JP2017067824A - Composition, method of producing the same, film, near-infrared cut filter, solid-state image sensor, camera module, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition capable of producing a film with little defects, a method of producing the same, a film, a near-infrared cut filter, a solid-state image sensor, a camera module, and an image display device.SOLUTION: A composition contains an infrared absorbent made of a copper compound and a solvent, and exhibits a dissolved oxygen content of 0.1-50 mg/L in a solution at 25°C and 0.1 MPa. The compound has a solid content concentration of 40 mass% or greater and a viscosity of 0.05-10 Pa s at 25°C, and contains a compound having a cross-linkable group with a partial structure represented by M-X.SELECTED DRAWING: None

Description

  The present invention relates to a composition comprising an infrared absorber and a solvent. Moreover, it is related with the manufacturing method of the said composition. The present invention also relates to a film, a near-infrared cut filter, a solid-state imaging device, a camera module, and an image display device using the above composition.

  A video camera, a digital still camera, a mobile phone with a camera function, and the like use a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor) which is a solid-state imaging device for color images. Since these solid-state imaging devices use silicon photodiodes having sensitivity to infrared rays in their light receiving parts, it is necessary to perform visibility correction and often use near-infrared cut filters.

  In Patent Document 1, 1 to 50 of a composite tungsten oxide compound is added to 100 parts by mass of an organic solvent on the surface of a molded product obtained by curing a curable composition containing a nonionic near-infrared absorbing compound. An infrared absorbing material having a layer formed by applying a solution containing parts by mass is described.

JP 2012-20448 A

  A near-infrared cut filter having a desired film thickness is manufactured by adjusting the viscosity and solid content concentration of the composition. For example, in the case of a composition using a copper compound as an infrared absorber, the film thickness of the near-infrared cut filter may be about 100 μm by adjusting the viscosity and solid content concentration of the composition.

  However, according to the study by the present inventors, it was found that defects are likely to occur in the near infrared cut filter as the viscosity and solid content concentration of the composition are increased. In recent years, further improvement in the liquid stability of the composition has been demanded. According to the study by the present inventors, it has been found that it is difficult for the method described in Patent Document 1 to achieve both the liquid stability of the composition and the suppression of film defects.

  Accordingly, an object of the present invention is to provide a composition capable of producing a film having good liquid stability and few defects, a method for producing the composition, a film, a near-infrared cut filter, a solid-state imaging device, a camera module, and an image display device. It is to provide.

As a result of intensive studies, the present inventors have found that the above object can be achieved by setting the amount of dissolved oxygen within a predetermined range in a composition containing an infrared absorber and a solvent, and the present invention has been completed. It came to do. The present invention provides the following.
<1> A composition comprising an infrared absorber and a solvent, wherein the dissolved oxygen content in a liquid at 25 ° C. is 0.1 to 50 mg / L at 0.1 MPa.
<2> The composition according to <1>, wherein the dissolved gas amount in the liquid at 25 ° C. is 0.1 to 50 mg / L at 0.1 MPa.
<3> The composition according to <1> or <2>, wherein the infrared absorber is a copper compound.
<4> The composition according to any one of <1> to <3>, wherein the solid content concentration is 40% by mass or more.
<5> The composition according to any one of <1> to <4>, wherein the viscosity at 25 ° C. is 0.05 to 10 Pa · s.
<6> The composition according to any one of <1> to <5>, further comprising a compound having a crosslinkable group.
<7> The composition according to <6>, wherein the compound having a crosslinkable group includes a compound having a partial structure represented by MX; wherein M is selected from Si, Ti, Zr and Al X is one selected from hydroxy, alkoxy, acyloxy, phosphoryloxy, sulfonyloxy, amino, oxime and O = C (R ^a ) (R ^b ) , R ^a and R ^b each independently represents a monovalent organic group, and when X is O═C (R ^a ) (R ^b ), M is a lone pair of oxygen atoms of the carbonyl group. Join.
<8> The composition according to <6> or <7>, wherein the content of the compound having a crosslinkable group is 15% by mass or more of the total solid content of the composition.
<9> A method for producing the composition according to any one of <1> to <8>, comprising a step of defoaming a composition A containing an infrared absorber and a solvent. Manufacturing method.
<10> The composition A includes two or more types of solvents, and the difference between the boiling point of the solvent having the highest boiling point and the boiling point of the solvent having the lowest boiling point is 10 ° C. or more. The manufacturing method of the composition as described in <9>.
<11> The method for producing a composition according to <9> or <10>, wherein the defoaming treatment is performed by at least one method selected from ultrasonic irradiation and reduced pressure.
<12> The method for producing a composition according to any one of <9> to <11>, wherein the composition A is filtered and then defoamed.
<13> A film formed using the composition according to any one of <1> to <8>.
<14> A near-infrared cut filter using the composition according to any one of <1> to <8>.
<15> A solid-state imaging device having the near infrared cut filter according to <14>.
<16> A camera module having the near-infrared cut filter according to <14>.
<17> An image display device having the near-infrared cut filter according to <14>.

  ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the composition which can manufacture a film | membrane with favorable liquid stability and few defects, and the manufacturing method of a composition. Further, it has become possible to provide a film, a near-infrared cut filter, a solid-state imaging device, a camera module, and an image display device.

It is a schematic sectional drawing which shows the structure of the camera module which has a near-infrared cut off filter based on embodiment of this invention. It is a schematic sectional drawing which shows an example of the near-infrared cut filter periphery part in a camera module. It is a schematic sectional drawing which shows an example of the near-infrared cut filter periphery part in a camera module. It is a schematic sectional drawing which shows an example of the near-infrared cut filter periphery part in a camera module.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “to” is used in the sense of including the numerical values described before and after it as lower and upper limits.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent. To do. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
The measuring method of the weight average molecular weight and the number average molecular weight of the compound used in the present invention can be measured by gel permeation chromatography (GPC), and is defined as a polystyrene conversion value by GPC measurement.
Near-infrared light refers to light (electromagnetic wave) having a maximum absorption wavelength region of 700 to 2500 nm.
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition. The solid content in the present invention is a solid content at 25 ° C.

<Composition>
The composition of the present invention is a composition containing an infrared absorber and a solvent, and the dissolved oxygen content in the liquid at 25 ° C. is 0.1 to 50 mg / L. The dissolved oxygen content of the composition is preferably from 0.1 to 30 mg / L, more preferably from 1 to 10 mg / L, still more preferably from 1 to 5 mg / L.

  By setting the dissolved oxygen content in the above range, the composition of the present invention can be made into a composition capable of producing a film having good liquid stability and few defects. That is, if the amount of dissolved oxygen is less than or equal to the above-described upper limit value, the ratio of the bubble component in the composition can be reduced, and a film such as a near infrared cut filter with few defects can be manufactured. Moreover, if the amount of dissolved oxygen is not less than the lower limit value described above, the detailed reason is unknown, but the liquid stability is excellent. The mechanism that improves the liquid stability by setting the dissolved oxygen amount to the above-mentioned lower limit or more is to quench radicals generated when the material decomposes in the composition by a small amount of oxygen contained in the composition. It is presumed that this is because it can be done.

In the composition of the present invention, the amount of dissolved gas in a liquid at 25 ° C. at 0.1 MPa is preferably 0.1 to 50 mg / L, more preferably 0.1 to 30 mg / L, and 1 to 10 mg / L. L is more preferable. Examples of dissolved gas in the composition include oxygen, hydrogen, carbon dioxide, and nitrogen.
In the present invention, the amount of dissolved gas and dissolved oxygen in the composition can be measured by a known method such as gas chromatography or dissolved oxygen meter. For example, the amount of dissolved oxygen can be calculated from the ratio of the partial pressure of oxygen with the saturated dissolved oxygen solution using an Orbis Fair 510 gas analyzer (manufactured by Hack Ultra Co., Ltd.).

The composition of the present invention preferably has a viscosity at 25 ° C. of 0.05 to 10 Pa · s. The upper limit is preferably 1.0 Pa · s or less, and more preferably 0.5 Pa · s or less. The lower limit is preferably 0.075 Pa · s or more, and more preferably 0.1 Pa · s or more. In the present specification, the value of viscosity is a value measured by the method shown in Examples described later.
The solid content concentration of the composition of the present invention is preferably 40% by mass or more, for example. The lower limit is preferably 45% by mass or more, and more preferably 50% by mass or more. The upper limit is preferably 95% by mass or less, and more preferably 60% by mass or less.
As the viscosity and solid content concentration of the composition is increased, bubbles are mixed in during the production of the composition, and the amount of dissolved oxygen in the composition tends to increase, resulting in defects in the film and liquid stability of the composition. However, according to the present invention, by setting the amount of dissolved oxygen in the above-described range, even a composition having such a viscosity and solid content concentration has good liquid stability, It can be set as the composition which can manufacture a film | membrane with few defects. That is, in the case of a composition having a viscosity or solid content concentration, the effect of the present invention is more remarkably obtained.
Hereinafter, the composition of the present invention will be described in detail.

<< Infrared absorber >>
The composition of the present invention contains an infrared absorber. The infrared absorber is preferably a compound having a maximum absorption wavelength in the range of 700 to 1200 nm, and more preferably a compound having in the range of 700 to 1000 nm. The infrared absorber is a compound that has absorption in the wavelength region of the infrared region (preferably, a wavelength range of 700 to 1200 mn) and transmits light having a wavelength in the visible region (preferably, a wavelength range of 400 to 650 mn). preferable.

  Examples of infrared absorbers include copper compounds, pyrrolopyrrole compounds, squarylium compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, diimmonium compounds, thiol complex compounds, transition metal oxide compounds, quaterrylene compounds, and croconium compounds. Etc. Among these, a copper compound, a pyrrolopyrrole compound, a squarylium compound, a cyanine compound, a phthalocyanine compound, and a naphthalocyanine compound are preferable because it is easy to form a film excellent in both near-infrared shielding and visible transmittance. More preferred are pyrrolopyrrole compounds, squarylium compounds, and cyanine compounds. The infrared absorber is particularly preferably a copper compound because the effects of the present invention are remarkably easily obtained.

(Copper compound)
In the present invention, the copper compound used as the infrared absorber is preferably a copper complex. As a copper complex, the complex of copper and the compound (ligand) which has a coordination site | part with respect to copper is preferable. As a coordination site | part with respect to copper, the coordination site | part coordinated by an anion and the coordination atom coordinated by a lone pair are mentioned. The copper complex may have two or more ligands. When having two or more ligands, the respective ligands may be the same or different. The copper complex is exemplified by 4-coordination, 5-coordination, and 6-coordination, and 4-coordination and 5-coordination are more preferable, and 5-coordination is more preferable. Moreover, it is preferable that the copper complex forms a 5-membered ring and / or a 6-membered ring with copper and a ligand. Such a copper complex is stable in shape and excellent in complex stability.

In the present invention, the copper complex is also preferably a copper complex other than the phthalocyanine copper complex. Here, the phthalocyanine copper complex is a copper complex having a compound having a phthalocyanine skeleton as a ligand. A compound having a phthalocyanine skeleton has a planar structure in which a π-electron conjugated system spreads throughout the molecule. The phthalocyanine copper complex absorbs light at the π-π * transition. In order to absorb light in the infrared region through the π-π * transition, the ligand compound needs to have a long conjugated structure. However, when the conjugated structure of the ligand is lengthened, the visible light transmittance tends to decrease. For this reason, the phthalocyanine copper complex may have insufficient visible light transmittance.
Moreover, it is also preferable that a copper complex is a copper complex which uses as a ligand the compound which does not have a maximum absorption wavelength in a 400-600 nm wavelength range. A copper complex having a compound having a maximum absorption wavelength in the wavelength region of 400 to 600 nm as a ligand has absorption in the visible region (for example, a wavelength region of 400 to 600 nm), and thus the visible light transmittance is insufficient. There is. Examples of the compound having a maximum absorption wavelength in the wavelength region of 400 to 600 nm include a compound having a long conjugated structure and large absorption of light of a π-π * transition. Specific examples include compounds having a phthalocyanine skeleton.

  A copper complex can be obtained, for example, by mixing and reacting a compound (ligand) having a coordination site with respect to copper with respect to a copper component (copper or a compound containing copper). The compound (ligand) having a coordination site for copper may be a low molecular compound or a polymer. Both can be used together.

  The copper component is preferably a compound containing divalent copper. 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, methido copper, alkoxy copper, phenoxy copper, copper hydroxide, copper carbonate, copper sulfate, copper nitrate, copper perchlorate, copper fluoride, copper chloride, copper bromide are preferred, copper carboxylate, copper sulfonate, Sulfonamide copper, imide copper, acylsulfonimide copper, bissulfonimide copper, alkoxy copper, phenoxy copper, copper hydroxide, copper carbonate, copper fluoride, copper chloride, copper sulfate, glass Copper is more preferable, copper carboxylate, acyl sulfonimide copper, phenoxy, copper chloride, copper sulfate, copper nitrate are more preferred, copper carboxylate, acyl sulfonimide, copper chloride, copper sulfate particularly preferred.

In the present invention, the copper complex is preferably a compound having a maximum absorption wavelength in a wavelength region of 700 to 1200 nm. The maximum absorption wavelength of the copper complex is more preferably in the wavelength region of 720 to 1200 nm, and further preferably in the wavelength region of 800 to 1100 nm. The maximum absorption wavelength can be measured using, for example, Cary 5000 UV-Vis-NIR (Spectrophotometer manufactured by Agilent Technologies).
The molar extinction coefficient at the maximum absorption wavelength in the above-described wavelength region of the copper complex is preferably 120 (L / mol · cm) or more, more preferably 150 (L / mol · cm) or more, and 200 (L / mol · cm). ) Or more, more preferably 300 (L / mol · cm) or more, and particularly preferably 400 (L / mol · cm) or more. Although an upper limit does not have limitation in particular, For example, it can be 30000 (L / mol * cm) or less. When the molar extinction coefficient of the copper complex is 100 (L / mol · cm) or more, a film having excellent infrared shielding properties can be formed even if it is a thin film.
The gram extinction coefficient at 800 nm of the copper complex is preferably 0.11 (L / g · cm) or more, more preferably 0.15 (L / g · cm) or more, and 0.24 (L / g · cm). The above is more preferable.
In the present invention, the molar extinction coefficient and gram extinction coefficient of the copper complex were determined by measuring the absorption spectrum of the solution in which the copper complex was dissolved by preparing a solution having a concentration of 1 g / L by dissolving the copper complex in a solvent. Can be obtained. As a measuring apparatus, UV-1800 (wavelength region 200 to 1100 nm) manufactured by Shimadzu Corporation, Cary 5000 (wavelength region 200 to 1300 nm) manufactured by Agilent, and the like can be used. Examples of the measurement solvent include water, N, N-dimethylformamide, propylene glycol monomethyl ether, 1,2,4-trichlorobenzene, and acetone. In the present invention, a solvent capable of dissolving the copper complex to be measured is selected and used from the measurement solvents described above. In particular, in the case of a copper complex that dissolves with propylene glycol monomethyl ether, it is preferable to use propylene glycol monomethyl ether as the measurement solvent. The term “dissolved” means a state in which the solubility of the copper complex in a solvent at 25 ° C. exceeds 0.01 g / 100 g Solvent.
In the present invention, the molar extinction coefficient and gram extinction coefficient of the copper complex are preferably values measured using any one of the above-described measurement solvents, and more preferably values of propylene glycol monomethyl ether. .

[Low molecular copper compound]
As the copper compound, for example, a copper complex represented by the following formula (Cu-1) can be used. This copper complex is a copper compound in which a ligand L is coordinated to copper as a central metal, and copper is usually divalent copper. For example, it can be obtained by mixing, reacting, etc., a compound that becomes the ligand L or a salt thereof with the copper component.
Cu (L) _n1 · (X) _n2 formula (Cu-1)
In the above formula, L represents a ligand coordinated to copper, and X represents a counter ion. n1 represents the integer of 1-4. n2 represents an integer of 0 to 4.

X represents a counter ion. The copper compound may become a cation complex or an anion complex in addition to a neutral complex having no charge. In this case, counter ions are present as necessary to neutralize the charge of the copper compound.
When the counter ion is a negative counter ion, for example, an inorganic anion or an organic anion may be used. Specific examples include hydroxide ions, halogen anions (eg, fluoride ions, chloride ions, bromide ions, iodide ions, etc.), substituted or unsubstituted alkyl carboxylate ions (acetate ions, trifluoroacetate ions). Etc.), substituted or unsubstituted aryl carboxylate ions (benzoate ions, etc.), substituted or unsubstituted alkyl sulfonate ions (methane sulfonate ions, trifluoromethane sulfonate ions, etc.), substituted or unsubstituted aryl sulfonic acids Ions (for example, para-toluenesulfonic acid ion, para-chlorobenzenesulfonic acid ion, etc.), aryl disulfonic acid ions (for example, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion) Ions), alkyl sulfur Ion (e.g., methyl sulfate ion, etc.), sulfate ion, thiocyanate ion, nitrate ion, perchlorate ion, tetrafluoroborate ion, tetraarylborate ion, tetrakis (pentafluorophenyl) borate ion (B ^- (C ₆ F ₅ ) ₄ ), hexafluorophosphate ions, picrate ions, amide ions (including amides substituted with acyl groups or sulfonyl groups), methide ions (including methides substituted with acyl groups or sulfonyl groups) Halogen anion, substituted or unsubstituted alkylcarboxylate ion, sulfate ion, nitrate ion, tetrafluoroborate ion, tetraarylborate ion, hexafluorophosphate ion, amide ion (substituted with acyl group or sulfonyl group) Including amide) Emissions (including methide substituted with an acyl group or a sulfonyl group).
When the counter ion is a positive counter ion, for example, inorganic or organic ammonium ion (for example, tetraalkylammonium ion such as tetrabutylammonium ion, triethylbenzylammonium ion, pyridinium ion, etc.), phosphonium ion (for example, tetrabutylphosphonium) Tetraalkylphosphonium ions such as ions, alkyltriphenylphosphonium ions, triethylphenylphosphonium ions, etc.), alkali metal ions or protons.
Further, the counter ion may be a metal complex ion, and in particular, the counter ion may be a copper complex, that is, a salt of a cationic copper complex and an anionic copper complex.

  The ligand L is a compound having a coordination site with respect to copper, and is selected from a coordination site that coordinates with copper by an anion, and a coordination atom that coordinates with copper by an unshared electron pair. The compound which has the above is mentioned. The coordination site coordinated by an anion may be dissociated or non-dissociated. The ligand L is preferably a compound (multidentate ligand) having two or more coordination sites for copper. In addition, it is preferable that the ligand L is not continuously bonded with a plurality of π-conjugated systems such as aromatic groups in order to improve visible transparency. Ligand L can also use together the compound (monodentate ligand) which has one coordination site | part with respect to copper, and the compound (multidentate ligand) which has 2 or more coordination site | parts with respect to copper. Examples of the monodentate ligand include a monodentate ligand coordinated by an anion or an unshared electron pair. Examples of ligands coordinated with anions include halide anions, hydroxide anions, alkoxide anions, phenoxide anions, amide anions (including amides substituted with acyl groups and sulfonyl groups), and imide anions (acyl groups and sulfonyl groups). Substituted imides), anilide anions (including acylides and sulfonyl substituted anilides), thiolate anions, bicarbonate anions, carboxylate anions, thiocarboxylate anions, dithiocarboxylate anions, hydrogen sulfate anions, sulfones Acid anion, phosphate dihydrogen anion, phosphate diester anion, phosphonate monoester anion, hydrogen phosphonate anion, phosphinate anion, nitrogen-containing heterocyclic anion, nitrate anion, hypochlorite anion, cyanide anion Cyanate anion, isocyanate anion, thiocyanate anion, isothiocyanate anions, such as azide anions. Monodentate ligands coordinated by lone pairs include water, alcohol, phenol, ether, amine, aniline, amide, imide, imine, nitrile, isonitrile, thiol, thioether, carbonyl compound, thiocarbonyl compound, sulfoxide, Examples include heterocycles, carbonic acid, carboxylic acid, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, phosphinic acid, nitric acid, and esters thereof.

