WO2018168231A1

WO2018168231A1 - Near-infrared blocking filter, method for producing near-infrared blocking filter, solid-state imaging element, camera module and image display device

Info

Publication number: WO2018168231A1
Application number: PCT/JP2018/003126
Authority: WO
Inventors: 昂広大河原; 敬史川島; 博昭津山
Original assignee: 富士フイルム株式会社
Priority date: 2017-03-14
Filing date: 2018-01-31
Publication date: 2018-09-20
Also published as: TW201840683A; JPWO2018168231A1

Abstract

Provide is a near-infrared blocking filter which has excellent heat resistance. Also provided are: a method for producing a near-infrared blocking filter; a solid-state imaging element; a camera module; and an image display device. This near-infrared blocking filter comprises a resin film that contains a resin and a specific copper complex; the total amount of the copper complex and the resin in the resin film is 60-100% by mass; and the resin does not form a three-dimensional crosslinked structure in the resin film.

Description

Near-infrared cut filter, method for manufacturing near-infrared cut filter, solid-state imaging device, camera module, and image display device

The present invention relates to a near infrared cut filter. More specifically, the present invention relates to a near infrared cut filter containing a copper complex. The present invention also relates to a method for manufacturing a near-infrared cut filter, a solid-state imaging device, a camera module, and an image display device.

Video cameras, digital still cameras, mobile phones with camera functions, etc. use charge coupled devices (CCD), complementary metal oxide semiconductors (CMOS), etc., which are solid-state imaging devices for color images. Since these solid-state imaging devices use silicon photodiodes having sensitivity to near infrared rays in their light receiving portions, it is necessary to perform visibility correction and often use near-infrared cut filters.

For example, Patent Document 1 discloses a light selective transmission filter including a resin sheet, the resin sheet has a resin layer including a dye and a resin component, and the dye has a nonionic conjugated skeleton. And a light selective transmission filter which is a compound having an absorption maximum wavelength in the wavelength region of 600 to 800 nm and having at least one absorption maximum wavelength in the range of 600 to 710 nm. In Patent Document 1, a phthalocyanine dye is used as the dye.

Patent Document 2 describes that a near-infrared cut filter is produced using a near-infrared absorbing composition containing a copper complex.

JP 2013-257532 A JP 2016-006476 A

According to the study of the present inventor, it was found that the light selective transmission filter described in Patent Document 1 has insufficient visible transparency and infrared shielding properties.

On the other hand, near-infrared cut filters formed using a near-infrared absorbing composition containing a copper complex are excellent in visible transparency and infrared shielding properties, but are required to further improve heat resistance.

An object of the present invention is to provide a near-infrared cut filter excellent in heat resistance. Moreover, the objective of this invention is providing the manufacturing method of a near-infrared cut filter, a solid-state image sensor, a camera module, and an image display apparatus.

As a result of intensive studies on the near-infrared cut filter having a resin film containing a copper complex and a resin by the present inventor, a copper complex and a cross-linking component (for example, a resin containing a cross-linkable group) are used for such a resin film. When it formed using the composition containing, it discovered that it exists in the tendency for heat resistance to fall easily. Further investigation was made on the cause of the heat resistance of the resin film formed using such a composition easily decreasing. As a result, by-products generated during the reaction of the crosslinking component interacted with the copper complex, It was thought that the unreacted cross-linking component remaining in the metal interacts with the copper complex to reduce the heat resistance of the copper complex. When a resin film containing a copper complex is formed using a resin that does not contain a crosslinkable group as a resin, such a resin film is less likely to be colored even after heating, and has excellent visible transparency and infrared shielding properties. As a result, the present invention has been completed. The present invention provides the following.
<1> A near-infrared cut filter having a resin film containing a copper complex and a resin,
The copper complex is a compound represented by the following formula (1),
The total amount of copper complex and resin in the resin film is 60 to 100% by mass,
A near-infrared cut filter in which the resin does not form a three-dimensional bridge in the resin film;
Cu · (L) _n1 · (X) _n2 (1)
In the formula, L is a ligand, and at least one selected from a coordination site coordinated by an anion to a copper atom and a coordination atom coordinated by a lone pair to the copper atom. A compound having one or more, X is a counter ion, n1 represents an integer of 1 to 4, and n2 represents an integer of 0 to 4.
<2> The near-infrared cut filter according to <1>, wherein the ligand L in the formula (1) is a compound having no maximum absorption wavelength in the wavelength range of 400 to 600 nm.
<3> At least one selected from a coordination site in which the ligand L in Formula (1) coordinates with an anion with respect to a copper atom and a coordination atom with an unshared electron pair with respect to the copper atom. The near-infrared cut filter according to <1> or <2>, which is a compound having 2 or more in total.
<4> The near-infrared cut filter according to <1> or <2>, wherein the ligand L in the formula (1) is at least one selected from a carboxylic acid compound, a sulfonic acid compound, and a phosphate ester compound.
<5> The near infrared cut filter according to any one of <1> to <4>, wherein the resin film has a thickness of 1 to 500 μm.
<6> The near-infrared cut filter according to any one of <1> to <5>, wherein the resin film contains 5% by mass or more of a copper complex.
<7> A method for producing a near-infrared cut filter including a step of applying a resin composition containing a copper complex and a resin on a support and drying to form a resin film,
The copper complex is a compound represented by the following formula (1),
The resin is a resin substantially free of crosslinkable groups,
A method for producing a near-infrared cut filter, wherein the total amount of the copper complex and the resin in the resin composition is 60 to 100% by mass relative to the total solid content of the resin composition;
Cu · (L) _n1 · (X) _n2 (1)
In the formula, L is a ligand, and at least one selected from a coordination site coordinated by an anion to a copper atom and a coordination atom coordinated by a lone pair to the copper atom. A compound having one or more, X is a counter ion, n1 represents an integer of 1 to 4, and n2 represents an integer of 0 to 4.
<8> A solid-state imaging device having the near-infrared cut filter according to any one of <1> to <6>.
<9> A camera module having the near-infrared cut filter according to any one of <1> to <6>.
<10> An image display device having the near infrared cut filter according to any one of <1> to <6>.

According to the present invention, a near-infrared cut filter having excellent heat resistance can be provided. Moreover, the manufacturing method of the near-infrared cut filter excellent in heat resistance can be provided. Moreover, the solid-state image sensor, camera module, and image display apparatus which have the near-infrared cut filter excellent in heat resistance can be provided.

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. 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.

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 present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) allyl” represents allyl and methallyl, “(meth) acryl” represents acryl and methacryl, “(meth) ) "Acryloyl" represents acryloyl and methacryloyl.
In the notation of group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes group (atomic group) which has a substituent with the group (atomic group) which does not have a substituent.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, near-infrared light refers to light (electromagnetic wave) having a wavelength of 700 to 2500 nm.
In this specification, the total solid content refers to the total mass of components obtained by removing the solvent from all components of the composition.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by a gel permeation chromatography (GPC) measurement.

<Near-infrared cut filter>
The near infrared cut filter of the present invention is a near infrared cut filter having a resin film containing a copper complex and a resin,
The copper complex is a compound represented by the formula (1) described below,
The total amount of copper complex and resin in the resin film is 60 to 100% by mass,
The resin is characterized in that the resin does not form a three-dimensional crosslink in the resin film.

The near-infrared cut filter of the present invention has excellent heat resistance, is hardly colored even after heating, and has excellent visible transparency and infrared shielding properties.

In the near-infrared cut filter of the present invention, the total amount of the copper complex and the resin in the resin film is 60 to 100% by mass, preferably 70 to 100% by mass, and preferably 80 to 100% by mass. More preferably, it is 90 to 100% by mass.

The content of the copper complex in the resin film is preferably 5% by mass or more, and more preferably 5 to 90% by mass. The lower limit is more preferably 10% by mass or more, further preferably 15% by mass or more, and still more preferably 20% by mass or more. The upper limit is more preferably 70% by mass or less, still more preferably 60% by mass or less, and still more preferably 50% by mass or less. Details of the copper complex will be described later. Especially, it is preferable that a copper complex has the compound which has 4 or 5 coordination site | parts with respect to copper as a ligand. According to this aspect, the visible transparency and the infrared shielding property of the near-infrared cut filter can be further improved. Moreover, it is preferable that a resin film contains 2 or more types of copper complexes. According to this aspect, a near-infrared cut filter having excellent infrared shielding properties can be obtained.

The content of copper atoms in the resin film is preferably 0.5% by mass or more, and more preferably 0.5 to 20% by mass. The lower limit is more preferably 1% by mass or more, further preferably 2% by mass or more, and still more preferably 3% by mass or more. The upper limit is more preferably 15% by mass or less, still more preferably 12% by mass or less, and still more preferably 10% by mass or less.

The resin content in the resin film is preferably 30 to 90% by mass. The lower limit is more preferably 35% by mass or more, still more preferably 40% by mass or more, and even more preferably 50% by mass or more. The upper limit is more preferably 85% by mass or less, still more preferably 80% by mass or less, and even more preferably 70% by mass or less.

In the near-infrared cut filter of the present invention, the resin film may contain a solvent as a component other than the copper complex and the resin. The solvent is preferably a compound that does not contain a crosslinkable group. Further, the content of the solvent in the resin film is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less.

In the near infrared cut filter of the present invention, the content of the compound containing a crosslinkable group in the resin film is preferably 1% by mass or less, more preferably 0.5% by mass or less, and the crosslinkable group It is particularly preferred that the compound containing is not substantially contained. Examples of the crosslinkable group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a styryl group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxysilyl group. That the resin film does not substantially contain a compound containing a crosslinkable group means that the content of the compound containing a crosslinkable group in the resin film is 0.1% by mass or less, and 0.05% by mass The following is preferable, and it is more preferable not to contain.

