JP2016006476A - Near-infrared absorbing composition, near-infrared cut-off filter and method for manufacturing the same, and camera module and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a near-infrared absorbing composition which can form a cured film having a high transmitting property in the visible light region, a high screening property in the near-infrared region and sufficient moisture resistance; a near-infrared cut-off filter; and a camera module.SOLUTION: The near-infrared absorbing composition includes a copper complex having a mass increase rate of 25% or less based on the mass before being left for five hours under the conditions of 25°C and a relative humidity of 95%.

Description

  The present invention relates to a near-infrared absorbing composition, a near-infrared cut filter and a manufacturing method thereof, and a camera module and a manufacturing method thereof.

A CCD or CMOS, which is a solid-state image sensor for color images, is used in video cameras, digital still cameras, mobile phones with camera functions, and the like. 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.
As a material for forming such a near-infrared cut filter, for example, a near-infrared absorbing composition using a phosphate ester copper complex is known (Patent Documents 1 to 3).

JP 2002-69305 A Japanese Patent Laid-Open No. 11-52127 JP 2011-63814 A

  Here, the IR cut filter using the copper complex described in Patent Document 1 and Patent Document 2 has insufficient visible light transmittance, shielding property in the near-infrared region, and moisture resistance when used as a cured film. I understood. The present invention is intended to solve such problems, and when used as a cured film, it has high transparency in the visible light region and high shielding property in the near infrared region, and has sufficient moisture resistance. It aims at providing a near-infrared absorptive composition.

式（Ｉ）中、Ｘ¹は、アニオンで配位する配位部位を含む基を表す；Ｙ¹は、窒素原子またはリン原子を表し、隣接する炭素原子とともに４〜７員環を構成する；Ｒ^X1は、置換基を表し、ｎ１は、０〜６の整数を表す。
＜１２＞式（Ｉ）中、Ｙ¹が隣接する炭素原子とともに形成する環が芳香族環である、＜１１＞に記載の近赤外線吸収性組成物。
＜１３＞アニオンで配位する配位部位が、以下の群（ＡＮ）から選択される少なくとも１種であり、
群（ＡＮ）

非共有電子対で配位する配位原子が、環に含まれる、または、以下の群（ＵＥ）から選択される少なくとも１種の部分構造に含まれ、
群（ＵＥ）

波線は、化合物（Ａ）を構成する原子団との結合位置であり、
Ｘは、ＮまたはＣＲを表し、ＲおよびＲ¹は、それぞれ独立して水素原子、アルキル基、アルケニル基、アルキニル基、アリール基またはヘテロアリール基を表し、Ｒ²は、それぞれ独立して水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオ基、アリールチオ基、ヘテロアリールチオ基、アミノ基またはアシル基を表す、＜２＞〜＜７＞のいずれかに記載の近赤外線吸収性組成物。
＜１３−１＞アニオンで配位する配位部位が、以下の群（ＡＮ−１１）から選択される少なくとも１種である、＜１３＞に記載の近赤外線吸収性組成物；ＸおよびＲは、群（ＡＮ）のＸおよびＲと同義である。
群（ＡＮ−１１）

＜１４＞化合物（Ａ）が下記一般式（ＩＶ）で表される、＜２＞〜＜７＞のいずれかに記載の近赤外線吸収性組成物；
Ｘ¹−Ｌ¹−Ｙ¹ 一般式（ＩＶ）
一般式（ＩＶ）中、Ｘ¹は、以下の群（ＡＮ）から選択される少なくとも１種のアニオンで配位する配位部位を表し、
群（ＡＮ）

Ｙ¹は、非共有電子対で配位する配位原子を含む環、または、以下の群（ＵＥ）から選択される少なくとも１種の非共有電子対で配位する配位原子を含む部分構造を表し、
群（ＵＥ）

波線は、化合物（Ａ）を構成する原子団との結合位置であり、
Ｘは、ＮまたはＣＲを表し、ＲおよびＲ¹は、それぞれ独立して水素原子、アルキル基、アルケニル基、アルキニル基、アリール基またはヘテロアリール基を表し、Ｒ²は、それぞれ独立して水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオ基、アリールチオ基、ヘテロアリールチオ基、アミノ基またはアシル基を表し、Ｌ¹は、単結合または２価の連結基を表す。
＜１４−１＞Ｘ¹が、以下の群（ＡＮ−１１）から選択される少なくとも１種である、＜１４＞に記載の近赤外線吸収性組成物；ＸおよびＲは、群（ＡＮ）のＸおよびＲと同義である。
群（ＡＮ−１１）

＜１５＞硬化性化合物および溶剤をさらに含有する、＜１＞〜＜１４＞のいずれかに記載の近赤外線吸収性組成物。
＜１６＞＜１＞〜＜１５＞のいずれかに記載の近赤外線吸収性組成物を硬化してなる近赤外線カットフィルタ。
＜１７＞固体撮像素子と、固体撮像素子の受光側に配置された近赤外線カットフィルタとを有するカメラモジュールであって、近赤外線カットフィルタが＜１＞〜＜１５＞のいずれかに記載の近赤外線吸収性組成物を硬化してなる近赤外線カットフィルタである、カメラモジュール。 Under such circumstances, as a result of intensive studies by the present inventors, it has been found that the above problems can be solved by a specific copper complex. The present invention provides the following.
<1> A near-infrared absorptive composition comprising a copper complex having a mass increase rate of 25% or less based on a condition before standing for 5 hours at 25 ° C. and a relative humidity of 95%.
<2> The compound (A) in which the copper complex has a coordination site coordinated by an anion and a coordination atom coordinated by an unshared electron pair, and 2 coordinate atoms coordinated by an unshared electron pair The near-infrared absorptive composition as described in <1> which is a copper complex which uses as a ligand 1 or more types of compounds chosen from the compound (B) which has two or more.
<3> The copper complex is a copper complex having a compound (A) having a coordination site coordinated by an anion and a coordination atom coordinated by an unshared electron pair as a ligand. Near-infrared absorbing composition.
<4> The near-infrared absorbing composition according to <2>, wherein the copper complex has a 5-membered ring and / or a 6-membered ring formed of copper and a ligand compound.
<5> The anion is an oxygen anion, a nitrogen anion or a sulfur anion, and the coordination atom coordinated by a lone pair is an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, <2> to <4 > The near-infrared absorptive composition in any one of>.
<6> The near infrared ray according to any one of <2> to <5>, wherein the compound (A) has 1 to 3 atoms connecting the anion and a coordination atom coordinated by an unshared electron pair. Absorbent composition.
The near-infrared absorptive composition in any one of <2>-<6> whose molecular weight of the compound which makes a <7> ligand is 50-1000.
<8> The compound constituting the ligand is a compound containing a 5-membered ring or a 6-membered ring, and the coordination atom coordinated by the lone pair is an atom constituting a 5-membered ring or a 6-membered ring. The near-infrared absorptive composition in any one of 2>-<7>.
<9> The near-infrared absorbing composition according to any one of <2> to <8>, wherein the coordination atom coordinated by the lone pair is a nitrogen atom.
<10> The near-infrared absorbing composition according to <9>, wherein the atom adjacent to the nitrogen atom is a carbon atom, and the carbon atom has a substituent.
<11> The near-infrared absorbing composition according to any one of <2> to <7>, wherein the compound (A) is represented by the formula (I);

In formula (I), X ¹ represents a group containing a coordination site coordinated with an anion; Y ¹ represents a nitrogen atom or a phosphorus atom, and constitutes a 4- to 7-membered ring together with an adjacent carbon atom; R ^X1 represents a substituent, and n1 represents an integer of 0 to 6.
<12> The near-infrared absorbing composition according to <11>, wherein the ring formed by Y ¹ together with the adjacent carbon atom in formula (I) is an aromatic ring.
<13> The coordination site coordinated by an anion is at least one selected from the following group (AN):
Group (AN)

A coordinating atom coordinated by a lone pair is included in the ring, or included in at least one partial structure selected from the following group (UE):
Group (UE)

The wavy line is the bonding position with the atomic group constituting the compound (A),
X represents N or CR, R and R ¹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and R ² each independently represents a hydrogen atom. Represents an alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, amino group or acyl group, <2 >-<7> The near-infrared absorptive composition in any one of.
<13-1> The near-infrared absorbing composition according to <13>, wherein the coordination site coordinated with an anion is at least one selected from the following group (AN-11); , Synonymous with X and R in group (AN).
Group (AN-11)

<14> The near-infrared absorbing composition according to any one of <2> to <7>, wherein the compound (A) is represented by the following general formula (IV);
X ¹ -L ¹ -Y ¹ formula (IV)
In general formula (IV), X ¹ represents a coordination site coordinated with at least one anion selected from the following group (AN):
Group (AN)

Y ¹ is a ring containing a coordinating atom coordinated by an unshared electron pair, or a partial structure containing a coordinating atom coordinated by at least one unshared electron pair selected from the following group (UE) Represents
Group (UE)

The wavy line is the bonding position with the atomic group constituting the compound (A),
X represents N or CR, R and R ¹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and R ² each independently represents a hydrogen atom. Represents an alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, amino group or acyl group, L ¹ Represents a single bond or a divalent linking group.
<14-1> X ¹ is at least one selected from the following group (AN-11), near-infrared absorbing composition according to <14>; X and R are groups (AN) Synonymous with X and R.
Group (AN-11)

<15> The near-infrared absorbing composition according to any one of <1> to <14>, further comprising a curable compound and a solvent.
<16> A near-infrared cut filter formed by curing the near-infrared absorbing composition according to any one of <1> to <15>.
<17> A camera module having a solid-state imaging device and a near-infrared cut filter disposed on a light-receiving side of the solid-state image pickup device, wherein the near-infrared cut filter is a near-infrared filter according to any one of <1> to <15> A camera module, which is a near-infrared cut filter formed by curing an infrared absorbing composition.

  ADVANTAGE OF THE INVENTION According to this invention, when it was set as the cured film, it became possible to provide the near-infrared absorptive composition with the high transmittance | permeability in visible region, and the shielding property in a near-infrared region.

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

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “to” is used in the sense of including the numerical values described before and after it as lower and upper limits.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent. To do. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous. A monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
In the present specification, a polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
The measuring method of the weight average molecular weight and the number average molecular weight of the compound used in the present invention can be measured by gel permeation chromatography (GPC), and is defined as a polystyrene conversion value by GPC measurement. For example, HLC-8220 (manufactured by Tosoh Corporation) is used, TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) is used as a column, and 10 mmol / L lithium bromide NMP (N— It can be determined by using a methylpyrrolidinone) solution.
Near-infrared light refers to light (electromagnetic wave) having a maximum absorption wavelength region of 700 to 2500 nm.
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition. The solid content in the present invention is a solid content at 25 ° C.

<Near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention (hereinafter also referred to as the composition of the present invention) has a mass increase rate of 25% or less based on the condition before standing at 25 ° C. and a relative humidity of 95% for 5 hours. Contains certain copper complexes. Hereinafter, a test that is allowed to stand at 25 ° C. and a relative humidity of 95% may be simply referred to as a water absorption test. The copper complex preferably has a mass increase rate of 25% or less, more preferably 15% or less, based on the condition before standing for 5 hours at 25 ° C. and a relative humidity of 95%. % Is more preferable, within 5% is more preferable, and within 3% is particularly preferable. Moreover, the time of a water absorption rate test may be set long and may be set with 10 hours and 20 hours. Even in this case, the increase rate of the mass of the copper complex is preferably within 25%, more preferably within 15%, further preferably within 10%, and even more preferably within 5%. It is preferably 3% or less. The near-infrared cut filter having higher moisture resistance can be obtained as the mass increase rate when set for a long time is smaller. Moreover, the minimum of the increase rate of the mass of a copper complex is 0%, and it is preferable that the mass of a copper complex does not increase after a water absorption test.
As the copper complex, specifically, a compound (A) having a coordination site coordinated by an anion and a coordination atom coordinated by an unshared electron pair with respect to the copper component, and an unshared electron A copper complex obtained by reacting one or more compounds selected from compounds (B) having two or more coordination atoms coordinated in pairs, or a coordination site coordinated with an anion and an unshared electron pair Copper having as a ligand one or more compounds selected from a compound (A) having a coordinated atom and a compound (B) having two or more coordinated atoms coordinated by an unshared electron pair A complex.