  The anion which the said ligand has should just be able to coordinate to the copper atom in a copper component, and an oxygen anion, a nitrogen anion, or a sulfur anion is preferable. The coordination site coordinated with an anion is preferably at least one selected from the following monovalent functional group (AN-1) or divalent functional group (AN-2). In addition, the wavy line in the following structural formula is the bonding position with the atomic group constituting the ligand.

Group (AN-1)

Group (AN-2)

In the above formula, X represents N or CR, and R each 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. 1-10 are preferable, as for carbon number of an alkyl group, 1-6 are more preferable, and 1-4 are more preferable. 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 carboxyl group, and a hetero 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 alkenyl group represented by R may be linear, branched or cyclic, but is preferably linear. 1-10 are preferable and, as for carbon number of an alkenyl group, 1-6 are more preferable. The alkenyl group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.
The alkynyl group represented by R may be linear, branched or cyclic, but is preferably linear. 1-10 are preferable and, as for carbon number of an alkynyl group, 1-6 are more preferable. The alkynyl group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.
The aryl group represented by R may be monocyclic or polycyclic, but is preferably monocyclic. 6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable. The aryl group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.
R represents.
The heteroaryl group 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, a sulfur atom or an oxygen atom. 6-18 are preferable and, as for carbon number of heteroaryl group, 6-12 are more preferable. The heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.

  As an example of the coordination site coordinated by an anion, a monoanionic coordination site may also be mentioned. 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 acid groups containing phosphorous atoms (phosphoric acid diester groups, phosphonic acid monoester groups, phosphinic acid groups, etc.), sulfo groups, carboxyl groups, imido acid groups, and the like. preferable.

  The coordination atom coordinated by the lone pair is preferably an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, more preferably an oxygen atom, a nitrogen atom or a sulfur atom, still more preferably an oxygen atom or a nitrogen atom, and a nitrogen atom. Is particularly preferred. When the coordinating atom coordinated by the lone pair is a nitrogen atom, the atom adjacent to the nitrogen atom is preferably a carbon atom or a nitrogen atom, and more preferably a carbon atom.

The coordination atom coordinated by the lone pair is contained in the ring, or the following monovalent functional group (UE-1), divalent functional group (UE-2), trivalent functionality It is preferably contained in at least one partial structure selected from the base group (UE-3). In addition, the wavy line in the following structural formula is the bonding position with the atomic group constituting the ligand.
Group (UE-1)

Group (UE-2)

Group (UE-3)

In the groups (UE-1) to (UE-3), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and R ² 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.

The coordinating atom coordinated by the lone pair may be contained in the ring. In the case where the ring includes a coordination atom that coordinates with an unshared electron pair, the ring that includes a coordination atom that coordinates with an unshared electron pair may be monocyclic or polycyclic, It may be aromatic or non-aromatic. As for the ring containing the coordinating | ligand atom coordinated by a lone pair, a 5-12 membered ring is preferable and a 5-7 membered ring is more preferable.
The ring containing a coordinating atom coordinated by a lone pair may have a substituent, and the substituent is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, carbon number A 6-12 aryl group, a halogen atom, a silicon atom, a C1-C12 alkoxy group, a C2-C12 acyl group, a C1-C12 alkylthio group, a carboxyl group, etc. are mentioned.
When the ring containing the coordination atom coordinated by the lone pair has a substituent, the ring may further have a substituent, and from the ring containing the coordination atom coordinated by the lone pair A group comprising at least one partial structure selected from the groups (UE-1) to (UE-3) described above, an alkyl group having 1 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, hydroxy Groups.

When the coordinating atom coordinated by the lone pair is included in the partial structures represented by the groups (UE-1) to (UE-3), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group. Represents an aryl group or a heteroaryl group, and R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group Represents a heteroarylthio group, an amino group or an acyl group.
The alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group are synonymous with the alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group described in the coordination site coordinated with the above anion. The preferable range is also the same.
1-12 are preferable and, as for carbon number of an alkoxy group, 3-9 are more preferable.
6-18 are preferable and, as for carbon number of an aryloxy group, 6-12 are more preferable.
The heteroaryloxy group may be monocyclic or polycyclic. The heteroaryl group which comprises heteroaryloxy group is synonymous with the heteroaryl group demonstrated by the coordination site | part coordinated with the said anion, and its preferable range is also the same.
1-12 are preferable and, as for carbon number of an alkylthio group, 1-9 are more preferable.
6-18 are preferable and, as for carbon number of an arylthio group, 6-12 are more preferable.
The heteroarylthio group may be monocyclic or polycyclic. The heteroaryl group which comprises a heteroarylthio group is synonymous with the heteroaryl group demonstrated by the coordination site | part coordinated with the said anion, and its preferable range is also the same.
2-12 are preferable and, as for carbon number of an acyl group, 2-9 are more preferable.

  When the ligand has a coordination site coordinated by an anion and a coordination atom coordinated by an unshared electron pair in one molecule, it is coordinated by a coordination site coordinated by an anion and an unshared electron pair. The number of atoms linking the coordinated coordination atoms is preferably 1 to 6, and more preferably 1 to 3. By adopting such a configuration, the structure of the copper complex becomes more easily distorted, so that the color value can be further improved, and the molar extinction coefficient can be easily increased while enhancing the visible light permeability. The kind of atom that connects the coordination site coordinated by the anion and the coordination atom coordinated by the lone pair may be one or more. A carbon atom or a nitrogen atom is preferable.

  When the ligand has two or more coordination atoms coordinated by a lone pair in one molecule, it may have three or more coordination atoms coordinated by a lone pair. It is preferable to have ˜5, and more preferably four. The number of atoms connecting the coordinating atoms coordinated by the lone pair is preferably 1 to 6, more preferably 1 to 3, further preferably 2 to 3, and particularly preferably 3. By setting it as such a structure, since the structure of a copper complex becomes easier to distort, color value can be improved more. 1 type (s) or 2 or more types may be sufficient as the atom which connects the coordination atoms coordinated by a lone pair. The atom connecting the coordinating atoms coordinated by the lone pair is preferably a carbon atom.

  The ligand is preferably a compound having at least two coordination sites (also referred to as a multidentate ligand). The ligand preferably has at least three coordination sites, more preferably 3 to 5, and particularly preferably 4 to 5. The multidentate ligand acts as a chelate ligand for the copper component. That is, at least two coordination sites of the polydentate ligand are chelate-coordinated with copper, so that the structure of the copper complex is distorted, high transparency in the visible light region is obtained, and infrared absorption ability is improved. It can be improved and the color value is also improved.

  A multidentate ligand is a compound comprising one or more coordination sites coordinated by an anion and one or more coordination atoms coordinated by an unshared electron pair, or coordinated by an unshared electron pair. Examples thereof include compounds having two or more atoms, compounds containing two coordination sites coordinated by anions, and the like. These compounds can be used independently or in combination of two or more. Moreover, the compound used as a ligand can also use the compound which has only one coordination site | part.

The multidentate ligand is preferably a compound represented by the following general formulas (IV-1) to (IV-14). For example, when the ligand is a compound having four coordination sites, compounds represented by the following formulas (IV-3), (IV-6), (IV-7), and (IV-12) Preferably, the compound represented by (IV-12) is more preferable because it coordinates more strongly with the metal center and easily forms a stable pentacoordination complex having high heat resistance. For example, when the ligand is a compound having five coordination sites, the following formulas (IV-4), (IV-8) to (IV-11), (IV-13), (IV- (14) is preferable, and (IV-9) to (IV-10), (IV) are preferable because they are more strongly coordinated with the metal center and easily form a stable 5-coordinate complex having high heat resistance. The compounds represented by (IV-13) and (IV-14) are more preferred, and the compound represented by (IV-13) is particularly preferred.

In general formulas (IV-1) to (IV-14), X ^{1 to} X ⁵⁹ each independently represent a coordination site, and L ^{1 to} L ²⁵ each independently represent a single bond or a divalent linking group. L ^{26 to} L ³² each independently represents a trivalent linking group, and L ^{33 to} L ³⁴ each independently represents a tetravalent linking group.
X ^{1 to} X ⁴² are each independently selected from the group consisting of a ring containing a coordinating atom coordinated by a lone pair, the group (AN-1), or the group (UE-1) described above. It is preferable to represent at least one.
X ^{43 to} X ⁵⁶ are each independently selected from the group consisting of a ring containing a coordinating atom coordinated by a lone pair, the group (AN-2), or the group (UE-2) described above It is preferable to represent at least one.
X ^{57 to} X ⁵⁹ each independently preferably represent at least one selected from the group (UE-3) described above.
L ^{1 to} L ²⁵ each independently represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —SO—, —O—, —SO ₂ —, or a group consisting of these in combination. A group consisting of a C 1-3 alkylene group, a phenylene group, —SO ₂ — or a combination thereof is more preferred.
L ^{26 to} L ³² each independently represents a trivalent linking group. Examples of the trivalent linking group include groups obtained by removing one hydrogen atom from the above-described divalent linking group.
L ^{33 to} L ³⁴ each independently represents a tetravalent linking group. Examples of the tetravalent linking group include groups obtained by removing two hydrogen atoms from the above-described divalent linking group.
Here, the group (AN-1) R in ~ (AN-2), and, R ¹ in group (UE-1) ~ (UE -3) is, R to each other, R ¹ or between, and R R ¹ may be linked to form a ring.

  Specific examples of the compound forming the ligand include the compounds shown below, compounds shown as preferred specific examples of the polydentate ligand described below, and salts of these compounds. Examples of the atoms constituting the salt include metal atoms and tetrabutylammonium. As the metal atom, an alkali metal atom or an alkaline earth metal atom is more preferable. Examples of the alkali metal atom include sodium and potassium. Examples of alkaline earth metal atoms include calcium and magnesium. In addition, the description in paragraphs 0022 to 0042 of JP-A-2014-41318 and the description of paragraphs 0021 to 0039 in JP-A-2015-43063 can be referred to, and the contents thereof are incorporated in the present specification.

For example, the following aspects (1) to (5) are preferable examples of the copper complex, (2) to (5) are more preferable, (3) to (5) are more preferable, (4) or (5) is more preferable.
(1) Copper complex having one or two compounds having two coordination sites as ligands (2) Copper complex having a compound having three coordination sites as ligands (3) Three coordinations Copper complex having a compound having a coordination site and a compound having two coordination sites as a ligand (4) Copper complex having a compound having four coordination sites as a ligand (5) Five coordination sites Copper complex having a compound containing

In the above aspect (1), the compound having two coordination sites is a compound having two coordination atoms coordinated by an unshared electron pair, or a coordination site and an unshared electron pair coordinated by an anion. A compound having a coordination atom coordinated with is preferable. Moreover, when it has two of the compounds which have two coordination site | parts as a ligand, the compound of a ligand may be the same and may differ.
In the embodiment (1), the copper complex may further have a monodentate ligand. The number of monodentate ligands can be 0 or 1-3. As the type of monodentate ligand, both a monodentate ligand coordinated by an anion and a monodentate ligand coordinated by an unshared electron pair are preferable, and a compound having two coordination sites is an unshared electron pair. In the case of a compound having two coordinating atoms, a monodentate ligand coordinated with an anion is more preferable because the coordinating power is strong, and a compound having two coordination sites coordinated with an anion. In the case of a compound having a coordination site and a coordinating atom coordinated by an unshared electron pair, a monodentate ligand coordinated by an unshared electron pair is more preferred because the entire complex has no charge.

In the above aspect (2), the compound having three coordination sites is preferably a compound having a coordination atom coordinated by a lone pair, and has three coordination atoms coordinated by a lone pair. More preferred are compounds.
In the embodiment (2), the copper complex can further have a monodentate ligand. The number of monodentate ligands can also be zero. Moreover, it can also be made into 1 or more, 1-3 or more are more preferable, 1-2 are more preferable, and 2 are still more preferable. As the type of monodentate ligand, either a monodentate ligand coordinated by an anion or a monodentate ligand coordinated by a lone pair is preferable, and for the reason described above, a monodentate ligand coordinated by an anion is used. More preferred.

In the above aspect (3), the compound having three coordination sites is preferably a compound having a coordination site coordinated by an anion and a coordination atom coordinated by an unshared electron pair. A compound having two coordination sites to be coordinated and one coordination atom coordinated by an unshared electron pair is more preferable. Furthermore, it is particularly preferable that the coordination sites coordinated by the two anions are different. In addition, the compound having two coordination sites is preferably a compound having a coordination atom coordinated by a lone pair, and more preferably a compound having two coordination atoms coordinated by a lone pair. Among them, a compound having three coordination sites is a compound having two coordination sites coordinated by an anion and one coordination atom coordinated by an unshared electron pair. A combination in which the compound having a site is a compound having two coordination atoms coordinated by an unshared electron pair is particularly preferable.
In the aspect (3), the copper complex may further have a monodentate ligand. The number of monodentate ligands can be zero, or one or more. 0 is more preferable.

In the above aspect (4), the compound having four coordination sites is preferably a compound having a coordination atom coordinated by a lone pair, and has two or more coordination atoms coordinated by a lone pair. A compound is more preferable, and a compound having four coordination atoms coordinated by an unshared electron pair is more preferable.
In the embodiment (4), the copper complex can further have a monodentate ligand. The number of monodentate ligands can be 0, 1 or more, or 2 or more. One is preferred. As the kind of monodentate ligand, both a monodentate ligand coordinated by an anion and a monodentate ligand coordinated by an unshared electron pair are preferable.

In the above aspect (5), the compound having five coordination sites is preferably a compound having a coordination atom coordinated by a lone pair, and has two or more coordination atoms coordinated by a lone pair. A compound is more preferable, and a compound having five coordinating atoms coordinated by an unshared electron pair is more preferable.
In the embodiment (5), the copper complex may further have a monodentate ligand. The number of monodentate ligands can be zero, or one or more. The number of monodentate ligands is preferably 0.

Examples of the multidentate ligand include compounds having two or more coordination sites among the compounds described in the specific examples of the ligand described above, and compounds shown below.

[Phosphate ester copper complex]
In this invention, a phosphate ester copper complex can also be used as a copper compound. The phosphate ester copper complex has copper as a central metal and a phosphate ester compound as a ligand. The phosphate compound forming the ligand of the phosphate ester copper complex is preferably a compound represented by the following formula (L-100) or a salt thereof.
_{(HO) n -P (= O} ) - (OR 1) 3-n Formula (L-100)
In the formula, R ¹ represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 1 to 18 carbon atoms, or an alkenyl group having 1 to 18 carbon atoms, or —OR ¹ is Represents a polyoxyalkyl group having 4 to 100 carbon atoms, a (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms, or a (meth) acryloyl polyoxyalkyl group having 4 to 100 carbon atoms, and n is 1 or 2 Represents. When n is 1, R ² may be the same or different.

In the above formula, it is preferable that at least one of —OR ¹ represents a (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms or a (meth) acryloyl polyoxyalkyl group having 4 to 100 carbon atoms. It is more preferable to represent 4 to 100 (meth) acryloyloxyalkyl groups. The number of carbon atoms of the polyoxyalkyl group, (meth) acryloyloxyalkyl group, and (meth) acryloyl polyoxyalkyl group is preferably 4-20, more preferably 4-10, respectively.
The molecular weight of the phosphoric ester compound is preferably 300 to 1500, and more preferably 320 to 900.

  Specific examples of the phosphoric acid ester compound include the ligands described above. Moreover, description of Paragraphs 0022-0042 of Unexamined-Japanese-Patent No. 2014-41318 can be referred, and these content is integrated in this-application specification.

[Sulphonic acid copper complex]
In the present invention, a sulfonic acid copper complex can also be used as the copper compound. The copper sulfonate complex has copper as a central metal and a sulfonic acid compound as a ligand. The sulfonic acid compound forming the ligand of the sulfonic acid copper complex is preferably a compound represented by the following formula (L-200) or a salt thereof.
R ² —SO ₂ —OH formula (L-200)

In the formula, R ² represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group, an aryl group, and a heteroaryl group.
The alkyl group may be linear, branched or cyclic, but is preferably linear. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable.
The aryl group may be monocyclic or polycyclic, but is preferably monocyclic. 6-25 are preferable and, as for carbon number of an aryl group, 6-10 are more preferable.
The heteroaryl group 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, a sulfur atom or an oxygen atom. 6-18 are preferable and, as for carbon number of heteroaryl group, 6-12 are more preferable.
The alkyl group, aryl group, and heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include a polymerizable group (preferably a group having an ethylenically unsaturated bond such as a vinyl group, a (meth) acryloyloxy group), a (meth) acryloyl group), a halogen atom (a fluorine atom, a chlorine atom, a bromine). Atom, iodine atom), alkyl group, carboxylic acid ester group (for example, —CO ₂ CH ₃ ), halogenated alkyl group (), alkoxy group, methacryloyloxy group, acryloyloxy group, ether group, alkylsulfonyl group, arylsulfonyl group , Sulfide groups, amide groups, acyl groups, hydroxy groups, carboxyl groups, sulfonic acid groups, acid groups containing phosphorus atoms, amino groups, carbamoyl groups, carbamoyloxy groups, and the like.
The halogenated alkyl group is preferably an alkyl group substituted with a fluorine atom. In particular, an alkyl group having 1 to 10 carbon atoms having two or more fluorine atoms is preferable. The halogenated alkyl group may be linear, branched or cyclic, but is preferably linear or branched. 1-10 are more preferable, as for carbon number in a halogenated alkyl group, 1-5 are more preferable, and 1-3 are more preferable. The terminal group of the alkyl group substituted with a fluorine atom is preferably (—CF ₃ ). The alkyl group substituted with a fluorine atom preferably has a fluorine atom substitution rate of 50 to 100%, and more preferably 80 to 100%. Here, the substitution rate of fluorine atoms refers to the ratio (%) in which hydrogen atoms are substituted with fluorine atoms in an alkyl group substituted with fluorine atoms. In particular, as the halogenated alkyl group, a perfluoroalkyl group is more preferable, a C 1-10 perfluoroalkyl group is more preferable, and a trifluoroethyl group and a trifluoromethyl group are further preferable.

The alkyl group, aryl group and heteroaryl group described above may have a divalent linking group. As the divalent linking group, — (CH ₂ ) _m — (m is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and a cyclic group having 5 to 10 carbon atoms. An alkylene group or a group composed of at least one of these groups and —O—, —COO—, —S—, —NH— and —CO— is preferable.

In formula (L-200), R ² is preferably an organic group having a formula weight of 300 or less, more preferably an organic group having a formula weight of 50 to 200, and still more preferably an organic group having a formula weight of 60 to 100. .
The molecular weight of the sulfonic acid compound represented by the formula (L-200) is preferably 80 to 750, more preferably 80 to 600, and still more preferably 80 to 450.

The copper sulfonate complex preferably has a structure represented by the following formula (L-201).
_{^{R 2A -SO 2 -O- * (L}} -201)
In the formula, R ^2A has the same meaning as R ² in formula (L-200), and the preferred range is also the same.