In the near-infrared cut filter of the present invention, the content of a cross-linked product derived from a monomer containing a crosslinkable group in the resin film is preferably 1% by mass or less, and more preferably 0.5% by mass or less. It is particularly preferable that the monomer-containing crosslinked product containing a crosslinkable group is substantially not contained. That the resin film does not substantially contain a cross-linked product derived from a monomer containing a crosslinkable group means that the content of the cross-linked product derived from a monomer containing a crosslinkable group in the resin film is 0.1% by mass or less. This means that it is preferably 0.05% by mass or less, and more preferably not contained.

In the near-infrared cut filter of the present invention, the average value of the transmittance of light irradiated from the direction perpendicular to the film surface of the near-infrared cut filter is preferably 20% or less in the wavelength range of 800 to 1000 nm. % Or less is more preferable, 10% or less is further preferable, and 5% or less is particularly preferable. In the near-infrared cut filter of the present invention, the transmittance of light irradiated from the direction perpendicular to the film surface of the near-infrared cut filter is preferably 20% or less over the entire wavelength range of 800 to 1000 nm. % Or less is more preferable, 10% or less is further preferable, and 5% or less is particularly preferable. According to this aspect, a near-infrared cut filter having excellent infrared shielding properties can be obtained.

In the near-infrared cut filter of the present invention, the average reflectance in the wavelength range of 800 to 1000 nm is preferably 20% or less, preferably 10% or less, and more preferably 5% or less. The near-infrared cut filter of the present invention has a reflectance of preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less over the entire wavelength range of 800 to 1000 nm. . According to this aspect, a near-infrared cut filter having a wide viewing angle and excellent infrared shielding properties can be obtained. The reflectance is a value measured using U-4100 (manufactured by Hitachi High-Technologies Corporation), setting the surface normal direction of the near-infrared cut filter to 0 °, and setting the incident angle to 5 °.

In the near-infrared cut filter of the present invention, it is preferable that the transmittance of light irradiated from the direction perpendicular to the film surface of the near-infrared cut filter satisfies at least one of the following conditions (1) to (9): It is more preferable to satisfy all the following conditions (1) to (8), and it is even more preferable to satisfy all the conditions (1) to (9).
(1) The transmittance of light having a wavelength of 400 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(2) The transmittance of light having a wavelength of 450 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(3) The transmittance of light having a wavelength of 500 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(4) The transmittance of light having a wavelength of 550 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(5) The transmittance of light having a wavelength of 700 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(6) The transmittance of light having a wavelength of 750 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(7) The transmittance of light having a wavelength of 800 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(8) The transmittance of light having a wavelength of 850 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(9) The transmittance of light having a wavelength of 900 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.

In the near-infrared cut filter of the present invention, the 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. The higher the transmittance in the visible region, the better.

In the near infrared cut filter, the thickness of the resin film can be appropriately selected according to the purpose. 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 even more preferable. For example, the lower limit of the thickness of the resin film is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.5 μm or more, and even more preferably 1 μm or more.

In the near-infrared cut filter of the present invention, the rate of change in absorbance at a wavelength of 450 nm represented by the following formula before and after heating at 200 ° C. for 1 minute is preferably 6% or less, and 4.5% or less. Is more preferable and 3% or less is particularly preferable. In addition, before and after heating at 200 ° C. for 1 minute, the average absorbance change rate in the range of wavelength 700 nm to less than 800 nm represented by the following formula is preferably 6% or less, and 4.5% or less. More preferably, it is particularly preferably 3% or less. Further, the change rate of the average absorbance in the wavelength range of 800 nm to 1100 nm represented by the following formula is preferably 6% or less, more preferably 4.5% or less, and more preferably 3% or less. Particularly preferred. If the rate of change in absorbance is within the above range, a near-infrared cut filter having excellent heat resistance and suppressed coloring due to heating can be obtained.
Rate of change in absorbance at wavelength 450 nm (%) = | (absorbance at wavelength 450 nm before heating−absorbance at wavelength 450 nm after heating) / absorbance at wavelength 450 nm before heating | × 100 (%)
Average absorbance change rate (%) in the wavelength range from 700 nm to less than 800 nm = | (average absorbance in the wavelength range from 700 nm to less than 800 nm before heating−average absorbance in the wavelength range from 700 nm to less than 800 nm after heating) / before heating Average absorbance in the wavelength range of 700 nm or more and less than 800 nm | × 100 (%)
Average absorbance change rate (%) in the wavelength range from 800 nm to 1100 nm = | (average absorbance in the wavelength range from 800 nm to 1100 nm before heating−average absorbance in the wavelength range from 800 nm to 1100 nm after heating) / before heating Average absorbance in the wavelength range of 800 nm to 1100 nm at | × 100 (%)

The near-infrared cut filter of the present invention may have a functional layer such as a dielectric multilayer film or an ultraviolet absorption layer in addition to the resin film described above. These functional layers may be formed on the resin film. When the near infrared cut filter further includes a dielectric multilayer film, a near infrared cut filter excellent in infrared shielding properties can be easily obtained. Moreover, it can be set as the near-infrared cut filter excellent in ultraviolet-shielding property because a near-infrared cut filter has an ultraviolet absorption layer further. As the ultraviolet absorbing layer, for example, the absorbing layer described in paragraph Nos. 0040 to 0070 and 0119 to 0145 of International Publication No. WO2015 / 099060 can be referred to, and the contents thereof are incorporated in the present specification. As the dielectric multilayer film, the description of paragraph numbers 0255 to 0259 of JP 2014-41318 A can be referred to, and the contents thereof are incorporated in the present specification.

The near-infrared cut filter of the present invention can be used for various devices such as a solid-state imaging device such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal Oxide Semiconductor), an infrared sensor, and an image display device.

<Resin composition>
Next, a resin composition that can be preferably used for forming a resin film in the near-infrared cut filter of the present invention will be described.

<< Copper Complex >>
The resin composition contains a compound represented by the following formula (1) as a copper complex.
_{Cu · (L) n1 · (} X) n2 ··· (1)
In the formula, L is a ligand, and at least one selected from a coordination site coordinated by an anion to a copper atom and a coordination atom coordinated by a lone pair to the copper atom. A compound having one or more, X is a counter ion, n1 represents an integer of 1 to 4, and n2 represents an integer of 0 to 4.

Examples of the compound represented by the formula (1) (copper complex) include tetracoordinate, pentacoordinate and hexacoordinate copper complexes, and tetracoordinate and pentacoordinate copper complexes are more preferred. More preferred is a copper complex at the position. The compound (copper complex) represented by the formula (1) preferably has a 5-membered ring and / or a 6-membered ring formed of copper and a ligand. Such a copper complex is stable in shape and excellent in complex stability.

In the formula (1), X represents a counter ion. The compound (copper complex) represented by the formula (1) may be 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 complex.
When the counter ion is a counter ion having a negative charge (counter anion), for example, an inorganic anion or an organic anion may be used. For example, as a counter ion, hydroxide ion, halogen anion (for example, fluoride ion, chloride ion, bromide ion, iodide ion, etc.), substituted or unsubstituted alkylcarboxylate ion (acetate ion, trifluoro ion) Acetate ion, etc.), substituted or unsubstituted aryl carboxylate ion (benzoate ion, etc.), substituted or unsubstituted alkyl sulfonate ion (methane sulfonate ion, trifluoromethane sulfonate ion, etc.), substituted or unsubstituted aryl Sulfonate ion (eg, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, etc.), aryl disulfonate ion (eg, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalene ion) Disulfonate ion, etc.), Al Sulfate ion (eg methyl sulfate ion), sulfate ion, thiocyanate ion, nitrate ion, perchlorate ion, borate ion (eg tetrafluoroborate ion, tetraarylborate ion, tetrakis (pentafluorophenyl) Borate ion (B ⁻ (C ₆ F ₅ ) ₄ ), etc.), sulfonate ion (eg, p-toluenesulfonate ion, etc.), imide ion (eg, sulfonimide ion, N, N-bis (fluorosulfonyl) imide ion, bis) (Trifluoromethanesulfonyl) imide ion, bis (nonafluorobutanesulfonyl) imide ion, N, N-hexafluoro-1,3-disulfonylimide ion, etc.), phosphate ion, hexafluorophosphate ion, picrate ion, amide ion ( Amide substituted with a sil group or a sulfonyl group), a methide ion (including a metide substituted with an acyl group or a sulfonyl group), a halogen anion, a substituted or unsubstituted alkylcarboxylate ion, a sulfate ion, Nitrate ion, tetrafluoroborate ion, tetraarylborate ion, hexafluorophosphate ion, amide ion (including amide substituted with acyl group or sulfonyl group), methide ion (methide substituted with acyl group or sulfonyl group) Including).
The counter anion is preferably a low nucleophilic anion. The low nucleophilic anion is an anion formed by dissociating a proton from an acid having a low pKa, generally called a super acid. The definition of superacid differs depending on the literature, but is a general term for acids having a lower pKa than methanesulfonic acid. Org. Chem. The structure described in 2011, 76, 391-395 Equilibrium Acids of Super Acids is known. The pKa of the low nucleophilic anion is, for example, preferably −11 or less, and preferably −11 to −18. pKa is, for example, J.P. Org. Chem. It can be measured by the method described in 2011, 76, 391-395. The pKa value in the present specification is pKa in 1,2-dichloroethane unless otherwise specified. When the counter anion is a low nucleophilic anion, the decomposition reaction of the copper complex or the resin hardly occurs, and the heat resistance is good. Low nucleophilic anions include tetrafluoroborate ion, tetraarylborate ion (including aryl substituted with halogen atom or fluoroalkyl group), hexafluorophosphate ion, imide ion (substituted with acyl group or sulfonyl group) Amides), methide ions (including methides substituted with acyl groups or sulfonyl groups), tetraarylborate ions (including aryls substituted with halogen atoms or fluoroalkyl groups), imide ions (including sulfonyl groups) And substituted amides) and methide ions (including methides substituted with sulfonyl groups) are particularly preferred.
The counter anion is also preferably a halogen anion, carboxylate ion, sulfonate ion, borate ion, sulfonate ion, or imide ion. Specific examples include chloride ion, bromide ion, iodide ion, acetate ion, trifluoroacetate ion, formate ion, phosphate ion, hexafluorophosphate ion, p-toluenesulfonate ion, tetrafluoroborate ion, tetrakis ( Pentafluorophenyl) borate ion, N, N-bis (fluorosulfonyl) imide ion, bis (trifluoromethanesulfonyl) imide ion, bis (nonafluorobutanesulfonyl) imide ion, nonafluoro-N-[(trifluoromethane) sulfonyl] butanesulfonylimide Ion, N, N-hexafluoro-1,3-disulfonylimide ion and the like. Among them, trifluoroacetate ion, hexafluorophosphate ion, tetrafluoroborate ion, tetrakis (pentafluorophenyl) borate ion, N, N-bis (fluorosulfonyl) imide ion, bis (trifluoromethanesulfonyl) imide ion, bis ( Nonafluorobutanesulfonyl) imide ion, nonafluoro-N-[(trifluoromethane) sulfonyl] butanesulfonylimide ion, N, N-hexafluoro-1,3-disulfonylimide ion are preferable, trifluoroacetate ion, tetrakis (pentafluoro) Phenyl) borate ion, N, N-bis (fluorosulfonyl) imide ion, bis (trifluoromethanesulfonyl) imide ion, bis (nonafluorobutanesulfonyl) imide ion, Nafuruoro -N - [(trifluoromethane) sulfonyl] butane sulfonyl imide ion, N, N-hexafluoro-1,3-imide ion is more preferable.
When the counter ion is a positively charged counter ion (counter cation), for example, inorganic or organic ammonium ion (for example, tetraalkylammonium ion such as tetrabutylammonium ion, triethylbenzylammonium ion, pyridinium ion, etc.), phosphonium Examples thereof include ions (for example, tetraalkylphosphonium ions such as tetrabutylphosphonium ion, alkyltriphenylphosphonium ions, triethylphenylphosphonium ions, etc.), alkali metal ions, protons, and the like.
Further, the counter ion may be a metal complex ion (for example, a copper complex ion).