According to the composition of the present invention, a near-infrared cut filter having high transmittance in the visible region, high near-infrared shielding properties, and sufficient water resistance can be obtained. Further, according to the present invention, the film thickness of the near-infrared cut filter can be reduced, which can contribute to the reduction in the height of the camera module.
The reason why such an effect of the present invention is obtained is not clear, but is estimated as follows. Compound (A) having at least one coordination atom coordinated by a copper component and an anion and a coordination atom coordinated by a lone pair, and two or more coordination atoms coordinated by a lone pair The compound (B) it has acts as a chelate ligand for the copper component.
That is, the coordination site coordinated by the anion of the compound (A) and the coordination atom coordinated by the lone pair, and the coordination atom coordinated by the lone pair of the compound (B) are copper, respectively. By chelate coordination with copper in the component, the structure of the copper complex is distorted, high transparency in the visible light region can be obtained, the ability to absorb near infrared light can be improved, and the color value is also considered to be improved.
Furthermore, copper complexes generally tend to absorb moisture in the air, but in the present invention, a copper complex with low water absorption can be designed as described above by selecting a specific ligand. It was. Accordingly, even if the near-infrared cut filter is used for a long period of time, its characteristics are not impaired, and the camera module can be stably manufactured.

The copper complex used in the present invention is a form of a copper complex (copper compound) in which a coordination atom coordinated by a lone pair of a compound (A) and a coordination site coordinated by an anion are chelated. One or more forms selected from the forms of a copper complex (copper compound) in which the coordination atoms coordinated by two unshared electron pairs of the compound (B) are chelated are preferable.
Copper in the copper complex used in the present invention is usually divalent copper, and can be obtained, for example, by mixing and reacting the compound (A) with a copper component (copper or a compound containing copper).
The copper complex used in the present invention is exemplified by 4-coordinate, 5-coordinate and hexacoordinate, and 4-coordinate and 5-coordinate are more preferred.
Here, if the structure of copper and compound (A) and / or compound (B) can be detected from the composition of the present invention, compound (A) and / or compound (B) in the composition of the present invention can be detected. It can be said that the copper complex which used as a ligand is formed. Examples of the method for detecting copper, compound (A) and compound (B) from the composition of the present invention include ICP emission analysis.

The copper complex used in the present invention preferably has a maximum absorption wavelength (λ _max ) in the near infrared wavelength region of 700 to 2500 nm, more preferably has a maximum absorption wavelength at 720 to 890 nm, and a maximum absorption at 730 to 880 nm. More preferably, it has a wavelength. The maximum absorption wavelength can be measured using, for example, Cary 5000 UV-Vis-NIR (Spectrophotometer manufactured by Agilent Technologies).

<< Compound (A) having at least one coordination atom coordinated by an anion and a coordinate atom coordinated by an unshared electron pair >>
The compound (A) has at least one coordination site coordinated by an anion in one molecule and may have two. In the compound (A), the total number of coordination atoms coordinated by an anion in one molecule and coordination atoms coordinated by a lone pair may be two or more, and may be three. There may be four.
The total number of coordination sites coordinated with anions and coordinated atoms coordinated with an unshared electron pair is three. Coordination sites coordinated with two anions and an unshared electron pair In the case of having a coordination atom that coordinates, there may be mentioned a case where it has a coordination site coordinated by one anion and a coordination atom coordinated by two unshared electron pairs.
The total number of coordination sites coordinated by anions and coordinated atoms coordinated by unshared electron pairs is four. Coordination sites coordinated by two anions and two unshared electron pairs are used. In the case of having a coordinating atom, a coordination site coordinated by one anion and a coordinating atom coordinated by three unshared electron pairs can be mentioned.
The maximum absorption wavelength (λmax) of the compound (A) is preferably 420 nm or less, more preferably 400 nm or less, and further preferably 350 nm or less. Further, the maximum absorption wavelength of the compound (A) is preferably 10 nm or more, and more preferably 50 nm or more. Moreover, it is preferable that the maximum absorption wavelength of a compound (A) does not exist in 430 nm or more.
A compound (A) can be used 1 type or in combination of 2 or more types.

化合物（Ａ）の分子量は、５０〜１０００が好ましく、５０〜６００がより好ましい。 In the compound (A), the number of atoms connecting the anion and the coordination atom coordinated by the lone pair is preferably 1 to 6, and more preferably 1 to 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.
One or two or more atoms may be connected to the anion and the coordination atom coordinated by the lone pair. The atom that connects the anion and the coordination atom coordinated by the lone pair is preferably a carbon atom.
In the following exemplary compounds, when a carboxylic acid proton is dissociated to form a carboxylate anion and coordinated to a copper ion as a ligand, the anion is an oxygen anion and coordinates with a lone pair of electrons. The coordinating atom is a nitrogen atom, and the atom connecting the anion and the coordinating atom coordinated by the lone pair is a carbon atom. The number of atoms connecting the anion and the coordinating atom coordinated by the lone pair is two. When the proton of this exemplary compound does not dissociate and coordinates to a copper ion in a nonionic state, it is interpreted as being coordinated by two unshared electron pairs of an oxygen atom and a nitrogen atom on the carboxylic acid. It is rare for example compounds to take such a coordination form.

50-1000 are preferable and, as for the molecular weight of a compound (A), 50-600 are more preferable.

In the compound (A), the anion may be any one that can coordinate to the copper atom in the copper component, and is preferably an oxygen anion, a nitrogen anion, or a sulfur anion.
The coordination site coordinated with an anion is preferably at least one selected from the following group (AN). In addition, the wavy line in the following structural formula is the bonding position with the atomic group constituting the compound (A).
Group (AN)

The coordination site coordinated by an anion is also preferably the following group (AN-11).
Group (AN-11)

In the coordination site coordinated with the anion, X represents N or CR, and each R preferably independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. .
The alkyl group may be linear, branched or cyclic, but is preferably linear. 1-10 are preferable, as for carbon number of an alkyl group, 1-6 are more preferable, and 1-4 are more preferable. Examples of the alkyl group include a methyl group. The alkyl group may have a substituent, and examples of the substituent include a halogen atom, a carboxyl group, and a 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.
1-10 are preferable and, as for carbon number of an alkenyl group, 1-6 are more preferable.
1-10 are preferable and, as for carbon number of an alkynyl group, 1-6 are more preferable.
The aryl group may be monocyclic or polycyclic, but is preferably monocyclic. 6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable.
The heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom or an oxygen atom. 6-18 are preferable and, as for carbon number of heteroaryl group, 6-12 are more preferable.

In the compound (A), 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, and further preferably a nitrogen atom. .
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, and the carbon atom preferably has a substituent.

It is preferable that the coordinating atom coordinated by the lone pair is included in the ring or in at least one partial structure selected from the following group (UE). In addition, the wavy line in the following structural formula is the bonding position with the atomic group constituting the compound (A).
Group (UE)

In the group (UE), each R ¹ independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and each R ² independently represents a hydrogen atom, an alkyl group, or an alkenyl group. Represents a group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, amino group or acyl group.

In the case where the ring includes a coordination atom that coordinates with an unshared electron pair, the ring that includes a coordination atom that coordinates with an unshared electron pair may be monocyclic or polycyclic, It may be aromatic or non-aromatic. As for the ring containing the coordinating | ligand atom coordinated by a lone pair, a 5-12 membered ring is preferable and a 5-7 membered ring is more preferable.
The ring containing a coordinating atom coordinated by a lone pair may have a substituent, and the substituent may be a hydrocarbon group (for example, having 1 to 30 carbon atoms (preferably 1 to 10 carbon atoms). Linear, branched or cyclic alkyl group, aryl group having 6 to 30 carbon atoms (preferably 6 to 12 carbon atoms), halogen atom, silicon atom, alkoxy group having 1 to 12 carbon atoms, carbon number 2 ˜12 acyl groups, C 1-12 alkylthio groups, carboxyl groups and the like. When the substituent is a hydrocarbon group, the hydrocarbon group is preferably a group composed of a combination with -O-.
When the ring containing the coordination atom coordinated by the lone pair has a substituent, the ring may further have a substituent, and from the ring containing the coordination atom coordinated by the lone pair Group, a group consisting of at least one partial structure selected from the group (UE) described above, an alkyl group having 1 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, and a hydroxy group.
When the ring containing the coordinating atom coordinated by the lone pair has a substituent, the substituent is preferably bonded to the atom bonded to the coordinating atom coordinated by the lone pair.

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

The compound (A) is also preferably represented by the following general formula (IV).
X ¹ -L ¹ -Y ¹ formula (IV)
In the general formula (IV), X ¹ represents a coordination site represented by the group (AN) or the group (AN-11) described above. Y ¹ represents a ring containing a coordinating atom coordinated by an unshared electron pair or a partial structure represented by a group (UE). L ¹ represents a single bond or a divalent linking group.
In the general formula (IV), X ¹ has the same meaning as coordination sites coordinating anion as described above, and preferred ranges are also the same.
In general formula (IV), Y ¹ is synonymous with the ring containing a coordination atom coordinated by the above-mentioned lone pair or the partial structure containing a coordination atom coordinated by the above-mentioned lone pair. The preferred range is also the same.
In the general formula (IV), when L ¹ represents a divalent linking group, an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —SO—, —O—, —SO ₂ — or , A group consisting of these combinations is preferable, and an alkylene group having 1 to 3 carbon atoms, a phenylene group, or —SO ₂ — is preferable.

群（ＡＮ−１２）

一般式（ＩＶ−１）〜（ＩＶ−８）中、Ｙ³、Ｙ⁵〜Ｙ⁷、Ｙ¹²〜Ｙ¹⁵はそれぞれ独立して、非共有電子対で配位する配位原子を含む環、または、上述した群（ＵＥ）から選択される少なくとも１種の部分構造を表す。また、Ｙ²、Ｙ⁴、Ｙ⁸〜Ｙ¹¹、Ｙ¹⁶はそれぞれ独立して、非共有電子対で配位する配位原子を含む環、または、以下の群（ＵＥ−１）から選択される少なくとも１種である。群（ＵＥ−１）中のＲは、非共有電子対で配位する配位原子が上述した群（ＵＥ）で表される部分構造に含まれる場合のＲ¹と同義である。波線は、化合物（Ａ）を構成する原子団との結合位置である。
群（ＵＥ−１）

As more detailed examples of the compound (A), compounds represented by the following general formulas (IV-1) to (IV-8) are also exemplified.
^{X 2 -L 2 -Y 2 -L 3} -X 3 (IV-1)
^{Y 3 -L 4 -Y 4 -L 5} -X 4 (IV-2)
^{Y 5 -L 6 -X 5 -L 7} -X 6 (IV-3)
^{Y 6 -L 7 -X 7 -L 8} -Y 7 (IV-4)
^{X 8 -L 9 -Y 8 -L 10} -Y 9 -L 11 -X 9 (IV-5)
^{X 9 -L 12 -Y 10 -L 13} -Y 11 -L 14 -Y 12 (IV-6)
^{Y 13 -L 15 -X 10 -L 16} -X 11 -L 17 -Y 14 (IV-7)
^{Y 15 -L 18 -X 12 -L 19} -Y 16 -L 20 -Y 17 (IV-8)
In the general formulas (IV-1) to (IV-8), X ^{2 to} X ⁴ , X ⁸ and X ⁹ are each independently selected from the group (AN) or the group (AN-11) described above. Represents at least one kind. X ⁵ , X ⁷ and X ^{10 to} X ¹² are each independently at least one selected from the following group (AN-1) or group (AN-12). X in group (AN-1) and group (AN-12) represents N or CR, and R has the same meaning as R described above for CR in group (AN). A wavy line is a coupling | bonding position with the atomic group which comprises a compound (A).
Group (AN-1)

Group (AN-12)

In general formulas (IV-1) to (IV-8), Y ³ , Y ^{5 to} Y ⁷ , and Y ^{12 to} Y ¹⁵ are each independently a ring containing a coordinating atom coordinated by a lone pair, Or at least 1 sort (s) of partial structure selected from the group (UE) mentioned above is represented. Y ² , Y ⁴ , Y ^{8 to} Y ¹¹ and Y ¹⁶ are each independently selected from a ring containing a coordination atom coordinated by an unshared electron pair, or the following group (UE-1): At least one kind. R in the group (UE-1) has the same meaning as R ^{1 in the} case where the coordinating atom coordinated by the lone pair is included in the partial structure represented by the group (UE) described above. A wavy line is a coupling | bonding position with the atomic group which comprises a compound (A).
Group (UE-1)

In general formulas (IV-1) to (IV-8), L ^{2 to} L ²⁰ each independently represents a single bond or a divalent linking group. A bivalent coupling group is synonymous with the case where L < ¹ > in general formula (IV) represents a bivalent coupling group, and its preferable range is also the same.

The compound (A) is also preferably a compound represented by the following general formulas (IV-11) to (IV-20).