  Specific examples of the sulfonic acid compound include the ligands described above. In addition, the description in paragraphs 0021 to 0039 of JP-A-2015-43063 can be referred to, and the contents thereof are incorporated in the present specification.

[Polymer type copper compound]
In the present invention, a copper-containing polymer having a copper complex site in the polymer side chain can be used as the copper compound. Since the copper-containing polymer has a copper complex site in the polymer side chain, it is considered that a crosslinked structure is formed between the side chains of the polymer starting from copper, and a film having excellent heat resistance is obtained. The polymer type copper compound (copper-containing polymer) is a component different from the resin described later.

  As a copper complex part, what has copper and the site | part (coordination site | part) coordinated with respect to copper is mentioned. As a site | part coordinated with respect to copper, the site | part coordinated by an anion or an unshared electron pair is mentioned. Moreover, it is preferable that a copper complex site | part has a site | part coordinated to tetradentate or pentadentate with respect to copper. The details of the coordination site include those described in the low molecular type copper compound described above, and the preferred range is also the same.

  The copper-containing polymer is a polymer obtained by a reaction between a coordination site-containing polymer (also referred to as polymer (B1)) and a copper component, or a polymer having a reactive site in the polymer side chain (hereinafter also referred to as polymer (B2)). ) And a copper complex having a functional group capable of reacting with the reactive site of the polymer (B2). The weight average molecular weight of the copper-containing polymer is preferably 2000 or more, more preferably 2000 to 2 million, and further preferably 6000 to 200,000.

一般式１中、環Ａおよび環Ｂは、それぞれ独立に、芳香族環を表し、
Ｘ^AおよびＸ^Bはそれぞれ独立に置換基を表し、
Ｇ^AおよびＧ^Bはそれぞれ独立に置換基を表し、
ｋＡは０〜ｎＡの整数を表し、ｋＢは０〜ｎＢの整数を表し、
ｎＡは、Ａ環に置換可能な最大の整数を表し、ｎＢは、Ｂ環に置換可能な最大の整数を表し、
Ｘ^AとＧ^A、Ｘ^BとＧ^Bは互いに結合して環を形成しても良く、Ｇ^AおよびＧ^Bがそれぞれ複数存在する場合は、互いに結合して環を形成していても良い。 (Squarylium compound)
The squarylium compound is preferably a compound represented by the following general formula 1.
General formula 1

In general formula 1, ring A and ring B each independently represent an aromatic ring,
X ^A and X ^B each independently represent a substituent,
G ^A and G ^B each independently represent a substituent,
kA represents an integer of 0 to nA, kB represents an integer of 0 to nB,
nA represents the largest integer that can be substituted on the A ring, nB represents the largest integer that can be substituted on the B ring,
X ^A and G ^A, X ^B and G ^B may combine with each other to form a ring, if G ^A and G ^B are present in plural may be bonded to each other to form a ring.

In General Formula 1, G ^A and G ^B each independently represent a substituent.
Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, —OR ^c1 , —COR ^c2 , —COOR ^c3 , —OCOR ^c4 , — NR ^c5 R ^c6 , —NHCOR ^c7 , —CONR ^c8 R ^c9 , —NHCONR ^c10 R ^c11 , —NHCOOR ^c12 , —SR ^c13 , —SO ₂ R ^c14 , —SO ₂ OR ^c15 , —NHSO ₂ R ^c16 or —SO ₂ NR ^c17 R ^c18 may be mentioned. R ^{c1 to} R ^c18 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. In addition, when R ^{c3 of} —COOR ^c3 is a hydrogen atom (that is, a carboxyl group), the hydrogen atom may be dissociated (that is, a carbonate group) or may be in a salt state. When R ^{c15 of} —SO ₂ OR ^c15 is a hydrogen atom (that is, a sulfo group), the hydrogen atom may be dissociated (that is, a sulfonate group) or may be in a salt state.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
1-20 are preferable, as for carbon number of an alkyl group, 1-12 are more preferable, and 1-8 are especially preferable. The alkyl group may be linear, branched or cyclic. The alkyl group may be unsubstituted or may have a substituent.
2-20 are preferable, as for carbon number of an alkenyl group, 2-12 are more preferable, and 2-8 are especially preferable. The alkenyl group may be linear, branched or cyclic.
2-20 are preferable, as for carbon number of an alkynyl group, 2-12 are more preferable, and 2-8 are especially preferable. The alkynyl group may be linear, branched or cyclic.
6-25 are preferable, as for carbon number of an aryl group, 6-15 are more preferable, and 6-10 are the most preferable.
The alkyl part of the aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group is the same as the above aryl group. 7-40 are preferable, as for carbon number of an aralkyl group, 7-30 are more preferable, and 7-25 are still more preferable.
The heteroaryl group is preferably 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 number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. 3-30 are preferable, as for the number of the carbon atoms which comprise the ring of a heteroaryl group, 3-18 are more preferable, and 3-12 are more preferable.
The alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group and heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents mentioned above for G ^A and G ^B , and examples include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, and an amino group.

In General Formula 1, X ^A and X ^B each independently represent a substituent. Substituent is preferably a group having an active hydrogen, -OH, -SH, -COOH, -SO 3 H, -NHR x1, -NR x1 R x2, -NHCOR x1, -CONR x1 R x2, -NHCONR x1 R _{^{x2, -NHCOOR x1, -NHSO 2 R}} x1, -B (OH) 2, -PO (OH) 3 and -NHBR ^x1 R ^x2 are ^{preferred, -OH, -NHCOR x1, -NHCONR x1} R x2, -NHCOOR x1 -NHSO ₂ R ^x1 and -NHBR ^x1 R ^x2 are more preferred, -NHCOR ^x1 , -NHCONR ^x1 R ^x2 , -NHCOOR ^x1 and -NHSO ₂ R ^x1 are more preferred, and -NHCOR ^x1 and -NHSO ₂ R ^x1 are particularly preferred preferable.

R ^x1 and R ^x2 each independently represent a substituent. Examples of the substituent include an alkyl group and an aryl group, and an alkyl group is preferable. 1-20 are preferable, as for carbon number of an alkyl group, 1-15 are more preferable, 1-8 are still more preferable, and 1-5 are especially preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. 6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are still more preferable. The alkyl group and the aryl group may have a substituent or may be unsubstituted, but preferably have a substituent. Examples of the substituent include the substituents described later for R _Z. For example, a halogen atom, an aryl group, an alkoxy group and the like can be mentioned. From the viewpoint of heat resistance and light resistance, a halogen atom is preferable, and a fluorine atom is more preferable.
R ^x1 and R ^x2 are preferably a group having a fluorine atom, more preferably an alkyl group having a fluorine atom or an aryl group having a fluorine atom, still more preferably an alkyl group having a fluorine atom, and a perfluorocarbon having 1 to 5 carbon atoms. A fluoroalkyl group is particularly preferred.

In general formula 1, ring A and ring B each independently represent an aromatic ring. The aromatic ring may be a single ring or a condensed ring. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Specific examples of the aromatic ring include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring , Triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, thiazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, Benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, Ntoren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and include phenazine ring, a benzene ring or a naphthalene ring are preferred, a naphthalene ring is more preferred.
The aromatic ring may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described in G ^A and G ^B.

In Formula 1, X ^A and G ^A, X ^B and G ^B may combine with each other to form a ring, if G ^A and G ^B are present in plural is, G ^A or between,, G ^B They may be bonded to each other to form a ring. The ring is preferably a 5-membered ring or a 6-membered ring. The ring may be monocyclic or multicyclic. X ^A and G ^A, X ^B and G ^B, when forming a G ^A or between G ^B are bonded to each other rings, may be they are attached directly to form a ring, an alkylene group, -CO-, A ring may be formed by bonding via a divalent linking group selected from the group consisting of —O—, —NH—, —BR— and combinations thereof. X ^A and G ^A, X ^B and G ^B, G ^A or between G ^B each other, it is preferable to form a ring via -BR-. R represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group. Alkyl group, an alkenyl group, an alkynyl group, an aryl group and that details of the heteroaryl group, is as defined and ranges described for the G ^A and G ^B.

In General Formula 1, kA represents an integer of 0 to nA, kB represents an integer of 0 to nB, nA represents the largest integer that can be substituted on the A ring, and nB represents the maximum that can be substituted on the B ring. Represents an integer.
kA and kB are each independently preferably 0 to 4, more preferably 0 to 2, and particularly preferably 0 to 1.

式中、Ｒ¹およびＲ²は、それぞれ独立に、アルキル基、アルケニル基、アリール基、ヘテロアリールまたは、下式（Ｗ）で表される基を表し、
Ｒ³およびＲ⁴は、それぞれ独立に、水素原子、または、アルキル基を表し、
Ｘ¹およびＸ²は、それぞれ独立に、酸素原子、または、−Ｎ（Ｒ⁵）−を表し、
Ｒ⁵は、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、
Ｙ¹〜Ｙ⁴は、それぞれ独立に、置換基を表し、Ｙ¹とＹ²、および、Ｙ³とＹ⁴は、互いに結合して環を形成していてもよく、
Ｙ¹〜Ｙ⁴は、それぞれ複数有する場合は、互いに結合して環を形成していてもよく、
ｐおよびｓは、それぞれ独立に０〜３の整数を表し、
ｑおよびｒは、それぞれ独立に０〜２の整数を表す；
−Ｓ¹−Ｌ¹−Ｔ¹ ・・・（Ｗ）
式（Ｗ）において、Ｓ¹は、単結合、アリーレン基またはヘテロアリーレン基を表し、
Ｌ¹は、アルキレン基、アルケニレン基、アルキニレン基、−Ｏ−、−Ｓ−、−ＮＲ^L1−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＲ^L1−、−ＮＲ^L1ＣＯ−、−ＳＯ₂−、−ＯＲ^L2−、または、これらを組み合わせてなる基を表し、Ｒ^L1は、水素原子またはアルキル基を表し、Ｒ^L2は、アルキレン基を表し、
Ｔ¹は、アルキル基、シアノ基、ヒドロキシ基、ホルミル基、カルボキシ基、アミノ基、チオール基、スルホ基、ホスホリル基、ボリル基、ビニル基、エチニル基、アリール基、ヘテロアリール基、トリアルキルシリル基またはトリアルコキシシリル基を表す。 The compound represented by the general formula 1 is preferably a compound represented by the following general formula 1-1. This compound is excellent in heat resistance.
Formula 1-1

In the formula, R ¹ and R ² each independently represent an alkyl group, an alkenyl group, an aryl group, a heteroaryl, or a group represented by the following formula (W):
R ³ and R ⁴ each independently represents a hydrogen atom or an alkyl group,
X ¹ and X ² each independently represent an oxygen atom or —N (R ⁵ ) —
R ⁵ represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group,
Y ^{1 to} Y ⁴ each independently represent a substituent, Y ¹ and Y ² , and Y ³ and Y ⁴ may be bonded to each other to form a ring,
Y ^{1 to} Y ⁴ may be bonded to each other to form a ring when there are a plurality of Y ^{1 to} Y ⁴ .
p and s each independently represent an integer of 0 to 3,
q and r each independently represents an integer of 0 to 2;
-S ¹ -L ¹ -T ¹ (W)
In the formula (W), S ¹ represents a single bond, an arylene group or a heteroarylene group,
L ¹ represents an alkylene group, an alkenylene group, an alkynylene group, —O—, —S—, —NR ^L1 —, —CO—, —COO—, —OCO—, —CONR ^L1 —, —NR ^L1 CO—, — SO ₂ —, —OR ^L2 —, or a combination thereof, R ^L1 represents a hydrogen atom or an alkyl group, R ^L2 represents an alkylene group,
T ¹ is alkyl group, cyano group, hydroxy group, formyl group, carboxy group, amino group, thiol group, sulfo group, phosphoryl group, boryl group, vinyl group, ethynyl group, aryl group, heteroaryl group, trialkylsilyl. Represents a group or trialkoxysilyl group.

In General Formula 1-1, R ¹ and R ² each independently represent an alkyl group, an alkenyl group, an aryl group, heteroaryl, or a group represented by Formula (W), and at least R ¹ and R ² One side preferably represents a group represented by the formula (W). In General Formula 1-1, R ¹ and R ² may be the same or different groups. More preferably, R ¹ and R ² are the same group. In the present specification, an aryl group means an aromatic hydrocarbon group, and a heteroaryl group means an aromatic heterocyclic group.

The number of carbon atoms of the alkyl group represented by R ¹ and R ² is 1 to 40 is preferred. The lower limit is more preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 13 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched. The number of branches of the branched alkyl group is preferably 2 to 10, for example, and more preferably 2 to 8. If the number of branches is in the above range, the solvent solubility is good.
The number of carbon atoms of the alkenyl group represented by R ¹ and R ² is 2 to 40 is preferred. For example, the lower limit is preferably 3 or more, more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkenyl group is preferably straight-chain or branched, particularly preferably branched. The number of branches of the branched alkenyl group is preferably 2 to 10, and more preferably 2 to 8. If the number of branches is in the above range, the solvent solubility is good.
R ¹ and the carbon number of the aryl group represented by R ² is preferably 6 to 30, more preferably 6 to 20, 6 to 12 is more preferable.
The heteroaryl group represented by R ¹ and R ² may be monocyclic or polycyclic. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. 3-30 are preferable, as for the number of the carbon atoms which comprise the ring of a heteroaryl group, 3-18 are more preferable, and 3-12 are more preferable.

(Group represented by Formula (W))
Next, the group represented by the formula (W) will be described.
In the formula (W), S ¹ represents a single bond, an arylene group or a heteroarylene group, and from the viewpoint of the stability of the bond with the boron atom, an arylene group or a heteroarylene group is preferable, and an arylene group is more preferable.
The arylene group may be monocyclic or polycyclic. A single ring is preferred. 6-20 are preferable and, as for carbon number of an arylene group, 6-12 are more preferable.
The heteroaryl group may be monocyclic or polycyclic. A single ring is preferred. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom. 3-30 are preferable, as for the number of the carbon atoms which comprise the ring of a heteroaryl group, 3-18 are more preferable, and 3-12 are more preferable.
Specific examples of the arylene group and heteroarylene group represented by S ¹ include the structures shown below.

式中、波線部分は一般式１−１のホウ素原子との結合位置を表し、＊は、Ｌ¹との結合位置を表し、Ｒ’は置換基を表し、Ｒ^Nは、水素原子またはアルキル基を表し、ｍは０以上の整数を表す。
Ｒ’が表す置換基としては、上述した一般式１のＧ^AおよびＧ^Bで説明した置換基が挙げられる。
Ｒ^Nが表すアルキル基の炭素数は、１〜２０が好ましく、１〜１０がより好ましく、１〜４が更に好ましく、１〜２が特に好ましい。アルキル基は、直鎖、分岐のいずれでもよい。
ｍは０以上の整数を表す。ｍの上限は、各基の最大置換数である。ｍは、０が好ましい。

In the formula, a wavy line part represents a bonding position with the boron atom of the general formula 1-1, * represents a bonding position with L ¹ , R ′ represents a substituent, and R ^N represents a hydrogen atom or an alkyl group. M represents an integer of 0 or more.
Examples of the substituent represented by R ′ include the substituents described above for G ^A and G ^B of General Formula 1.
R ^N number of carbon atoms of the alkyl group represented by is preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 4, 1 to 2 is particularly preferred. The alkyl group may be linear or branched.
m represents an integer of 0 or more. The upper limit of m is the maximum number of substitutions for each group. m is preferably 0.

In the formula (W), L ¹ represents an alkylene group, an alkenylene group, an alkynylene group, —O—, —S—, —NR ^L1 —, —CO—, —COO—, —OCO—, —CONR ^L1 —, — NR ^L1 CO—, —SO ₂ —, —OR ^L2 — or a group formed by a combination thereof, R ^L1 represents a hydrogen atom or an alkyl group, and R ^L2 represents an alkylene group.
In the formula (W), L ¹ represents an alkylene group, an alkenylene group, an alkynylene group, —O—, —S—, —NR ^L1 —, —COO—, —OCO—, —CONR ^L1 —, —SO ₂ —, -OR ^L2 -or a group formed by combining these is preferable, and from the viewpoint of flexibility and solvent solubility, an alkylene group, an alkenylene group, -O-, -OR ^L2 -or a group formed by combining these is more preferable. , An alkylene group, an alkenylene group, —O— or —OR ^L2 — is more preferable, and an alkylene group, —O— or —OR ^L2 — is particularly preferable.

L number of carbon atoms of the alkylene ^{group 1} represents the 1 to 40 is preferred. The lower limit is more preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 13 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkylene group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched. For example, the number of branches is preferably 2 to 10, and more preferably 2 to 8. If the number of branches is in the above range, the solvent solubility is good.
L number of carbon atoms in the alkenylene group and alkynylene group ¹ represents the 2-40 is preferred. For example, the lower limit is preferably 3 or more, more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkenylene group and the alkynylene group may be either linear or branched, but are preferably linear or branched, particularly preferably branched. The number of branches is preferably 2 to 10, and more preferably 2 to 8. If the number of branches is in the above range, the solvent solubility is good.

R ^L1 represents a hydrogen atom or an alkyl group, and preferably a hydrogen atom. 1-20 are preferable, as for carbon number of an alkyl group, 1-10 are more preferable, 1-4 are more preferable, and 1-2 are especially preferable. The alkyl group may be linear or branched.

R ^L2 represents an alkylene group. The alkylene group represented by R ^L2 has the same meaning as the alkylene group described for L ¹ , and the preferred range is also the same.

In the formula (W), T ¹ is an alkyl group, cyano group, hydroxy group, formyl group, carboxy group, amino group, thiol group, sulfo group, phosphoryl group, boryl group, vinyl group, ethynyl group, aryl group, hetero group. Represents an aryl group, a trialkylsilyl group or a trialkoxysilyl group;
The number of carbon atoms of the alkyl group, the alkyl group of the trialkylsilyl group, and the alkyl group of the trialkoxysilyl group is preferably 1 to 40. The lower limit is more preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 13 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
The aryl group and heteroaryl group are synonymous with the aryl group and heteroaryl group described in R ¹ and R ² , and the preferred ranges are also the same.

In the formula (W), when S ¹ is a single bond, L ¹ is an alkylene group, and T ¹ is an alkyl group, the total number of carbon atoms contained in L ¹ and T ¹ is preferably 13 or more. From the viewpoint of solvent solubility, 21 or more is preferable. For example, the upper limit is preferably 40 or less, and more preferably 35 or less.
When S ¹ is an arylene group, the total number of carbon atoms contained in L ¹ and T ¹ is preferably 5 or more, preferably 9 or more, more preferably 10 or more, from the viewpoint of solvent solubility. For example, the upper limit is preferably 40 or less, and more preferably 35 or less.

In a preferred embodiment of the formula (W), S ¹ is an arylene group or heteroarylene group, L ¹ is an alkylene group, an alkenylene group, an alkynylene group, —O—, —S—, —NR ^L1 —, —COO—. , —OCO—, —CONR ^L1 —, —SO ₂ —, —OR ^L2 —, or a combination of these, and combinations in which T ¹ is an alkyl group or a trialkylsilyl group. S ¹ is more preferably an arylene group. L ¹ is alkylene group, alkenylene group, -O -, - OR ^L2 - or group is more preferably made of a combination of these, an alkylene group, an alkenylene group, -O- or -OR ^L2 - more preferably, an alkylene group , -O-, or -OR ^L2 -is particularly preferred. T ¹ is more preferably an alkyl group.