In the formula (1), L is a ligand, and at least one selected from a coordination site coordinated with an anion to a copper atom and a coordination atom coordinated with a lone pair to the copper atom. A compound having one or more species is represented. The coordination site coordinated by an anion may be dissociated or non-dissociated. The ligand L has a total of two or more of at least one selected from a coordination site coordinated with an anion to a copper atom and a coordination atom coordinated with a lone pair to the copper atom. Examples thereof include compounds, carboxylic acid compounds, sulfonic acid compounds, and phosphate ester compounds. Hereinafter, a coordination site that coordinates with an anion with respect to a copper atom and a coordination atom that coordinates with an unshared electron pair with respect to the copper atom are collectively referred to as a coordination site. In addition, a multidentate compound having a total of at least one selected from a coordination site coordinated with an anion to a copper atom and a coordination atom coordinated with a lone pair to the copper atom It is also called a rank.

Examples of the carboxylic acid compound include a compound represented by the following formula (L-100) or a salt thereof. Examples of the sulfonic acid compound include a compound represented by the following formula (L-200) or a salt thereof. Examples of the phosphoric acid ester compound include a compound represented by the formula (L-300) or a salt thereof.

R ¹⁰⁰ —COOH Formula (L-100)
R ²⁰⁰ —SO ₂ —OH Formula (L-200)
(HO) _n -P (= O)-(OR ³⁰⁰ ) _3-n Formula (L-300)

In the formula (L-100) and the formula (L-200), R ¹⁰⁰ and R ²⁰⁰ each independently represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group, an aryl group, a heteroaryl group, and a divalent linking group (for example, a linear or branched alkylene group, a cyclic alkylene group, an arylene group, —O A group formed by bonding via —, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NR— (wherein R is a hydrogen atom or an alkyl group). . The alkyl group, aryl group, and heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a carboxyl group, a sulfo group, a phosphate ester group, a hydroxyl group, and a halogen atom.

In the formula (L-300), R ³⁰⁰ represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms , -OR ³⁰⁰ is represents polyoxyethylene alkyl group having 4 to 100 carbon atoms, having 4 to 100 carbon atoms (meth) acryloyloxy alkyl group, or, having 4 to 100 carbon atoms of (meth) acryloyl polyoxyalkyl group, n represents 1 or 2. When n is 1, two R ³⁰⁰ may be the same or different. Details of the sulfonic acid compound can be referred to the descriptions in paragraphs 0010 to 0039 of JP-A-2015-43063, the contents of which are incorporated herein. Details of the phosphoric acid ester compound can be referred to the descriptions in paragraphs 0018 to 0042 of JP-A-2014-41318, the contents of which are incorporated herein.

The ligand L is preferably a compound (multidentate ligand) having two or more coordination sites with respect to a copper atom. The polydentate ligand is preferably a compound having 3 or more coordination sites with respect to a copper atom, more preferably a compound having 3 to 5 ligands, and a compound having 4 to 5 ligands. Further preferred. Multidentate ligands act as chelate ligands for copper atoms. That is, at least two coordination sites of the multidentate ligand are chelate-coordinated with copper, so that the structure of the copper complex is distorted, and excellent visible transparency is obtained. It is thought that the color value can also be 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. The multidentate ligand is preferably a compound containing a coordinating atom coordinated by an unshared electron pair, and more preferably a compound containing a nitrogen atom as a coordinating atom coordinated by an unshared electron pair. More preferably, the compound includes a nitrogen atom as a coordinating atom coordinated by an unshared electron pair, and an alkyl group (preferably a methyl group) is substituted on the nitrogen atom.

The ligand L uses a compound having one coordination site for a copper atom (monodentate ligand) and a compound having two or more coordination sites for a copper atom (multidentate ligand). It is also preferable. As a monodentate ligand, a compound having one coordination site coordinated by an anion (also referred to as a monodentate ligand coordinated by an anion), a compound having one coordination atom coordinated by an unshared electron pair (Also referred to as a monodentate ligand coordinated by an unshared electron pair). Monodentate ligands coordinated with anions include halide anions, hydroxide anions, alkoxide anions, phenoxide anions, amide anions (including amides substituted with acyl and sulfonyl groups), imide anions (acyl and sulfonyl groups). Imide substituted with), anilide anion (including anilide substituted with acyl group or sulfonyl group), thiolate anion, hydrogen carbonate anion, carboxylate anion, thiocarboxylate anion, dithiocarboxylate anion, hydrogen sulfate anion, Sulfonate anion, dihydrogen phosphate anion, phosphate diester anion, phosphonate monoester anion, hydrogen phosphonate anion, phosphinate anion, nitrogen-containing heterocyclic anion, nitrate anion, hypochlorite anion, cyanide anion Emissions, 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.

In the formula (1), the ligand L is preferably a compound in which a plurality of π-conjugated systems such as aromatic are not continuously bonded in order to improve visible transparency.

The compound represented by the formula (1) is also preferably a copper complex having a compound having no maximum absorption wavelength in the wavelength range of 400 to 600 nm as a ligand. A copper complex having a compound having a maximum absorption wavelength in the wavelength range 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 transparency may be insufficient. is there. 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.

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 must have a long conjugated structure. However, when the conjugated structure of the ligand is lengthened, the visible transparency tends to decrease. For this reason, the phthalocyanine copper complex may have insufficient visible transparency.

In the formula (1), the anion in the ligand L may be any one that can coordinate to a copper atom, and an oxygen anion, a nitrogen anion, or a sulfur anion is preferable. The coordination site coordinated with the copper atom by an anion is at least one selected from the following monovalent functional group (AN-1) or divalent functional group (AN-2) It is preferable that 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. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, a carboxyl group, and a heterocyclic group. The heterocyclic group as a substituent may be monocyclic or polycyclic, and may be aromatic or non-aromatic. The number of heteroatoms constituting the heterocycle is preferably 1 to 3, and preferably 1 or 2. The hetero atom constituting the hetero ring is preferably a nitrogen atom. When the alkyl group has a substituent, it may further have a substituent.
The alkenyl group represented by R may be linear, branched or cyclic, but is preferably linear. The alkenyl group preferably has 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms. 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. The alkynyl group preferably has 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms. 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. The aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 carbon atoms. The aryl group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.
The heteroaryl group represented by R may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom or an oxygen atom. The heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. The heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.

Examples of coordination sites coordinated by anions also include monoanionic coordination sites. A monoanionic coordination site | part represents the site | part coordinated with a copper atom through the functional group which has one negative charge. For example, an acid group having an acid dissociation constant (pKa) of 12 or less can be mentioned. Specific examples include 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 of electrons is included in the ring, or the following monovalent functional group (UE-1), divalent functional group (UE-2), trivalent It is preferably contained in at least one partial structure selected from the functional group 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, 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. The ring containing a coordination atom coordinated by a lone pair is preferably a 5- to 12-membered ring, and more preferably a 5- to 7-membered ring.
The ring containing a coordinating atom coordinated by a lone pair may have a substituent, such as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, carbon number Examples include 6-12 aryl groups, halogen atoms, silicon atoms, alkoxy groups having 1 to 12 carbon atoms, acyl groups having 2 to 12 carbon atoms, alkylthio groups having 1 to 12 carbon atoms, and carboxyl groups.
When the ring containing the coordination atom coordinated by the lone pair has a substituent, the ring may further have a substituent, and as the substituent, the coordination coordinated by the lone pair A group comprising a ring containing an atom, a group comprising at least one partial structure selected from the groups (UE-1) to (UE-3), an alkyl group having 1 to 12 carbon atoms, and 2 to 12 carbon atoms And an acyl group, a hydroxy group, and the like.