In general formulas (IV-11) to (IV-20), Z ^{1 to} Z ³⁴ , Z ^{101 to} Z ¹⁰⁸ , and Z ^{201 to} Z ²⁰³ each independently represent a coordination site, and L ^{11 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. Represent.
Z ^{1 to} Z ³⁴ are each independently a group consisting of a ring containing a coordinating atom coordinated by a lone pair, at least one selected from the group (AN-11) or group (UE) described above. It is preferable to represent.
Z ^{101 to} Z ¹⁰⁸ are each independently selected from the group consisting of a ring containing a coordinating atom coordinated by a lone pair, the group (AN-12), or the group (UE-1) described above. It is preferable to represent at least one.
Z ^{201 to} Z ²⁰³ each independently preferably represent at least one selected from the following group (UE-2).
L ^{11 to} L ²⁵ each independently represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —SO—, —O—, —SO ₂ —, or a group consisting of these in combination. A group consisting of a C 1-3 alkylene group, a phenylene group, —SO ₂ — or a combination thereof is more preferred.
L ^{26 to} L ³² each independently represents a trivalent linking group. Examples of the trivalent linking group include groups obtained by removing one hydrogen atom from the above-described divalent linking group.
L ^{33 to} L ³⁴ each independently represents a tetravalent linking group. Examples of the tetravalent linking group include groups obtained by removing two hydrogen atoms from the above-described divalent linking group.
Group (UE-2)

  In addition, in the compound (A), it is preferable that a plurality of π-conjugated systems such as aromatic are not continuously bonded in order to improve visible light transmittance.

The compound (A) is also preferably a compound containing a 5-membered ring or a 6-membered ring, and it is also preferable that the coordinating atom coordinated by the lone pair constitutes a 5-membered ring or a 6-membered ring.
It is also preferred that the coordinating atom coordinated by the lone pair of compound (A) is a nitrogen atom. Moreover, it is also preferable that the atom adjacent to the nitrogen atom as a coordinating atom coordinated by the lone pair of the compound (A) is a carbon atom, and the carbon atom has a substituent. By setting it as such a structure, since the structure of a copper complex becomes easier to distort, color value can be improved more. A substituent is synonymous with the substituent which the ring containing the coordinating | ligand atom coordinated by the lone pair mentioned above may have, and a C1-C30 hydrocarbon group (for example, C1-C1). 30 alkyl groups, aryl groups having 6 to 30 carbon atoms), carboxyl groups, alkoxy groups having 1 to 12 carbon atoms, acyl groups having 1 to 12 carbon atoms, alkylthio groups having 1 to 12 carbon atoms, and halogen atoms are preferable. In particular, an alkyl group, an aryl group, a carboxyl group, and a halogen atom are preferable.

式（ＩＩ）中、Ｘ²は、アニオンで配位する配位部位を含む基を表す。Ｙ²は、酸素原子、窒素原子、硫黄原子またはリン原子を表す。Ａ¹およびＡ⁵は、それぞれ独立して炭素原子、窒素原子またはリン原子を表す。Ａ²〜Ａ⁴は、それぞれ独立して炭素原子、酸素原子、窒素原子、硫黄原子またはリン原子を表す。Ｒ¹は、置換基を表す。Ｒ^X2は、置換基を表す。ｎ２は０〜３の整数を表す。
式（ＩＩＩ）中、Ｘ³は、上記アニオンで配位する配位部位を含む基を表す。Ｙ³は、酸素原子、窒素原子、硫黄原子またはリン原子を表す。Ａ⁶およびＡ⁹は、それぞれ独立して炭素原子、窒素原子またはリン原子を表す。Ａ⁷およびＡ⁸は、それぞれ独立して炭素原子、酸素原子、窒素原子、硫黄原子またはリン原子を表す。Ｒ²は、置換基を表す。Ｒ^X3は、置換基を表す。ｎ３は０〜２の整数を表す。 The compound (A) is also preferably represented by the formula (II) or the formula (III).

In formula (II), X ² represents a group containing a coordination site coordinated by an anion. Y ² represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ¹ and A ⁵ each independently represent a carbon atom, a nitrogen atom or a phosphorus atom. A ^{2 to} A ⁴ each independently represents a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. R ¹ represents a substituent. R ^X2 represents a substituent. n2 represents an integer of 0 to 3.
In formula (III), X ³ represents a group containing a coordination site coordinated with the anion. Y ³ represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ⁶ and A ⁹ each independently represents a carbon atom, a nitrogen atom or a phosphorus atom. A ⁷ and A ⁸ each independently represent a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. R ² represents a substituent. R ^X3 represents a substituent. n3 represents an integer of 0-2.

In formula (II), X ² may consist of, for example, only a group containing a coordination site coordinated with the anion, or the group containing a coordination site coordinated with the anion has a substituent. You may do it. Examples of the substituent that the group containing a coordination site coordinated by an anion may have 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.
In formula (II), Y ² represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, preferably an oxygen atom, a nitrogen atom or a sulfur atom, more preferably an oxygen atom or a nitrogen atom, further preferably a nitrogen atom.
In the formula (II), A ¹ and A ⁵ each independently represent a carbon atom, a nitrogen atom or a phosphorus atom, preferably a carbon atom.
In formula (II), A ^{2 to} A ⁴ each independently represent a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ² and A ³ preferably represent carbon atoms. A ⁴ preferably represents a carbon atom or a nitrogen atom.
In Formula (II), R ¹ represents a substituent, and when the atom adjacent to the nitrogen atom as the coordination atom coordinated by the lone pair of the compound (A) described above is a carbon atom, It is synonymous with the substituent which the said carbon atom has, and its preferable range is also the same. R ¹ is preferably a hydrophobic substituent from the viewpoint of water absorption, more preferably a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and alkyl having 1 to 30 carbon atoms. Group or an aryl group having 6 to 30 carbon atoms is more preferable, and an alkyl group having 1 to 10 carbon atoms is particularly preferable. When R ¹ represents an alkyl group, a primary or secondary alkyl group is preferable, and a primary alkyl group is more preferable.
In the formula (II), R ^X2 represents a substituent, and has the same meaning as the substituent that the ring containing a coordinating atom coordinated by the above-mentioned lone pair may have, and the preferred range is also the same. is there. R ^X2 is preferably a substituent of any one of A ^{2 to} A ⁴ in formula (II), and it is preferable that Y ² is not substituted.
In formula (II), n2 represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
When compound (A) is represented by formula (II), the heterocyclic ring containing Y ² in formula (II) may be a monocyclic structure or a polycyclic structure. Specific examples when the heterocycle containing Y ² has a monocyclic structure include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a pyran ring, and the like. Specific examples when the heterocycle containing Y ² has a polycyclic structure include a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring and the like.
When the compound (A) is a compound containing a pyridine ring and has a primary or secondary alkyl group at the 6-position of the pyridine ring, the transmittance in the visible light region can be further improved. In the present specification, when the compound (A) is a compound containing a pyridine ring, the 6-position of the pyridine ring means that Y ² in the above formula (II) represents a nitrogen atom, and A ^{1 to} A ⁵ are carbon atoms. Is the substitution position of R ¹ . When the compound (A) has a primary or secondary alkyl group at the 6-position of the pyridine ring, the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3. When the compound (A) has a primary or secondary alkyl group at the 6-position of the pyridine ring, the alkyl group is preferably a group composed of a combination with —O—. The alkyl group that the compound (A) has at the 6-position of the pyridine ring is preferably a primary alkyl group.

In formula (III), X ³ represents a group containing a coordination site coordinated by an anion, which is synonymous with X ² in formula (II), and the preferred range is also the same.
In formula (III), Y ³ represents an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, preferably an oxygen atom, a nitrogen atom or a sulfur atom, and more preferably an oxygen atom or a nitrogen atom.
In formula (III), A ⁶ and A ⁹ each independently represent a carbon atom, a nitrogen atom or a phosphorus atom. A ⁶ is preferably a carbon atom or a nitrogen atom. A ⁹ is preferably a carbon atom.
In the formula (III), A ⁷ and A ⁸ each independently represent a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A ⁷ is preferably a carbon atom. A ⁸ is preferably a carbon atom, a nitrogen atom or a sulfur atom.
In formula (III), R ² represents a substituent and has the same meaning as R ¹ in formula (II). R ² is preferably a hydrophobic substituent from the viewpoint of water absorption, more preferably a hydrocarbon group having 1 to 30 carbon atoms, an alkyl group having 3 to 30 carbon atoms, or 6 to 6 carbon atoms. A 30 aryl group is more preferable, and an alkyl group having 3 to 15 carbon atoms is particularly preferable. When R ² represents an alkyl group, a secondary or tertiary alkyl group is preferred.
In formula (III), R ^X3 represents a substituent, and has the same meaning as R ^X2 in formula (II), and the preferred range is also the same.
In the formula (III), n3 represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
Note that R ^x1 and R ^X2 are preferably not a substituent in which a plurality of π-conjugated systems are continuously bonded in order to improve visible light transmittance.
When compound (A) is represented by formula (III), the heterocycle containing Y ³ in formula (III) may be a monocyclic structure or a polycyclic structure. Specific examples when the heterocycle containing Y ³ has a monocyclic structure include a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, an isothiazole ring, and the like. Specific examples when the heterocycle containing Y ³ has a polycyclic structure include an indole ring, an isoindole ring, a benzofuran ring, an isobenzofuran ring, and the like.
When the compound (A) is a compound containing a pyrazole ring and has a secondary or tertiary alkyl group at the 5-position of the pyrazole ring, the transparency in the visible light region can be further improved. In this specification, when the compound (A) is a compound containing a pyrazole ring, the 5-position of the pyrazole ring means that Y ³ and A ⁶ in the above formula (III) represent a nitrogen atom, and A ^{7 to} A ⁹ Refers to the substitution position of R ² when represents a carbon atom. When the compound (A) has a secondary or tertiary alkyl group at the 5-position of the pyrazole ring, the number of carbon atoms of the alkyl group is preferably from 3 to 15, and more preferably from 3 to 12.

式（Ｉ）中、Ｘ¹は、アニオンで配位する配位部位を含む基を表す。Ｙ¹は、窒素原子またはリン原子を表し、隣接する炭素原子とともに４〜７員環を構成する。Ｒ^X1は、置換基を表し、ｎ１は、０〜６の整数を表す。
式（Ｉ）中、Ｘ¹は、アニオンで配位する配位部位を含む基を表し、式（ＩＩ）中のＸ²と同義であり、好ましい範囲も同様である。
式（Ｉ）中、Ｙ¹は、窒素原子またはリン原子を表し、隣接する炭素原子とともに４〜７員環を構成する。特に、式（Ｉ）中のＹ¹は、窒素原子を表し、隣接する炭素原子とともに５または６員環を構成することが好ましい。式（Ｉ）中、Ｒ^X1は、置換基を表し、上述した非共有電子対で配位する配位原子が環に含まれる場合に有していてもよい置換基と同義であり、好ましい範囲も同様である。
なお、Ｒ^x1は、可視光透過性を向上させるために、π共役系が連続して複数結合している置換基でないことが好ましい。
式（Ｉ）中、ｎ１は、０〜６の整数を表し、０〜２が好ましく、０または１がより好ましい。 The compound (A) is also preferably represented by the following formula (I). By setting it as such a structure, heat resistance can be improved more.

In formula (I), X ¹ represents a group containing a coordination site coordinated by an anion. Y ¹ represents a nitrogen atom or a phosphorus atom and constitutes a 4- to 7-membered ring together with the adjacent carbon atom. R ^X1 represents a substituent, and n1 represents an integer of 0 to 6.
In formula (I), X ¹ represents a group containing a coordination site coordinated by an anion, which is synonymous with X ² in formula (II), and the preferred range is also the same.
In formula (I), Y ¹ represents a nitrogen atom or a phosphorus atom, and constitutes a 4- to 7-membered ring together with an adjacent carbon atom. In particular, Y ¹ in formula (I) represents a nitrogen atom, and preferably forms a 5- or 6-membered ring together with the adjacent carbon atom. In formula (I), R ^X1 represents a substituent, and is synonymous with the substituent that may be possessed when the above-described coordination atom coordinated by the lone pair is contained in the ring, and a preferred range Is the same.
Note that R ^x1 is preferably not a substituent in which a plurality of π-conjugated systems are continuously bonded in order to improve visible light transmittance.
In formula (I), n1 represents the integer of 0-6, 0-2 are preferable and 0 or 1 is more preferable.

式（１）中、Ｒ¹は、炭化水素基を表す。Ｒ²およびＲ³は、それぞれ独立して水素原子、ハロゲン原子または１価の有機基を表す。Ｒ¹と、Ｒ²またはＲ³とは、互いに結合して環を形成していてもよい。 Moreover, it is also preferable that a compound (A) is represented by Formula (1).

