may be provided in this order.
As shown in FIG. 8, the camera module includes a solid-state imaging device 100, a near-infrared absorbing layer 82, an ultraviolet / infrared light reflecting film 80, a planarizing layer 46, an antireflection layer 83, and a transparent substrate 81. And an antireflection layer 83 in this order.

As described above, one embodiment of the camera module has been described with reference to FIGS. 4 to 8. However, the above embodiment is not limited to the embodiment shown in FIGS.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
　以下の例において、親水性領域または疎水性領域の近赤外線吸収性組成物に対する接触角は、ＪＩＳ Ｒ ３２５７「基板ガラス表面のぬれ性試験方法」に準拠して測定した。
　また、以下の例において、膜厚のバラつきとは、各実施例および比較例で作製した５種類の膜について、膜厚の平均値をそれぞれ算出し、各サンプル間の膜厚を比較した際の最大値（平均膜厚が最も厚い膜）と最小値（平均膜厚が最も薄い膜）の差を表す。膜厚は、触針式表面形状測定器（DektakXT：ブルカー・エイエックス社製）により測定した。
　以下の例において、以下の記号はそれぞれ以下の化合物を表す。
＜下記合成例で得られたスルホン酸銅錯体ポリマーＸ＞
＜＜合成例＞＞
　３つ口フラスコに水（６０ｇ）を入れ、窒素雰囲気下において５７℃に昇温した。２－アクリルアミド－２－メチルプロパンスルホン酸（１００ｇ）を水（１６０ｇ）に溶解させたモノマー溶液、およびＶＡ－０４６Ｂ（和光純薬工業株式会社製水溶性アゾ系重合開始剤、2,2'-Azobis[2-(2-imidazolin-2-yl)propane］disulfate dihydrate、１．１６４ｇ、モノマーに対して０．５ｍｏｌ％）を水（８０ｇ）に溶解させた開始剤溶液を、同時に２時間かけて滴下した。滴下終了後２時間攪拌した後、６５℃に昇温しさらに２時間撹拌し反応を終了させることで重合体（Ｐ－１）を得た。
　得られた重合体（Ｐ－１）溶液に対して、重合体（Ｐ－１）の酸基量に対して０．４当量の水酸化銅（１８．８３ｇ）を加え、５０℃で１時間撹拌することでスルホン酸銅錯体ポリマーＸを得た。
＜下記合成例で得られたスルホン酸銅錯体ポリマーＹ＞
＜＜合成例＞＞
　ポリエーテルスルホン(ＢＡＳＦ社製、Ｕｌｔｒａｓｏｎ　Ｅ６０２０Ｐ)５．０ｇを硫酸４６ｇに溶解し、窒素気流下、室温にてクロロスルホン酸１６．８３ｇを滴下した。室温にて４８時間反応した後、氷水で冷却したヘキサン／酢酸エチル（１／１）混合液１Ｌ中に反応液を滴下した。上澄みを除き、得られた沈殿物をメタノールに溶解した。得られた溶液を、酢酸エチル０．５Ｌ中に滴下し、得られた沈殿物をろ過により回収した。得られた固体を減圧乾燥することで、下記重合体（Ａ－１）を４．９ｇ得た。中和滴定により算出した、重合体（Ａ－１）中のスルホン酸基含有量（ｍｅｑ／ｇ）は３．０ｍｅｑ／ｇであった。また、ゲルパーミエーションクロマトグラフィーより測定した重量平均分子量(Ｍｗ)は５３，０００であった。
　重合体（Ａ－１）の２０質量％水溶液２０ｇに対し、水酸化銅５５６ｍｇを加え、室温で３時間撹拌し、水酸化銅を溶解させた。以上により、スルホン酸銅錯体ポリマーＹの水溶液が得られた。
重合体（Ａ－１）
Figure JPOXMLDOC01-appb-C000032
 In the following examples, the contact angle of the hydrophilic region or the hydrophobic region with respect to the near-infrared absorbing composition was measured in accordance with JIS R 3257 “Test method for wettability of substrate glass surface”.
Moreover, in the following examples, the variation in film thickness means that the average value of the film thickness was calculated for each of the five types of films prepared in each Example and Comparative Example, and the film thickness between the samples was compared. It represents the difference between the maximum value (film with the average film thickness) and the minimum value (film with the average film thickness). The film thickness was measured with a stylus type surface shape measuring instrument (DektakXT: manufactured by Bruker Ax).
In the following examples, the following symbols represent the following compounds, respectively.