The alkyl group, alkenyl group, alkynyl group, aryl group and heteroaryl group represented by R ¹ and R ^{2 in} groups (UE-1) to (UE-3) are the groups (AN-1) and (AN- It is synonymous with the alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group demonstrated by R of 2), and its preferable range is also the same.
The number of carbon atoms of the alkoxy group represented by R ² is preferably 1 to 12, and more preferably 3 to 9.
The number of carbon atoms of the aryloxy group represented by R ² is preferably 6-18, and more preferably 6-12.
The heteroaryloxy group represented by R ² may be monocyclic or polycyclic. The heteroaryl group which comprises a heteroaryloxy group is synonymous with the heteroaryl group mentioned above, and its preferable range is also the same.
The alkylthio group represented by R ² preferably has 1 to 12 carbon atoms, and more preferably 1 to 9 carbon atoms.
The number of carbon atoms of the arylthio group represented by R ² is preferably 6-18, and more preferably 6-12.
The heteroarylthio group represented by R ² may be monocyclic or polycyclic. The heteroaryl group which comprises a heteroarylthio group is synonymous with the heteroaryl group mentioned above, and its preferable range is also the same.
The acyl group represented by R ² preferably has 2 to 12 carbon atoms, and more preferably 2 to 9 carbon atoms.

In the groups (UE-1) to (UE-3), R ¹ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is more preferable. By making the substituent on the N atom, that is, R ¹ an alkyl group, the contribution ratio of the ligand to the molecular orbital of the copper complex is improved, the molar extinction coefficient at the maximum absorption wavelength is improved, and the infrared shielding property. In addition, the visible transparency tends to be further improved. From the standpoint of balance between heat resistance and infrared shielding property and visible transparency, it is preferred that R ¹ is an alkyl group.

When the ligand L has a coordination site coordinated by an anion and a coordination atom coordinated by an unshared electron pair in one molecule, the coordination site coordinated by an anion and an unshared electron pair The number of atoms linking the coordinating coordinate atoms is preferably 1 to 6, and more preferably 1 to 3. With 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 transparency. 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 L has two or more coordination atoms coordinated by an unshared electron pair in one molecule, the ligand L must have three or more coordination atoms coordinated by an unshared electron pair. Preferably, 3 to 5 are more preferable, 3 or 4 are more preferable, and 4 is particularly preferable. The number of atoms connecting the coordinating atoms coordinated by the lone pair is preferably 1 to 6, more preferably 1 to 3, and still more preferably 2 to 3. It is particularly preferable that the number is 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. The number of atoms connecting the coordinating atoms coordinated by the lone pair may be one, or two or more. The atom connecting the coordinating atoms coordinated by the lone pair is preferably a carbon atom.

The multidentate ligand is preferably a compound represented by the following 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) are: The compound represented by (IV-12) is more preferable because it is more strongly coordinated with the metal center and easily forms a stable 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 preferred, and (IV-9) to (IV-10), (IV-13) are preferred because they are more strongly coordinated with the metal center and easily form a stable complex with high heat resistance. ) And (IV-14) are more preferred, and compounds represented by (IV-13) are particularly preferred.

In 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 represents 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. As the divalent linking group, an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —SO—, —O—, —SO ₂ —, or a combination thereof is preferable. A group consisting of an alkylene group of 1 to 3 groups, a phenylene group, —SO ₂ — or a combination thereof is more preferable.
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 ~ L ³⁴ each independently represent 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.

Specific examples of the compound forming the ligand include the following compounds, compounds shown as preferred specific examples of the polydentate ligand described below, and salts of these compounds. Examples of the atoms or atomic groups 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 of paragraphs 0022 to 0042 of JP 2014-41318 A and the description of paragraphs 0021 to 0039 of JP 2015-43063 A can be referred to, and the contents thereof are incorporated in this specification.

Examples of the copper complex include the following embodiments (1) to (5) as preferred examples, (2) to (5) are more preferred, (3) to (5) are more preferred, and (4) Or (5) is more preferable.
(1) A copper complex having one or two compounds having two coordination sites as the ligand L.
(2) A copper complex having a compound having three coordination sites as the ligand L.
(3) A copper complex having as a ligand L a compound having three coordination sites and a compound having two coordination sites.
(4) A copper complex having a compound having four coordination sites as the ligand L.
(5) A copper complex having a compound having five coordination sites as the ligand L.

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.
Moreover, in the aspect of (1), the copper complex can further have a monodentate ligand as the ligand L. The number of monodentate ligands can be 0, or 1 to 3. In the case where the compound having two coordination sites is a compound having two coordination atoms coordinated by an unshared electron pair, the monodentate ligand is a coordination coordinated by an anion because of its high coordination power. A compound having one coordination site is preferred. In the case of a compound in which a compound having two coordination sites has a coordination site coordinated by an anion and a coordination atom coordinated by an unshared electron pair, the monodentate ligand is coordinated by an unshared electron pair. It is preferable that the compound has one coordinating atom.

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 may further have a monodentate ligand. The number of monodentate ligands can also be zero. Moreover, it can also be 1 or more, 1 to 3 or more is more preferable, 1 to 2 is more preferable, and 2 is more preferable. As a kind of monodentate ligand, a compound having one coordination site coordinated by an anion is preferable for the above-described reason.

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 embodiment (3), 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 more preferably 0.

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 may further have a monodentate ligand. The number of monodentate ligands can be 0, 1 or more, or 2 or more. The number of monodentate ligands is preferably one. As the kind of monodentate ligand, both a compound having one coordination site coordinated by an anion and a compound having one coordination atom 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.

As content of metals other than copper in a copper complex, 10 mass% or less is preferable with respect to solid content of a copper complex, 5 mass% or less is more preferable, and 2 mass% or less is still more preferable. According to this aspect, it is easy to form a resin film in which foreign object defects are suppressed. Moreover, it is preferable that lithium content of a copper complex is 100 mass ppm or less. Moreover, it is preferable that the potassium content of a copper complex is 30 mass ppm or less. Examples of the method for reducing the content of metals other than copper in the copper complex include a method for purifying the copper complex by a method such as reprecipitation, recrystallization, column chromatography, and sublimation purification. Moreover, after dissolving a copper complex in a solvent, the method of filtering with a filter and refine | purifying can also be used. The content of metals other than copper in the copper complex can be measured by inductively coupled plasma emission spectroscopy.

The water content of the copper complex is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less. According to this aspect, the temporal stability of the resin composition can be improved.

The total amount of free halogen anions and halogen compounds in the copper complex is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less based on the total solid content of the copper complex. According to this aspect, the temporal stability of the resin composition can be improved.

The copper complex represented by the formula (1) can be obtained, for example, by mixing and reacting a compound (ligand) having a coordination site for copper with a copper component (copper or a compound containing copper). it can. 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. The copper component is preferably used after being diluted with methanol or dissolved and then filtered. The pore size of the filter paper or filter used for filtration is preferably 1 μm or less.

Regarding ligands in which copper and ligand are coordinated stoichiometrically in a molar ratio of copper: ligand = 1: p, the molarity of the reaction between the copper component and the ligand in the copper complex synthesis. The ratio is preferably 1: q (where q ≧ p, and q is an arbitrary number). When q <p, the copper component as a raw material is likely to remain in the copper complex, resulting in a decrease in visible transparency and a cause of foreign matter defects. The residual ratio of the copper component which is a raw material in the copper complex (content of the copper component not coordinated with the ligand) is preferably 10% by mass or less with respect to the solid content of the copper complex, and 5% by mass or less. Is more preferable, and 2 mass% or less is still more preferable. In addition, if excessive ligands remain in the copper complex, the visible transparency may decrease, the number of foreign matter defects may increase, and the thermal stability of the composition may decrease, so p ≦ q ≦ 2p is preferable, p ≦ q ≦ 1.5p is more preferable, and p ≦ q ≦ 1.2p is still more preferable. The residual ratio of ligand in the copper complex (content of ligand not coordinated with copper) is preferably 10% by mass or less, more preferably 5% by mass or less, based on the solid content of the copper complex. 2 mass% or less is still more preferable. Moreover, in the production of the copper complex, it is preferable to provide a plurality of crystallization steps. At the time of crystallization, the good solvent is preferably less than the poor solvent. Moreover, when providing a multiple times of crystallization process, after making solid content of a copper complex into 80 mass%, it is preferable to transfer to the following crystallization process.

In the resin composition, the content of the copper complex is preferably 5 to 95% by mass with respect to the total solid content of the resin composition. The lower limit is more preferably 10% by mass or more, further preferably 15% by mass or more, and still more preferably 20% by mass or more. The upper limit is more preferably 70% by mass or less, still more preferably 60% by mass or less, and still more preferably 50% by mass or less. A copper complex may be used individually by 1 type and can also use 2 or more types together. It is preferable to use two or more copper complexes in combination. When using 2 or more types of copper complexes together, it is preferable that those total amount is the said range.

<< other infrared absorbers >>
The resin composition can contain an infrared absorbent (also referred to as other infrared absorbent) other than the copper complex. Examples of other infrared absorbers include cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, diiminium compounds, thiol complex compounds, transition metal oxides, quaterylene compounds, and croconium compounds.

Examples of the pyrrolopyrrole compound include compounds described in paragraph Nos. 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph Nos. 0037 to 0052 of JP-A-2011-68731, and the like. The contents are incorporated herein. Examples of the squarylium compound include compounds described in JP-A-2011-208101, paragraphs 0044 to 0049, the contents of which are incorporated herein. Examples of the cyanine compound include compounds described in paragraph Nos. 0044 to 0045 of JP-A-2009-108267, and compounds described in paragraph Nos. 0026 to 0030 of JP-A No. 2002-194040. Incorporated herein. Examples of the diiminium compound include compounds described in JP-T-2008-528706, and the contents thereof are incorporated in the present specification. Examples of the phthalocyanine compound include compounds described in paragraph No. 0093 of JP2012-77153A, oxytitanium phthalocyanine described in JP2006-343631, paragraph Nos. 0013 to 0029 of JP2013-195480A. And the contents of which are incorporated herein. Examples of the naphthalocyanine compound include compounds described in paragraph No. 0093 of JP2012-77153A, the contents of which are incorporated herein. In addition, as the cyanine compound, phthalocyanine compound, diiminium compound, squarylium compound, and croconium compound, the compounds described in paragraph numbers 0010 to 0081 of JP 2010-1111750 A may be used, the contents of which are incorporated herein. It is. In addition, as for the cyanine compound, for example, “functional pigment, Nobu Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein. It is. Further, as other infrared absorbers, compounds described in JP-A-2016-146619, JP-A-2017-031394, JP-A-2016-200771 and JP-A-2016-142891 may be used. The contents of which are incorporated herein. Moreover, as another infrared absorber, a compound having the following structure may be used.