In formula (1), R ¹ represents a hydrocarbon group. R ² and R ³ each independently represents a hydrogen atom, a halogen atom or a monovalent organic group. R ¹ and R ² or R ³ may be bonded to each other to form a ring.

  By using the composition of the present invention, the transparency in the visible light region can be lowered when the cured film is formed, and the near-infrared shielding property can also be enhanced.

In formula (1), R ¹ represents a hydrocarbon group, and preferably represents an alkyl group or an aryl group.
When R ¹ in Formula (1) represents an alkyl group, the alkyl group may be linear, branched or cyclic. 1-12 are preferable, as for carbon number of an alkyl group, 1-10 are more preferable, and 1-5 are more preferable. Specifically, the alkyl group is preferably a methyl group, an ethyl group or a propyl group. When R ¹ in formula (1) represents an alkyl group, it may further have a substituent. Examples of the substituent that the alkyl group may have include an alkyloxy group, an alkylcarbonyl group, an acyl group, an alkoxycarbonyl group, a halogen atom (for example, a fluorine atom), a heterocyclic group (for example, an oxolane ring, an oxane ring, and a dioxolane). Ring, furan ring, dioxane ring, pyran ring), polymerizable group (for example, vinyl group, (meth) acryloyl group) and the like. The alkyl group having a substituent may further have a substituent.
When R < ¹ > in Formula (1) represents an aryl group, 6-18 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable. The aryl group is preferably a phenyl group. When R ¹ in Formula (1) represents an aryl group, it may further have a substituent. The substituent that the alkyl group may have has the same meaning as in the case where R ¹ in formula (1) represents an alkyl group.

In formula (1), R ² and R ³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group.
The first aspect of the embodiment of the present invention is an aspect in which both R ² and R ³ are hydrogen atoms in the formula (1), and the second aspect of the embodiment of the present invention is the formula (1). Among these, at least one of R ² and R ³ is an embodiment representing a halogen atom or a monovalent organic group, and both are preferred.
When R ² and R ^{3 in} formula (1) represent a halogen atom, a fluorine atom is preferred.
When R ² and R ³ in the formula (1) represent a monovalent organic group, an alkyl group or an aryl group is preferable, and an alkyl group is more preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. 1-8 are preferable and, as for carbon number of an alkyl group, 1-5 are more preferable. In particular, the alkyl group is preferably a methyl group, an ethyl group or a propyl group. 6-18 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable. The aryl group is preferably a phenyl group.

In formula (1), it is also preferable that R ¹ and R ² are bonded to each other to form a 5-membered or 6-membered ring containing an oxygen atom, and R ³ is a hydrogen atom.
The 5-membered ring or 6-membered ring containing an oxygen atom may be an aromatic ring or a non-aromatic ring. However, from the viewpoint of transparency in the visible light region and shielding property in the near-infrared region, the non-aromatic ring is preferable. The 5-membered or 6-membered ring containing an oxygen atom is preferably an aromatic ring from the viewpoint of improving the results of the water absorption test. The atoms constituting the 5-membered or 6-membered ring containing an oxygen atom are preferably an oxygen atom and a carbon atom. 1-3 are preferable, as for the number of the oxygen atoms in the 5-membered ring or 6-membered ring containing an oxygen atom, 1 or 2 is more preferable, and 1 is more preferable. 1-5 are preferable and, as for the number of the carbon atoms in the 5-membered ring or 6-membered ring containing an oxygen atom, 4 or 5 is more preferable. Specific examples of the 5-membered or 6-membered ring containing an oxygen atom include an oxolane ring, an oxane ring, a dioxolane ring, a furan ring, a dioxane ring, and a pyran ring.

式（２）中、Ｒ¹²およびＲ¹³は、それぞれ独立して水素原子、ハロゲン原子または１価の有機基を表す。Ｌは、ｎ価の炭化水素基、または、炭化水素基と−Ｏ−との組み合わせからなるｎ価の基を表す。ｎは２〜６の整数を表す。 The compound represented by the formula (1) is also preferably represented by the formula (2).
Formula (2)

In the formula (2), R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group. L represents an n-valent hydrocarbon group or an n-valent group composed of a combination of a hydrocarbon group and —O—. n represents an integer of 2 to 6.

In formula (2), R ¹² and R ¹³ have the same meanings as R ² and R ^{3 in} formula (1), and preferably both represent hydrogen atoms.
In formula (2), L represents an n-valent hydrocarbon group or an n-valent group composed of a combination of a hydrocarbon group and —O—. The hydrocarbon group may be linear, branched or cyclic. 2-12 are preferable and, as for carbon number in case a hydrocarbon group is linear, 2-5 are more preferable. 3-12 are preferable and, as for carbon number in case a hydrocarbon group is branched, 6-10 are more preferable. 3-12 are preferable, as for carbon number in case a hydrocarbon group is cyclic, 6-12 are more preferable, and 6 is more preferable. When the hydrocarbon group is cyclic, it may be an aromatic ring or a non-aromatic ring, but a non-aromatic ring is preferred. The hydrocarbon group is preferably branched or cyclic from the viewpoint of improving the water absorption test result.
In Formula (2), n represents an integer of 2 to 6, an integer of 2 to 4 is preferable, 2 or 3 is more preferable, and 2 is more preferable.

  1-3 are preferable and, as for the carboxyl group equivalent of the compound represented by Formula (1), 1-2 are more preferable.

<< Compound (B) having two or more coordination atoms coordinated by an unshared electron pair >>
The compound (B) may have two or more coordination atoms coordinated by a lone pair in one molecule, may have three or more, and has two to five. Preferably, it has four.
The maximum absorption wavelength (λmax) of the compound (B) is preferably 420 nm or less, more preferably 400 nm or less, and further preferably 350 nm or less. Moreover, 10 nm or more is preferable and, as for the maximum absorption wavelength of a compound (B), 50 nm or more is more preferable. Moreover, it is preferable that the maximum absorption wavelength of a compound (B) does not exist in 430 nm or more.
The compound (B) may or may not have a coordination site coordinated by the above-described anion in the molecule. A compound (B) can be used 1 type or in combination of 2 or more types.
In the compound (B), the number of atoms connecting the coordinating atoms coordinated by an unshared electron pair is preferably 1 to 6, more preferably 1 to 3, and still more preferably 2 to 3. . By setting it as such a structure, since the structure of a copper complex becomes easier to distort, color value can be improved more.
1 type (s) or 2 or more types may be sufficient as the atom which connects the coordination atoms coordinated by a lone pair. The atom connecting the coordinating atoms coordinated by the lone pair is preferably a carbon atom.
The number of unsaturated bonds that the compound (B) may have is preferably 9 or less, and more preferably 1-9.
50-1000 are preferable and, as for the molecular weight of a compound (B), 50-600 are more preferable.

In the compound (B), 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, and further preferably a nitrogen atom. .
Moreover, it is preferable that the coordinating | ligand atom coordinated by a lone pair is contained in the ring or at least 1 type of partial structure selected from (UE) mentioned above.
As for the details of the coordination atom coordinated by the lone pair, those described for the compound (A) can be mentioned, and the preferred ranges are also the same.

The compound (B) is also preferably represented by the following general formula (IVa).
Y ^1a -L ^1a -Y ^2a general formula (IVa)
In General Formula (IVa), Y ^1a and Y ^2a each independently represent a ring containing a coordination atom coordinated by an unshared electron pair or a partial structure represented by the group (UE). As the partial structure represented by the ring or the group (UE) containing the coordinating atom coordinated by the lone pair, those described in the compound (A) can be mentioned, and the preferred ranges are also the same.
L ^1a represents a single bond or a divalent linking group. When L ^1a represents a divalent linking group, a group consisting of an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —SO—, —O—, or a combination thereof is preferable. A C 1-3 alkylene group, a phenylene group or —SO ₂ — is preferable.

As a more detailed example of compound (B), the compound represented with the following general formula (IV-1a) or (IV-2a) is also mentioned.
^{Y 3a -L 2a -Y 4a -L 3a} -Y 5a (IV-1a)
^{Y 6a -L 6a -Y 7a -L 7a} -Y 8a -L 8a -Y 9a (IV-2a)
Y ^3a , Y ^5a , Y ^6a and Y ^9a each independently represent a ring containing a coordination atom coordinated by an unshared electron pair or a partial structure represented by the group (UE) described above.
Y ^4a , Y ^7a and Y ^8a are each independently at least one selected from the ring containing a coordination atom coordinated by an unshared electron pair, or the group (UE-1) described above.
L ^{2a to} L ^8a each independently represents a single bond or a divalent linking group. The divalent linking group is synonymous with the case where L ^1a in the general formula (IVa) represents a divalent linking group, and the preferred range is also the same.

The compound (B) is also preferably a compound represented by the following general formulas (IV-11a) to (IV-20a). Especially, the compound represented by the following general formula (IV-18a) is more preferable.

In formulas (IV-11a) to (IV-20a), Z ^{1a to} Z ^34a , Z ^{101a to} Z ^108a , Z ^{201a to} Z ^203a each independently represent a coordination site, and L ^{11a to} L ^25a Each independently represents a single bond or a divalent linking group, L ^{26a to} L ^32a each independently represents a trivalent linking group, and L ^{33a to} L ^34a each independently represents a tetravalent linking group. Represent.
Z ^{1a to} Z ^34a each independently represent at least one selected from the group consisting of a ring containing a coordinating atom coordinated by an unshared electron pair and the group (UE) described above.
Z ^{101a to} Z ^108a each independently represent at least one selected from the group consisting of a ring containing a coordinating atom coordinated by a lone pair or the group (UE-1) described above.
Z ^{201a to} Z ^203a each independently represent at least one selected from the group (UE-2) described above.
L ^{11a to} L ^25a each independently represents a single bond or a divalent linking group. As a bivalent coupling group, it is synonymous with the case where L ^<1a > in general formula (IVa) represents a bivalent coupling group, and its preferable range is also the same.
L ^{26a to} L ^32a 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 ^{33a to} L ^34a each independently represents a tetravalent linking group. Examples of the tetravalent linking group include groups obtained by removing two hydrogen atoms from the above-described divalent linking group.

The compound (B) is also preferably a compound containing a 5-membered ring or a 6-membered ring, and it is also preferable that the coordination atom coordinated by the lone pair constitutes a 5-membered ring or a 6-membered ring.
It is also preferred that the coordinating atom coordinated by the lone pair of compound (B) is a nitrogen atom. Moreover, it is also preferable that the atom adjacent to the nitrogen atom as a coordinating atom coordinated by the lone pair of the compound (B) is a carbon atom, and the carbon atom has a substituent. By setting it as such a structure, since the structure of a copper complex becomes easier to distort, color value can be improved more. A substituent is synonymous with the substituent which the ring containing the coordination atom coordinated by the lone pair mentioned above may have, a C1-C10 alkyl group, a C6-C12 aryl. Group, a carboxyl group, a C1-C12 alkoxy group, a C2-C12 acyl group, a C1-C12 alkylthio group, and a halogen atom are preferable.

Specific examples of the compound (A) and the compound (B) include the following compounds and salts of the following compounds (for example, metal salts (alkali metal salts) such as sodium), but are not limited thereto. . By using the following compounds, a copper complex with low water absorption can be designed.

<< other compounds >>
The copper complex used in the present invention has, as a ligand, a compound having two coordination sites coordinated by anions and not having a coordination atom coordinated by a lone pair of electrons. Also good. Examples of such compounds include the following.

<< monodentate ligand >>
The copper complex used in the present invention may have a monodentate ligand coordinated by an anion or an unshared electron pair. Examples of ligands coordinated with anions include halide anions, hydroxide anions, alkoxide anions, phenoxide anions, amide anions (including amides substituted with acyl groups and sulfonyl groups), and imide anions (acyl groups and sulfonyl groups). Substituted imides), anilide anions (including acylides and sulfonyl substituted anilides), thiolate anions, bicarbonate anions, carboxylate anions, thiocarboxylate anions, dithiocarboxylate anions, hydrogen sulfate anions, sulfones Acid anion, phosphate dihydrogen anion, phosphate diester anion, phosphonate monoester anion, hydrogen phosphonate anion, phosphinate anion, nitrogen-containing heterocyclic anion, nitrate anion, hypochlorite anion, cyanide anion Cyanate anion, isocyanate anion, thiocyanate anion, isothiocyanate anions, such as azide anions. Monodentate ligands coordinated by lone pairs include water, alcohol, phenol, ether, amine, aniline, amide, imide, imine, nitrile, isonitrile, thiol, thioether, carbonyl compound, thiocarbonyl compound, sulfoxide, Examples include heterocycles, carbonic acid, carboxylic acid, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, phosphinic acid, nitric acid, and esters thereof. The kind and number of monodentate ligands can be appropriately selected according to the compound (A) coordinated to the copper complex. Specific examples of the monodentate ligand include the following, but are not limited thereto.