<Sulphonic acid copper complex polymer X obtained in the following synthesis example>
<< Synthesis Example >>
Water (60 g) was placed in a three-necked flask and heated to 57 ° C. in a nitrogen atmosphere. A monomer solution prepared by dissolving 2-acrylamido-2-methylpropanesulfonic acid (100 g) in water (160 g), and VA-046B (water-soluble azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd., 2,2′- An initiator solution prepared by dissolving Azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 1.164 g, 0.5 mol% with respect to the monomer) in water (80 g) was simultaneously added over 2 hours. It was dripped. After completion of the dropwise addition, the mixture was stirred for 2 hours, and then heated to 65 ° C. and further stirred for 2 hours to complete the reaction, whereby a polymer (P-1) was obtained.
To the obtained polymer (P-1) solution, 0.4 equivalent of copper hydroxide (18.83 g) with respect to the amount of acid groups of the polymer (P-1) was added, and the mixture was stirred at 50 ° C. for 1 hour. The copper sulfonate complex polymer X was obtained by stirring.
<Sulphonic acid copper complex polymer Y obtained in the following synthesis example>
<< Synthesis Example >>
Polyethersulfone (manufactured by BASF, Ultrason E6020P) (5.0 g) was dissolved in 46 g of sulfuric acid, and 16.83 g of chlorosulfonic acid was added dropwise at room temperature under a nitrogen stream. After reacting at room temperature for 48 hours, the reaction solution was dropped into 1 L of a hexane / ethyl acetate (1/1) mixture cooled with ice water. The supernatant was removed and the resulting precipitate was dissolved in methanol. The obtained solution was dropped into 0.5 L of ethyl acetate, and the resulting precipitate was collected by filtration. The obtained solid was dried under reduced pressure to obtain 4.9 g of the following polymer (A-1). The sulfonic acid group content (meq / g) in the polymer (A-1) calculated by neutralization titration was 3.0 meq / g. Moreover, the weight average molecular weight (Mw) measured by gel permeation chromatography was 53,000.
To 20 g of a 20 mass% aqueous solution of the polymer (A-1), 556 mg of copper hydroxide was added and stirred at room temperature for 3 hours to dissolve the copper hydroxide. As a result, an aqueous solution of the copper sulfonate complex polymer Y was obtained.
Polymer (A-1)
Figure JPOXMLDOC01-appb-C000032
＜近赤外線吸収性組成物の調製＞
　スルホン酸銅錯体ポリマーＸ（１．００ｇ）に、純水（２．８０ｇ）およびジメチルホルムアミド（１．２０ｇ）を加え、近赤外線吸収性組成物Ａを得た。調製した近赤外線吸収性組成物Ａは、固形分濃度２０質量％の青色の透明液であった。
　また、近赤外線吸収性組成物Ａに純水を加え、固形分濃度を１０質量％に調整した近赤外線吸収性組成物Ｂを得た。
＜基材上への親水性領域および疎水性領域の形成＞
＜＜親水性領域（α）が形成されたガラス基板Ａの作製＞＞
　ガラス基板（厚さ１．１０ｍｍ）をアセトン、エタノールに順次浸漬して各々１０分間超音波処理し、次いで、純水で５分間流水リンスした後に、窒素ブローにより乾燥し、親水性領域（α）が形成されたガラス基板Ａを作製した。親水性領域（α）の表面の上記近赤外線吸収性組成物Ａに対する接触角を測定したところ、接触角は１９．７°であった。
＜＜親水性領域（β）が形成されたガラス基板Ｂ＞＞
　また、上記ガラス基板Ａ上に、樹脂膜（ベンジルメタクリレート（７０ｗｔ％）／メタクリル酸（３０ｗｔ％）共重合体（重量平均分子量２万５千）のシクロヘキサノン溶液（固形分重量２０重量部））を３ｍｌ塗布し、酸素プラズマアッシング処理を行って、親水性領域（β）が形成されたガラス基板Ｂを作製した。親水性領域（β）の表面の上記近赤外線吸収性組成物Ａに対する接触角を測定したところ、接触角は１７．３°であった。
＜＜親水性領域（α）を囲む疎水性領域（γ）が形成されたガラス基板Ｃ＞＞
　上記ガラス基板Ａ上に、疎水性領域を形成するためのレジスト組成物（製品名：（ＦＨｉ－４７５０：富士フイルムエレクトロニクスマテリアルズ社製））を３ｍｌ塗布し、リソグラフィーによりパターニングして、親水性領域（α）を囲む疎水性領域（γ）が形成されたガラス基板Ｃを作製した。疎水性領域（γ）の表面の上記近赤外線吸収性組成物Ａに対する接触角を測定したところ、接触角は７９．２°であった。
＜＜親水性領域（α）を囲む疎水性領域（δ）が形成されたガラス基板Ｄ＞＞
　上記ガラス基板Ａ上の周囲に、疎水性領域を形成するためのカプトンテープ（登録商標）を貼り付け、親水性領域（α）を囲む疎水性領域（δ）が形成されたガラス基板Ｄを作製した。図９は、本発明の近赤外線カットフィルタの製造工程の一例を示す概略図であり、（Ａ）は親水性領域および疎水性領域が形成された基材の平面図であり、（Ｂ）は上記基材の正面図である。図９に示す例において、ガラス基板１Ａの表面に親水性領域２（親水性領域（α））と、親水性領域２を囲む疎水性領域３（疎水性領域（δ））を形成した。疎水性領域（δ）の表面の上記近赤外線吸収性組成物Ａに対する接触角を測定したところ、接触角は８３．４°であった。
＜＜親水性領域（β）を囲む疎水性領域（γ）が形成されたガラス基板Ｅ＞＞