Moreover, inorganic particles can also be used as other infrared absorbers. The inorganic particles are preferably metal oxide particles or metal particles from the viewpoint of better infrared shielding properties. Examples of the metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, and fluorine-doped tin dioxide (F-doped). SnO ₂ ) particles, niobium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, and the like. Examples of the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles. In addition, a tungsten oxide compound can be used as the inorganic particles. The tungsten oxide compound is preferably cesium tungsten oxide. For details of the tungsten oxide-based compound, paragraph No. 0080 of JP-A-2016-006476 can be referred to, the contents of which are incorporated herein. The shape of the inorganic particles is not particularly limited, and may be a sheet shape, a wire shape, or a tube shape regardless of spherical or non-spherical.

The average particle size of the inorganic particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. If the average particle diameter of the inorganic particles is 800 nm or less, the visible transparency is good. The average particle size of the inorganic particles is preferably as small as possible, but from the viewpoint of handling properties, the average particle size of the inorganic particles is preferably 1 nm or more.

When the resin composition contains another infrared absorber, the content of the other infrared absorber is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the copper complex. The lower limit is more preferably 0.5 parts by mass or more, and still more preferably 1 part by mass or more. The upper limit is more preferably 45 parts by mass or less, still more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less.

<< Resin >>
The resin composition contains a resin. In the present invention, a resin having substantially no crosslinkable group is used as the resin. Examples of the crosslinkable group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a styryl group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxysilyl group. That is, in the present invention, the resin substantially has a crosslinkable group selected from vinyl group, (meth) allyl group, (meth) acryloyl group, styryl group, epoxy group, oxetanyl group, methylol group and alkoxysilyl group. It is preferable to use a resin that does not. In the present invention, the resin having substantially no crosslinkable group means that the resin does not form a three-dimensional crosslink after heating. More specifically, the resin having substantially no crosslinkable group is preferably a resin that does not form a three-dimensional crosslink even after being heated to 100 ° C. Whether the resin forms a three-dimensional cross-linkage is determined by physical structure analysis such as molecular structure analysis by NMR (nuclear magnetic resonance), thermogravimetry, differential thermal analysis or thermophysical analysis by differential scanning calorimetry, Young's modulus or elongation at break It can be analyzed by methods such as physical property analysis. In any of these methods, if there is no significant change in the profile before and after heating, it can be said that the resin does not form a three-dimensional crosslink. That is, it can be said that the resin is a resin having substantially no crosslinkable group.
The amount of the crosslinkable group in the resin is preferably less than the detection limit value in NMR (nuclear magnetic resonance) analysis. More preferably, the resin does not have a crosslinkable group.

The type of resin is not particularly limited as long as it has substantially no crosslinkable group. The resin is preferably a highly transparent resin. Specifically, polyolefin resin such as polyethylene, polypropylene, carboxylated polyolefin, chlorinated polyolefin, cycloolefin polymer; polystyrene resin; (meth) acrylic resin such as (meth) acrylic ester resin, (meth) acrylamide resin; vinyl acetate Resin; Halogenated vinyl resin; Polyvinyl alcohol resin; Polyamide resin; Polyurethane resin; Polyester resin such as polyethylene terephthalate (PET) and polyarylate (PAR); Polycarbonate resin; Polymaleimide resin; Polyurea resin; Polyvinyl acetal such as polyvinyl butyral resin Examples thereof include resins. Among these, (meth) acrylic resins, polyurethane resins, polyester resins, polymaleimide resins, and polyurea resins are preferable, and (meth) acrylic resins, polyurethane resins, and polyester resins are more preferable. The weight average molecular weight of the resin is preferably 1000 to 300,000. The lower limit is more preferably 2000 or more, and further preferably 3000 or more. The upper limit is more preferably 100,000 or less, and even more preferably 50,000 or less. The number average molecular weight of the resin is preferably 500 to 200,000. The lower limit is more preferably 1000 or more, and further preferably 2,000 or more. The upper limit is more preferably 150,000 or less, and even more preferably 100,000 or less.

The resin is preferably a resin having at least one repeating unit represented by the following formulas (A1-1) to (A1-7).

In the formula, R ¹ represents a hydrogen atom or an alkyl group, L ¹ to L ⁴ 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. To express. R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom or a substituent.

The number of carbon atoms of the alkyl group represented by R ¹ is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. R ¹ is preferably a hydrogen atom or a methyl group.

Examples of the divalent linking group L ¹ ~ L ⁴ represents an alkylene group, an arylene group, -O -, - S -, - SO -, - CO -, - COO -, - OCO -, - SO 2 -, Examples include —NR ^a — (R ^a represents a hydrogen atom or an alkyl group), or a group consisting of a combination thereof. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. 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. The number of carbon atoms of the arylene group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10.

The alkyl group represented by R ¹⁰ to R ¹³ may be linear, branched or cyclic. The alkyl group may have a substituent or may be unsubstituted. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The aryl group represented by R ¹⁰ to R ¹³ preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 carbon atoms.
R ¹⁰ is preferably a linear or branched alkyl group or an aryl group, and more preferably a linear or branched alkyl group.
R ¹¹ and R ¹² are preferably each independently a linear or branched alkyl group, and more preferably a linear alkyl group.
R ¹³ is preferably a linear or branched alkyl group or an aryl group.

The substituents represented by R ¹⁴ and R ¹⁵ are halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, aralkyl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, Alkylthio group, arylthio group, heteroarylthio group, —NR ^a1 R ^a2 , —COR ^a3 , —COOR ^a4 , —OCOR ^a5 , —NHCOR ^a6 , —CONR ^a7 R ^a8 , —NHCONR ^a9 R ^a10 , —NHCOOR ^a11 , — SO ₂ R ^a12 , —SO ₂ OR ^a13 , —NHSO ₂ R ^a14, or —SO ₂ NR ^a15 R ^a16 may be mentioned. R ^a1 to R ^a16 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. Of these, at least one of R ¹⁴ and R ¹⁵ preferably represents a cyano group or —COOR ^a4 . R ^a4 preferably represents a hydrogen atom, an alkyl group or an aryl group.

Examples of a commercially available resin having a repeating unit represented by the formula (A1-7) include ARTON F4520 (manufactured by JSR Corporation). The details of the resin having a repeating unit represented by the formula (A1-7) can be referred to the descriptions in paragraph numbers 0053 to 0075 and 0127 to 0130 of JP2011-100084A. Embedded in the book.

The resin is preferably a resin having a repeating unit represented by the formula (A1-4), and a repeating unit represented by the formula (A1-1) and a repeating unit represented by the formula (A1-4). A resin having a unit is more preferable. According to this aspect, the thermal shock resistance of the resin film tends to be improved. Furthermore, the compatibility between the copper complex and the resin is improved, and a resin film with few precipitates is easily obtained.

Resin may contain other repeating units in addition to the repeating units described above. Regarding the components constituting other repeating units, the description in paragraph Nos. 0068 to 0075 of JP-A-2010-106268 (paragraph Nos. 0112 to 0118 of the corresponding US Patent Application Publication No. 2011/0124824) can be referred to. The contents of which are incorporated herein.

In the resin composition, the resin content is preferably 30 to 90% by mass with respect to the total solid content of the resin composition. The lower limit is more preferably 35% by mass or more, still more preferably 40% by mass or more, and still more preferably 50% by mass or more. The upper limit is more preferably 85% by mass or less, and still more preferably 80% by mass or less. The total amount of the copper complex and the resin is 60 to 100% by mass, preferably 70 to 100% by mass, and preferably 80 to 100% by mass with respect to the total solid content of the resin composition. More preferably, it is 90 to 100% by mass.

<< Solvent >>
The resin composition preferably contains a solvent. The solvent is not particularly limited and may be appropriately selected depending on the purpose as long as each component can be uniformly dissolved or dispersed. For example, water or an organic solvent can be used. Preferable examples of the organic solvent include alcohols, ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and the like. These may be used alone or in combination of two or more. Moreover, it is preferable that a solvent is a compound which does not contain a crosslinkable group. Specific examples of alcohols, aromatic hydrocarbons, and halogenated hydrocarbons include the solvents described in paragraph 0136 of JP2012-194534A, the contents of which are incorporated herein. Specific examples of the esters, ketones, and ethers include the solvents described in paragraph 0497 of JP2012-208494A (paragraph number 0609 of the corresponding US Patent Application Publication No. 2012/0235099). . As the solvent, an ester solvent substituted with a cyclic alkyl group or a ketone solvent substituted with a cyclic alkyl group can also be used. Specific examples of the solvent include: n-amyl acetate, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, ethylene glycol monobutyl ether acetate, 1-methoxy-2-propanol Cyclohexyl acetate, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, 3-methoxybutyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Acetate, triacetin, 3-methoxybutanol, dipropylene glycol methyl ether acetate, 1,4-butane All diacetate, cyclohexanol acetate, dipropylene glycol dimethyl ether, propylene glycol diacetate, dipropylene glycol methyl -n- propyl ether, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate. These may be used alone or in combination of two or more.