The copper complex used in the present invention may become a cation complex or an anion complex in addition to a neutral complex having no charge, depending on the number of coordination sites coordinated by an anion. In this case, counter ions are present as necessary to neutralize the charge of the copper complex.
When the counter ion is a negative counter ion, for example, an inorganic anion or an organic anion may be used. Specific examples include hydroxide ions, halogen anions (eg, fluoride ions, chloride ions, bromide ions, iodide ions, etc.), substituted or unsubstituted alkylcarboxylate ions (acetate ions, trifluoroacetic acid, etc.) ), Substituted or unsubstituted arylcarboxylate ions (such as benzoate ions), substituted or unsubstituted alkylsulfonate ions (such as methanesulfonate and trifluoromethanesulfonate ions), substituted or unsubstituted arylsulfonate ions ( For example, p-toluenesulfonic acid ion, p-chlorobenzenesulfonic acid ion, etc.), aryl disulfonic acid ion (for example, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion, etc.) ), Alkyl sulfate ions (eg Til sulfate ion, sulfate ion, thiocyanate ion, nitrate ion, perchlorate ion, tetrafluoroborate ion, tetraarylborate ion, hexafluorophosphate ion, picrate ion, amide ion (acyl group or sulfonyl group) And methide ions (including methides substituted with acyl groups and sulfonyl groups), halogen anions, substituted or unsubstituted alkylcarboxylate ions, sulfate ions, nitrate ions, tetrafluoro A borate ion, a tetraarylborate ion, a hexafluorophosphate ion, an amide ion (including an amide substituted with an acyl group or a sulfonyl group), or a methide ion (including a metide substituted with an acyl group or a sulfonyl group) is preferable.
When the counter ion is a positive counter ion, for example, inorganic or organic ammonium ion (for example, tetraalkylammonium ion such as tetrabutylammonium ion, triethylbenzylammonium ion, pyridinium ion, etc.), phosphonium ion (for example, tetrabutylphosphonium) Tetraalkylphosphonium ions such as ions, alkyltriphenylphosphonium ions, triethylphenylphosphonium ions, etc.), alkali metal ions or protons.
Further, the counter ion may be a metal complex ion, and in particular, the counter ion may be a copper complex, that is, a salt of a cationic copper complex and an anionic copper complex.

<< Copper component >>
As the copper component used in the present invention, copper or a compound containing copper can be used. As the compound containing copper, for example, copper oxide or a copper salt can be used. The copper salt is preferably monovalent or divalent copper, and more preferably divalent copper. Copper salts include copper acetate, copper chloride, copper formate, copper hydroxide, copper stearate, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate, copper citrate, copper nitrate, copper sulfate, copper carbonate Copper chlorate, copper (meth) acrylate, and copper perchlorate are more preferable, and copper acetate, copper chloride, copper sulfate, copper hydroxide, copper benzoate, and copper (meth) acrylate are more preferable.
The amount of the copper component to be reacted with the compound (A) is preferably 1: 0.5 to 1: 8 in a molar ratio (compound (A): copper component), and is 1: 0.5 to 1: 4. More preferably.
Moreover, it is preferable that the reaction conditions at the time of making a copper component and a compound (A) react are 20-50 degreeC, for 0.5 hour or more, for example.
Specific examples of the copper complex include the examples shown in the following table, but are not limited thereto.
Compounds (A) and (B) in the table represent the compounds described above and the compounds shown below. Moreover, the monodentate ligand in a table | surface represents the compound mentioned above and a monodentate ligand. In the following tables, Ph represents a phenyl group.
In addition, as for the copper complex used by this invention, components (solvent, various additives, etc.) other than the copper complex of the composition of this invention may further coordinate, and a part of ligand of a copper complex May exist in a state where it is replaced with a component other than the copper complex. This is a property common to copper (II) complexes having substitution active d ⁹ electron configurations.

The content of the copper complex in the composition of the present invention (as well as the copper complex obtained by reacting one or more compounds selected from the compound (A) and the compound (B) with a copper component) is the composition of the present invention. 1 mass% or more is preferable with respect to (a solvent is also included), and 5 mass% or more is more preferable. Moreover, 1-60 mass% is preferable with respect to the composition (a solvent is included) of this invention, and, as for content of the copper complex in the composition of this invention, 5-40 mass% is more preferable, and 5-20 mass. % Is more preferable.
15 mass% or more is preferable with respect to the total solid of the composition of this invention, content of the copper complex in the composition of this invention has more preferable 20 mass% or more, and 25 mass% or more is further more preferable. The content of the copper complex in the composition of the present invention is preferably 15 to 60% by mass, more preferably 20 to 50% by mass, and further preferably 25 to 45% by mass with respect to the total solid content of the composition of the present invention. preferable.
0-20 mass% is preferable with respect to the composition of this invention, and, as for content of other copper complexes (near-infrared absorptive substance) other than the said copper complex in the composition of this invention, 0-10 mass% is. More preferably, 0-5 mass% is further more preferable.
1 mass% or more is preferable with respect to the composition, and, as for the total solid of the near-infrared absorptive composition of this invention, 10 mass% or more is more preferable. Moreover, it is preferable that it is 1-50 mass% with respect to the composition, as for the total solid of the near-infrared absorptive composition of this invention, it is more preferable that it is 1-40 mass%, and 10-35 mass%. More preferably.
Of the near-infrared absorbing substance contained in the composition of the present invention, the proportion of the compound obtained by reacting one or more compounds selected from the compound (A) and the compound (B) with a copper component is 80% by mass. The above is preferable, 90 mass% or more is more preferable, and 95 mass% or more is further preferable.
0.1 mass% or more is preferable with respect to the total solid of a composition, as for copper content in the composition of this invention, 1 mass% or more is more preferable, and 5 mass% or more is further more preferable. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.
The composition of this invention may use the copper complex used by this invention mentioned above individually by 1 type, and may use 2 or more types together. When using 2 or more types of copper complexes used by this invention mentioned above, it is preferable that the total amount is in the said range.

  Although the near-infrared absorptive composition of this invention should just contain the copper complex mentioned above, as needed, another near-infrared absorptive compound, a solvent, a sclerosing | hardenable compound, a binder polymer, surfactant, You may mix | blend a polymerization initiator and another component.

<< Other near-infrared absorbing compounds >>
Other near-infrared absorbing compounds that can be used in the present invention include a copper compound obtained by a reaction between a compound containing a low molecular (for example, a molecular weight of 1000 or less) coordination site and a copper component, and a coordination site. The copper compound obtained by reaction with the polymer and copper component to contain can be used. Examples of the coordination site include a coordination site coordinated by an anion such as an acid group or a salt of an acid group, and a coordination atom coordinated by an unshared electron pair.
When the composition of the present invention contains another near-infrared absorbing compound, the content of the other near-infrared absorbing compound is 0.01% by mass or more based on the total solid content of the composition of the present invention. Is preferable, 1 mass% or more is more preferable, and 5 mass% or more is further more preferable. The upper limit is preferably 60% by mass or less, more preferably 40% by mass or less, and further preferably 20% by mass or less. In addition, this invention can also be set as the composition which does not contain another near-infrared absorptive compound.

(Low molecule type)
A copper complex represented by the following formula (i) can be used as a compound obtained by the reaction of a compound containing a coordination site and a copper component, which can be used in the present invention.
Cu (L) _n1 · (X) _n2 formula (i)
In the above formula (i), L represents a ligand coordinated to copper, and X does not exist or is a halogen atom, H ₂ O, NO ₃ , ClO ₄ , SO ₄ , CN, SCN, or BF _4. , PF ₆ , BPh ₄ (Ph represents a phenyl group) or alcohol. n1 and n2 each independently represents an integer of 1 to 4.
The ligand L has a substituent containing C, N, O, and S as atoms capable of coordinating to copper, and more preferably has a group having a lone pair such as N, O, and S It is. The group capable of coordinating is not limited to one type in the molecule and may include two or more types, and may be dissociated or non-dissociated. In the case of non-dissociation, X is not present.
The copper complex is a copper compound in which a ligand is coordinated to copper as a central metal, and copper is usually divalent copper. For example, it can be obtained by mixing and reacting a compound serving as a ligand or a salt thereof with a copper component.
Although it does not specifically limit as a compound used as the said ligand or its salt, For example, the compound containing at least 1 sort (s) selected from the group (AN) mentioned above is mentioned, For example, an organic acid compound (For example, a sulfonic acid compound, Preferred examples include carboxylic acid compounds, phosphoric acid compounds) or salts thereof.

（一般式（ｉｉ）中、Ｒ¹はｎ価の有機基を表し、Ｘ¹は酸基を表し、ｎ３は１〜６の整数を表す。）
一般式（ｉｉ）中、ｎ価の有機基は、炭化水素基またはオキシアルキレン基が好ましく、脂肪族炭化水素基または芳香族炭化水素基がより好ましい。炭化水素基は、置換基を有していてもよく、置換基としては、ハロゲン原子（好ましくはフッ素原子）、（メタ）アクリロイル基、不飽和二重結合を有する基が挙げられる。また、置換基としては、アルキル基、重合性基（例えば、ビニル基、エポキシ基、オキセタン基など）、スルホン酸基、カルボン酸基、リン原子を含有する酸基、カルボン酸エステル基（例えば−ＣＯ₂ＣＨ₃）、水酸基、アルコキシ基（例えばメトキシ基）、アミノ基、カルバモイル基、カルバモイルオキシ基、ハロゲン化アルキル基（例えばフルオロアルキル基、クロロアルキル基）等も挙げられる。炭化水素基が置換基を有する場合、さらに置換基を有していてもよく、置換基としてはアルキル基、上記重合性基、ハロゲン原子等が挙げられる。
上記炭化水素基が１価の場合、アルキル基またはアリール基が好ましく、アリール基がより好ましい。また、上記炭化水素基が１価の場合、アルケニル基であってもよい。２価の場合、アルキレン基、アリーレン基、オキシアルキレン基が好ましく、アリーレン基がより好ましい。また３価以上の場合には、上記１価の炭化水素基または２価の炭化水素基に対応するものが好ましい。
上記アルキル基およびアルキレン基の炭素数は、１〜２０が好ましく、１〜１０がより好ましい。アルキル基及びアルキレン基は、直鎖状、分岐状または環状のいずれであってもよい。直鎖状のアルキル基及びアルキレン基の炭素数は、１〜２０が好ましく、１〜１２がより好ましく、１〜８がさらに好ましい。分岐状のアルキル基及びアルキレン基の炭素数は、３〜２０が好ましく、３〜１２がより好ましく、３〜８がさらに好ましい。環状のアルキル基及びアルキレン基は、単環、多環のいずれであってもよい。環状のアルキル基及びアルキレン基の炭素数は、３〜２０が好ましく、４〜１０がより好ましく、６〜１０がさらに好ましい。
アルケニル基の炭素数は、２〜１０が好ましく、２〜８がより好ましく、２〜４がさらに好ましい。
上記アリール基およびアリーレン基の炭素数は、６〜１８が好ましく、６〜１４がより好ましく、６〜１２がさらに好ましく、６〜１０が特に好ましい。
一般式（ｉｉ）中、Ｘ¹は、例えば、リン原子を含有する酸基（リン酸ジエステル基、ホスホン酸モノエステル基、ホスフィン酸基等）、スルホ基、カルボキシル基、ヒドロキシル基等が挙げられる。Ｘ¹は、１種単独でも２種以上であってもよいが、２種以上であることが好ましく、スルホ基及びカルボキシ基を有するものが好ましい。
一般式（ｉｉ）中、ｎ３は、１〜３が好ましく、２または３がより好ましく、３がさらに好ましい。
上記配位子となる化合物またはその塩（酸基またはその塩を含有する化合物）の分子量は、１０００以下が好ましく、８０〜７５０が好ましく、８０〜６００がより好ましい。 Examples of the compound serving as the ligand or a salt thereof include those represented by the following general formula (i).
Formula (ii)