　上記と同様にして、親水性領域（β）が形成されたガラス基板Ｂ上に、上記疎水性領域を形成するためのフォトレジストを塗布し、リソグラフィーによりパターニングして、親水性領域（β）を囲む疎水性領域（γ）が形成されたガラス基板Ｅを作製した。
＜＜疎水性領域δが形成されたガラス基板Ｆ＞＞
　ガラス基板に親水性領域αを形成せずに（すなわち洗浄せずに）、疎水性領域δが形成された基板Ｆを作製した。ガラス基板Ｆ上での赤外線吸収性組成物Ａの接触角は３９．８°であった。 <Preparation of near-infrared absorbing composition>
Pure water (2.80 g) and dimethylformamide (1.20 g) were added to copper sulfonate complex polymer X (1.00 g) to obtain a near-infrared absorbing composition A. The prepared near-infrared absorbing composition A was a blue transparent liquid having a solid content concentration of 20% by mass.
Moreover, the near-infrared absorptive composition B which added the pure water to the near-infrared absorptive composition A, and adjusted solid content concentration to 10 mass% was obtained.
<Formation of hydrophilic region and hydrophobic region on substrate>
<< Production of Glass Substrate A Formed with Hydrophilic Region (α) >>
A glass substrate (thickness: 1.10 mm) is dipped in acetone and ethanol in order and subjected to ultrasonic treatment for 10 minutes each, then rinsed with pure water for 5 minutes, dried by nitrogen blowing, and hydrophilic region (α) A glass substrate A on which was formed was produced. When the contact angle with respect to the said near-infrared absorptive composition A of the surface of a hydrophilic region ((alpha)) was measured, the contact angle was 19.7 degrees.
<< Glass substrate B on which hydrophilic region (β) is formed >>
Further, on the glass substrate A, a resin film (a cyclohexanone solution of benzyl methacrylate (70 wt%) / methacrylic acid (30 wt%) copolymer (weight average molecular weight 25,000) (solid content weight 20 parts by weight)) is formed. 3 ml of the glass substrate B was applied and subjected to oxygen plasma ashing to prepare a glass substrate B on which a hydrophilic region (β) was formed. When the contact angle with respect to the said near-infrared absorptive composition A of the surface of a hydrophilic region ((beta)) was measured, the contact angle was 17.3 degrees.
<< Glass Substrate C with Hydrophobic Region (γ) Surrounding Hydrophilic Region (α) >>
On the glass substrate A, 3 ml of a resist composition (product name: (FHi-4750: manufactured by FUJIFILM Electronics Materials)) for forming a hydrophobic region is applied and patterned by lithography to form a hydrophilic region. A glass substrate C on which a hydrophobic region (γ) surrounding (α) was formed was produced. When the contact angle of the surface of the hydrophobic region (γ) with respect to the near-infrared absorbing composition A was measured, the contact angle was 79.2 °.
<< Glass Substrate D Formed with Hydrophobic Region (δ) Surrounding Hydrophilic Region (α) >>
A Kapton tape (registered trademark) for forming a hydrophobic region is pasted around the glass substrate A to produce a glass substrate D in which a hydrophobic region (δ) surrounding the hydrophilic region (α) is formed. did. FIG. 9 is a schematic view showing an example of the manufacturing process of the near-infrared cut filter of the present invention, (A) is a plan view of a substrate on which a hydrophilic region and a hydrophobic region are formed, and (B) is It is a front view of the said base material. In the example shown in FIG. 9, a hydrophilic region 2 (hydrophilic region (α)) and a hydrophobic region 3 (hydrophobic region (δ)) surrounding the hydrophilic region 2 were formed on the surface of the glass substrate 1A. When the contact angle of the surface of the hydrophobic region (δ) to the near-infrared absorbing composition A was measured, the contact angle was 83.4 °.