As the solvent, a solvent having a boiling point of 150 ° C. or lower (preferably having a boiling point of 30 to 145 ° C., more preferably 50 to 140 ° C.) may be used alone. May be used alone (hereinafter, also referred to as a high boiling point solvent) having a boiling point of 155 to 300 ° C. (preferably a boiling point of 155 to 300 ° C., more preferably 160 to 250 ° C.). May be used in combination. By using a high boiling point solvent, the evaporation rate of the solvent in the resin composition becomes slow, and it is easy to stabilize drying and prevent precipitation of residues. In particular, when the solid content concentration of the resin composition is low (for example, when the solid content concentration is 35% by mass or less), a high-boiling solvent and a low-boiling point solvent are used from the viewpoints of stabilization of drying and precipitation of residues. It is preferable to use a solvent together. When a high boiling point solvent and a low boiling point solvent are used in combination, the difference between the boiling point of the high boiling point solvent and the boiling point of the low boiling point solvent is preferably 20 to 250 ° C., more preferably 50 to 150 ° C. . The mass ratio of the high-boiling solvent to the low-boiling solvent is not particularly limited, but is preferably high-boiling solvent: low-boiling solvent = 99: 1 to 55:45, and 95: 5 to 70:30. More preferably.
Examples of the high boiling point solvent include 3-methoxybutyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, 3-methoxybutanol, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, cyclohexanol. Examples include acetate, dipropylene glycol dimethyl ether, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate.
Examples of the low boiling point solvent include cyclopentanone, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and the like.

In the present invention, it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably 10 mass ppb (parts per billion) or less, for example. If necessary, a solvent having a mass ppt (parts per trillation) level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds having the same number of atoms and different structures). Moreover, only 1 type may be included and the isomer may be included multiple types.

The content of the solvent is preferably such that the total solid content of the resin composition is 5 to 80% by mass. The lower limit is more preferably 10% by weight or more, further preferably 20% by weight or more, still more preferably 30% by weight or more, still more preferably 50% by weight or more, still more preferably 55% by weight or more, and 60% by weight or more. Is particularly preferred. The upper limit is more preferably 75% by mass or less, and still more preferably 70% by mass or less. By increasing the solid content concentration (total solid content) of the resin composition, a thick resin layer can be formed by a single application. For example, when the total solid content of the resin composition is 50% by mass or more, a resin layer having a thickness of 5 to 40 μm can be formed by a single application. Moreover, if the total solid content of a resin composition is 80 mass% or less, the solubility of the component in a resin composition is favorable. Only one type of solvent may be used, or two or more types may be used, and in the case of two or more types, the total amount is preferably within the above range. In addition, for reasons such as environmental aspects, it may be preferable that the composition does not contain aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent.

<< Radical trapping agent >>
The resin composition can also contain a radical trapping agent. Examples of radical trapping agents include oxime compounds. Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 (manufactured by ADEKA Corporation), Adeka Arkles NCI-930 (manufactured by ADEKA Corporation), Adekaoptomer N-1919 (manufactured by ADEKA Corporation, photopolymerization described in JP 2012-14052 A Initiator 2) and the like can be used.

Also, as the oxime compound, an oxime compound having a fluorine atom can be used. 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 JP-A 2013-164471. Compound (C-3). This content is incorporated herein.

Further, as the oxime compound, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Examples include compounds described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071, Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

Further, as the oxime compound, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.

Further, as the oxime compound, an oxime compound having a benzofuran skeleton can also be used. Specific examples include compounds OE-01 to OE-75 described in International Publication No. WO2015 / 036910.

The content of the radical trapping agent is preferably 0.01 to 30% by mass with respect to the total solid content of the resin composition. The lower limit is more preferably 0.1% by mass or more. The upper limit is more preferably 20% by mass or less, and still more preferably 10% by mass or less.

<< Surfactant >>
The resin composition can also contain a surfactant. Only one type of surfactant may be used, or two or more types may be combined. The content of the surfactant is preferably 0.0001 to 5% by mass with respect to the total solid content of the resin composition. The lower limit is more preferably 0.005% by mass or more, and still more preferably 0.01% by mass or more. The upper limit is more preferably 2% by mass or less, and still more preferably 1% by mass or less. By including a surfactant in the resin composition, for example, when the resin layer is formed by repeatedly applying the resin composition, the wettability of the resin composition can be improved.

As the surfactant, various surfactants such as a fluorosurfactant, nonionic surfactant, cationic surfactant, anionic surfactant, and silicone surfactant can be used. And a silicone-based surfactant are preferable, and a fluorine-based surfactant is more preferable. The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass. The lower limit is more preferably 5% by mass or more, and further preferably 7% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 25% by mass or less. If the fluorine content in the fluorosurfactant is in the above-described range, it is effective in terms of uniformity of coating film thickness and liquid-saving properties.

Examples of the fluorosurfactant include surfactants described in paragraph numbers 0060 to 0064 of JP-A-2014-41318 (paragraph numbers 0060 to 0064 of corresponding international publication 2014/17669), JP-A-2011-132503. And surfactants described in paragraph Nos. 0117 to 0132 of the publication, and the contents thereof are incorporated herein. Examples of commercially available fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (and above, DIC). ), FLORARD FC430, FC431, FC171 (Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC- 381, SC-383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA).

In addition, as the fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and the fluorine atom is volatilized by cleavage of the functional group containing the fluorine atom when heated. Can also be suitably used. Examples of such a fluorosurfactant include Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016 and Nikkei Sangyo Shimbun, February 23, 2016), such as Megafac DS- 21 can be used, and these can be used.

A block polymer can also be used as the fluorosurfactant. Examples thereof include compounds described in JP2011-89090A. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meta). ) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. 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. In the above compounds,% indicating the ratio of repeating units is mol%.

Further, as the fluorosurfactant, a fluoropolymer having an ethylenically unsaturated group in the side chain can also be used. Specific examples thereof include compounds described in paragraph Nos. 0050 to 0090 and paragraph Nos. 0289 to 0295 of JP2010-164965A, for example, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation. RS-72-K and the like. As the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.

Examples of nonionic surfactants include nonionic surfactants described in paragraph No. 0553 of JP2012-208494A (paragraph number 0679 of the corresponding US Patent Application Publication No. 2012/0235099), This content is incorporated herein. Examples of the cationic surfactant include a cationic surfactant described in paragraph No. 0554 of JP2012-208494A (paragraph number 0680 of the corresponding US Patent Application Publication No. 2012/0235099). This content is incorporated herein. Examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like. Examples of the silicone surfactant include KF6001 (manufactured by Shin-Etsu Silicone) and paragraph number 0556 of JP 2012-208494 A (corresponding to paragraph number 0682 of US Patent Application Publication No. 2012/0235099). Of silicone surfactants, the contents of which are incorporated herein.

<< UV absorber >>
The resin composition can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, or the like can be used. Among them, the benzotriazole compound has good compatibility with the copper compound, and further, the copper compound and the absorption wavelength are suitable, and the ultraviolet shielding property can be improved while maintaining excellent visible transparency. And hydroxyphenyltriazine compounds are preferred. For details of these, reference can be made to the descriptions of paragraph numbers 0052 to 0072 of JP2012-208374A and paragraph numbers 0317 to 0334 of JP2013-68814A, the contents of which are incorporated herein. Examples of commercially available benzotriazole compounds include TINUVIN PS, TINUVIN 99-2, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, and TINUVIN 1130 (above, manufactured by BASF). Moreover, as a benzotriazole compound, you may use the MYUA series (Chemical Industry Daily, February 1, 2016) made from Miyoshi oil and fat. The content of the ultraviolet absorber is preferably from 0.01 to 10% by mass, more preferably from 0.01 to 5% by mass, based on the total solid content of the resin composition.

<< Other ingredients >>

The resin composition further includes a dispersant, a sensitizer, a filler, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, Leveling agents, peeling accelerators, antioxidants, surface tension modifiers, chain transfer agents, etc.). With respect to these components, descriptions in paragraph numbers 0101 to 0104 and 0107 to 0109 of JP-A-2008-250074 can be referred to, and the contents thereof are incorporated in the present specification. 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, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an 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 ethyl bis (2,4-di-tert-butyl-6-methylphenyl) phosphite. These are readily available as commercial products, such as 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) and the like. The content of the antioxidant is preferably 0.01 to 20% by mass and more preferably 0.3 to 15% by mass with respect to the total solid content of the resin composition. 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.

In the resin composition, the content of the monomer containing a crosslinkable group is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the total solid content of the resin composition. It is particularly preferable that the monomer containing a functional group is substantially not contained. That the resin composition does not substantially contain a monomer containing a crosslinkable group means that the content of the monomer containing a crosslinkable group is 0.1% by mass or less based on the total solid content of the resin composition. This means that it is preferably 0.05% by mass or less, and more preferably not contained. Examples of the monomer containing a crosslinkable group include monomers having at least one selected from vinyl group, (meth) allyl group, (meth) acryloyl group, styryl group, epoxy group, oxetanyl group, methylol group and alkoxysilyl group. It is done.

As content of metals other than copper in a resin composition, 10 mass% or less is preferable with respect to solid content of a copper complex, 5 mass% or less is more preferable, and 2 mass% or less is still more preferable. According to this aspect, it is easy to form a resin film in which foreign object defects are suppressed. Moreover, it is preferable that lithium content in a resin composition is 100 mass ppm or less. Moreover, it is preferable that potassium content in a resin composition is 30 mass ppm or less. The content of metals other than copper in the resin composition can be measured by inductively coupled plasma emission spectroscopy.

As content of the water in a resin composition, 5 mass% or less is preferable with respect to solid content of a copper complex, 3 mass% or less is more preferable, and 1 mass% or less is still more preferable.

The total amount of free halogen anions and halogen compounds in the resin composition is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less, based on the total solid content of the copper complex. .

The residual ratio of the copper component that is the raw material of the copper complex in the resin composition (content of the copper component not coordinated with the ligand) is preferably 10% by mass or less based on the solid content of the copper complex, 5 mass% or less is more preferable, and 2 mass% or less is still more preferable. Further, the residual ratio of the ligand that is a raw material of the copper complex in the resin composition (content of the ligand not coordinated with copper) is preferably 10% by mass or less based on the solid content of the copper complex. 5 mass% or less is more preferable, and 2 mass% or less is still more preferable.