(In general formula (ii), R ¹ represents an n-valent organic group, X ¹ represents an acid group, and n 3 represents an integer of 1 to 6.)
In general formula (ii), the n-valent organic group is preferably a hydrocarbon group or an oxyalkylene group, more preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom (preferably a fluorine atom), a (meth) acryloyl group, and a group having an unsaturated double bond. In addition, examples of the substituent include an alkyl group, a polymerizable group (for example, a vinyl group, an epoxy group, an oxetane group, etc.), a sulfonic acid group, a carboxylic acid group, an acid group containing a phosphorus atom, and a carboxylic acid ester group (for example,- CO ₂ CH ₃ ), hydroxyl group, alkoxy group (for example, methoxy group), amino group, carbamoyl group, carbamoyloxy group, halogenated alkyl group (for example, fluoroalkyl group, chloroalkyl group) and the like can also be mentioned. When the hydrocarbon group has a substituent, the hydrocarbon group may further have a substituent, and examples of the substituent include an alkyl group, the polymerizable group, and a halogen atom.
When the hydrocarbon group is monovalent, an alkyl group or an aryl group is preferable, and an aryl group is more preferable. Further, when the hydrocarbon group is monovalent, it may be an alkenyl group. In the case of divalent, an alkylene group, an arylene group, and an oxyalkylene group are preferable, and an arylene group is more preferable. In the case of being trivalent or more, those corresponding to the above monovalent hydrocarbon group or divalent hydrocarbon group are preferred.
1-20 are preferable and, as for carbon number of the said alkyl group and an alkylene group, 1-10 are more preferable. The alkyl group and the alkylene group may be linear, branched or cyclic. 1-20 are preferable, as for carbon number of a linear alkyl group and an alkylene group, 1-12 are more preferable, and 1-8 are more preferable. 3-20 are preferable, as for carbon number of a branched alkyl group and an alkylene group, 3-12 are more preferable, and 3-8 are more preferable. The cyclic alkyl group and alkylene group may be monocyclic or polycyclic. 3-20 are preferable, as for carbon number of a cyclic | annular alkyl group and an alkylene group, 4-10 are more preferable, and 6-10 are more preferable.
2-10 are preferable, as for carbon number of an alkenyl group, 2-8 are more preferable, and 2-4 are more preferable.
6-18 are preferable, as for carbon number of the said aryl group and arylene group, 6-14 are more preferable, 6-12 are more preferable, and 6-10 are especially preferable.
In general formula (ii), X ¹ includes, for example, an acid group containing a phosphorus atom (phosphoric acid diester group, phosphonic acid monoester group, phosphinic acid group, etc.), sulfo group, carboxyl group, hydroxyl group, and the like. . X ¹ may be one kind or two or more kinds, but is preferably two kinds or more, and preferably has a sulfo group and a carboxy group.
In general formula (ii), n3 is preferably 1 to 3, more preferably 2 or 3, and still more preferably 3.
1000 or less are preferable, as for the molecular weight of the compound used as the said ligand or its salt (compound containing an acid group or its salt), 80-750 are preferable and 80-600 are more preferable.

As an example of a copper compound obtained by a reaction between a compound containing a low molecular acid group or a salt thereof and a copper component, a compound having two monoanionic coordination sites or a salt thereof with respect to the copper component Those obtained by reacting can also be used. Here, the monoanionic coordination site represents a site coordinated with a copper atom via a functional group having one negative charge in coordination with a copper atom. Examples of the structure having such a monoanionic coordination site include those described for X ¹ in the general formula (i).

Examples of the structure having a monoanionic coordination site include those containing at least one selected from the group (AN) described above. For example, a structure having a monoanionic coordination site forms a copper complex by coordinating with a copper atom as shown below. For example, a carboxyl group-copper complex, a phosphoric acid diester group-copper complex, a phosphonic acid monoester group-copper complex, a phosphinic acid group-copper complex, a sulfo group-copper complex, and a hydroxyl group-copper complex are formed.

Examples of the compound having two monoanionic coordination sites include those represented by the following general formula (10).
X ¹ -L ¹ -X ² general formula (10)
(In the general formula (10), X ¹ and X ² each independently represent the monoanionic coordination site, and L ¹ represents an alkylene group, an alkenylene group, an arylene group, a heterocyclic group, —O—, Represents a divalent linking group consisting of —S—, —NR ^N1 —, —CO—, ^—CS— , —SO ₂ —, or a combination thereof, wherein R ^N1 represents a hydrogen atom, an alkyl group, an aryl group; Represents a group or an aralkyl group.)
In the general formula (10), L ¹ represents an alkylene group, an alkenylene group, an arylene group, a heterocyclic group, —O—, —S—, —NR ^N1 —, —CO—, ^—CS— , —SO ₂ —. Or a divalent linking group composed of a combination thereof. Here, NR ^N1 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.
Examples of the alkylene group include a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms and a substituted or unsubstituted cyclic alkylene group having 3 to 20 carbon atoms.
The alkenylene group is preferably a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, and more preferably a substituted or unsubstituted alkenylene group having 2 to 8 carbon atoms.
As the arylene group, a substituted or unsubstituted arylene group having 6 to 18 carbon atoms is preferable, and a substituted or unsubstituted arylene group having 6 to 14 carbon atoms is more preferable. The arylene group is a single ring or a condensed ring, preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations. Specific examples include a phenylene group and a naphthylene group.
The heterocyclic group includes an alicyclic group having a hetero atom or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group is a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having 2 to 8 condensations, and more preferably a monocyclic or a condensed ring having 2 to 4 condensations. Specific examples include a heteroarylene group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms. Examples of the heterocycle include, for example, oxolane ring, oxane ring, thiolane ring, oxazole ring, thiophene ring, thiathrene ring, furan ring, pyran ring, isobenzofuran ring, chromene ring, xanthene ring, phenoxazine ring, pyrrole ring, Pyrazole ring, isothiazole ring, isoxazole ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, isoindolizine ring, indole ring, indazole ring, purine ring, quinolidine ring, isoquinoline ring, phthalazine ring, naphthyridine ring, Examples thereof include a quinazoline ring, a sinoline ring, a pteridine ring, a carbazole ring, a carboline ring, a phenanthrine ring, an acridine ring, a perimidine ring, a phenanthrolin ring, a phthalazine ring, a phenazazine ring, a phenoxazine ring, and a furazane ring.

In —NR ^N1 —, R ^N1 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
The alkyl group in R ^N1 may be any of a chain, a branch, and a ring. As the linear or branched alkyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms is preferable, and a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms is more preferable. The cyclic alkyl group may be monocyclic or polycyclic. As the cyclic alkyl group, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms is preferable, and a substituted or unsubstituted cycloalkyl group having 4 to 14 carbon atoms is more preferable.
As the aryl group in R ^N1 , a substituted or unsubstituted aryl group having 6 to 18 carbon atoms is preferable, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms is more preferable, and an unsubstituted aryl group having 6 to 14 carbon atoms is preferable. More preferred is an aryl group. Specific examples include a phenyl group and a naphthyl group.
As the aralkyl group in R ^N1 , a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms is preferable, and an unsubstituted aralkyl group having 7 to 15 carbon atoms is more preferable.

Examples of the substituent that the above-described group may have include a polymerizable group (preferably a polymerizable group containing a carbon-carbon double bond), a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom). , Alkyl group, carboxylate group, halogenated alkyl group, alkoxy group, methacryloyloxy group, acryloyloxy group, ether group, sulfonyl group, sulfide group, amide group, acyl group, hydroxy group, carboxyl group, aralkyl group,- Examples thereof include Si— (OR ^N22 ) ₃ .
In addition, the substituent that the above-described group may have includes a combination of at least one of the above-described substituents and at least one of —O—, —CO—, —COO—, and —COOR ′. It may be. Here, R ′ is preferably a linear alkyl group having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms.
Examples of the polymerizable group include a polymerizable group containing a carbon-carbon double bond (preferably a vinyl group, a (meth) acryloyloxy group), a (meth) acryloyl group, an epoxy group, and an aziridinyl group.
The alkyl group may be chain, branched, or cyclic. As a linear or branched alkyl group, a C1-C10 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is more preferable. The cyclic alkyl group may be monocyclic or polycyclic. As the cyclic alkyl group, a cycloalkyl group having 3 to 20 carbon atoms is preferable, and a cycloalkyl group having 4 to 10 carbon atoms is more preferable.
As the halogenated alkyl group, an alkyl group substituted with a fluorine atom is preferred. In particular, an alkyl group having 1 to 10 carbon atoms having 2 or more fluorine atoms is preferable, and may be linear, branched or cyclic, but is preferably linear or branched. . 1-10 are more preferable, as for carbon number in the alkyl group substituted by the fluorine atom, 1-5 are more preferable, and 1-3 are more preferable. The terminal group of the alkyl group substituted with a fluorine atom is preferably (—CF ₃ ). The alkyl group substituted with a fluorine atom preferably has a fluorine atom substitution rate of 50 to 100%, and more preferably 80 to 100%. Here, the substitution rate of fluorine atoms refers to the ratio (%) in which hydrogen atoms are substituted with fluorine atoms in an alkyl group substituted with fluorine atoms.
In particular, as the halogenated alkyl group, a perfluoroalkyl group is more preferable, and a C 1-10 perfluoroalkyl group is more preferable.
In —Si— (OR ^N22 ) ₃ , R ^N22 is an alkyl group having 1 to 3 carbon atoms or a phenyl group, and n is an integer of 1 to 3.
Specifically, in the general formula (10), when L ¹ is a group consisting of a combination of an arylene group and —O—, an alkyl group is preferable as the substituent that the arylene group may have. .

Among the specific examples of the structure represented by L ¹ in the general formula (10), the following structure is preferable.

In the general formula (10), X ¹ and X ² represent the monoanionic coordination site, and more specifically, carboxyl group, phosphoric diester group, phosphonic monoester group, phosphinic acid group, sulfo group. Group, hydroxyl group and the like.
In the general formula (10), X ¹ and X ² may have the same monoanionic coordination site, or may have different monoanionic coordination sites.

(一般式（１２）中、Ｒ¹はアルキル基、アルケニル基、アリール基、アラルキル基を表す。Ａ¹およびＡ²は、各々独立に、酸素原子、硫黄原子または単結合を表す。一般式（１２）、（１３）および（１３Ａ）中、＊は上記Ｌ¹への連結部を表す。) In the general formula (10), X ¹ and X ² are preferably structures represented by the following general formula (12), (13) or (13A).

(In the general formula (12), R ¹ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group. A ¹ and A ² each independently represents an oxygen atom, a sulfur atom or a single bond. 12), (13) and (13A), * represents the connecting part to L ¹ above.)

In general formula (12), R ¹ represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group.
The alkyl group may be chain, branched, or cyclic. The linear or branched alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms, and a substituted or unsubstituted alkyl group. An alkyl group having 1 to 6 carbon atoms is more preferable. The cyclic alkyl group may be monocyclic or polycyclic. As the cyclic alkyl group, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms is preferable, a substituted or unsubstituted cycloalkyl group having 4 to 10 carbon atoms is more preferable, and an unsubstituted alkyl group having 4 to 8 carbon atoms. The cycloalkyl group is particularly preferred.
As the alkenyl group, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms is preferable, and a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms is more preferable.
As the aryl group, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms is preferable, and a substituted or unsubstituted aryl group having 6 to 14 carbon atoms is more preferable. Specific examples include a phenyl group and a naphthyl group.
As the aralkyl group, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms is preferable, and a substituted or unsubstituted aralkyl group having 7 to 16 carbon atoms is more preferable.
The substituent that R ¹ in the general formula (12) may have is the same as the substituent that L ¹ in the general formula (10) may have, an alkyl group, an aryl Group, ether group, -Si- (OR ^N22 ) _{3 and the} like are preferable.
In the general formula (12), A ¹ and A ² each independently represents an oxygen atom, a sulfur atom or a single bond. In particular, A ¹ and A ² are preferably single bonds from the viewpoint of further improving the heat resistance of the composition of the present invention.

Among the specific examples of the structure represented by R ¹ in the general formula (12), the following structure is preferable.