In formula (W), -L ¹ -T ¹ moiety preferably comprises a branched alkyl structure. Specifically, the -L ¹ -T ¹ moiety is particularly preferably a branched alkyl group or a branched alkoxy group. -L number of branches ¹ -T ¹ part, preferably from 2 to 10, 2 to 8 is more preferred. -L Number ¹ -T ¹ part of carbon is preferably 5 or more, preferably at least 9, and more preferably 10 or more. For example, the upper limit is preferably 40 or less, and more preferably 35 or less.

In formula (W), -L ¹ -T ¹ moiety preferably comprises an asymmetric carbon. According to this aspect, the compound represented by General Formula 1-1 can include a plurality of optical isomers, and as a result, the solvent solubility of the compound can be further improved. The number of asymmetric carbons is preferably 1 or more. The upper limit of the asymmetric carbon is not particularly limited, but is preferably 4 or less, for example.

In General Formula 1-1, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group. R ³ and R ⁴ may be the same or different groups. More preferably, R ³ and R ⁴ are the same group.
R ³ and R ⁴ carbon atoms in the alkyl group represented by is preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 4, 1 to 2 is particularly preferred. The alkyl group may be linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
R ³ and R ⁴ are each independently preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

In General Formula 1-1, X ¹ and X ² each independently represent an oxygen atom (—O—) or —N (R ⁵ ) —. X ¹ and X ² may be the same or different, but are preferably the same.
R ⁵ represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
R ⁵ is preferably a hydrogen atom, an alkyl group or an aryl group. The alkyl group, aryl group, and heteroaryl group represented by R ⁵ may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described above for G ^A and G ^B in the general formula 1.
1-20 are preferable, as for carbon number of an alkyl group, 1-10 are more preferable, 1-4 are more preferable, and 1-2 are especially preferable. The alkyl group may be linear or branched.
6-20 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable.
The heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. 3-30 are preferable, as for the number of the carbon atoms which comprise the ring of a heteroaryl group, 3-18 are more preferable, and 3-12 are more preferable.

式中、Ｒ^5aはアルキル基を表し、Ｒ⁶〜Ｒ⁸は、それぞれ独立に、置換基を表し、ａは０〜５の整数を表し、ｂおよびｃはそれぞれ０〜７の整数を表し、＊は連結手を表す。
Ｒ⁶〜Ｒ⁸が表す、置換基としては、上述した一般式１のＧ^AおよびＧ^Bで説明した置換基が挙げられる。 X ¹ and X ² are preferably each independently represented by an oxygen atom or any of the following.

In the formula, R ^5a represents an alkyl group, R ^{6 to} R ⁸ each independently represents a substituent, a represents an integer of 0 to 5, b and c each represents an integer of 0 to 7, * Represents a connecting hand.
R ⁶ to R ⁸ represent, examples of the substituent include the substituents described in G ^A and G ^B of the general formula 1 described above.

In General Formula 1-1, Y ^{1 to} Y ⁴ each independently represent a substituent.
Examples of the substituent include the substituents described above for G ^A and G ^B in the general formula 1.

In General Formula 1-1, Y ¹ and Y ² , and Y ³ and Y ⁴ may be bonded to each other to form a ring. For example, Y ¹ and Y ² may be bonded to each other and may be combined with a naphthalene ring directly connected to Y ¹ and Y ² to form, for example, a tricyclic ring such as an acenaphthene ring or an acenaphthylene ring.
When there are a plurality of Y ^{1 to} Y ⁴ , they may be bonded to each other to form a ring structure. For example, if Y ¹ is a plurality, Y ¹ bonded to each other to each other, along with a naphthalene ring which is directly linked to Y ¹ and Y ^2, for example, anthracene ring, even though a 3 ring, a phenanthrene ring, Good. In the case where Y ¹ each other to form a ring system with one another, Y ² to Y ⁴ is a substituent other than Y ¹ need not necessarily have a plurality. Y ^{2 to} Y ⁴ may not be present. The same applies to the case where Y ² , Y ^3, and Y ⁴ are bonded to form a ring structure.
p and s each independently represent an integer of 0 to 3, preferably 0 to 1, and particularly preferably 0.
q and r each independently represents an integer of 0 to 2, preferably 0 to 1, and particularly preferably 0.

In the general formula (1), cations are delocalized as follows.

Examples of the squarylium compound represented by the general formula 1 include the following compounds. Moreover, the compound of Unexamined-Japanese-Patent No. 2011-208101, Paragraph Nos. 0044-0049 is mentioned, The content shall be integrated in this-application specification.

一般式２中、Ｒ^1aおよびＲ^1bは、それぞれ独立に、アルキル基、アリール基またはヘテロアリール基を表し、
Ｒ²〜Ｒ⁵は、それぞれ独立に、水素原子または置換基を表し、Ｒ²とＲ³、Ｒ⁴とＲ⁵は、それぞれ結合して環を形成していてもよく、
Ｒ⁶およびＲ⁷は、それぞれ独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、−ＢＲ^AＲ^B、または金属原子を表し、Ｒ^AおよびＲ^Bは、各々独立に、水素原子または置換基を表し、
Ｒ⁶は、Ｒ^1aまたはＲ³と、共有結合もしくは配位結合していてもよく、Ｒ⁷は、Ｒ^1bまたはＲ⁵と、共有結合もしくは配位結合していてもよい。 (Pyrrolopyrrole compound)
The pyrrolopyrrole compound is preferably a compound represented by the following general formula 2.
General formula 2

In General Formula 2, R ^1a and R ^1b each independently represents an alkyl group, an aryl group, or a heteroaryl group,
R ^{2 to} R ⁵ each independently represents a hydrogen atom or a substituent, and R ² and R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring,
R ⁶ and R ⁷ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR ^A R ^B , or a metal atom, and R ^A and R ^B each independently represent a hydrogen atom or Represents a substituent,
R ⁶ may be covalently or coordinated with R ^1a or R ^3, and R ⁷ may be covalently or coordinated with R ^1b or R ⁵ .

In General Formula 2, R ^1a and R ^1b each independently represents an alkyl group, an aryl group, or a heteroaryl group, preferably an aryl group or a heteroaryl group, and more preferably an aryl group.
1-40 are preferable, as for carbon number of the alkyl group which R ^{< 1a>} and R ^<1b> represent, 1-30 are more preferable, and 1-25 are especially preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched.
6-30 are preferable, as for carbon number of the aryl group which R ^{< 1a>} and R ^<1b> represent, 6-20 are more preferable, and 6-12 are still more preferable. The aryl group is preferably phenyl.
The heteroaryl group represented by R ^1a and R ^1b is preferably a single ring or a condensed ring, more 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 number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. 3-30 are preferable, as for the number of the carbon atoms which comprise a heteroaryl group, 3-18 are more preferable, 3-12 are more preferable, and 3-10 are especially preferable. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring.

The above-described aryl group and heteroaryl group may have a substituent or may be unsubstituted. It is preferable that it has a substituent from a viewpoint that the solubility with respect to a solvent can be improved.
As the substituent, a hydrocarbon group which may contain an oxygen atom, an amino group, an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an aryl Sulfinyl group, ureido group, phosphoric acid amide group, mercapto group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, silyl group, hydroxy group, halogen atom, cyano group, etc. It is done.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group.
As for carbon number of an alkyl group, 1-40 are preferable. The lower limit is more preferably 3 or more, more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched. As for carbon number of a branched alkyl group, 3-40 are preferable. For example, the lower limit is more preferably 5 or more, still more preferably 8 or more, and still more preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The number of branches of the branched alkyl group is preferably 2 to 10, for example, and more preferably 2 to 8. If the number of branches is in the above range, the solvent solubility is good.
As for carbon number of an alkenyl group, 2-40 are preferable. For example, the lower limit is preferably 3 or more, more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkenyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched. As for carbon number of a branched alkenyl group, 3-40 are preferable. For example, the lower limit is more preferably 5 or more, still more preferably 8 or more, and still more preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The number of branches of the branched alkenyl group is preferably 2 to 10, and more preferably 2 to 8. If the number of branches is in the above range, the solvent solubility is good.
6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are still more preferable.
Examples of the hydrocarbon group containing an oxygen atom include a group represented by ^-LRx1 .
L represents —O—, —CO—, —COO—, —OCO—, — (OR ^x2 ) _m — or — (R ^x2 O) _m —. R ^x1 represents an alkyl group, an alkenyl group or an aryl group. R ^x2 represents an alkylene group or an arylene group. m represents an integer of 2 or more, and m R ^x2 may be the same or different.
L is preferably -O-,-(OR ^x2 ) _m- ^or- (R ^x2 O) _m- , more preferably -O-.
The alkyl group, alkenyl group and aryl group represented by R ^x1 have the same ^{meanings as} described above, and the preferred ranges are also the same. R ^x1 is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
1-20 are preferable, as for carbon number of the alkylene group which ^Rx2 represents, 1-10 are more preferable, and 1-5 are still more preferable. The alkylene group may be linear, branched or cyclic, but is preferably linear or branched. 6-20 are preferable and, as for carbon number of the arylene group which ^Rx2 represents, 6-12 are more preferable. R ^x2 is preferably an alkylene group.
m represents an integer greater than or equal to 2, 2-20 are preferable and 2-10 are more preferable.

The substituent is preferably a group having a branched alkyl structure. According to this aspect, the solvent solubility is further improved. The substituent is preferably a hydrocarbon group that may contain an oxygen atom, and more preferably a hydrocarbon group containing an oxygen atom. The hydrocarbon group containing an oxygen atom is preferably a group represented by —O—R ^x1 . R ^x1 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and particularly preferably a branched alkyl group. That is, the substituent is more preferably an alkoxy group, and particularly preferably a branched alkoxy group. When the substituent is an alkoxy group, an infrared absorber having excellent heat resistance and light resistance can be obtained. And since it is a branched alkoxy group, solvent solubility is favorable.
As for carbon number of an alkoxy group, 1-40 are preferable. For example, the lower limit is preferably 3 or more, more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The alkoxy group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched. As for carbon number of a branched alkoxy group, 3-40 are preferable. For example, the lower limit is more preferably 5 or more, still more preferably 8 or more, and still more preferably 10 or more. The upper limit is more preferably 35 or less, and still more preferably 30 or less. The number of branches of the branched alkoxy group is preferably 2 to 10, and more preferably 2 to 8.

R ^{2 to} R ⁵ each independently represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, amino group (including alkylamino group, arylamino group and heterocyclic amino group), alkoxy group, aryloxy group, heteroaryloxy Group, acyl group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio Group, arylthio group, heteroarylthio group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, ureido group, phosphoric acid amide group, hydroxy group, mercapto Group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, sulfino group, a hydrazino group, an imino group, and a silyl group.

One of R ² and R ³ and one of R ⁴ and R ⁵ are preferably an electron-withdrawing group.
A substituent having a positive Hammett σp value (sigma para value) acts as an electron-withdrawing group.
In the present invention, a substituent having a Hammett σp value of 0.2 or more can be exemplified as an electron-withdrawing group. The σp value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80.
Specific examples of the electron withdrawing group include a cyano group (0.66), a carboxyl group (—COOH: 0.45), an alkoxycarbonyl group (—COOMe: 0.45), an aryloxycarbonyl group (—COOPh: 0). .44), a carbamoyl group (—CONH ₂ : 0.36), an alkylcarbonyl group (—COMe: 0.50), an arylcarbonyl group (—COPh: 0.43), an alkylsulfonyl group (—SO ₂ Me: 0) 72), an arylsulfonyl group (—SO ₂ Ph: 0.68), and the like. Particularly preferred is a cyano group. Here, Me represents a methyl group, and Ph represents a phenyl group.
Regarding the Hammett σp value, for example, paragraphs 0024 to 0025 of JP-A-2009-263614 can be referred to, and the contents thereof are incorporated herein.

Either one of R ² and R ³ and one of R ⁴ and R ⁵ are preferably a heteroaryl group.
The heteroaryl group is preferably 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 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 one or more nitrogen atoms. 3-30 are preferable, as for the number of the carbon atoms which comprise a heteroaryl group, 3-18 are more preferable, 3-12 are more preferable, and 3-10 are especially preferable. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. Specific examples of the heteroaryl group include imidazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, pyridazyl group, triazyl group, quinolyl group, quinoxalyl group, isoquinolyl group, indolenyl group, furyl group, thienyl group, benzoxazolyl group. Group, benzimidazolyl group, benzthiazolyl group, naphthothiazolyl group, benzoxazolyl group, m-carbazolyl group, azepinyl group, and benzo-fused group or naphtho-fused group of these groups.
The heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents represented by R ^{2 to} R ⁵ described above. A halogen atom, an alkyl group, an alkoxy group or an aryl group is preferred. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a chlorine atom is particularly preferable. 1-40 are preferable, as for carbon number of an alkyl group and an alkoxy group, 1-30 are more preferable, and 1-25 are especially preferable. The alkyl group and the alkoxy group are preferably linear or branched, and particularly preferably linear. 6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are still more preferable.

In General Formula 2, R ² and R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring. When R ² and R ³ , R ⁴ and R ⁵ are bonded to each other to form a ring, it is preferable to form a 5- to 7-membered ring (preferably a 5- or 6-membered ring). The ring formed is preferably a merocyanine dye used as an acidic nucleus. Specific examples include the structure described in paragraph No. 0026 of Japanese Patent Application Laid-Open No. 2010-222557, and the contents thereof are incorporated in the present specification.
The ring formed by combining R ² and R ³ and R ⁴ and R ⁵ is preferably a 1,3-dicarbonyl nucleus, a pyrazolinone nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (also a thioketone body). 2-thio-2,4-thiazolidinedione nucleus, 2-thio-2,4-oxazolidinedione nucleus, 2-thio-2,5-thiazolidinedione nucleus, 2,4-thiazolidinedione nucleus, 2,4 -With an imidazolidinedione nucleus, a 2-thio-2,4-imidazolidinedione nucleus, a 2-imidazoline-5-one nucleus, a 3,5-pyrazolidinedione nucleus, a benzothiophen-3-one nucleus, or an indanone nucleus More preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine nucleus (including thioketone body), 3,5-pyrazolidinedione nucleus, benzothiophene-3 Is one nucleus or an indanone nucleus,.

R ⁶ and R ⁷ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR ^A R ^B , or a metal atom, and —BR ^A R ^B is more preferable.
1-40 are preferable, as for carbon number of an alkyl group, 1-30 are more preferable, and 1-25 are especially preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear. The alkyl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents represented by R ^{2 to} R ⁵ described above.
6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are still more preferable. The aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents represented by R ^{2 to} R ⁵ described above.
The heteroaryl group is preferably a single ring or a condensed ring, and more preferably a single ring. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. 3-30 are preferable, as for the number of the carbon atoms which comprise a heteroaryl group, 3-18 are more preferable, 3-12 are more preferable, and 3-5 are especially preferable. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents represented by R ^{2 to} R ⁵ described above.
As a metal atom, magnesium, aluminum, calcium, barium, zinc, tin, aluminum, zinc, tin, vanadium, iron, cobalt, nickel, copper, palladium, iridium, platinum are preferable, and aluminum, zinc, vanadium, iron, copper Palladium, iridium and platinum are particularly preferred.

In the group represented by —BR ^A R ^B , R ^A and R ^B each independently represent a substituent. Examples of the substituent represented by R ^A and R ^B include the substituents represented by R ^{2 to} R ⁵ described above. A halogen atom, an alkyl group, an alkoxy group, an aryl group and a heteroaryl group are preferred. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom is particularly preferable. 1-40 are preferable, as for carbon number of an alkyl group and an alkoxy group, 1-30 are more preferable, and 1-25 are especially preferable. The alkyl group and the alkoxy group are preferably linear or branched, and particularly preferably linear. The alkyl group and the alkoxy group may have a substituent or may be unsubstituted. Examples of the substituent include an aryl group, a heteroaryl group, and a halogen atom. 6-20 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom. The heteroaryl group 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. 3-30 are preferable, as for the number of the carbon atoms which comprise a heteroaryl group, 3-18 are more preferable, 3-12 are more preferable, and 3-5 are especially preferable. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom.

In General Formula 2, R ⁶ may be covalently or coordinately bonded to R ^1a or R ³ . R ⁷ may be covalently bonded or coordinated to R ^1b or R ⁵ .

Examples of the pyrrolopyrrole compound represented by the general formula 2 include the following compounds. Further, compounds D-1 to D-162 described in paragraph Nos. 0049 to 0062 of JP 2010-222557 A may be mentioned, the contents of which are incorporated in the present specification. In the following formula, Ph represents a phenyl group.

一般式３中、Ｚ¹およびＺ²は、それぞれ独立に、縮環してもよい５員または６員の含窒素複素環を形成する非金属原子群であり、
Ｒ¹⁰¹およびＲ¹⁰²は、それぞれ独立に、アルキル基、アルケニル基、アルキニル基、アラルキル基またはアリール基を表し、
Ｌ¹は、奇数個のメチン基を有するメチン鎖を表し、
ａおよびｂは、それぞれ独立に、０または１であり、
ａが０の場合は、炭素原子と窒素原子とが二重結合で結合し、ｂが０の場合は、炭素原子と窒素原子とが単結合で結合し、
式中のＣｙで表される部位がカチオン部である場合、Ｘ¹はアニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位がアニオン部である場合、Ｘ¹はカチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位の電荷が分子内で中和されている場合、ｃは０である。 (Cyanine compound)
The cyanine compound is preferably a compound represented by the following general formula 3.
General formula 3

In General Formula 3, Z ¹ and Z ² are each independently a nonmetallic atom group that forms a 5-membered or 6-membered nitrogen-containing heterocycle that may be condensed,
R ¹⁰¹ and R ¹⁰² each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,
L ¹ represents a methine chain having an odd number of methine groups,
a and b are each independently 0 or 1,
When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents the number necessary for balancing the charge, and the site represented by Cy in the formula is an anion moiety. X ¹ represents a cation, c represents a number necessary to balance the charge, and when the charge at the site represented by Cy in the formula is neutralized in the molecule, c is 0.

In General Formula 3, Z ¹ and Z ² each independently represent a nonmetallic atom group that forms a 5-membered or 6-membered nitrogen-containing heterocyclic ring that may be condensed. The nitrogen-containing heterocycle may be condensed with another heterocycle, aromatic ring or aliphatic ring. The nitrogen-containing heterocycle is preferably a 5-membered ring. A structure in which a benzene ring or a naphthalene ring is condensed to a 5-membered nitrogen-containing heterocycle is more preferable. Specific examples of the nitrogen-containing heterocycle include an oxazole ring, an isoxazole ring, a benzoxazole ring, a naphthoxazole ring, an oxazolocarbazole ring, an oxazodibenzobenzofuran ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, an indolenine ring, Examples include benzoindolenin ring, imidazole ring, benzimidazole ring, naphthimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, furopyrrole ring, indolizine ring, imidazoquinoxaline ring, quinoxaline ring, quinoline ring, indolenine ring Benzoindolenine ring, benzoxazole ring, benzothiazole ring and benzimidazole ring are preferable, and indolenine ring, benzothiazole ring and benzimidazole ring are particularly preferable. The nitrogen-containing heterocyclic ring and the ring condensed thereto may have a substituent. Examples of the substituent include the substituents described in G ^A and G ^B of the general formula 1.