The viscosity of the resin composition is preferably 1 to 3000 mPa · s when a resin film is formed by coating. The lower limit is more preferably 10 mPa · s or more, and still more preferably 100 mPa · s or more. The upper limit is more preferably 2000 mPa · s or less, and even more preferably 1500 mPa · s or less.

<Method for preparing resin composition>
Said resin composition can be prepared by mixing each component. In producing the resin composition, it is preferable to use a kettle whose inner wall is coated with metal. In preparing the resin composition, the components constituting the resin composition may be blended together, or may be blended sequentially after each component is dissolved and / or dispersed in a solvent. Further, the order of addition and the working conditions when blending are not particularly limited, but it is preferable to add a high-viscosity component last from the viewpoint of ensuring agitation. In addition, the resin composition is preferably prepared in a closed system to prevent volatilization. The resin composition is preferably prepared in an atmosphere of dried air or nitrogen gas (preferably nitrogen gas).

Further, when the resin composition contains particles, it is preferable to include a process of dispersing the particles. In the process of dispersing the particles, the mechanical force used for dispersing the particles includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high speed impeller, a sand grinder, a flow jet mixer, a high pressure wet atomization, and an ultrasonic dispersion. Further, in the pulverization of particles in a sand mill (bead mill), it is preferable to use beads having a small diameter or to increase the pulverization efficiency by increasing the filling rate of beads. Further, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. Also, the process and disperser for dispersing particles are described in “Dispersion Technology Taizen, Issued by Information Technology Corporation, July 15, 2005” and “Dispersion technology and industrial application centering on suspension (solid / liquid dispersion system)”. In fact, the process and the disperser described in Paragraph No. 0022 of Japanese Unexamined Patent Publication No. 2015-157893 can be suitably used. In the process of dispersing the particles, the particles may be refined in the salt milling process. For the materials, equipment, processing conditions, etc. used in the salt milling process, for example, descriptions in JP-A Nos. 2015-194521 and 2012-046629 can be referred to.

In preparing the resin composition, it is preferable to filter the resin composition with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight) And a filter using a material such as polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable. The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm. The thickness of the filter is preferably 25.4 mm or more, and more preferably 50.8 mm or more. 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, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co. . As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is preferably 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, and still more preferably 0.3 to 6.0 μm.

When filling the container with the resin composition, the filling rate of the resin composition in the container may be 70 to 100% for the purpose of avoiding contact between the resin composition and moisture in the container. preferable. Moreover, it is also preferable that the space | gap in a storage container shall be dry air or dry nitrogen. There is no limitation in particular as a container of a resin composition, A well-known container can be used. For example, a container made of various resins such as polypropylene can be used. In addition, as a container, for the purpose of suppressing impurities from being mixed into raw materials and resin compositions, a multilayer bottle in which the inner wall of the container is composed of six types and six layers of resin, and a bottle having six types of resin having a seven layer structure. It is also preferred to use Examples of such a container include a container described in JP-A-2015-123351.

<Method for manufacturing near-infrared cut filter>
Next, the manufacturing method of the near-infrared cut filter of this invention is demonstrated. The method for producing a near-infrared cut filter of the present invention is a method for producing a near-infrared cut filter including a step of applying a resin composition containing a copper complex and a resin on a support and drying to form a resin film. And
The copper complex is a compound represented by the formula (1) described above,
The resin is a resin substantially free of crosslinkable groups,
A resin composition in which the total amount of the copper complex and the resin in the resin composition is 60 to 100% by mass with respect to the total solid content of the resin composition is used. About the detail of a resin composition, the resin composition mentioned above is mentioned.

The type of support is not particularly limited. For example, examples of the material for the support include general glass, tempered glass such as sapphire glass and gorilla glass, transparent ceramic, and plastic. Moreover, you may use a solid-state image sensor as a support body. Further, another substrate provided on the light receiving side of the solid-state imaging device can be used as a support. In addition, a layer such as a planarization layer provided on the light receiving side of the solid-state imaging device can be used as the support. In the case where the resin film is peeled from the support and used, a substrate having no transparency can be used as the support. For example, a metal substrate, a resin substrate, a silicon substrate, etc. are mentioned. In the case where the resin film is peeled from the support and used, it is preferable that a release layer is formed on the surface of the support in order to easily peel the resin film from the support.

As a coating method of the resin composition, a known method can be used. Drip method (drop casting); slit coating method; spray method; roll coating method; spin coating method (spin coating); casting coating method; slit and spin method; prewet method (for example, in JP 2009-145395 A) Described method); ink jet (for example, on-demand method, piezo method, thermal method), discharge printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, various printing such as metal mask printing Examples thereof include: a transfer method using a mold or the like; a nanoimprint method; a blade coating method; a bar coating method; an applicator coating method. The application method by ink jet is not particularly limited as long as it is a method capable of ejecting the composition. For example, “Expanding and usable ink jet-unlimited possibilities seen in patents, published in February 2005, Sumibe Techno Research” The methods described in the patent publications indicated (particularly, pages 115 to 133), JP-A 2003-262716, JP-A 2003-185831, JP-A 2003-261827, JP-A 2012-126830 The method described in JP-A-2006-169325 can be used. Of these, the casting method is preferred from the viewpoint of productivity.

The drying conditions of the resin composition (resin composition layer) applied to the support vary depending on the type and content of each component contained in the resin composition. For example, the drying temperature is preferably 40 to 150 ° C. The lower limit is more preferably 50 ° C. or higher, and further preferably 55 ° C. or higher. The upper limit is more preferably 130 ° C. or less, and even more preferably 110 ° C. or less. The heating time is preferably 1 minute to 100 hours. The lower limit is more preferably 5 minutes or more, and still more preferably 10 minutes or more. The upper limit is more preferably 50 hours or less, still more preferably 25 hours or less, and even more preferably 20 hours or less. Another example is a method in which the temperature is raised from room temperature (for example, 25 ° C.) to a predetermined drying temperature at a constant heating rate, and the temperature is maintained and dried. The rate of temperature rise is preferably 0.5 to 10 ° C./min, more preferably 1.0 to 5 ° C./min.

Further, aging may be performed on the dried resin composition layer. In aging, the resin composition layer is preferably subjected to a high temperature and high humidity treatment. The aging temperature is preferably 60 to 150 ° C. The lower limit is more preferably 70 ° C. or higher, and still more preferably 80 ° C. or higher. The upper limit is more preferably 140 ° C. or less, and further preferably 130 ° C. or less. The humidity is preferably 30 to 100%. The lower limit is more preferably 40% or more, and further preferably 50% or more. The upper limit is more preferably 95% or less, and still more preferably 90% or less. The aging time is preferably 0.5 to 100 hours. The lower limit is more preferably 1 hour or longer, and further preferably 2 hours or longer. The upper limit is more preferably 50 hours or less, and even more preferably 25 hours or less. If it is the conditions of these ranges, the resin film which has the mechanical property mentioned above will be easy to be obtained. There is no restriction | limiting in particular as an aging apparatus, According to the objective, it can select suitably from well-known apparatuses, For example, a high temperature / humidity furnace etc. are mentioned.

<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 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. As the near-infrared cut filter 13, only the resin film having the physical properties described above may be used, or a laminate of the resin film and the support may be used. Examples of the material for the support include general glass, tempered glass such as sapphire glass and gorilla glass, transparent ceramic, and plastic. Examples of the material for the imaging lens 14 include general glass, tempered glass such as sapphire glass and gorilla glass, transparent ceramic, and plastic.

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 the near infrared cut filter 13 is provided at this position, the process of forming the near infrared cut filter can be simplified. Furthermore, unnecessary near-infrared light incident on the microlens can be sufficiently cut, and the infrared shielding property can be further improved. In FIG. 1, the number of imaging lenses 14 is one, but the number of imaging lenses 14 may be two or more.

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 subjected to 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 has a 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” means that the characteristics as a near-infrared cut filter are maintained even after heating at 180 ° C. for 1 minute. More preferably, the characteristics are maintained even after heating at 230 ° C. for 10 minutes. More preferably, the characteristics are maintained even after heating at 250 ° C. for 3 minutes. When it does not have solder reflow resistance, when it heats on the said conditions, the infrared shielding property of a near-infrared cut filter may fall, or the function as a film | membrane may become inadequate.
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 in International Publication No. WO2015 / 099060 can be referred to for the ultraviolet absorbing layer, and the contents thereof are incorporated herein.

2 to 4 are schematic cross-sectional views showing an example of the peripheral portion 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, a near-infrared cut filter 21, and an antireflection layer 22. May be included in this order. As for the ultraviolet / infrared light reflection film 19, for example, paragraph numbers 0033 to 0039 of JP2013-68688A and paragraph numbers 0110 to 0114 of international publication WO2015 / 099060 can be referred to. Incorporated herein. 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 antireflection layer 22 has a function of improving the transmittance by preventing reflection of light incident on the near-infrared cut filter 21 and efficiently using incident light. For example, Japanese Patent Application Laid-Open No. 2013-68688. Reference can be made to the description of paragraph number 0040 of the publication, the contents of which are incorporated herein.