<< Glass substrate E on which a hydrophobic region (γ) surrounding the hydrophilic region (β) is formed >>
In the same manner as described above, a photoresist for forming the hydrophobic region is applied on the glass substrate B on which the hydrophilic region (β) is formed, and patterned by lithography to form the hydrophilic region (β). A glass substrate E on which a surrounding hydrophobic region (γ) was formed was produced.
<< Glass Substrate F with Hydrophobic Region δ >>
A substrate F in which a hydrophobic region δ was formed without forming the hydrophilic region α on the glass substrate (that is, without washing) was produced. The contact angle of the infrared absorbing composition A on the glass substrate F was 39.8 °.
＜近赤外線カットフィルタの作製＞
＜＜実施例１＞＞
　上記ガラス基板Ｄの親水性領域αに、上記近赤外線吸収性組成物Ａを３ｍｌ滴下したところ、上記近赤外線吸収性組成物Ａは親水性領域α内に濡れ広がり、疎水性領域δ上には膜形成しなかった。この塗布膜付き基板を２４時間室温放置により乾燥させた後、塗布膜厚を評価したところ、膜厚は１９２μｍであった。
　同様の実験を５回行ったところ、膜厚のバラつきは±７μｍであり、再現性は良好であった。
＜＜実施例２～４および比較例１、２＞＞
　下記表に示す通りにしたこと以外は、実施例１と同様にして、実施例２～４および比較例１、２について、塗布膜を形成し、膜厚のバラつきを評価した。 <Production of near-infrared cut filter>
<< Example 1 >>
When 3 ml of the near-infrared absorbing composition A was dropped on the hydrophilic region α of the glass substrate D, the near-infrared absorbing composition A spreads in the hydrophilic region α, and on the hydrophobic region δ. No film was formed. The substrate with the coating film was dried at room temperature for 24 hours, and then the coating film thickness was evaluated. The film thickness was 192 μm.
When the same experiment was conducted five times, the film thickness variation was ± 7 μm, and the reproducibility was good.
<< Examples 2 to 4 and Comparative Examples 1 and 2 >>
Except as described below, coating films were formed in Examples 2 to 4 and Comparative Examples 1 and 2 in the same manner as in Example 1, and the variation in film thickness was evaluated.
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
　実施例２では、実施例１との比較から、固形分濃度の調整で膜厚を調整できることが確認された。
　実施例１～４で用いた近赤外線吸収性組成物において、スルホン酸銅錯体ポリマーＸをスルホン酸銅錯体ポリマーＹに替えた場合も、これらと同様の効果が得られる。
　比較例１では、近赤外線吸収性組成物Ａがガラス基板上で濡れ広がり、近赤外線吸収性組成物Ａの一部が基板外に漏洩した。
　比較例２では、塗布組成物は塗れ広がらず、膜形成ができなかった。 In Example 2, it was confirmed from the comparison with Example 1 that the film thickness can be adjusted by adjusting the solid content concentration.
In the near-infrared absorbing compositions used in Examples 1 to 4, when the sulfonic acid copper complex polymer X is replaced with the sulfonic acid copper complex polymer Y, the same effects as these can be obtained.
In Comparative Example 1, the near-infrared absorbing composition A wets and spreads on the glass substrate, and a part of the near-infrared absorbing composition A leaks out of the substrate.
In Comparative Example 2, the coating composition did not spread and film formation was not possible.
＜蒸着膜付き近赤外線カットフィルタの作成＞
　さらに近赤外線カットフィルタの上に、蒸着温度２００℃で、近赤外線を反射する誘電体多層膜として、シリカ（ＳｉＯ2：膜厚２０～２５０ｎｍ）層とチタニア（ＴｉＯ2：膜厚７０～１３０ｎｍ）層とが交互に積層された層を形成した。具体的な層構成は、近赤外線カットフィルタ上にシリカ層（膜厚８０ｎｍ）、その上にチタニア層（膜厚１０３ｎｍ）とシリカ層（膜厚１５９ｎｍ）の交互積層膜を計４１層、最上部にシリカ層（膜厚８０ｎｍ）とした。 <Creation of near-infrared cut filter with vapor deposition film>
Further, on the near infrared cut filter, as a dielectric multilayer film that reflects near infrared rays at a deposition temperature of 200 ° C., a silica (SiO 2 : film thickness 20 to 250 nm) layer and titania (TiO 2 : film thickness 70 to 130 nm). A layer in which layers were alternately stacked was formed. A specific layer structure is a total of 41 layers of alternating laminated films of a silica layer (film thickness of 80 nm) on the near infrared cut filter and a titania layer (film thickness of 103 nm) and a silica layer (film thickness of 159 nm). A silica layer (film thickness 80 nm) was used.