In General Formula 3, R ¹⁰¹ and R ¹⁰² each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group.
1-20 are preferable, as for carbon number of an alkyl group, 1-12 are more preferable, and 1-8 are especially preferable. The alkyl group may be linear, branched or cyclic.
2-20 are preferable, as for carbon number of an alkenyl group, 2-12 are more preferable, and 2-8 are especially preferable. The alkenyl group may be linear, branched or cyclic.
2-20 are preferable, as for carbon number of an alkynyl group, 2-12 are more preferable, and 2-8 are especially preferable. The alkynyl group may be linear, branched or cyclic.
6-25 are preferable, as for carbon number of an aryl group, 6-15 are more preferable, and 6-10 are the most preferable. The aryl group may be unsubstituted or may have a substituent.
The alkyl part of the aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group is the same as the above aryl group. 7-40 are preferable, as for carbon number of an aralkyl group, 7-30 are more preferable, and 7-25 are still more preferable.
The alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, and an amino group. A carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may have a hydrogen atom dissociated or a salt state.

式（ａ）中、＊は、メチン鎖との連結部を表し、Ａ¹は、酸素原子または硫黄原子を表す。 In Formula 3, L ¹ represents a methine chain having an odd number of methine groups. L ¹ is preferably a methine chain having 3, 5 or 7 methine groups.
The methine group may have a substituent. The methine group having a substituent is preferably a central (meso-position) methine group. Specific examples of the substituent include a substituent that the nitrogen-containing heterocycle of Z ¹ and Z ² may have, and a group represented by the following formula (a). Further, two substituents of the methine chain may be bonded to form a 5- or 6-membered ring.

In formula (a), * represents a connecting part with a methine chain, and A ¹ represents an oxygen atom or a sulfur atom.

In General Formula 3, a and b are each independently 0 or 1. When a is 0, the carbon atom and the nitrogen atom are bonded by a double bond, and when b is 0, the carbon atom and the nitrogen atom are bonded by a single bond. Both a and b are preferably 0. When a and b are both 0, general formula 3 is expressed as follows.

In the general formula 3, when the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, and c represents a number necessary for balancing the charge. Examples of anions include halide ions (Cl ⁻ , Br ⁻ , I ⁻ ), p-toluenesulfonate ions, ethyl sulfate ions, PF ₆ ⁻ , BF ₄ ⁻ or ClO ₄ ⁻ , tris (halogenoalkylsulfonyl) methide anions ( For example, (CF ₃ SO ₂ ) ₃ C ⁻ ), di (halogenoalkylsulfonyl) imide anion (for example, (CF ₃ SO ₂ ) ₂ N ⁻ ), tetracyanoborate anion and the like can be mentioned.
In general formula 3, when moiety represented by Cy in the formula is an anion portion, X ¹ represents a cation, c is represents a number necessary to balance the charge. Examples of the cation include alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ etc.), alkaline earth metal ions (Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Sr ²⁺ etc.), transition metal ions (Ag ⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ²⁺ ), other metal ions (such as Al ³⁺ ), ammonium ion, triethylammonium ion, tributylammonium ion, pyridinium ion, tetrabutylammonium Ion, guanidinium ion, tetramethylguanidinium ion, diazabicycloundecenium and the like. As the cation, Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , and diazabicycloundecenium are preferable.
In General Formula 3, when the charge at the site represented by Cy in the formula is neutralized in the molecule, X ¹ does not exist. That is, c is 0.

式（３−１）および（３−２）中、Ｒ^1A、Ｒ^2A、Ｒ^1BおよびＲ^2Bは、それぞれ独立に、アルキル基、アルケニル基、アルキニル基、アラルキル基またはアリール基を表し、
Ｌ^1AおよびＬ^1Bは、それぞれ独立に奇数個のメチン基を有するメチン鎖を表し、
Ｙ¹およびＹ²は、各々独立に−Ｓ−、−Ｏ−、−ＮＲ^X1−または−ＣＲ^X2Ｒ^X3−を表し、
Ｒ^X1、Ｒ^X2およびＲ^X3は、各々独立に水素原子またはアルキル基を表し、
Ｖ^1A、Ｖ^2A、Ｖ^1BおよびＶ^2Bは、それぞれ独立に、ハロゲン原子、シアノ基、ニトロ基、アルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基、ヘテロアリール基、−ＯＲ^c1、−ＣＯＲ^c2、−ＣＯＯＲ^c3、−ＯＣＯＲ^c4、−ＮＲ^c5Ｒ^c6、−ＮＨＣＯＲ^c7、−ＣＯＮＲ^c8Ｒ^c9、−ＮＨＣＯＮＲ^c10Ｒ^c11、−ＮＨＣＯＯＲ^c12、−ＳＲ^c13、−ＳＯ₂Ｒ^c14、−ＳＯ₂ＯＲ^c15、−ＮＨＳＯ₂Ｒ^c16または−ＳＯ₂ＮＲ^c17Ｒ^c18を表し、Ｖ^1A、Ｖ^2A、Ｖ^1BおよびＶ^2Bは、縮合環を形成していてもよく、
Ｒ^c1〜Ｒ^c18は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基またはヘテロアリール基を表し、
−ＣＯＯＲ^c3のＲ^c3が水素原子の場合および−ＳＯ₂ＯＲ^c15のＲ^c15が水素原子の場合は、水素原子が解離しても、塩の状態であってもよく、
ｍ１およびｍ２は、それぞれ独立に０〜４を表し、
式中のＣｙで表される部位がカチオン部である場合、Ｘ¹はアニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、
式中のＣｙで表される部位がアニオン部である場合、Ｘ¹はカチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、
式中のＣｙで表される部位の電荷が分子内で中和されている場合、Ｘ¹は存在しない。 The compound represented by General Formula 3 is also preferably a compound represented by the following (3-1) or (3-2). This compound is excellent in heat resistance.

In formulas (3-1) and (3-2), R ^1A , R ^2A , R ^1B and R ^2B each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,
L ^1A and L ^1B each independently represent a methine chain having an odd number of methine groups,
Y ¹ and Y ² each independently represent —S—, —O—, —NR ^X1 — or —CR ^X2 R ^X3 —
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group,
V ^1A , V ^2A , V ^1B and V ^2B are each independently a halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heteroaryl group, -OR ^c1 ,- COR ^c2 , -COOR ^c3 , -OCOR ^c4 , -NR ^c5 R ^c6 , -NHCOR ^c7 , -CONR ^c8 R ^c9 , -NHCONR ^c10 R ^c11 , -NHCOOR ^c12 , -SR ^c13 , -SO ₂ R ^c14 , -SO ₂ OR ^c15 , —NHSO ₂ R ^c16 or —SO ₂ NR ^c17 R ^c18 , and V ^1A , V ^2A , V ^1B and V ^2B may form a condensed ring,
R ^{c1 to} R ^c18 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group,
When R ^{c3 of} —COOR ^c3 is a hydrogen atom and R ^{c15 of} —SO ₂ OR ^c15 is a hydrogen atom, the hydrogen atom may be dissociated or in a salt state,
m1 and m2 each independently represent 0 to 4,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents a number necessary to balance the charge,
When the site represented by Cy in the formula is an anion moiety, X ¹ represents a cation, c represents a number necessary for balancing the charge,
When the charge at the site represented by Cy in the formula is neutralized in the molecule, X ¹ does not exist.

The groups represented by R ^1A , R ^2A , R ^1B and R ^2B are synonymous with the alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group described for R ¹⁰¹ and R ¹⁰² in formula 3, and preferred ranges are also included. It is the same. These groups may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, and an amino group. A carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may have a hydrogen atom dissociated or a salt state. When R ^1A , R ^2A , R ^1B and R ^2B represent an alkyl group, it is more preferably a linear alkyl group.

Y ¹ and Y ² are each independently -S -, - O -, - NR X1 - or -CR ^X2 R ^X3 - represents, -NR ^X1 - is preferred. R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. 1-10 are preferable, as for carbon number of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear. The alkyl group is particularly preferably a methyl group or an ethyl group.

L ^1A and L ^1B have the same meaning as L ^{1 in} formula 3, and the preferred range is also the same.
Group V ^1A, V ^2A, the V ^1B and V ^2B represent are the same as the range described in G ^A and G ^B of the formula 1, preferred ranges are also the same.
m1 and m2 each independently represent 0 to 4, with 0 to 2 being preferred.
The anion and cation represented by X ¹ have the same meaning as the range described for X ¹ in formula 3, and the preferred range is also the same.

  Examples of the compound represented by the general formula 3 include the following compounds. Further, compounds described in paragraph numbers 0044 to 0045 of JP-A-2009-108267 can be mentioned, and the contents thereof are incorporated in the present specification. In the following table, Et represents an ethyl group.

  The compound represented by the general formula 3 is “Heterocyclic Compounds Cyanine Dies and Related Compounds” written by FM Harmer.・ John Wiley & Sons-New York, London, 1964, and DM Starmer, "Heterocyclic Compounds in Special Topics in Heterocy" Click chemistry (Heterocyclic Compounds-Special topic in heterocyclic chemistry) , Chapter 14, Section 14, 482-515, John Wiley & Sons-New York, London, 1977, "Rods' Chemistry of Carbon Compounds (Rodd's Chemistry of Carbon Compounds) ”2nd. Ed. vol. IV, part B, 1977, Chapter 15, pages 369-422, published by Elsevier Science Publishing Company Inc., New York, JP-A-6-313939 and JP-A-5- It can be easily synthesized with reference to Japanese Patent No. 88293.

(Phthalocyanine compound)
The phthalocyanine compound is preferably a compound represented by the following formula (PC).

In General Formula (PC), X ^{1 to} X ¹⁶ each independently represent a hydrogen atom or a substituent, and M ¹ represents Cu or V═O.

Examples of the substituent represented by X ^{1 to} X ¹⁶ include the groups described above for the substituent T, and an alkyl group, a halogen atom, an alkoxy group, a phenoxy group, an alkylthio group, a phenylthio group, an alkylamino group, and an anilino group are preferable. .
Of X ^{1 to} X ¹⁶ , the number of substituents is preferably 0 to ¹⁶ , more preferably 0 to 4, still more preferably 0 to 1, and particularly preferably 0. M ¹ is preferably Ti═O.

  Specific examples of the compound represented by the general formula (PC) include, for example, the compound described in paragraph No. 0093 of JP2012-77153A, the oxytitanium phthalocyanine described in JP2006-343631A, and the like. Can be mentioned.

一般式（ＮＰＣ）において、Ｘ¹〜Ｘ²⁴は、各々独立に、水素原子又は置換基を表し、Ｍ¹は、Ｃｕ又はＶ＝Ｏを表す。Ｘ¹〜Ｘ²⁴が表す置換基は、上述した置換基Ｔ群で説明した基が挙げられ、アルキル基、ハロゲン原子、アルコキシ基、フェノキシ基、アルキルチオ基、フェニルチオ基、アルキルアミノ基、アニリノ基が好ましい。Ｍ¹は、Ｖ＝Ｏが好ましい。 (Naphthalocyanine compound)
The naphthalocyanine compound is preferably a compound represented by the following formula (NPC).

In the general formula (NPC), X ^{1 to} X ²⁴ each independently represent a hydrogen atom or a substituent, and M ¹ represents Cu or V═O. Examples of the substituent represented by X ^{1 to} X ²⁴ include the groups described in the above-described substituent group T, and include an alkyl group, a halogen atom, an alkoxy group, a phenoxy group, an alkylthio group, a phenylthio group, an alkylamino group, and an anilino group. preferable. M ¹ is preferably V = O.

  Specific examples of the compound represented by the general formula (NPC) include, for example, compounds described in paragraph No. 0093 of JP2012-77153A.

As for content of an infrared absorber, 1-80 mass% is preferable with respect to the total solid of a composition. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 70% by mass or less.
When using a copper compound as an infrared absorber, the content of the copper compound is preferably 30 to 70 mass% with respect to the total solid content of the composition. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less. The lower limit is preferably 35% by mass or more, and more preferably 40% by mass or more.
Moreover, 50-100 mass% is preferable, as for content of the copper compound in an infrared absorber, 60-100 mass% is more preferable, and 70-100 mass% is still more preferable. Further, the infrared absorber may be substantially only a copper compound. When the infrared absorber is substantially only a copper compound, the content of the copper compound in the infrared absorber is, for example, preferably 99% by mass or more, more preferably 99.9% by mass or more, and only the copper compound. More preferably, it is configured.

<< Solvent >>
The composition of the present invention contains a solvent. There is no restriction | limiting in particular in the solvent, If it can melt | dissolve or disperse | distribute each component of a composition uniformly, it can select suitably according to the objective. For example, water and an organic solvent can be used, and an organic solvent is preferable.

Preferable examples of the organic solvent include alcohols (for example, methanol), ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, and dimethylformamide, dimethylacetamide, dimethylsulfoxide, and sulfolane. . Specific examples of the alcohols, aromatic hydrocarbons and halogenated hydrocarbons include those described in paragraph 0136 of JP 2012-194534 A, the contents of which are incorporated herein. Specific examples of esters, ketones, and ethers include those described in paragraph 0497 of JP2012-208494A (corresponding to [0609] of US 2012/0235099 corresponding). It is done.
Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (for example, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate) 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, 2-methoxy) Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (e.g. Methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate And ethyl 2-oxobutanoate .
Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Examples thereof include monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.
Examples of aromatic hydrocarbons include toluene and xylene.

A solvent may be used individually by 1 type and may be used in combination of 2 or more type. When using 2 or more types in combination, a combination in which the difference between the boiling point of the solvent having the highest boiling point and the boiling point of the solvent having the lowest boiling point is 10 ° C. or more is preferable. The difference in boiling points is preferably 20 ° C. or higher, more preferably 50 ° C. or higher, and still more preferably 70 ° C. or higher. The upper limit is preferably 100 ° C. or lower, for example. In the present invention, the boiling point of the solvent is a value at 0.1 MPa.
By using two or more kinds of solvents in combination as described above, it is easy to adjust the dissolved gas amount and dissolved oxygen amount of the composition to the ranges specified in the present invention. For example, when a composition containing an infrared absorber and a solvent is subjected to a treatment such as defoaming to adjust the dissolved gas amount or dissolved oxygen amount to a range specified in the present invention, the composition is dissolved in the composition. It is easy to defoam gas and oxygen, and it is easy to adjust the dissolved gas amount and dissolved oxygen amount of the composition to the ranges specified in the present invention. In addition, since a solvent with a low boiling point may be removed from the composition together with bubbles during defoaming, it may hardly remain in the composition after adjusting the dissolved oxygen concentration.
As a combination of the above organic solvents, for example, a solvent A having a boiling point of 100 ° C. or higher (preferably 120 ° C. or higher, more preferably 150 ° C. or higher) and a boiling point of 130 ° C. or lower (preferably 100 ° C. or lower, more preferably Is preferably selected from the solvent A and the solvent B so that the difference in boiling point is 10 ° C. or more. Examples of the solvent A include cyclohexanone, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl acetate, and butyl acetate. Examples of the solvent B include methanol, ethanol, 2-butanol and the like. Examples of the combination of the solvent A and the solvent B include a combination of cyclohexanone and methanol.

  The amount of the solvent in the composition is preferably such that the solid content is 10 to 90% by mass. The lower limit is preferably 15% by mass or more, and more preferably 20% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less.

<< Resin >>
The composition of the present invention can contain a resin. There is no limitation in particular as resin. For example, (meth) acrylic resin, styrene resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyarylene ether phosphine oxide Resin, polyimide resin, polyamide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, maleimide resin, acrylonitrile resin, polyvinyl acetal resin, poly-N-vinylacetamide resin, polyvinylpyrrolidone resin, fluorene polycarbonate resin, fluorene polyester Resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, allyl ester resin, silsesquioxane resin, etc. That. One of these resins may be used alone, or two or more thereof may be mixed and used. Regarding the above-mentioned resin, description in paragraphs 0056 to 0060 of JP-A-2014-218597 and description of paragraphs 0074 to 0156 in JP-A-2013-218312 can be referred to, and the contents thereof are incorporated in the present specification.

  The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more. In the case of an epoxy resin, the weight average molecular weight (Mw) is preferably 100 or more, and more preferably 200 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.

  Examples of the (meth) acrylic resin include a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. Specific examples include polymers obtained by polymerizing at least one selected from (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamide and (meth) acrylonitrile.

  Examples of the polyester resin include polyols (for example, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), polybasic acids (for example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and aromatic nucleus thereof. Fatty dicarboxylic acids having 2 to 20 carbon atoms, such as aromatic dicarboxylic acids, adipic acid, sebacic acid, dodecanedicarboxylic acid, etc., in which hydrogen atoms are substituted with methyl groups, ethyl groups, phenyl groups, etc., and cyclohexanedicarboxylic acid, etc. A polymer obtained by reaction with a cyclic dicarboxylic acid and the like, and a polymer obtained by ring-opening polymerization of a cyclic ester compound such as a caprolactone monomer (for example, polycaprolactone).

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.

  The resin may have an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. These acid groups may be used alone or in combination of two or more. Examples of the resin having an acid group include alkali-soluble resins described in paragraphs 0180 to 0202 of JP-A-2015-043063, and the contents thereof are incorporated in the present specification. The acid value of the resin having an acid group is preferably 30 to 200 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more. The upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less. The acid value of the resin having an acid group is preferably 30 to 200 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more. The upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.

式中、Ｒ⁵は水素原子またはアルキル基を表し、Ｌ⁴〜Ｌ⁷はそれぞれ独立に、単結合または２価の連結基を表し、Ｒ¹⁰〜Ｒ¹³はそれぞれ独立にアルキル基またはアリール基を表す。 In the present invention, the resin preferably has structural units represented by the following formulas (A3-1) to (A3-6).

In the formula, R ⁵ represents a hydrogen atom or an alkyl group, L ^{4 to} L ⁷ each independently represents a single bond or a divalent linking group, and R ^{10 to} R ¹³ each independently represents an alkyl group or an aryl group. Represent.

R ⁵ represents a hydrogen atom or an alkyl group. 1-5 are preferable, as for carbon number of an alkyl group, 1-3 are more preferable, and 1 is especially preferable. R ⁵ is preferably a hydrogen atom or a methyl group.

L ^{4 to} L ⁷ each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NR ¹⁰ — (R ¹⁰ represents a hydrogen atom or An alkyl group, preferably a hydrogen atom), or a group composed of a combination thereof, and a group composed of a combination of at least one of an alkylene group, an arylene group, and an alkylene group and -O-. 1-30 are preferable, as for carbon number of an alkylene group, 1-15 are more preferable, and 1-10 are more preferable. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be monocyclic or polycyclic. 6-18 are preferable, as for carbon number of an arylene group, 6-14 are more preferable, and 6-10 are more preferable.

The alkyl group represented by R ¹⁰ may be linear, branched or cyclic, and is preferably cyclic. The alkyl group may have the above-described substituent and may be unsubstituted. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. The number of carbon atoms of the aryl group R ¹⁰ represents preferably 6 to 18, more preferably 6 to 12, 6 is more preferable. R ¹⁰ is preferably a cyclic alkyl group or an aryl group.

The alkyl group represented by R ¹¹ and R ¹² may be linear, branched or cyclic, and is preferably linear or branched. The alkyl group may have the above-described substituent and may be unsubstituted. 1-12 are preferable, as for carbon number of an alkyl group, 1-6 are more preferable, and 1-4 are still more preferable. R ^11, R ¹² the number of carbon atoms of the aryl group represented by preferably 6 to 18, more preferably 6 to 12, 6 is more preferable. R ¹¹ and R ¹² are preferably a linear or branched alkyl group.