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

FIG. 5 shows another embodiment of the camera module of the present invention. This camera module is different from the camera module shown in FIG. 1 in that the near infrared cut filter 13 is arranged outside the lens holder 15 in the camera module shown in FIG. That is, in the camera module shown in FIG. 5, the near-infrared cut filter 13 is arranged on the incident light side from the outside with respect to the imaging lens 14. In this camera module, incident light from the outside sequentially passes through the near-infrared cut filter 13, the imaging lens 14, and the planarization layer 12, and then reaches the imaging device portion of the solid-state imaging device 11. When the near-infrared cut filter 13 is arranged on the incident light side from the outside of the imaging lens 14, even if the near-infrared cut filter has a defect because the distance between the near-infrared cut filter 13 and the light receiving unit increases. These defects are blurred and the influence of these defects on the image can be reduced.
In FIG. 5, the near-infrared cut filter 13 is disposed outside the lens holder 15, but may be disposed within the lens holder 15. In FIG. 5, the near infrared cut filter 13 is arranged at a predetermined interval from the surface of the imaging lens 14, but the near infrared cut filter 13 may be directly formed on the surface of the imaging lens 14.
In FIG. 5, the imaging lens 14 is one, but the imaging lens 14 may be two or more. In the case of having two or more imaging lenses 14, the near-infrared cut filter 13 may be disposed on the outer side (incident light side) than the imaging lens 14 disposed on the outermost side (incident light side). A near-infrared cut filter 13 may be disposed between the imaging lenses. For example, when two imaging lenses 14 are provided, the near-infrared cut filter, the imaging lens, and the imaging lens may be arranged in this order from the incident light side. The imaging lens, the near-infrared cut filter, and the imaging lens Each may be arranged in 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 the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (Junaki Ibuki, Sangyo Tosho 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, JP 2003-45676 A, supervised by Akiyoshi Mikami, “Frontier of Organic EL Technology Development-High Brightness, High Precision, 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, “part” and “%” are based on mass.

<Weight average molecular weight (Mw)>
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) by the following method.
Equipment: HLC-8220 GPC (manufactured by Tosoh Corporation)
Detector: RI (Refractive Index) Detector column: Guard column HZ-L, TSK gel Super HZM-M, TSK gel Super HZ4000, TSK gel Super HZ3000, TSK gel Super HZ2000 (Tosoh Corporation) Column eluent coupled with: Tetrahydrofuran (containing stabilizer)
Column temperature: 40 ° C
Injection volume: 10 μL
Analysis time: 26 min.
Flow rate (flow rate): 0.35 mL / min. (Sample pump) 0.20 mL / min. (Reference pump)
Calibration curve base resin: polystyrene

<Preparation of resin composition>
The materials shown in the table below were mixed in the blending amounts (parts by mass) shown in the table below to prepare resin compositions having solid content concentrations shown in the table below. The solid content concentration of the resin composition was adjusted by adjusting the amount of the solvent.

The raw materials listed in the table are as follows. In the resins shown below, the numerical values appended to the main chain are molar ratios.

(Infrared absorber)
A-1 to A-4: Copper complex having the following structure

A-5: Copper complex having the following compound as a ligand

A-6: Copper complex having the following compound as a ligand

A-7: Copper complex having the following compound as a ligand

A-12: Compound s-1 (squarylium compound) described in Table 1 of paragraph No. 0059 of JP-A-2016-200771
A-13: Compound s-5 (squarylium compound) described in Table 1 of paragraph No. 0059 of JP-A-2016-200771

(resin)
B-1: Resin having the following structure (Mw = 8,000)
B-2: Resin having the following structure (Mw = 12,000)
B-3: A resin synthesized by the following method was used. 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3-ene (100 parts by mass), 1-hexene (18 parts by mass) and toluene (300 parts by mass) were placed in a nitrogen-substituted reaction vessel, and the solution was heated to 80 ° C. Next, 0.2 parts by mass of a toluene solution of triethylaluminum (concentration 0.6 mol / liter) and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) were added to the solution in the reaction vessel as a polymerization catalyst. 0.9 parts by mass was added, and the resulting solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%. 1,000 parts by mass of the ring-opening polymer solution thus obtained was put in an autoclave, and RuCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution in an amount of 0.12 mass. A hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. The reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, which was dried to obtain Resin B-3. Resin B-3 had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 ° C. Resin B-3 was a resin containing no crosslinkable group.
B-4: Resin having the following structure (Mw = 10,000)

(Surfactant)
W-1: The following compound (weight average molecular weight = 14,000.% Indicating the ratio of repeating units is mol%)

(solvent)
CP: cyclopentanone CH: cyclohexanone PGMEA: propylene glycol monomethyl ether acetate

<Production of near-infrared cut filter>
(Examples 1 to 13, 15 to 17, Comparative Example 1)
On the glass substrate, the resin composition described in the following table was cast and formed to form a resin composition layer. Next, the resin composition layer was dried at 60 ° C. for 12 hours using a hot plate to prepare a resin film (near infrared cut filter) having a thickness of 100 μm.

(Example 14)
On the glass substrate, the resin composition described in the following table was cast and formed to form a resin composition layer. Next, the resin composition layer was dried at 40 ° C. for 24 hours using a hot plate to prepare a resin film (near infrared cut filter) having a thickness of 100 μm.

<Evaluation of heat resistance>
(Evaluation of change in visible transparency before and after heat test)
The near-infrared cut filter was heated at 200 ° C. for 1 minute. Based on the absorbance at a wavelength of 450 nm of the near-infrared cut filter before and after heating, the change rate of the absorbance at a wavelength of 450 nm was calculated from the following formula, and the change in visible transparency before and after the heat resistance test was evaluated.
Rate of change in absorbance at wavelength 450 nm (%) = | (absorbance at wavelength 450 nm before heating−absorbance at wavelength 450 nm after heating) / absorbance at wavelength 450 nm before heating | × 100 (%)
A: Change rate of absorbance is 3% or less B: Change rate of absorbance is greater than 3% and 4.5% or less C: Change rate of absorbance is greater than 4.5% and 6% or less D: Absorbance change rate is greater than 6%

(Evaluation of change in infrared shielding property 1 before and after the heat resistance test (shielding property of light having a wavelength of 700 nm to less than 800 nm after heat resistance))
The near-infrared cut filter was heated at 200 ° C. for 1 minute. Based on the average absorbance in the wavelength range from 700 nm to less than 800 nm of the near-infrared cut filter before and after heating, the change rate of the average absorbance in the wavelength range from 700 nm to less than 800 nm is calculated from the following formula, and the infrared shielding property 1 before and after the heat resistance test is calculated. Changes were evaluated.
Average absorbance change rate (%) in the wavelength range from 700 nm to less than 800 nm = | (average absorbance in the wavelength range from 700 nm to less than 800 nm before heating−average absorbance in the wavelength range from 700 nm to less than 800 nm after heating) / before heating Average absorbance in the wavelength range of 700 nm or more and less than 800 nm | × 100 (%)
A: Change rate of absorbance is 3% or less B: Change rate of absorbance is greater than 3% and 4.5% or less C: Change rate of absorbance is greater than 4.5% and 6% or less D: Absorbance change rate is greater than 6%

(Evaluation of change in infrared shielding property 2 before and after the heat resistance test (light shielding property at a wavelength of 800 nm to 1100 nm after heat resistance))
The near-infrared cut filter was heated at 200 ° C. for 1 minute. Based on the average absorbance in the wavelength range of 800 nm to 1100 nm of the near-infrared cut filter before and after heating, the change rate of the average absorbance in the wavelength range of 800 nm to 1100 nm is calculated from the following formula, and the infrared shielding property 2 before and after the heat resistance test is calculated. Changes were evaluated.
Average absorbance change rate (%) in the wavelength range from 800 nm to 1100 nm = | (average absorbance in the wavelength range from 800 nm to 1100 nm before heating−average absorbance in the wavelength range from 800 nm to 1100 nm after heating) / before heating Average absorbance in the wavelength range of 800 nm to 1100 nm at | × 100 (%)
A: Change rate of absorbance is 3% or less B: Change rate of absorbance is greater than 3% and 4.5% or less C: Change rate of absorbance is greater than 4.5% and 6% or less D: Absorbance change rate is greater than 6%

As is clear from the above table, the near-infrared cut filters of the examples were excellent in heat resistance, and had excellent visible transparency and infrared shielding properties even after heating.

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 cut filter, 22 Antireflection layer

Claims

A near-infrared cut filter having a resin film containing a copper complex and a resin,
The copper complex is a compound represented by the following formula (1):
The total amount of the copper complex and the resin in the resin film is 60 to 100% by mass,
A near-infrared cut filter in which the resin does not form a three-dimensional bridge in the resin film;
Cu · (L) n1 · (X) n2 (1)
In the formula, L is a ligand, and at least one selected from a coordination site coordinated by an anion to a copper atom and a coordination atom coordinated by a lone pair to the copper atom. A compound having one or more, X is a counter ion, n1 represents an integer of 1 to 4, and n2 represents an integer of 0 to 4.
The near-infrared cut filter according to claim 1, wherein the ligand L in the formula (1) is a compound having no maximum absorption wavelength in a wavelength range of 400 to 600 nm.
The ligand L in the formula (1) is a total of at least one selected from a coordination site coordinated by an anion to a copper atom and a coordination atom coordinated by a lone pair to the copper atom. The near-infrared cut filter of Claim 1 or 2 which is a compound which has 2 or more by.
The near-infrared cut filter according to claim 1 or 2, wherein the ligand L in the formula (1) is at least one selected from a carboxylic acid compound, a sulfonic acid compound, and a phosphate ester compound.
The near-infrared cut filter according to any one of claims 1 to 4, wherein the resin film has a thickness of 1 to 500 µm.
6. The near-infrared cut filter according to claim 1, wherein the resin film contains 5% by mass or more of the copper complex.
A method for producing a near-infrared cut filter comprising a step of applying a resin composition comprising a copper complex and a resin on a support and drying to form a resin film,
The copper complex is a compound represented by the following formula (1):
The resin is a resin substantially free of crosslinkable groups;
A method for producing a near-infrared cut filter, wherein a total amount of the copper complex and the resin in the resin composition is 60 to 100% by mass with respect to a total solid content of the resin composition;
Cu · (L) n1 · (X) n2 (1)
In the formula, L is a ligand, and at least one selected from a coordination site coordinated by an anion to a copper atom and a coordination atom coordinated by a lone pair to the copper atom. A compound having one or more, X is a counter ion, n1 represents an integer of 1 to 4, and n2 represents an integer of 0 to 4.
A solid-state imaging device having the near-infrared cut filter according to any one of claims 1 to 6.
A camera module having the near infrared cut filter according to any one of claims 1 to 6.
An image display device comprising the near infrared cut filter according to any one of claims 1 to 6.