＜実施例２０＞
　実施例１の近赤外線吸収性組成物において、以下に示す低分子銅錯体Ａをさらに追加し、固形分基準でスルホン酸銅錯体ポリマーＸと低分子銅錯体Ａとの比が７：３となるようにしたこと以外は、実施例１と同様にして実施例２０の近赤外線吸収性組成物を得た。
（実施例２１～２４）
　実施例２０の近赤外線吸収性組成物において、低分子銅錯体Ａをそれぞれ低分子銅錯体Ｂ、Ｃ、ＤまたはＥに変えたこと以外は、実施例２０と同様にして、実施例２１～２４の近赤外線吸収性組成物を得た。
＜実施例２５～２７＞
　実施例２０の近赤外線吸収性組成物において、固形分基準でスルホン酸銅錯体ポリマーＸと低分子銅錯体Ａとの比を、それぞれ５：５、６：４、８：２と変えたこと以外は、実施例２０と同様にして、実施例２５～２７の近赤外線吸収性組成物を得た。
　これら、スルホン酸銅錯体ポリマーＸと低分子銅錯体との混合タイプでは、さらに高い近赤外線遮蔽性を達成できることを確認できた。
＜低分子銅錯体＞
　低分子銅錯体Ａ：下記（Ｍ－１）を配位子として有する銅錯体。合成方法は後述する。
　低分子銅錯体Ｂ：下記化合物（Ａ１－２１）を配位子とする銅錯体。合成方法は後述する。
　低分子銅錯体Ｃ：フタル酸モノブチル銅、東京化成工業株式会社
　低分子銅錯体Ｄ：下記化合物（Ａ２－１）を配位子とする銅錯体。合成方法は後述する。
　低分子銅錯体Ｅ：下記化合物（ａ－０）を配位子とする銅錯体。合成方法は後述する。
Figure JPOXMLDOC01-appb-C000034
 <Example 20>
In the near-infrared absorbing composition of Example 1, the low-molecular copper complex A shown below is further added, and the ratio of the sulfonic acid copper complex polymer X and the low-molecular copper complex A is 7: 3 on a solid basis. A near-infrared absorbing composition of Example 20 was obtained in the same manner as Example 1 except for the above.
(Examples 21 to 24)
In the near-infrared absorbing composition of Example 20, Examples 21 to 24 were carried out in the same manner as in Example 20 except that the low molecular copper complex A was changed to low molecular copper complexes B, C, D, or E, respectively. A near infrared ray absorbing composition was obtained.
<Examples 25 to 27>
In the near-infrared absorbing composition of Example 20, except that the ratio of the sulfonic acid copper complex polymer X to the low molecular copper complex A was changed to 5: 5, 6: 4, and 8: 2, respectively, based on the solid content. Were the same as in Example 20 to obtain near-infrared absorbing compositions of Examples 25 to 27.
It was confirmed that the mixed type of the sulfonic acid copper complex polymer X and the low-molecular copper complex can achieve higher near-infrared shielding properties.
<Low molecular copper complex>
Low molecular copper complex A: a copper complex having the following (M-1) as a ligand. The synthesis method will be described later.
Low molecular copper complex B: a copper complex having the following compound (A1-21) as a ligand. The synthesis method will be described later.
Low molecular copper complex C: Monobutyl copper phthalate, Tokyo Chemical Industry Co., Ltd. Low molecular copper complex D: Copper complex having the following compound (A2-1) as a ligand. The synthesis method will be described later.
Low molecular copper complex E: a copper complex having the following compound (a-0) as a ligand. The synthesis method will be described later.