The alkyl group represented by R ¹³ may be linear, branched or cyclic, and is preferably linear or branched. The alkyl group may have the above-described substituent and may be unsubstituted. 1-12 are preferable, as for carbon number of an alkyl group, 1-6 are more preferable, and 1-4 are still more preferable. The number of carbon atoms of the aryl group R ¹³ represents preferably 6 to 18, more preferably 6 to 12, 6 is more preferable. R ¹³ is preferably a linear or branched alkyl group or an aryl group.

  The content of the resin is preferably 1 to 70% by mass with respect to the total solid content of the composition. The lower limit is more preferably 5% by mass or more, and further preferably 10% by mass or more. The upper limit can be, for example, 65% by mass or less, or 60% by mass or less. Only one type of resin may be used, or two or more types of resins may be used. In the case of two or more types, the total amount is preferably within the above range.

<< Compound having a crosslinkable group (crosslinkable compound) >>
The composition of the present invention can contain a compound having a crosslinkable group (crosslinkable compound). When the composition of this invention contains a crosslinkable compound, the near-infrared cut filter excellent in heat resistance and solvent resistance can be manufactured. As the crosslinkable compound, known compounds that can be crosslinked by radicals, acids, and heat can be used. Examples thereof include a compound having a group having an ethylenically unsaturated bond, a compound having a cyclic ether group, a compound having a methylol group, and a compound having a partial structure represented by MX described below. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a styryl group, a (meth) allyl group, a (meth) acryloyl group, and a (meth) allyl group and a (meth) acryloyl group are preferable. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, and an epoxy group is preferable.

The crosslinkable compound may be in the form of a monomer or a polymer. Examples of the polymer type crosslinkable compound include an epoxy resin described later and a resin including a structural unit having a crosslinkable group. Examples of the structural unit having a crosslinkable group include the following (A2-1) to (A2-4).

R ¹ represents a hydrogen atom or an alkyl group. 1-5 are preferable, as for carbon number of an alkyl group, 1-3 are more preferable, and 1 is especially preferable. R ¹ is preferably a hydrogen atom or a methyl group.

L ⁵¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NR ¹⁰ — (R ¹⁰ represents a hydrogen atom or An alkyl group, preferably a hydrogen atom), or a group composed of a combination thereof, and a group composed of a combination of at least one of an alkylene group, an arylene group, and an alkylene group and -O-. 1-30 are preferable, as for carbon number of an alkylene group, 1-15 are more preferable, and 1-10 are more preferable. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be monocyclic or polycyclic. 6-18 are preferable, as for carbon number of an arylene group, 6-14 are more preferable, and 6-10 are more preferable.

P ¹ represents a crosslinkable group. The crosslinkable group, a group having an ethylenically unsaturated bond, cyclic ether groups, methylol groups, a group represented by the -M- (X ²⁾ _n and the like. In the group represented by -M- (X ² ) _n , M represents an atom selected from Si, Ti, Zr and Al, X ² represents a substituent or a ligand, and n X ² Among them, at least one is one selected from a hydroxy group, an alkoxy group, an acyloxy group, a phosphoryloxy group, a sulfonyloxy group, an amino group, an oxime group, and O═C (R ^a ) (R ^b ). X ² may be bonded to each other to form a ring, and n represents the number of bonds of M with X ² .

  The molecular weight of the monomer type crosslinkable compound is preferably less than 2000, more preferably 100 or more and less than 2000, and further preferably 200 or more and less than 2000. The upper limit is preferably 1500 or less, for example. The weight average molecular weight (Mw) of the polymer type crosslinkable compound is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more. In the case of a compound having a cyclic ether group, the weight average molecular weight (Mw) is preferably 100 or more, and more preferably 200 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.

(Compound having a group having an ethylenically unsaturated bond)
The compound having a group having an ethylenically unsaturated bond is preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (meth) acrylate compound. As examples of the compound containing a group having an ethylenically unsaturated bond, description in paragraphs 0033 to 0034 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. Specific examples include ethyleneoxy-modified pentaerythritol tetraacrylate (as a commercial product, NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; 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, 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., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are ethylene glycol, The Structures through a propylene glycol residue are preferable. These oligomer types can also be used. Moreover, description of the polymeric compound of Paragraph 0034-0038 of Unexamined-Japanese-Patent No. 2013-253224 can be referred, This content is integrated in this specification. Moreover, the polymerizable monomer etc. as described in Unexamined-Japanese-Patent No. 2012-208494 Paragraph 0477 (corresponding US Patent Application Publication No. 2012/0235099 [0585]) etc. are mentioned, The content of these is incorporated in this specification. It is. Further, diglycerin EO (ethylene oxide) modified (meth) acrylate (as a commercial product, M-460; manufactured by Toa Gosei) is preferable. Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT) and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) are also preferable. These oligomer types can also be used. For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) etc. are mentioned.

  The compound containing a group having an ethylenically unsaturated bond may further have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Examples of the compound having an acid group include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids. A polyfunctional monomer in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group is preferred, and particularly preferably, the aliphatic polyhydroxy compound is pentaerythritol and / or Or it is a dipentaerythritol. Examples of commercially available products include Aronix series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. The acid value of the compound having an acid group is preferably from 0.1 to 40 mgKOH / g. The lower limit is preferably 5 mgKOH / g or more. The upper limit is preferably 30 mgKOH / g or less.

  A compound containing a group having an ethylenically unsaturated bond is also a preferred embodiment of a compound having a caprolactone structure. As the compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated herein. Examples of commercially available products include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd. And TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

  In the present invention, the compound having a group having an ethylenically unsaturated bond may be a polymer having a group having an ethylenically unsaturated bond in the side chain. The content of the structural unit having a group having an ethylenically unsaturated bond in the side chain is preferably 5 to 100% by mass of all structural units constituting the polymer. The lower limit is more preferably 10% by mass or more, and still more preferably 15% by mass or more. The upper limit is more preferably 90% by mass or less, still more preferably 80% by mass or less, and particularly preferably 70% by mass or less.

  The polymer may contain other structural units in addition to the structural unit having a group having an ethylenically unsaturated bond in the side chain. The other structural unit may contain a functional group such as an acid group. It does not have to contain a functional group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Only one type of acid group may be included, or two or more types of acid groups may be included. The proportion of the structural unit having an acid group is preferably 0 to 50% by mass of the total structural units constituting the polymer. The lower limit is more preferably 1% by mass or more, and still more preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, and still more preferably 30% by mass or less.

Specific examples of the polymer include (meth) allyl (meth) acrylate / (meth) acrylic acid copolymer. Commercially available products of the above-mentioned polymers include a dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shammock Co. Ltd., viscoat R-264, KS resist 106 (all Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (both made by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), Acryl-RD-F8 (Japan) Catalyst). Moreover, the polymer shown below is also mentioned.

(Compound having a cyclic ether group)
In the present invention, a compound having a cyclic ether group can also be used as the crosslinkable compound. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, and an epoxy group is preferable.
Examples of the compound having a cyclic ether group include a polymer having a cyclic ether group in the side chain, and a monomer or oligomer having two or more cyclic ether groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin, and the like can be given. Moreover, a monofunctional or polyfunctional glycidyl ether compound is also mentioned, and a polyfunctional aliphatic glycidyl ether compound is preferable. As the compound having a cyclic ether group, a compound having a glycidyl group such as glycidyl (meth) acrylate or allyl glycidyl ether, or a compound having an alicyclic epoxy group can also be used. As such a thing, description of Unexamined-Japanese-Patent No. 2009-265518 Paragraph 0045 etc. can be considered, and these content is integrated in this-application specification.

A commercial item can also be used for the compound which has a cyclic ether group. As a commercial item of the compound which has a cyclic ether group, description of Unexamined-Japanese-Patent No. 2012-155288 Paragraph 0191 etc. can be considered, for example, These content is integrated in this-application specification.
As bisphenol A type epoxy resins, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1051, EPICLON1051, EPICLON105, EPICLON1055 Etc.).
As bisphenol F type epoxy resins, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, manufactured by DIC Corporation), LCE-21, RE-602S (Nippon Kayaku Co., Ltd.) and the like.
Phenol novolac epoxy resins include JER152, JER154, JER157S70, JER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC) Etc.).
Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) ), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) and the like.
As the aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA) Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation) and the like.
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER1031S (manufactured by Mitsubishi Chemical Corporation), lipoxy SPCF-9X (manufactured by Showa Denko KK) and the like can be mentioned.

(Compound having a partial structure represented by MX)
In the present invention, a compound having a partial structure represented by MX can be used as the crosslinkable compound. In particular, when a copper compound is used as the infrared absorber, it is preferable to use a compound having a partial structure represented by MX as the crosslinkable compound. According to this aspect, it is easy to manufacture a near-infrared cut filter excellent in heat resistance and solvent resistance.

  In the compound having a partial structure represented by MX, M is an atom selected from Si, Ti, Zr and Al, Si, Ti and Zr are preferable, and Si is more preferable.

In the compound having a partial structure represented by MX, X represents a hydroxy group, an alkoxy group, an acyloxy group, a phosphoryloxy group, a sulfonyloxy group, an amino group, an oxime group, and O═C (R ^a ) (R ^b And an alkoxy group, an acyloxy group, and an oxime group are preferable, and an alkoxy group is more preferable. In addition, when X is O = C (R ^a ) (R ^b ), it is bonded to M by an unshared electron pair of the oxygen atom of the carbonyl group (—CO—). R ^a and R ^b each independently represents a monovalent organic group.
The partial structure represented by MX is preferably a combination in which M is Si and X is an alkoxy group. According to this combination, since it has moderate reactivity, the storage stability of the composition can be improved. Furthermore, it is easy to produce a near-infrared cut filter with better heat resistance.

1-20 are preferable, as for carbon number of the alkoxy group which X represents, 1-10 are more preferable, 1-5 are more preferable, and 1-2 are especially preferable. The alkoxy group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear. The alkoxy group may be unsubstituted or may have a substituent, but is preferably unsubstituted. Substituents include halogen atoms (preferably fluorine atoms), vinyl groups, (meth) acryloyl groups, styryl groups, epoxy groups, oxetanyl groups, amino groups, isocyanato groups, isocyanurate groups, ureido groups, mercapto groups, sulfide groups. , Sulfo group, carboxyl group, hydroxyl group and the like.
Examples of the acyloxy group represented by X include a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, and the like. Examples include formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy, benzoyloxy group, p-methoxyphenylcarbonyloxy group, and the like. Examples of the substituent include those described above.
1-20 are preferable, as for carbon number of the oxime group which X represents, 1-10 are more preferable, and 1-5 are more preferable. For example, an ethylmethylketoxime group and the like can be mentioned.
The amino group represented by X includes an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a heterocyclic amino group having 0 to 30 carbon atoms. Groups and the like. For example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino and the like can be mentioned. Examples of the substituent include those described above.
Examples of the monovalent organic group represented by R ^a and R ^b include an alkyl group, an aryl group, and a group represented by —R ¹⁰¹ —COR ¹⁰² . 1-20 are preferable and, as for carbon number of an alkyl group, 1-10 are more preferable. The alkyl group may be linear, branched or cyclic. The alkyl group may be unsubstituted or may have the above-described substituent. 6-20 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable. The aryl group may be unsubstituted or may have the above-described substituent. In the group represented by —R ¹⁰¹ —COR ¹⁰² , R ¹⁰¹ represents an arylene group, and R ¹⁰² represents an alkyl group or an aryl group. The number of carbon atoms of the arylene group R ¹⁰¹ represents preferably 1 to 20, 1 to 10 is more preferable. The arylene group may be linear, branched or cyclic. The arylene group may be unsubstituted or may have the above-described substituent. ^Examples of the alkyl group and aryl group represented by R ¹⁰² include those described for R ^a and R ^b , and the preferred ranges are also the same.

  The compound having a partial structure represented by MX may be in the form of either a low molecular compound or a polymer, but a polymer is preferred because it is easy to form a film with better heat resistance. Of the compounds having a partial structure represented by MX, the molecular weight of the low molecular weight compound is preferably 100 to 1,000. The upper limit is preferably 800 or less, and more preferably 700 or less. The molecular weight is a theoretical value obtained from the structural formula. Of the compounds having a partial structure represented by MX, the polymer type compound preferably has a weight average molecular weight of 500 to 300,000. The lower limit is preferably 1000 or more, and more preferably 2000 or more. The upper limit is preferably 250,000 or less, and more preferably 200000 or less.

Among the compounds having a partial structure represented by MX, examples of the low molecular compound include compounds represented by the following (MX1).
M- (X ¹ ) _m (MX1)
M represents an atom selected from Si, Ti, Zr and Al, X ¹ represents a substituent or a ligand, and at least one of m X ¹ is a hydroxy group, an alkoxy group, an acyloxy group , A phosphoryloxy group, a sulfonyloxy group, an amino group, an oxime group, and O═C (R ^a ) (R ^b ), and X ¹ are bonded to each other to form a ring. M represents the number of bonds of M with X ¹ . R ^a and R ^b each independently represents a monovalent organic group. Note that when X ¹ is O═C (R ^a ) (R ^b ), it is bonded to M by an unshared electron pair of the oxygen atom of the carbonyl group (—CO—).

M is an atom selected from Si, Ti, Zr and Al, and Si, Ti and Zr are preferable, and Si is more preferable. X ¹ represents a substituent or a ligand, and at least ^one of m X ¹ is a hydroxy group, an alkoxy group, an acyloxy group, a phosphoryloxy group, a sulfonyloxy group, an amino group, an oxime group, and O═C. (R ^a ) (R ^b ) is preferably selected, and at least one of m X ¹ is preferably selected from an alkoxy group, an acyloxy group, and an oxime group, m of pieces of X ^1, more preferably at least one is an alkoxy group, all of X ¹ is more preferably an alkoxy group.

Of the substituents and ligands, hydroxy group, alkoxy group, acyloxy group, phosphoryloxy group, sulfonyloxy group, amino group, oxime group, and O = C (R ^a ) (R ^b ) are as defined above. The preferred range is also the same.

As a substituent other than the hydroxy group, alkoxy group, acyloxy group, phosphoryloxy group, sulfonyloxy group, amino group, and oxime group, a hydrocarbon group is preferable. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group. The hydrocarbon group may have a substituent or may be unsubstituted. Substituents include alkyl groups, halogen atoms (preferably fluorine atoms), vinyl groups, (meth) acryloyl groups, styryl groups, epoxy groups, oxetanyl groups, amino groups, isocyanate groups, isocyanurate groups, ureido groups, mercapto groups. , Sulfide groups, sulfo groups, carboxyl groups, hydroxyl groups, alkoxy groups and the like.
The alkyl group may be linear, branched or cyclic. 1-20 are preferable, as for carbon number of a linear alkyl group, 1-12 are more preferable, and 1-8 are more preferable. 3-20 are preferable, as for carbon number of a branched alkyl group, 3-12 are more preferable, and 3-8 are more preferable. The cyclic alkyl group may be monocyclic or polycyclic. 3-20 are preferable, as for carbon number of a cyclic | annular alkyl group, 4-10 are more preferable, and 6-10 are more preferable.
2-10 are preferable, as for carbon number of an alkenyl group, 2-8 are more preferable, and 2-4 are more preferable.
6-18 are preferable, as for carbon number of an aryl group, 6-14 are more preferable, and 6-10 are more preferable.

The compounds in which M is represented by Si include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, and n-propyl. Triethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, vinyltri Methoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl Methoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- Phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltriethoxy Examples thereof include silane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and 3-isocyanatopropyltriethoxysilane.
As commercially available products, KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM-3063, KBE-3063 manufactured by Shin-Etsu Silicone, KBE-3083, KBM-3103, KBM-3066, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE- 403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KB M-802, KBM-803, KBE-846, KBE-9007 and the like.

  The compounds in which M is represented by Ti include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium diisopropoxybis (Ethyl acetoacetate), titanium phosphate compound, titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), titanium diisopropoxybis (ethylacetoacetate), titanium lactate ammonium salt, titanium Lactate, titanium diisopropoxybis (triethanolaminate), tertiary amyl titanate, tetratertiary butyl titanate, tetrastearyl titanate, titanium-1,3-propa Jiokishibisu (ethylacetoacetate), dodecylbenzenesulfonic acid titanium compound, titanium isostearate, titanium diethanol aminate, and titanium-aminoethylamino ethanolate. As commercially available products, the ORGATIX series (for example, TA-10, TA-21, TA-23, TA-30, TC-100, TC-401, TC-710, TC-1040, TC- manufactured by Matsumoto Fine Chemical Co., Ltd.) 201, TC-750, TC-300, TC-310, TC-315, TC-400, TA-60, TA-80, TA-90, TC-120, TC-220, TC-730, TC-810, TC-800, TC-500, TC-510, etc.), Anomoto Fine Techno's Plenact series (for example, TTS, 46B, 55, 41B, 38S, 138S, 238S, 338X, 44, 9SA, ET, etc.) Can be mentioned.

  Examples of the compound in which M is represented by Zr include zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetraacetyl acetonate, zirconium tributoxy monoacetyl acetonate, zirconium dibutoxy bis (ethyl acetoacetate) and the like. Commercially available products include the ORGATIX series (for example, ZA-45, ZA-65, ZC-150, ZC-540, ZC-700, ZC-580, ZC-200, ZC-320, ZC-, manufactured by Matsumoto Fine Chemical Co., Ltd. 126, ZC-300, etc.).

  Examples of the compound in which M is represented by Al include alkyl acetoacetate aluminum diisopropylate. As a commercial item, Ajinomoto Fine Techno Co., Ltd. Preneact AL-M etc. are mentioned.

Among the compounds having a partial structure represented by MX, examples of the polymer type compound include acrylic resins, acrylamide resins, styrene resins, and polysiloxanes. Of these, acrylic resin, acrylamide resin, or styrene resin is preferable because of improving the film property and facilitating the adjustment of the coating solution viscosity.
Specific examples of the polymer type compound include, for example, a structural unit represented by the following (MX2-1), a structural unit represented by the following (MX2-2), and a structural unit represented by the following (MX2-3) And a polymer having one selected from:

M represents an atom selected from Si, Ti, Zr and Al, X ² represents a substituent or a ligand, and at least one of n X ² is a hydroxy group, an alkoxy group, an acyloxy group , A phosphoryloxy group, a sulfonyloxy group, an amino group, an oxime group, and O═C (R ^a ) (R ^b ), and X ² are bonded to each other to form a ring. R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a single bond or a divalent linking group, and n represents the number of bonds of M to X ² . R ^a and R ^b each independently represents a monovalent organic group. In addition, when X ² is O═C (R ^a ) (R ^b ), it is bonded to M by an unshared electron pair of the oxygen atom of the carbonyl group (—CO—).

M and X ² have the same meanings as M and X ^{1 in} (MX1), and preferred ranges thereof are also the same.
R ¹ represents a hydrogen atom or an alkyl group. 1-5 are preferable, as for carbon number of an alkyl group, 1-3 are more preferable, and 1 is especially preferable. The alkyl group is preferably linear or branched, and more preferably linear. In the alkyl group, part or all of the hydrogen atoms may be substituted with a halogen atom (preferably a fluorine atom).
L ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NR ¹⁰ — (R ¹⁰ represents a hydrogen atom or An alkyl group, preferably a hydrogen atom), or a group composed of a combination thereof, and a group composed of a combination of at least one of an alkylene group, an arylene group, and an alkylene group and -O-.
1-30 are preferable, as for carbon number of an alkylene group, 1-15 are more preferable, and 1-10 are more preferable. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be monocyclic or polycyclic.
6-18 are preferable, as for carbon number of an arylene group, 6-14 are more preferable, 6-10 are more preferable, and a phenylene group is especially preferable.