(Polymer type)
A copper compound obtained by the reaction of a polymer containing a coordination site and a copper component is coordinated by, for example, a coordination site coordinated by an anion such as an acid group or a salt of an acid group, and an unshared electron pair. The polymer which has 1 or more types chosen from a coordination atom, and the polymer type copper compound containing a copper ion are mentioned. Preferably, it is a polymer containing an acid group ion site which is an acid group or a salt of an acid group and a copper compound of a polymer type containing a copper ion, and a more preferred embodiment is that the acid group ion site in the polymer is a ligand. It is a polymer type copper compound. This polymer type copper compound usually has a coordination site such as an acid group ion site in the side chain of the polymer, and the coordination site such as an acid group ion site is bonded to copper (for example, coordinate bond). A cross-linked structure is formed between the side chains starting from copper. The polymer type copper complex includes a polymer copper complex having a carbon-carbon bond in the main chain, a polymer copper complex having a carbon-carbon bond in the main chain, and a copper complex containing a fluorine atom, a main chain And a copper complex of a polymer having an aromatic hydrocarbon group and / or an aromatic heterocyclic group (hereinafter referred to as an aromatic group-containing polymer).
As the copper component, a compound containing divalent copper is preferable. The copper content in the copper component is preferably 2 to 40% by mass, more preferably 5 to 40% by mass. A copper component may use only 1 type and may use 2 or more types. As the compound containing copper, for example, copper oxide or a copper salt can be used. The copper salt is more preferably divalent copper. As the copper salt, copper hydroxide, copper acetate, and copper sulfate are particularly preferable.
Although it will not specifically limit as an acid group if it can react with the copper component mentioned above, What has a coordinate bond with a copper component is preferable. Specific examples include acid groups having an acid dissociation constant (pKa) of 12 or less, and sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, phosphinic acid groups, imidoic acid groups, and the like are preferable. The polymer may have only one acid group or two or more acid groups.
Examples of the atom or atomic group constituting the acid group salt used in the present invention include a metal atom such as sodium (particularly alkali metal atom), an atomic group such as tetrabutylammonium. In addition, in the polymer containing an acid group or a salt thereof, the acid group or a salt thereof may be contained in at least one of the main chain and the side chain, and is preferably contained in at least the side chain.
The polymer containing an acid group or a salt thereof is preferably a polymer containing a carboxylic acid group or a salt thereof and / or a sulfonic acid group or a salt thereof, and more preferably a polymer containing a sulfonic acid group or a salt thereof.
Examples of the coordination site coordinated with an anion include those described in the above-described compound (A).

（式（Ａ１−１）中、Ｒ¹は水素原子またはメチル基を表し、Ｌ¹は単結合または２価の連結基を表し、Ｍ¹は水素原子、または、スルホン酸基と塩を構成する原子もしくは原子団を表す。）
上記式（Ａ１−１）中、Ｒ¹は水素原子であることが好ましい。
上記式（Ａ１−１）中、Ｌ¹が２価の連結基を表す場合、２価の連結基としては、特に限定されないが、例えば、２価の炭化水素基、ヘテロアリーレン基、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂−、−ＮＸ−（Ｘは水素原子あるいはアルキル基を表し、水素原子が好ましい）、または、これらの組み合わせからなる基が挙げられる。
２価の炭化水素基としては、直鎖状、分岐状または環状のアルキレン基や、アリーレン基が挙げられる。炭化水素基は、置換基を有していてもよいが、無置換であることが好ましい。
直鎖状のアルキレン基の炭素数としては、１〜３０が好ましく、１〜１５がより好ましく、１〜６がさらに好ましい。また、分岐状のアルキレン基の炭素数としては、３〜３０が好ましく、３〜１５がより好ましく、３〜６がさらに好ましい。
環状のアルキレン基は、単環、多環のいずれであってもよい。環状のアルキレン基の炭素数としては、３〜２０が好ましく、４〜１０がより好ましく、６〜１０がさらに好ましい。
アリーレン基の炭素数としては、６〜１８が好ましく、６〜１４がより好ましく、６〜１０がさらに好ましく、フェニレン基が特に好ましい。
ヘテロアリーレン基としては、特に限定されないが、５員環または６員環が好ましい。また、ヘテロアリーレン基は、単環でも縮合環であってもよく、単環または縮合数が２〜８の縮合環が好ましく、単環または縮合数が２〜４の縮合環がより好ましい。
上記式（Ａ１−１）中、Ｍ¹で表されるスルホン酸基と塩を構成する原子または原子団は、上述した酸基の塩を構成する原子または原子団と同義であり、水素原子またはアルカリ金属原子であることが好ましい。 <<< Polymer containing first acid group or salt thereof >>>
A preferable example of the polymer containing an acid group or a salt thereof is a structure in which the main chain has a carbon-carbon bond, and preferably includes a structural unit represented by the following formula (A1-1).

(In formula (A1-1), R ¹ represents a hydrogen atom or a methyl group, L ¹ represents a single bond or a divalent linking group, and M ¹ constitutes a salt with a hydrogen atom or a sulfonic acid group. Represents an atom or atomic group.)
In the above formula (A1-1), R ¹ is preferably a hydrogen atom.
In the above formula (A1-1), when L ¹ represents a divalent linking group, the divalent linking group is not particularly limited, and examples thereof include a divalent hydrocarbon group, a heteroarylene group, —O—. , —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NX— (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a group comprising a combination thereof Is mentioned.
Examples of the divalent hydrocarbon group include a linear, branched or cyclic alkylene group and an arylene group. The hydrocarbon group may have a substituent, but is preferably unsubstituted.
As carbon number of a linear alkylene group, 1-30 are preferable, 1-15 are more preferable, and 1-6 are more preferable. Moreover, as carbon number of a branched alkylene group, 3-30 are preferable, 3-15 are more preferable, and 3-6 are more preferable.
The cyclic alkylene group may be monocyclic or polycyclic. As carbon number of a cyclic | annular alkylene group, 3-20 are preferable, 4-10 are more preferable, and 6-10 are more preferable.
As carbon number of an arylene group, 6-18 are preferable, 6-14 are more preferable, 6-10 are more preferable, and a phenylene group is especially preferable.
Although it does not specifically limit as a heteroarylene group, A 5-membered ring or a 6-membered ring is preferable. The heteroarylene group may be a single ring or a condensed ring, and is preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations.
In the formula (A1-1), the atom or atomic group constituting the salt with the sulfonic acid group represented by M ¹ is synonymous with the atom or atomic group constituting the salt of the acid group described above, and a hydrogen atom or An alkali metal atom is preferred.

式（Ａ１−２）中、Ｒ³は水素原子またはメチル基を表し、水素原子であることが好ましい。
Ｙ²は単結合または２価の連結基を表し、２価の連結基としては、上述した上記式（Ａ１）の２価の連結基と同義である。特に、Ｙ²としては、−ＣＯＯ−、−ＣＯ−、−ＮＨ−、直鎖状または分岐状のアルキレン基、またはこれらの組み合わせからなる基か、単結合であることが好ましい。
式（Ａ１−２）中、Ｘ²は、−ＰＯ₃Ｈ、−ＰＯ₃Ｈ₂、−ＯＨまたはＣＯＯＨを表し、−ＣＯＯＨであることが好ましい。
上記式（Ａ１−１）で表わされる構成単位を含む重合体が、他の構成単位（好ましくは上記式（Ａ１−２）で表される構成単位）を含む場合、上記式（Ａ１−１）で表される構成単位と上記式（Ａ１−２）で表される構成単位のモル比は、９５：５〜２０：８０であることが好ましく、９０：１０〜４０：６０であることがより好ましい。 As structural units other than the structural unit represented by the formula (A1-1), paragraph numbers 0068 to 0075 of JP 2010-106268 A (in the corresponding US Patent Application Publication No. 2011/0124824 [ [0112]-[0118]) can be referred to the description of the copolymerization component disclosed, and the contents thereof are incorporated herein.
Preferable other structural units include structural units represented by the following formula (A1-2).

In formula (A1-2), R ³ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
Y ² represents a single bond or a divalent linking group, and the divalent linking group has the same meaning as the divalent linking group of the above formula (A1). In particular, Y ² is preferably —COO—, —CO—, —NH—, a linear or branched alkylene group, a group consisting of a combination thereof, or a single bond.
In formula (A1-2), X ² represents —PO ₃ H, —PO ₃ H ₂ , —OH or COOH, and preferably —COOH.
When the polymer containing the structural unit represented by the above formula (A1-1) contains another structural unit (preferably the structural unit represented by the above formula (A1-2)), the above formula (A1-1) The molar ratio of the structural unit represented by formula (A1-2) to the structural unit represented by formula (A1-2) is preferably 95: 5 to 20:80, more preferably 90:10 to 40:60. preferable.

<<< Polymer containing second acid group or salt thereof >>>
As a copper compound that can be used in the present invention, a polymer having an acid group or a salt thereof and having an aromatic hydrocarbon group and / or an aromatic heterocyclic group in the main chain (hereinafter, containing an aromatic group) A polymer-type copper compound obtained by a reaction between a polymer and a copper component may be used. The aromatic group-containing polymer only needs to have at least one of an aromatic hydrocarbon group and an aromatic heterocyclic group in the main chain, and may have two or more types. About an acid group or its salt, and a copper component, it is synonymous with the copper compound obtained by reaction of the polymer containing the acid group or its salt mentioned above, and a copper component, and its preferable range is also the same.
As the aromatic hydrocarbon group, for example, an aryl group is preferable. 6-20 are preferable, as for carbon number of an aryl group, 6-15 are more preferable, and 6-12 are more preferable. In particular, a phenyl group, a naphthyl group, or a biphenyl group is preferable. The aromatic hydrocarbon group may be monocyclic or polycyclic, but is preferably monocyclic.
As the aromatic heterocyclic group, for example, an aromatic heterocyclic group having 2 to 30 carbon atoms can be used. The aromatic heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The aromatic heterocyclic group is a single ring or a condensed ring, and examples thereof include a single ring or a condensed ring having 2 to 8 condensations. Examples of heteroatoms contained in the heterocycle include nitrogen, oxygen, and sulfur atoms, with nitrogen or oxygen being preferred.
When the aromatic hydrocarbon group and / or the aromatic heterocyclic group has a substituent T, examples of the substituent T include an alkyl group and a polymerizable group (preferably a carbon-carbon double bond). Containing polymerizable group), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxylic acid ester group, halogenated alkyl group, alkoxy group, methacryloyloxy group, acryloyloxy group, ether group, sulfonyl group, sulfide Group, amide group, acyl group, hydroxy group, carboxyl group, aralkyl group and the like are exemplified, and an alkyl group (particularly an alkyl group having 1 to 3 carbon atoms) is preferable.
In particular, aromatic group-containing polymers are polyethersulfone polymers, polysulfone polymers, polyetherketone polymers, polyphenylene ether polymers, polyimide polymers, polybenzimidazole polymers, polyphenylene polymers. It is preferably at least one polymer selected from a polymer, a phenol resin polymer, a polycarbonate polymer, a polyamide polymer, and a polyester polymer. Examples of each polymer are shown below.
Polyethersulfone polymer: a polymer having a main chain structure represented by (—O—Ph—SO ₂ —Ph—) (Ph represents a phenylene group, the same shall apply hereinafter) Polysulfone polymer: (—O— Ph-Ph-O-Ph- SO 2 -Ph-) having a main chain structure represented by the polymer polyether ketone polymer: (- O-Ph-O -Ph-C (= O) -Ph- ) Polymer having main chain structure represented by: Polyphenylene ether polymer: Polymer having main chain structure represented by (-Ph-O-, -Ph-S-) Polyphenylene polymer: (-Ph - polymeric phenolic resin polymer having a main chain structure represented by): (- Ph (OH) -CH 2 -) having a main chain structure represented by the polymer polycarbonate-based polymer: (- Ph- It has a main chain structure represented by O—C (═O) —O—) Polymer As a polyamide-based polymer, for example, a polymer having a main chain structure represented by (-Ph-C (= O) -NH-) As a polyester-based polymer, for example, (-Ph-C ( = O) Polymer having main chain structure represented by O-) Examples of the polyethersulfone-based polymer, polysulfone-based polymer, and polyetherketone-based polymer include paragraph 0022 of JP-A-2006-310068. And the main chain structure described in paragraph 0028 of JP-A-2008-27890 can be taken into consideration, and the contents thereof are incorporated in the present specification.
As the polyimide-based polymer, the main chain structure described in paragraphs 0047 to 0058 of JP-A No. 2002-367627 and paragraphs 0018 to 0019 of JP-A No. 2004-35891 can be taken into consideration. Embedded in the book.

（式（Ａ１−３）中、Ａｒ¹は芳香族炭化水素基および／または芳香族ヘテロ環基を表し、Ｙ¹は単結合または２価の連結基を表し、Ｘ¹は酸基またはその塩を表す。） A preferred example of the aromatic group-containing polymer preferably includes a structural unit represented by the following formula (A1-3).

(In the formula (A1-3), Ar ¹ represents an aromatic hydrocarbon group and / or an aromatic heterocyclic group, Y ¹ represents a single bond or a divalent linking group, and X ¹ represents an acid group or a salt thereof. Represents.)