Figure JPOXMLDOC01-appb-C000034
＜低分子銅錯体Ａの合成＞
　三ツ口フラスコに、窒素雰囲気下、ピラゾール－３－カルボン酸エチル４．０ｇ、炭酸セシウム１１．１６ｇ、３－ブロモペンタン５．１７ｇ、２，６－ジメチル－４－ヘプタノン６０ｍＬを加え、１５０℃で１時間加熱した。室温に冷却後、濾過により不溶物を除去し、濾液を濃縮して得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶媒：ヘキサン／酢酸エチル）で精製することにより、１－（３－ペンチル）ピラゾール－３－カルボン酸エチルを３．３ｇ得た。
　フラスコに上記生成物を０．８７ｇ、エタノール６ｍＬを加え、室温で撹拌しながら水０．１ｇ、ｔｅｒｔ－ブトキシカリウム０．４６ｇを加えた後、７０℃で３０分間撹拌した。室温に冷却後、硫酸銅０．５２ｇを水５ｍＬに溶かした溶液を加え、室温で一時間攪拌した。析出した固体を濾別し、減圧下で乾燥することで低分子銅錯体Ａを０．７ｇ得た。
＜低分子銅錯体Ｂの合成＞
　化合物Ａ１－２１（８８６ｍｇ、９．８４ｍｍｏｌ）をメタノール２０ｍｌに溶解した。この溶液を５０℃に昇温した後、水酸化銅(４４９ｍｇ、４．６０ｍｍｏｌ）のメタノール溶液(１６０ｍｌ)を滴下し、５０℃にて２時間反応させた。反応終了後、エバポレータにて発生した水および溶剤を留去することで低分子銅錯体Ｂ（１．００ｇ）を得た。
＜低分子銅錯体Ｄの合成＞
　化合物Ａ２－１（０．２ｇ、１．１ｍｍｏｌ）をエタノール５ｍｌに溶解した。この溶液を７０℃に昇温した後、酢酸銅（０．２ｇ、１．１ｍｍｏｌ）のエタノール溶液（５ｍｌ）を滴下し、７０℃にて２時間反応させた。反応終了後、エバポレータにて発生した水および溶剤を留去することで低分子銅錯体Ｄ（０．６ｇ）を得た。
＜低分子銅錯体Ｅの合成＞
　化合物ａ－０（スルホフタル酸）５３．１質量％水溶液（１３．４９ｇ、２９．１ｍｍｏｌ）をメタノール５０ｍＬに溶かし、この溶液を５０℃に昇温した後、水酸化銅（２．８４ｇ，２９．１ｍｍｏｌ）を加え５０℃で２時間反応させた。反応終了後、エバポレータにて溶剤及び発生した水を留去することで低分子銅錯体Ｅ（８．５７ｇ）を得た。
　実施例２０～２７の近赤外線吸収性組成物において、低分子銅錯体Ａ～Ｅを、等量の上記（Ａ１－１）～（Ａ－１０）、（Ａ１－１２）～（Ａ１－２０）、（Ａ１－２２）～（Ａ１－３１）、（Ａ２－２）～（Ａ２－６）、（ａ－１）～（ａ－１７）のいずれかを配位子として有する銅錯体に変更した場合でも、同様の効果が得られる。 <Synthesis of low molecular copper complex A>
Under a nitrogen atmosphere, 4.0 g of ethyl pyrazole-3-carboxylate, 11.16 g of cesium carbonate, 5.17 g of 3-bromopentane, and 60 mL of 2,6-dimethyl-4-heptanone were added to a three-necked flask. Heated for hours. After cooling to room temperature, insoluble matters are removed by filtration, and the filtrate is concentrated, and the resulting crude product is purified by silica gel column chromatography (solvent: hexane / ethyl acetate) to give 1- (3-pentyl). 3.3 g of ethyl pyrazole-3-carboxylate was obtained.
To the flask, 0.87 g of the above product and 6 mL of ethanol were added, and 0.1 g of water and 0.46 g of tert-butoxypotassium were added while stirring at room temperature, followed by stirring at 70 ° C. for 30 minutes. After cooling to room temperature, a solution prepared by dissolving 0.52 g of copper sulfate in 5 mL of water was added, and the mixture was stirred at room temperature for 1 hour. The precipitated solid was separated by filtration and dried under reduced pressure to obtain 0.7 g of low-molecular copper complex A.
<Synthesis of low molecular copper complex B>
Compound A1-21 (886 mg, 9.84 mmol) was dissolved in 20 ml of methanol. After the temperature of this solution was raised to 50 ° C., a methanol solution (160 ml) of copper hydroxide (449 mg, 4.60 mmol) was added dropwise and reacted at 50 ° C. for 2 hours. After completion of the reaction, the low-molecular copper complex B (1.00 g) was obtained by distilling off the water and the solvent generated in the evaporator.