The polymer type compound may contain other structural units in addition to the structural units represented by the formulas (MX2-1), (MX2-2), and (MX2-3). As components constituting other structural units, those disclosed in paragraph Nos. 0068 to 0075 (corresponding to [0112] to [0118] of the corresponding US Patent Application Publication No. 2011/0124824) of JP-A-2010-106268. The description of the copolymerization component can be taken into account, the contents of which are incorporated herein.
Moreover, it can also have the structural unit represented by (A3-1)-(A3-6) demonstrated with resin mentioned above. Examples of the polymer type compound include the following polymers.

  When the polymer type compound includes other structural units (preferably structural units represented by formulas ((A3-1) to (A3-6)), formulas (MX2-1) to (MX2-3) Is preferably 95: 5 to 20:80, and more preferably 90:10 to 40:60. The molar ratio of the total of the structural units represented by By increasing the content of the structural units represented by (MX2-1) to (MX2-3) within the above range, the moisture resistance and solvent resistance tend to be further improved. ) To (MX2-3), the content of the structural units represented by (MX2-3) is lowered within the above range, whereby the heat resistance tends to be further improved.

The content of the crosslinkable compound is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more with respect to the total solid content of the composition. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.
The total content of the resin and the crosslinkable compound is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more based on the total solid content of the composition. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.
In the crosslinkable compound, the content of the polymer type crosslinkable compound (preferably, a resin having a structural unit having a crosslinkable group) is preferably 10 to 100% by mass of the total crosslinkable compound. A lower limit can also be 30 mass% or more, and can also be 50 mass% or more. An upper limit can also be 90 mass% or less, and can also be 70 mass% or less.
Only one type of crosslinkable compound may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.

<< Gelatin >>
The composition of the present invention may contain gelatin. By containing gelatin, it is easy to form a near-infrared cut filter excellent in heat resistance. Although the detailed mechanism is unknown, it is assumed that it is because an aggregate is easily formed with an infrared absorber and gelatin. In particular, when a cyanine compound is used as an infrared absorber, it is easy to form a near-infrared cut filter excellent in heat resistance.

  In the present invention, gelatin includes acid-treated gelatin and alkali-treated gelatin (such as lime treatment) depending on the synthesis method, and both can be preferably used. The molecular weight of gelatin is preferably 10,000 to 1,000,000. In addition, modified gelatin modified by utilizing the amino group or carboxyl group of gelatin can be used (for example, phthalated gelatin). As gelatin, inert gelatin (for example, Nitta gelatin 750), phthalated gelatin (for example, Nitta gelatin 801), or the like can be used.

  In order to increase the water resistance and mechanical strength of the near infrared cut filter, it is preferable to harden gelatin using various compounds. As the curing agent, conventionally known curing agents can be used. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, compounds having reactive halogen described in US Pat. No. 3,288.775 and the like, Compounds having reactive ethylenically unsaturated bonds described in U.S. Pat. No. 3,642.486, JP-B-49-13563 and others, aziridines described in U.S. Pat. No. 3,017,280, etc. Compounds, Ehoshi compounds described in US Pat. No. 3,091,537, halogen carboxyl aldehydes such as mucochloric acid, dioxanes such as dihydroxydioxane and dichlorodioxane, or inorganic dura mater Examples of the agent include chromium alum and zirconium sulfate. Specific examples include 1,3-divinylsulfonyl-2-propanol.

  The content of gelatin is preferably 1 to 99% by mass with respect to the total solid content of the composition. The lower limit is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is preferably 95% by mass or less, and more preferably 90% by mass or less.

<< photopolymerization initiator >>
The composition of the present invention may contain a photopolymerization initiator. As for content of a photoinitiator, 0.01-30 mass% is preferable with respect to the total solid of a composition. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. Only one type or two or more types of photopolymerization initiators may be used, and in the case of two or more types, the total amount is preferably within the above range.

  The photopolymerization initiator is not particularly limited as long as it has the ability to initiate crosslinking (polymerization) of the crosslinkable compound by light, 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.

The photopolymerization initiator is preferably a compound having at least an aromatic group. For example, acylphosphine compound, acetophenone compound, α-aminoketone compound, benzophenone compound, benzoin ether compound, ketal derivative compound, thioxanthone compound Oxime compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, benzoin ether compounds, ketal derivative compounds, metallocene compounds and other onium salt compounds , Organic boron salt compounds, disulfone compounds, thiol compounds, and the like.
As the photopolymerization initiator, the description in paragraphs 0217 to 0228 of JP2013-253224A can be referred to, and the contents thereof are incorporated herein.
Examples of oxime compounds include IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), and Adeka Arcles NCI-831. (ADEKA), Adeka Arkles NCI-930 (ADEKA), etc. can be used.
As acetophenone compounds, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the acylphosphine compound, IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) which are commercially available products can be used.
In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP 2013-164471 A ( C-3). This content is incorporated herein.
Moreover, it is also possible to use the oxime compound which has a nitro group as a photoinitiator. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A, and ADEKA. Arcles NCI-831 (made by ADEKA) is mentioned.

<< Thermal stability imparting agent >>
The composition of the present invention can also contain an oxime compound as a heat stability imparting agent. In particular, when a copper compound is used as the infrared absorber, the heat resistance of the infrared absorption layer can be further improved by blending a thermal stability imparting agent such as an oxime compound. Examples of oxime compounds include IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), and Adeka Arcles NCI-831. (ADEKA), Adeka Arkles NCI-930 (ADEKA), etc. can be used. Moreover, the oxime compound which has the fluorine atom mentioned above, and the oxime compound which has a nitro group can also be used.
The content of the heat stability imparting agent is preferably 0.01 to 30% by mass with respect to the total solid content of the composition. The lower limit is preferably 0.1% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less.

<< Catalyst >>
The composition of the present invention may contain a catalyst. By containing a catalyst, an infrared cut filter excellent in solvent resistance and heat resistance is easily obtained. In particular, when the compound having the partial structure represented by MX described above is used as the crosslinkable compound, the crosslinking reaction is promoted, and an infrared cut filter excellent in solvent resistance and heat resistance is easily obtained. Examples of the catalyst include an organometallic catalyst, an acid catalyst, and an amine catalyst, and an organometallic catalyst is preferable. Examples of the organometallic catalyst include tris (2,4-pentanedionato) aluminum (III). The content of the catalyst is preferably 0.01 to 5% by mass with respect to the total solid content of the composition. The lower limit is preferably 0.05% by mass or more. The upper limit is preferably 3% by mass or less, and more preferably 1% by mass or less.

<< Surfactant >>
The composition of the present invention may contain a surfactant. Only one type of surfactant may be used, or two or more types may be combined. As for content of surfactant, 0.0001-5 mass% is preferable with respect to the total solid of a composition. The lower limit is preferably 0.005% by mass or more, and more preferably 0.01% by mass or more. The upper limit is preferably 2% by mass or less, and more preferably 1% by mass or less.
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. The infrared absorbing composition preferably contains at least one of a fluorine-based surfactant and a silicone-based surfactant. The interfacial tension between the coated surface and the coating liquid is reduced, and the wettability to the coated surface is improved. For this reason, the liquid characteristic (especially fluidity | liquidity) of a composition improves, and the uniformity of coating thickness and liquid-saving property improve more. As a result, even when a thin film of about several μm is formed with a small amount of liquid, it is possible to form a film with a uniform thickness with small thickness unevenness.

上記の化合物の重量平均分子量は、好ましくは３，０００〜５０，０００であり、例えば、１４，０００である。
また、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開２０１０−１６４９６５号公報００５０〜００９０段落および０２８９〜０２９５段落に記載された化合物、例えばＤＩＣ社製のメガファックＲＳ−１０１、ＲＳ−１０２、ＲＳ−７１８Ｋ、ＲＳ−７２−Ｋ等が挙げられる。なお、エチレン性不飽和基を側鎖に有する含フッ素重合体は、界面活性剤に該当し、上述した架橋性基を有する樹脂および架橋性化合物とは異なる成分である。
フッ素系界面活性剤は、特開２０１５−１１７３２７号公報の段落００１５〜０１５８に記載の化合物を用いることもできる。 The fluorine content of the fluorosurfactant is preferably 3 to 40% by mass. The lower limit is preferably 5% by mass or more, and more preferably 7% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less. When the fluorine content is within the above-described range, it is effective in terms of uniformity of coating film thickness and liquid-saving properties, and good solubility.
Specific examples of the fluorosurfactant include the surfactants described in paragraphs 0060 to 0064 of JP 2014-41318 A (paragraphs 0060 to 0064 of the corresponding international publication WO 2014/17669 pamphlet) and the like. These contents are incorporated herein. Commercially available fluorosurfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, R30, F-437, F-475, F-479, F-482, F-554, F-780 (above, manufactured by DIC Corporation) , FLORARD FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC -381, SC-383, S393, KH-40 (manufactured by Asahi Glass Co., Ltd.) and the like.
A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A No. 2011-89090. The following compounds are also exemplified as the fluorosurfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
Moreover, the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant. Specific examples include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and 0289 to 0295, such as Megafac RS-101, RS-102, RS-718K, and RS-72- manufactured by DIC. K etc. are mentioned. The fluorine-containing polymer having an ethylenically unsaturated group in the side chain corresponds to a surfactant and is a component different from the above-described resin having a crosslinkable group and a crosslinkable compound.
As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used.

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.
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.

<< Polymerization inhibitor >>
The composition of the present invention may contain a polymerization inhibitor. As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like can be mentioned, and p-methoxyphenol is preferred. As for content of a polymerization inhibitor, 0.01-5 mass% is preferable with respect to the total solid of a composition.

<< UV absorber >>
The composition of the present invention may contain an ultraviolet absorber. A well-known compound can be used for a ultraviolet absorber. As a commercial item, UV503 (Daito Chemical Co., Ltd.) etc. are mentioned, for example. The content of the ultraviolet absorber is preferably 0.01 to 10% by mass and more preferably 0.01 to 5% by mass with respect to the total solid content of the composition.

(Antioxidant)
The composition of the present invention may contain an antioxidant. Examples of the antioxidant include a phenol compound, a phosphite compound, and a thioether compound. A phenol compound having a molecular weight of 500 or more, a phosphite compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is more preferable. You may use these in mixture of 2 or more types. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferable phenolic compounds include hindered phenolic compounds. In particular, a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable, methyl group, ethyl group, propionyl group, isopropionyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl. Group, t-pentyl group, hexyl group, octyl group, isooctyl group and 2-ethylhexyl group are more preferable. A compound (antioxidant) having a phenol group and a phosphite group in the same molecule is also preferred.

  Moreover, phosphorus antioxidant can also be used suitably for antioxidant. As the phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl And at least one compound selected from the group consisting of) oxy] ethyl] amine and ethylbisbis (2,4-ditert-butyl-6-methylphenyl) phosphite.

  These are easily available as commercial products, and are ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G and ADK STAB AO. -80, ADK STAB AO-330 (Adeka Co., Ltd.) and the like.

  It is preferable that content of antioxidant is 0.01-20 mass% with respect to the total solid of a composition, and it is more preferable that it is 0.3-15 mass%. Only one type of antioxidant may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.

<< other ingredients >>
The composition of the present invention includes, for example, a dispersant, a sensitizer, a curing accelerator, a filler, a plasticizer, an adhesion promoter, and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants). , A leveling agent, a peeling accelerator, an antioxidant, a fragrance, a surface tension adjusting agent, a chain transfer agent and the like. These components include, for example, paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding US Patent Application Publication No. 2013/0034812 [0237] to [0309]), JP2008-250074A. Paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, paragraph numbers 0159 to 0184 of JP 2013-195480 A, and the like can be referred to, and the contents thereof are incorporated in the present specification. .

<Method for producing composition>
In the composition of the present invention, an infrared absorber, a solvent, and other components as necessary are mixed to prepare a composition A. The amount of dissolved oxygen in a liquid at 25 ° C. at 0.1 MPa is adjusted to 0. It can be manufactured by adjusting to 1 to 50 mg / L. In the production of the composition, the respective components may be blended together, or may be blended sequentially after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending.
As a method of adjusting the dissolved oxygen amount of the composition to the above-mentioned range, for example, when the dissolved oxygen amount of the composition is too small, the composition is aerated by a method such as aeration of a gas such as oxygen or air to the composition. The method of adjusting the dissolved oxygen amount of a thing to the above-mentioned range is mentioned. Moreover, when there is too much dissolved oxygen amount of a composition, the method of performing a deaeration process and adjusting the dissolved oxygen amount of a composition is mentioned. Examples of the deaeration treatment include ultrasonic irradiation and deaeration by reduced pressure. The method of performing deaeration by decompression under the pressure of 0.001-0.01 Pa and the temperature of 0-50 degreeC for 1 to 10 minutes is mentioned.

In preparing the composition, it is preferable to perform a filtration treatment for the purpose of removing foreign substances and reducing defects. The filtration treatment is preferably performed with a filter. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight) For example). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The filter has a pore diameter of about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of a uniform and smooth composition in a post process. Further, it is also preferable to use a fiber-like filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like. Specifically, SBP type series (SBP008 etc.), TPR type series (TPR002) manufactured by Loki Techno Co., Ltd. , TPR005, etc.) and SHPX type series (SHPX003 etc.) filter cartridges can be used.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, selected from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. can do.
As the second filter, a filter formed of the same material as the first filter described above can be used.

  When performing a filtration process, it is preferable to adjust the amount of dissolved oxygen to the above-mentioned range with respect to the composition after a filtration process. This is because the amount of dissolved oxygen may vary due to filter filtration.

It is preferable that the manufacturing method of the composition of this invention includes the process of carrying out the defoaming process of the above-mentioned composition A. According to this aspect, it is easy to adjust the dissolved oxygen amount of the composition to the above range.
The composition A includes two or more types of solvents, and the difference between the boiling point of the solvent having the highest boiling point and the boiling point of the solvent having the lowest boiling point of two or more types of solvents is 10 ° C. or more (preferably It is preferably 20 ° C. or higher, more preferably 50 ° C. or higher, particularly preferably 70 ° C. or higher. As a combination of the above organic solvents, for example, a solvent A having a boiling point of 100 ° C. or higher (preferably 120 ° C. or higher, more preferably 150 ° C. or higher) and a boiling point of 130 ° C. or lower (preferably 100 ° C. or lower, more preferably Is preferably selected from the solvent A and the solvent B so that the difference in boiling point is 10 ° C. or more. About the solvent A and the solvent B, what was demonstrated by the organic solvent mentioned above is mentioned. According to this aspect, when the composition A is defoamed, the gas and oxygen dissolved in the composition A are easily defoamed, and the dissolved oxygen amount of the composition is adjusted to the range specified in the present invention. It's easy to do.

<Membrane, near-infrared cut filter>
Next, the film of the present invention will be described. The film of the present invention is formed using the above-described composition of the present invention. Since the film | membrane of this invention is excellent in infrared shielding property and visible transparency, it can be preferably used as an infrared cut filter. That is, the composition of the present invention is also a near-infrared absorbing composition. The composition of the present invention can be suitably used as a composition for a near infrared cut filter. The film of the present invention may have a pattern, or may be a film without a pattern (flat film).
Moreover, the near-infrared cut filter of this invention uses the composition of this invention mentioned above.

  In the near-infrared cut filter of the present invention, the light transmittance in the entire range of wavelengths from 400 to 550 nm is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. preferable. The higher the transmittance in the visible region, the better, and it is preferable that the transmittance is high at a wavelength of 400 to 550 nm. Further, the light transmittance at at least one point in the wavelength range of 700 to 800 nm is preferably 20% or less, and the light transmittance in the entire range of wavelength 700 to 800 nm is more preferably 20% or less. .

  The film thickness of the near-infrared cut filter of this invention can be suitably selected according to the objective. For example, 500 μm or less is preferable, 300 μm or less is more preferable, 250 μm or less is further preferable, and 200 μm or less is particularly preferable. The lower limit of the film thickness is, for example, preferably 0.1 μm or more, more preferably 0.2 μm or more, and more preferably 0.5 μm or more.

  The near-infrared cut filter of the present invention may further have an ultraviolet / infrared light reflecting film or an ultraviolet absorbing layer. By having the ultraviolet / infrared light reflecting film, an effect of improving the incident angle dependency can be obtained. As the ultraviolet / infrared light reflecting film, for example, the reflecting layers described in paragraphs 0033 to 0039 of JP2013-68688A and paragraphs 0110 to 0114 of WO2015 / 099060 can be referred to. Incorporated in the description. By having an ultraviolet absorbing layer, a near infrared cut filter excellent in ultraviolet shielding properties can be obtained. As the ultraviolet absorbing layer, for example, the absorbing layer described in paragraphs 0040 to 0070 and 0119 to 0145 of WO2015 / 099060 can be referred to, and the contents thereof are incorporated in the present specification.

  The near-infrared cut filter of the present invention has a function of absorbing / cutting near-infrared rays (a lens for a camera such as a digital camera, a mobile phone, or an in-vehicle camera, an optical lens such as an f-θ lens, a pickup lens) and a semiconductor light receiving device. Optical filters for elements, near-infrared absorbing films and near-infrared absorbing plates that block heat rays for energy saving, agricultural coating agents for selective use of sunlight, recording media that use near-infrared absorbing heat, Used for electronic devices and photographic near infrared filters, protective glasses, sunglasses, heat ray blocking films, optical character reading and 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.

<Method for manufacturing near-infrared cut filter>
The near-infrared cut filter of the present invention can be produced using the composition of the present invention. Specifically, the composition of the present invention can be produced through a step of forming a composition layer by applying it to a support, a step of drying the composition layer, and / or a step of curing the composition layer. Further, a step of forming a pattern may be performed. About a film thickness, laminated structure, etc., it can select suitably according to the objective.

The step of forming the composition layer is carried out by, for example, using the composition of the present invention on the support by a dropping method (drop casting), a spin coater, a slit spin coater, a slit coater, screen printing, applicator application, etc. it can. In the case of the dropping method (drop casting), it is preferable to form a dropping region of a composition having a photoresist as a partition on the support so that a uniform film can be obtained with a predetermined film thickness. A desired film thickness can be obtained by adjusting the dropping amount and solid content concentration of the composition and the area of the dropping region. There is no restriction | limiting in particular as thickness of the film | membrane after drying, According to the objective, it can select suitably.
The support may be a transparent substrate such as glass. Moreover, a solid-state image sensor may be sufficient. Moreover, another board | substrate provided in the light-receiving side of the solid-state image sensor may be sufficient. Further, it may be a layer such as a flattening layer provided on the light receiving side of the solid-state imaging device.

  In the step of drying the composition layer, the drying conditions vary depending on each component, the type of solvent, the use ratio, and the like. For example, the temperature is preferably 80 ° C. to 200 ° C. and 30 seconds to 15 minutes.