<Synthesis of low molecular copper complex D>
Compound A2-1 (0.2 g, 1.1 mmol) was dissolved in 5 ml of ethanol. After heating this solution to 70 degreeC, the ethanol solution (5 ml) of copper acetate (0.2g, 1.1mmol) was dripped, and it was made to react at 70 degreeC for 2 hours. After completion of the reaction, the low-molecular copper complex D (0.6 g) was obtained by distilling off the water and the solvent generated in the evaporator.
<Synthesis of low molecular copper complex E>
Compound a-0 (sulfophthalic acid) 53.1 mass% aqueous solution (13.49 g, 29.1 mmol) was dissolved in 50 mL of methanol, and this solution was heated to 50 ° C., and then copper hydroxide (2.84 g, 29.29 g). 1 mmol) was added and reacted at 50 ° C. for 2 hours. After completion of the reaction, a low molecular copper complex E (8.57 g) was obtained by distilling off the solvent and generated water with an evaporator.
In the near-infrared absorbing compositions of Examples 20 to 27, the low-molecular copper complexes A to E were used in an equal amount of the above (A1-1) to (A-10), (A1-12) to (A1-20). , (A1-22) to (A1-31), (A2-2) to (A2-6), or (a-1) to (a-17) was changed to a copper complex having as a ligand Even in this case, the same effect can be obtained.
１　基材、１Ａ　ガラス基板、２　親水性領域、３　疎水性領域、４　近赤外線吸収性組成物、５　レジスト組成物、５Ａ　レジストパターン、
６　銅イオン、７　主鎖、８　側鎖、９　酸基イオン部位、
１０　シリコン基板、１２　撮像素子部、１３　層間絶縁膜、１４　ベース層、１５　カラーフィルタ、１６　オーバーコート、１７　マイクロレンズ、１８　遮光膜、
２０　接着剤、２２　絶縁膜、２３　金属電極、２４　ソルダレジスト層、２６　内部電極、２７　素子面電極、
３０　ガラス基板、４０　撮像レンズ、４２　近赤外線カットフィルタ、４４　遮光兼電磁シールド、４５　接着剤、４６　平坦化層、
５０　レンズホルダー、６０　ハンダボール、７０　回路基板、８０　紫外・赤外光反射膜、８１　透明基材、８２　近赤外線吸収層、８３　反射防止層、１００　固体撮像素子 1 base material, 1A glass substrate, 2 hydrophilic region, 3 hydrophobic region, 4 near-infrared absorbing composition, 5 resist composition, 5A resist pattern,
6 copper ion, 7 main chain, 8 side chain, 9 acid group ion site,
DESCRIPTION OF SYMBOLS 10 Silicon substrate, 12 Image pick-up element part, 13 Interlayer insulation film, 14 Base layer, 15 Color filter, 16 Overcoat, 17 Micro lens, 18 Light shielding film,
20 Adhesive, 22 Insulating film, 23 Metal electrode, 24 Solder resist layer, 26 Internal electrode, 27 Element surface electrode,
30 glass substrate, 40 imaging lens, 42 near-infrared cut filter, 44 light shielding and electromagnetic shield, 45 adhesive, 46 flattening layer,
50 Lens holder, 60 Solder ball, 70 Circuit board, 80 Ultraviolet / infrared light reflection film, 81 Transparent base material, 82 Near infrared absorption layer, 83 Antireflection layer, 100 Solid-state imaging device

Claims (13)

  1. 基材上に親水性領域および／または疎水性領域を形成する工程、および、
    親水性領域の表面に、および／または、疎水性領域で囲まれた領域内に、近赤外線吸収物質を含む近赤外線吸収性組成物を適用する工程、
    を有する近赤外線カットフィルタの製造方法。     Forming a hydrophilic region and / or a hydrophobic region on a substrate; and
    Applying a near-infrared absorbing composition comprising a near-infrared absorbing material to the surface of the hydrophilic region and / or within the region surrounded by the hydrophobic region;
    The manufacturing method of the near-infrared cut filter which has NO.
  2. 前記近赤外線吸収性組成物がさらに水を含み、固形分が５～３０質量％である、請求項１に記載の近赤外線カットフィルタの製造方法。 The method for producing a near-infrared cut filter according to claim 1, wherein the near-infrared absorbing composition further contains water and has a solid content of 5 to 30% by mass.
  3. 前記親水性領域の表面、または、基材の表面の前記近赤外線吸収性組成物に対する接触角が０～４５°である、請求項１または２に記載の近赤外線カットフィルタの製造方法。 The method for producing a near-infrared cut filter according to claim 1 or 2, wherein a contact angle of the surface of the hydrophilic region or the surface of the substrate with the near-infrared absorbing composition is 0 to 45 °.