In the step of curing the composition layer, the curing method of the composition layer is not particularly limited and can be appropriately selected according to the purpose. For example, a full exposure process, a full heat treatment, and the like are preferable. 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. Examples of the exposure method include stepper exposure and exposure with a high-pressure mercury lamp. Exposure is preferably 5~3000mJ / cm ^2, and more preferably ^{10~2000mJ / cm 2, 50~1000mJ / cm} 2 is particularly preferred. Examples of the entire surface exposure processing method include a method of exposing the entire surface of the composition layer. The entire surface exposure promotes curing of the cross-linking component in the film, further curing the film, and improves the solvent resistance and heat resistance of the film. 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, ultraviolet exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably. Moreover, as a method of the whole surface heat treatment, a method of heating the entire surface of the composition layer can be mentioned. Whole surface heating improves the solvent resistance and heat resistance of the film.
The heating temperature in the entire surface heating is preferably 120 ° C to 250 ° C, and more preferably 160 ° C to 220 ° C. When the heating temperature is 120 ° C. or higher, the film strength is improved by the heat treatment, and when the heating temperature is 250 ° C. or lower, the decomposition of the film components can be suppressed. The heating time in the entire surface heating is preferably 3 minutes to 180 minutes, and more preferably 5 minutes to 120 minutes. There is no restriction | limiting in particular as an apparatus which performs whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, an infrared (IR) heater etc. are mentioned.

  In the step of curing the composition layer, pre-baking (preheating) may be performed before the curing treatment. The heating temperature is preferably 80 ° C to 200 ° C, more preferably 90 ° C to 150 ° C. The heating time is preferably 30 to 240 seconds, more preferably 60 to 180 seconds.

  In the step of curing the composition layer, post-baking (post-heating) may be further performed after performing the curing treatment. The post-heating is a heat treatment for completing the curing of the film after the curing treatment. The heating temperature is preferably 100 to 240 ° C. From the viewpoint of film curing, 200 to 230 ° C. is more preferable. The heating time is preferably 30 to 1000 seconds, and more preferably 60 to 500 seconds.

  In the pattern forming step, examples of the pattern forming method include pattern formation by a photolithography method and patterns by a dry etching method.

<Solid-state imaging device, camera module>
The solid-state imaging device of the present invention includes the near-infrared cut filter of the present invention. The camera module of the present invention includes the near-infrared cut filter of the present invention.

FIG. 1 is a schematic cross-sectional view showing the configuration of a camera module having a near-infrared cut filter according to an embodiment of the present invention.
A camera module 10 illustrated in FIG. 1 includes a solid-state image sensor 11, a planarization layer 12 provided on the main surface side (light-receiving side) of the solid-state image sensor, a near-infrared cut filter 13, and a near-infrared cut filter. And a lens holder 15 having an imaging lens 14 in the internal space. In the camera module 10, incident light hν from the outside passes through the imaging lens 14, the near-infrared cut filter 13, and the planarization layer 12 in order, and then reaches the imaging device portion of the solid-state imaging device 11.

  The solid-state imaging device 11 includes, for example, a photodiode, an interlayer insulating film (not shown), a base layer (not shown), a color filter 17, an overcoat (not shown), and a microlens 18 on the main surface of the substrate 16. Are provided in this order. The color filter 17 (red color filter, green color filter, blue color filter) and the microlens 18 are respectively disposed so as to correspond to the solid-state imaging device 11. Instead of providing the near-infrared cut filter 13 on the surface of the planarizing layer 12, the surface of the microlens 18, between the base layer and the color filter 17, or between the color filter 17 and the overcoat The form in which the infrared cut filter 13 is provided may be sufficient. For example, the near-infrared cut filter 13 may be provided at a position within 2 mm (more preferably within 1 mm) from the surface of the microlens. 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 shielding property can be further improved.

Since the near-infrared cut filter of this invention is excellent in heat resistance, it can use for 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 used in the solder reflow process, the near-infrared cut filter is exposed to a temperature of about 250 to 270 ° C. Therefore, the near-infrared cut filter is also referred to as heat resistance that can withstand the solder reflow process (hereinafter also referred to as “solder reflow resistance”). ). In the present specification, “having solder reflow resistance” refers to retaining characteristics as a near-infrared cut filter before and after heating at 180 ° C. for 1 minute. 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 shielding property of the near-infrared cut filter may be deteriorated or the function as a film may be insufficient when held under the above conditions.
The camera module of the present invention can further have an ultraviolet absorbing layer. According to this aspect, the ultraviolet shielding property can be enhanced. For example, the description of paragraphs 0040 to 0070 and 0119 to 0145 of WO2015 / 090960 can be referred to for the ultraviolet absorbing layer, and the contents thereof are incorporated herein. Further, it can further have an ultraviolet / infrared light reflection film described later. The ultraviolet absorbing layer and the ultraviolet / infrared light reflecting film may be used in combination, or only one of them.

  2 to 4 are schematic cross-sectional views showing an example of the vicinity of the near-infrared cut filter in the camera module.

  As shown in FIG. 2, the camera module includes a solid-state imaging device 11, a planarization layer 12, an ultraviolet / infrared light reflection film 19, a transparent base material 20, and a near infrared absorption layer (near infrared cut filter) 21. And an antireflection layer 22 in this order. The ultraviolet / infrared light reflection film 19 has an effect of imparting or enhancing the function of a near-infrared cut filter. For example, paragraphs 0033 to 0039 of JP2013-68688A, paragraphs 0110 to 0114 of WO2015 / 099060 This content is incorporated herein by reference. The transparent substrate 20 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 in the present specification. The near-infrared absorbing layer 21 can be formed by applying the above-described composition of the present invention. The antireflection layer 22 has a function of improving the transmittance by preventing reflection of light incident on the near-infrared cut filter and efficiently using incident light. For example, JP 2013-68688 A Paragraph 0040, which is incorporated herein by reference.

  As shown in FIG. 3, the camera module includes a solid-state imaging device 11, a near infrared absorption layer (near infrared cut filter) 21, an antireflection layer 22, a planarization layer 12, an antireflection layer 22, and a transparent substrate. The material 20 and the ultraviolet / infrared light reflection film 19 may be provided in this order.

  As shown in FIG. 4, the camera module includes a solid-state imaging device 11, a near infrared absorption layer (near infrared cut filter) 21, an ultraviolet / infrared light reflection film 19, a planarization layer 12, and an antireflection layer 22. And you may have the transparent base material 20 and the reflection preventing layer 22 in this order.

<Image display device>
The image display device of the present invention has the near infrared cut filter of the present invention. The near-infrared cut filter of the present invention can also be used for image display devices such as liquid crystal display devices and organic electroluminescence (organic EL) display devices. For example, when used with each colored pixel (for example, red, green, blue), the infrared light contained in the backlight of the display device (for example, white light emitting diode (white LED)) is blocked, and malfunction of peripheral devices is prevented. It can be used for the purpose of forming an infrared pixel in addition to each colored display pixel.

  For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

  The image display device may have a white organic EL element. The white organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, Japanese Patent Application Laid-Open No. 2003-45676, supervised by Akiyoshi Mikami, “The Forefront of Organic EL Technology Development-High Brightness, High Accuracy, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc. The spectrum of white light emitted from the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm) and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable.

  The 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. Unless otherwise specified, “%” and “parts” are based on mass. Hereinafter, propylene glycol monomethyl ether acetate is referred to as PGMEA. NMR is an abbreviation for nuclear magnetic resonance.

<Measurement of weight average molecular weight (Mw)>
The weight average molecular weight (Mw) was measured by the following method.
Column type: TSKgel Sup
er AWM-H (manufactured by Tosoh Corporation, 6.0 mm (inner diameter) x 15.0 cm)
Developing solvent: 10 mmol / L Lithium bromide NMP (N-methylpyrrolidinone) solution Column temperature: 40 ° C.
Flow rate (sample injection volume): 10 μL
Device name: HLC-8220 (manufactured by Tosoh Corporation)
Calibration curve base resin: polystyrene

<Measurement method of viscosity>
The viscosity of the composition at 25 ° C. was measured using a B-type viscometer.

樹脂１：下記構造（Ｍｗ＝１．５万、主鎖に付記した数値は、各構成単位のモル比である）

<Method for preparing composition>
(Composition 1)
45 parts by mass of copper complex 1 shown below, 49.95 parts by mass of resin 1 shown below, 5 parts by mass of IRGACURE-OXE02 (manufactured by BASF), and tris (2,4-pentanedionato) aluminum (III) After mixing 0.05 parts by weight (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 parts by weight of cyclohexanone and stirring, a nylon filter having a pore diameter of 0.45 μm (manufactured by Nippon Pole Co., Ltd.) ) To prepare composition 1. The viscosity of this composition at 25 ° C. was 150 mP · s.
Copper complex 1: the following structure

Resin 1: The following structure (Mw = 15,000, the numerical value attached to the main chain is the molar ratio of each structural unit)

(Composition 2)
A composition 2 was prepared in the same manner as the composition 1 except that the same amount of the copper complex 2 was used instead of the copper complex 1. The viscosity of this composition at 25 ° C. was 150 mP · s.
Copper complex 2: the following structure

(Composition 3)
A composition 3 was prepared in the same manner as the composition 1 except that the same amount of the copper complex 3 was used instead of the copper complex 1. The viscosity of this composition at 25 ° C. was 150 mP · s.
Copper complex 3: the following structure

(Composition 4)
A composition 4 was prepared in the same manner as the composition 1 except that the same amount of the copper complex 4 was used instead of the copper complex 1. The viscosity of this composition at 25 ° C. was 150 mP · s.
Copper complex 4: A copper complex having the following compound as a ligand.

(Composition 5)
A composition 5 was prepared in the same manner as the composition 1 except that the same amount of the copper complex 5 was used instead of the copper complex 1. The viscosity of this composition at 25 ° C. was 150 mP · s.
Copper complex 5: A copper complex having the following compound as a ligand.

(Composition 6)
To the eggplant flask, 7.00 g (35.06 mmol) of copper acetate monohydrate and 140 g of methanol were added and stirred at 20 ° C. for 1 hour to obtain a solution (solution A). In a separate container, 1.75 g of PRISURF A219B (Daiichi Kogyo Seiyaku Co., Ltd.) and 4.82 g of n-butylphosphonic acid were dissolved in 100 g of methanol to obtain a solution (liquid B). B liquid was dripped over 3 hours with respect to A liquid. The reaction was stirred at 20 ° C. for 10 hours. Thereafter, the solvent was distilled off from the reaction solution with an evaporator (water bath 60 ° C.). 100 g of toluene was added to the solid content from which the solvent had been distilled off, and the solvent was distilled off with an evaporator until a constant weight was obtained and the acetic acid odor disappeared. A blue-green solid with a yield of 8.75 g (100% yield) was obtained. To this was added 211 g of toluene, and ultrasonic irradiation was performed for 6 hours to obtain an n-butylphosphonic acid copper salt toluene dispersion (1).
Next, 1.90 g of triethylene glycol bis (2-ethylhexanoate), 250 ml of toluene, and 5.00 g of polyvinyl butyral (PVB) were added to the flask. A solution prepared by dissolving 4.8 mg of meso-erythritol in 1 ml of methanol was added thereto. To this, 3.65 g of the above n-butylphosphonic acid copper salt toluene dispersion (1) (containing 0.583 mmol of copper salt) was added, stirred at 20 ° C. for 10 hours, and then subjected to ultrasonic irradiation for 1.5 hours. Was uniformly dissolved to obtain a composition 6.

(Composition 7)
8.04 parts by mass of the resin 2 shown below, 0.1 parts by mass of the compound SQ-23 shown below, and 0.07 parts by mass of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a crosslinkable compound And 0.265 parts by mass of MegaFac RS-72K (manufactured by DIC Corporation), 0.38 parts by mass of the following compound as a photopolymerization initiator, and 82.51 parts by mass of PGMEA as a solvent. After stirring, the mixture was filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 0.45 μm to prepare composition 7. The viscosity of this composition at 25 ° C. was 4 mP · s.

化合物ＳＱ−２３：下記構造

光重合開始剤：下記構造

Resin 2: the following compound (Mw: 41000, the numerical value attached to the main chain is the molar ratio of each structural unit)

Compound SQ-23: The following structure

Photopolymerization initiator: Structure below

(Composition 8)
A composition 8 was prepared in the same manner as the composition 7, except that the same amount of the following compound A-52 was used instead of the compound SQ-23. The viscosity of this composition at 25 ° C. was 4 mP · s.
Compound A-52: The following structure

(Composition 9)
0.5 parts by mass of the following compound C-15 is dissolved in 69.5 parts by mass of ion-exchanged water, 30.0 parts by mass of a 10% by mass aqueous solution of gelatin is further added, and 1,3-divinylsulfonyl- A composition 9 was prepared by adding 0.3 parts by mass of 2-propanol and stirring. The viscosity of this composition at 25 ° C. was 10 mP · s.
Compound C-15: following structure

(Composition 10)
A composition 10 was prepared in the same manner as the composition 9 except that the same amount of the following compound 31 was used instead of the compound C-15. The viscosity of this composition at 25 ° C. was 10 mP · s.
Compound 31: Structure shown below

(Composition 11)
A composition 11 was prepared in the same manner as the composition 7 except that the same amount of Acryl-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) was used instead of the resin 2. The viscosity of this composition at 25 ° C. was 4 mP · s.

(Composition 12)
A composition 12 was prepared in the same manner as the composition 1 except that the same amount of Acryl-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) was used instead of the resin 1. The viscosity of this composition at 25 ° C. was 4 mP · s.

(Composition 13)
In composition 5, composition 13 was prepared in the same manner as composition 5 except that filter filtration was not performed. The viscosity of this composition at 25 ° C. was 150 mP · s.

(Composition 14)
In composition 1, composition 14 was prepared in the same manner as composition 1, except that 5 parts by mass of methanol was added. The viscosity of this composition at 25 ° C. was 145 mP · s.

(Composition 15)
A composition 15 was prepared in the same manner as the composition 1 except that the composition 1 was changed to 66.6 parts by mass of cyclohexanone. The viscosity of this composition at 25 ° C. was 300 mP · s.

(Composition 16)
In composition 7, composition 16 was prepared in the same manner as composition 7, except that PGMEA was changed to 13 parts by mass. The viscosity of this composition at 25 ° C. was 16 mP · s.

(Composition 17)
A composition 17 was prepared in the same manner as the composition 16 except that the same amount of the compound A-52 was used instead of the compound SQ-23. The viscosity of this composition at 25 ° C. was 16 mP · s.

(Composition 18)
A composition 18 was prepared in the same manner as the composition 16 except that the same amount of Acryl-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) was used instead of the resin 2. The viscosity of this composition at 25 ° C. was 16 mP · s.

<Method for adjusting the amount of dissolved oxygen>
(Adjustment method 1)
With respect to the prepared composition, oxygen was bubbled at a rate of 0.5 L / min at room temperature (25 ° C.) and 1 atmosphere (0.1 MPa) to adjust the dissolved oxygen amount described in the following table. In addition, the amount of dissolved oxygen described in the following table is a value in a liquid at 25 ° C. at 0.1 MPa. The amount of dissolved oxygen was calculated from the ratio of the oxygen partial pressure with the saturated dissolved oxygen solution using an Orbis Fair 510 gas analyzer (manufactured by Hack Ultra Co., Ltd.).

(Adjustment method 2)
The adjusted composition was decompressed to 0.1 atm (0.01 MPa) with an aspirator, and adjusted to the dissolved oxygen amount described in the following table.

(Adjustment method 3)
The adjusted composition was adjusted to the dissolved oxygen amount described in the following table by irradiating with ultrasonic waves at 25 ° C.

<Manufacture of near-infrared cut filter>
(Manufacture example 1) The manufacturing method of the near-infrared cut filter which uses composition 1-7, 12-15 The film thickness after drying each composition which adjusted dissolved oxygen amount to the following table | surface to 100 micrometers It was applied using a spin coater and heat-treated for 1.5 hours using a 160 ° C. hot plate to produce a near infrared cut filter.

<Manufacture of near-infrared cut filter>
(Manufacture example 2) The manufacturing method of the near-infrared cut filter which uses composition 8-11, 16-18 Forming a coating film by apply | coating each composition which adjusted dissolved oxygen amount to the following table | surface using a spin coater Then, after preheating (prebaking) at 100 ° C. for 120 seconds, the entire surface was exposed at 1000 mJ / cm ² using an i-line stepper. Subsequently, post heating (post-baking) was performed at 220 ° C. for 300 seconds to produce a near-infrared cut filter having a film thickness of 0.8 μm.

<Evaluation of defects>
The range of 7.5 × 7.5 cm of the near infrared cut filter was observed with a magnifying glass (magnification 15 times), and the presence or absence of bubbles was evaluated. The case where no bubbles were observed was A, the case where there were 1 to 3 bubbles was B, and the case where there were 4 or more bubbles was C.

<Evaluation of liquid stability>
Each composition adjusted to the dissolved oxygen amount described in the following table was heated at 45 ° C. for 3 days, and the liquid stability was evaluated by the ratio of the viscosity before heating and after heating. The case where the viscosity variation is less than 1% is A, the case where the viscosity variation is 1% or more and less than 5% is B, and the case where the viscosity variation is 5% or more is C.

  From the above results, the examples were excellent in liquid stability. Moreover, the near-infrared cut filter of an Example had few defects. On the other hand, the near-infrared cut filter of the comparative example had many defects.

DESCRIPTION OF SYMBOLS 10 Camera module, 11 Solid-state image sensor, 12 Flattening layer, 13 Near-infrared cut filter, 14 Imaging lens, 15 Lens holder, 16 Silicon substrate, 17 Color filter, 18 Micro lens, 19 Ultraviolet / infrared light reflection film, 20 Transparent substrate, 21 Near infrared absorbing layer, 22 Antireflection layer

Claims (17)

A composition comprising an infrared absorber and a solvent,
The composition whose dissolved oxygen amount in a 25 degreeC liquid in 0.1 Mpa is 0.1-50 mg / L.   The composition according to claim 1, wherein the amount of dissolved gas in a liquid at 25 ° C at 0.1 MPa is 0.1 to 50 mg / L.   The composition of Claim 1 or 2 whose said infrared absorber is a copper compound.   The composition of any one of Claims 1-3 whose solid content concentration is 40 mass% or more.   The composition according to any one of claims 1 to 4, wherein the viscosity at 25 ° C is 0.05 to 10 Pa · s.   Furthermore, the composition of any one of Claims 1-5 containing the compound which has a crosslinkable group. The composition according to claim 6, wherein the compound having a crosslinkable group includes a compound having a partial structure represented by MX, wherein M is an atom selected from Si, Ti, Zr and Al X is one selected from a hydroxy group, an alkoxy group, an acyloxy group, a phosphoryloxy group, a sulfonyloxy group, an amino group, an oxime group, and O = C (R ^a ) (R ^b ), ^a and R ^b each independently represent a monovalent organic group, and when X is O═C (R ^a ) (R ^b ), it binds to M through an unshared electron pair of the oxygen atom of the carbonyl group. .   The composition of Claim 6 or 7 whose content of the compound which has the said crosslinkable group is 15 mass% or more of the total solid of the said composition. A method for producing the composition according to any one of claims 1 to 8,
The manufacturing method of a composition including the process of carrying out the defoaming process of the composition A containing an infrared absorber and a solvent.   The composition A includes two or more types of solvents, and the difference between the boiling point of the solvent having the highest boiling point and the boiling point of the solvent having the lowest boiling point of two or more types of solvents is 10 ° C or more. A method for producing the composition according to claim 9.   The method for producing a composition according to claim 9 or 10, wherein the defoaming treatment is performed by at least one method selected from ultrasonic irradiation and reduced pressure.   The manufacturing method of the composition of any one of Claims 9-11 which performs the said defoaming process after filtering the said composition A.   The film | membrane formed using the composition of any one of Claims 1-8.   The near-infrared cut filter which uses the composition of any one of Claims 1-8.   A solid-state imaging device having the near-infrared cut filter according to claim 14.   A camera module comprising the near-infrared cut filter according to claim 14.   An image display device comprising the near-infrared cut filter according to claim 14.

Images