  4. 基材の表面を親水化処理することによって、前記親水性領域の表面の前記近赤外線吸収性組成物に対する接触角を０～４５°の範囲にする、請求項１～３のいずれか１項に記載の近赤外線カットフィルタの製造方法。 4. The contact angle of the surface of the hydrophilic region with respect to the near-infrared absorbing composition by making the surface of the substrate hydrophilic, in the range of 0 to 45 °. The manufacturing method of the near-infrared cut filter of description.
  5. 基材上に親水性領域および／または疎水性領域を形成する工程では、基材上に親水性領域および前記親水性領域を囲む疎水性領域を形成し、
    前記近赤外線吸収性組成物を適用する工程では、前記近赤外線吸収性組成物を親水性領域の表面に適用する、請求項１～４のいずれか１項に記載の近赤外線カットフィルタの製造方法。     In the step of forming the hydrophilic region and / or the hydrophobic region on the substrate, the hydrophilic region and the hydrophobic region surrounding the hydrophilic region are formed on the substrate,
    The method for producing a near-infrared cut filter according to any one of claims 1 to 4, wherein, in the step of applying the near-infrared absorbing composition, the near-infrared absorbing composition is applied to a surface of a hydrophilic region. .
  6. 前記疎水性領域を形成する工程は、基材上に適用されたレジスト組成物をリソグラフィーによりパターニングすること、表面が疎水性のテープを基材上に貼ることを含む、請求項１～５のいずれか１項に記載の近赤外線カットフィルタの製造方法。 The step of forming the hydrophobic region includes patterning a resist composition applied on the base material by lithography, and applying a tape having a hydrophobic surface on the base material. The manufacturing method of the near-infrared cut filter of Claim 1.
  7. 前記適用の方法が、ドロップキャスト、ディップコート、スリットコート、スクリーン印刷、スプレーコートおよびスピンコートから選択される少なくとも１つである、請求項１～６のいずれか１項に記載の近赤外線カットフィルタの製造方法。 The near-infrared cut filter according to any one of claims 1 to 6, wherein the application method is at least one selected from drop casting, dip coating, slit coating, screen printing, spray coating, and spin coating. Manufacturing method.
  8. 前記適用の方法がドロップキャストである、請求項７に記載の近赤外線カットフィルタの製造方法。 The method for producing a near-infrared cut filter according to claim 7, wherein the application method is drop casting.
  9. 前記近赤外線吸収物質が、配位部位を含む重合体と銅成分との反応で得られる化合物を含む、請求項１～８のいずれか１項に記載の近赤外線カットフィルタの製造方法。 The method for producing a near-infrared cut filter according to any one of claims 1 to 8, wherein the near-infrared absorbing substance contains a compound obtained by a reaction between a polymer containing a coordination site and a copper component.
  10. 前記重合体が、スルホン酸基またはその塩から選択される少なくとも１種を有する、請求項９に記載の近赤外線カットフィルタの製造方法。 The method for producing a near-infrared cut filter according to claim 9, wherein the polymer has at least one selected from a sulfonic acid group or a salt thereof.
  11. 前記近赤外線吸収物質が銅錯体を含む、請求項１～１０のいずれか１項に記載の近赤外線カットフィルタの製造方法。 The method for producing a near-infrared cut filter according to any one of claims 1 to 10, wherein the near-infrared absorbing substance contains a copper complex.
  12. 前記近赤外線吸収性組成物中の前記銅錯体の含有量が３０質量％以下であり、
    前記銅錯体が、酸基イオンを含む重合体中の酸基イオン部位を配位子とする銅錯体である、請求項１１に記載の近赤外線カットフィルタの製造方法。     The content of the copper complex in the near-infrared absorbing composition is 30% by mass or less,
    The manufacturing method of the near-infrared cut off filter of Claim 11 whose said copper complex is a copper complex which makes the acid group ion site | part in the polymer containing an acid group ion a ligand.
  13. 請求項１～１２のいずれか１項に記載の近赤外線カットフィルタの製造方法で得られた近赤外線カットフィルタを有する固体撮像素子。 A solid-state imaging device having a near-infrared cut filter obtained by the method for producing a near-infrared cut filter according to any one of claims 1 to 12.
PCT/JP2014/068491 2013-07-12 2014-07-10 Method for producing near infrared cutoff filter, and solid-state imaging element WO2015005448A1 (en)

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