In Formula (A1-3), when Ar ¹ represents an aromatic hydrocarbon group, it is synonymous with the aromatic hydrocarbon group described above, and the preferred range is also the same. When Ar ¹ represents an aromatic heterocyclic group, it is synonymous with the aromatic heterocyclic group described above, and the preferred range is also the same.
Ar ¹ may have a substituent in addition to —Y ¹ —X ^{1 in} the above formula (A1-3). When Ar ¹ has a substituent, the substituent has the same meaning as the substituent T described above, and the preferred range is also the same.

In formula (A1-3), Y ¹ is preferably a single bond. When Y ¹ represents a divalent linking group, examples of the divalent linking group include a hydrocarbon group, an aromatic heterocyclic group, —O—, —S—, —SO ₂ —, —CO—, — C (═O) —O—, —O—C (═O) —O—, —SO ₂ —, —NX— (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), —C (R ^Y1 ) (R ^Y2 ) —, or a group consisting of a combination thereof. Here, R ^Y1 and R ^Y2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group.
Examples of the hydrocarbon group include a linear, branched or cyclic alkylene group and an arylene group. As carbon number of a linear alkylene group, 1-20 are preferable, 1-10 are more preferable, and 1-6 are more preferable. As carbon number of a branched alkylene group, 3-20 are preferable, 3-10 are more preferable, and 3-6 are more preferable. The cyclic alkylene group may be monocyclic or polycyclic. As carbon number of a cyclic | annular alkylene group, 3-20 are preferable, 4-10 are more preferable, and 6-10 are more preferable. In these linear, branched or cyclic alkylene groups, a hydrogen atom in the alkylene group may be substituted with a fluorine atom.
An arylene group is synonymous with the case where the bivalent coupling group of the formula (A1-1) is an arylene group.
Although it does not specifically limit as an aromatic heterocyclic group, A 5-membered ring or a 6-membered ring is preferable. The aromatic heterocyclic group may be a single ring or a condensed ring, and is preferably a single ring or a condensed ring having 2 to 8 condensations, more preferably a single ring or a condensed ring having 2 to 4 condensations. .
In formula (A1-3), the acid group represented by X ¹ or a salt thereof is synonymous with the above-described acid group or a salt thereof, and the preferred range is also the same.
1000 or more are preferable, as for the weight average molecular weight of the polymer containing the structural unit represented by Formula (A1-1), Formula (A1-2), or Formula (A1-3), 1000 to 10 million are more preferable, and 3000 To 1 million is more preferable, and 4000 to 400,000 is particularly preferable.

  Specific examples of the polymer containing the structural unit represented by the above formula (A1-1), formula (A1-2) or formula (A1-3) include the following compounds and salts of the following compounds. However, it is not limited to these.

(Inorganic fine particles)
The composition of the present invention may contain inorganic fine particles in order to obtain the desired near infrared shielding property. Only one type of inorganic fine particles may be used, or two or more types may be used.
The inorganic fine particles are particles that mainly play a role of shielding (absorbing) infrared rays. The inorganic fine particles are preferably at least one selected from the group consisting of metal oxide particles and metal particles in terms of better infrared light shielding properties.
Examples of the inorganic fine particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide that may be doped with aluminum (ZnO that may be doped with Al), and fluorine-doped tin dioxide ( Metal oxide particles such as F-doped SnO ₂ ) particles or niobium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, silver (Ag) particles, gold (Au) particles, copper (Cu) particles, or nickel (Ni) particles And metal particles. In order to achieve both infrared light shielding properties and photolithographic properties, it is desirable that the transmittance at the exposure wavelength (365-405 nm) is higher, and indium tin oxide (ITO) particles or antimony tin oxide (ATO) particles are preferable.
The shape of the inorganic fine particles is not particularly limited, and may be a sheet shape, a wire shape, or a tube shape regardless of spherical or non-spherical.
As the inorganic fine particles, a tungsten oxide compound can be used. Specifically, a tungsten oxide compound represented by the following general formula (composition formula) (I) is more preferable.
M _x W _y O _z (I)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0
As the metal of M, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi are preferable, but an alkali metal is preferable, and Rb or Cs is preferable. , Cs is more preferable. The metal of M may be one type or two or more types.
When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when 1.1 or less, the generation of an impurity phase in the tungsten oxide compound is more reliably avoided. Can do.
When z / y is 2.2 or more, chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.
The metal oxide is preferably cesium tungsten oxide.
Specific examples of the tungsten oxide compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like, and Cs _0.33 WO ₃ or it is preferably Rb _0.33 WO _3, and more preferably a Cs _0.33 WO _3.
The metal oxide is preferably fine particles. The average particle diameter of the metal oxide is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. When the average particle diameter is in such a range, it becomes difficult for the metal oxide to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding photoacid disturbance, the average particle size is preferably as small as possible, but for reasons such as ease of handling during production, the average particle size of the metal oxide is usually 1 nm or more.
The tungsten oxide compound is available as a dispersion of tungsten fine particles such as YMF-02, YMF-02A, YMS-01A-2, and YMF-10A-1 manufactured by Sumitomo Metal Mining Co., Ltd., for example.
The content of the metal oxide is preferably 0.01 to 30% by mass and more preferably 0.1 to 20% by mass with respect to the total solid mass of the composition containing the metal oxide. Preferably, it is 1 to 10% by mass.

  In the composition of the present invention, the phthalocyanine compound described in paragraphs 0013 to 0029 of JP2013-195480A can also be used as another near-infrared absorbing compound, the contents of which are incorporated herein.

<Solvent>
The composition of the present invention may contain a solvent.
The solvent used in the present invention is not particularly limited, and can be appropriately selected depending on the purpose as long as it can uniformly dissolve or disperse each component of the composition of the present invention. A solvent can be used. Since the composition of the present invention uses the above-mentioned compound (A), even when an organic solvent is used as the solvent, the influence on the spectral characteristics can be reduced.
Preferable examples of the 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. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
Specific examples of the alcohols, aromatic hydrocarbons and halogenated hydrocarbons include those described in paragraph 0136 of JP 2012-194534 A, the contents of which are incorporated herein. Specific examples of esters, ketones, and ethers include those described in paragraph 0497 of JP2012-208494A (corresponding to [0609] of US 2012/0235099 corresponding). Furthermore, acetic acid-n-amyl, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, ethylene glycol monobutyl ether acetate and the like can be mentioned.
10 mass% or more is preferable with respect to the composition of this invention, as for content of a solvent, 20 mass% or more is more preferable, 30 mass% or more is further more preferable, and 40 mass% or more is further more preferable. Moreover, it is preferable that content of a solvent is contained in the ratio of 10-90 mass% with respect to the composition of this invention, It is more preferable that 20-80 mass% is contained, It is especially included 30-70 mass%. preferable. 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 falls within the above range.

<Curable compound>
The composition of the present invention may contain a curable compound. The curable compound may be a polymerizable compound or a non-polymerizable compound such as a binder. Moreover, as a curable compound, a thermosetting compound may be sufficient, and a photocurable compound may be sufficient, but since the reaction rate is higher, the thermosetting composition is preferable.

<Compound having a polymerizable group>
The curable composition preferably contains a compound having a polymerizable group (hereinafter sometimes referred to as “polymerizable compound”). Such compound groups are widely known in this industrial field, and in the present invention, these compounds can be used without any particular limitation. These may be any of chemical forms such as a monomer, an oligomer, a prepolymer, and a polymer.
The polymerizable compound may be monofunctional or polyfunctional, but is preferably polyfunctional. By including a polyfunctional compound, the near-infrared shielding property and heat resistance can be further improved. The number of functional groups is not particularly defined, but 2 to 8 functions are preferable, and 3 to 6 functions are more preferable.

  When a curable compound is contained with the said copper complex in the composition of this invention, the following are mentioned as a preferable form of a curable compound. The present invention is not limited to the following forms. Examples of the curable compound include monofunctional (meth) acrylate, polyfunctional (meth) acrylate (preferably 3 to 6 functional (meth) acrylate), polybasic acid-modified acrylic oligomer, epoxy resin, or polyfunctional epoxy. Resin.

<< Polymerizable monomer and polymerizable oligomer >>
In a first preferred embodiment of the composition of the present invention, a polymerizable compound is a monomer having a polymerizable group (polymerizable monomer) or an oligomer having a polymerizable group (polymerizable oligomer) (hereinafter, polymerizable with a polymerizable monomer). In some cases, the polymerizable oligomers are sometimes referred to as “polymerizable monomers”).

Examples of the polymerizable monomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. These are esters of saturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

The polymerizable monomer or the like is preferably a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure. Bifunctional (meth) acrylates and trifunctional or higher functional (meth) acrylates (eg, 3-6 functional (meth) acrylates) are preferred.
Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate;
Polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Ethylene with polyfunctional alcohols such as dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane (Meth) acrylated after adding oxide or propylene oxide,
Urethane (meth) acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy polymer and (meth) acrylic acid, and mixtures thereof described in JP-B No. 52-30490 Can be mentioned.

Among them, as the polymerizable compound, ethyleneoxy-modified pentaerythritol tetraacrylate (as a commercially available product, NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; Nippon Kayaku) Yakuhin Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd.) Company-made), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and these (meth) acryloyl groups via ethylene glycol and propylene glycol residues And that structure is preferable. These oligomer types can also be used.
Examples of the polymerizable compound include polyfunctional (meth) acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group.
Further, as other preferable polymerizable monomers, etc., compounds having a fluorene ring and having two or more functional ethylenic polymerizable groups described in JP 2010-160418 A, JP 2010-129825 A, Patent 4364216, etc. Polymers can also be used.
Further, compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group are disclosed in paragraphs [0254] to [0257] of JP-A-2008-292970. The compounds described are also suitable.
In addition, compounds that are (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof are also included. Can be used as a polymerizable monomer.

（式中、ｎは、それぞれ、０〜１４であり、ｍは、それぞれ、１〜８である。一分子内に複数存在するＲ、ＴおよびＺは、それぞれ、同一であっても、異なっていてもよい。Ｔがオキシアルキレン基の場合には、炭素原子側の末端がＲに結合する。Ｒのうち少なくとも１つは、重合性基である。） The polymerizable monomer used in the present invention is further preferably a polymerizable monomer represented by the following general formulas (MO-1) to (MO-6).

(In the formula, each of n is 0 to 14 and m is 1 to 8. Each of R, T and Z present in a molecule is the same or different. When T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R. At least one of R is a polymerizable group.)

Ｒは、上記４つの構造のうち以下の２つの構造が好ましい。

上記一般式（ＭＯ−１）〜（ＭＯ−６）で表される、ラジカル重合性モノマーの具体例としては、特開２００７−２６９７７９号公報の段落番号０２４８〜段落番号０２５１に記載されている化合物を本発明においても好適に用いることができる。 n is preferably 0 to 5, and more preferably 1 to 3.
m is preferably 1 to 5, and more preferably 1 to 3.
R preferably has the following four structures.

R is preferably the following two structures among the above four structures.

Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-6) include compounds described in paragraph numbers 0248 to 0251 of JP-A-2007-2699779. Can also be suitably used in the present invention.

Among them, examples of the polymerizable monomer include the polymerizable monomers described in paragraph 0477 of JP2012-208494A (corresponding to [0585] of the corresponding US Patent Application Publication No. 2012/0235099), and the like. The contents are incorporated herein. Further, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available product is M-460; manufactured by Toagosei Co., Ltd.). Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT) and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) are also preferable. These oligomer types can also be used.
For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) etc. are mentioned.

  As a polymerizable monomer etc., it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. When two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferable to prepare the acid value as a whole polyfunctional monomer within the above range. .

Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone modified structure as a polymerizable monomer.
The polyfunctional monomer having a caprolactone-modified structure is not particularly limited as long as it has a caprolactone-modified structure in the molecule. For example, the polyfunctional monomer having a caprolactone-modified structure includes trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylol Mention may be made of ε-caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as melamine, (meth) acrylic acid and ε-caprolactone. Of these, a polyfunctional monomer having a caprolactone-modified structure represented by the following formula (20) is preferable.

（式中、６個のＲは全てが下記式（２１）で表される基であるか、または６個のＲのうち１〜５個が下記式（２１）で表される基であり、残余が下記式（２２）で表される基である。） Formula (20)

(In the formula, all 6 Rs are groups represented by the following formula (21), or 1 to 5 of 6 Rs are groups represented by the following formula (21), The remainder is a group represented by the following formula (22).)

（式中、Ｒ¹は水素原子またはメチル基を示し、ｍは１または２の数を示し、「＊」は結合手であることを示す。） Formula (21)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

（式中、Ｒ¹は水素原子またはメチル基を示し、「＊」は結合手であることを示す。） Formula (22)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)

The polyfunctional monomer having such a caprolactone-modified structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (m = in the above formulas (20) to (22)). 1, number of groups represented by formula (21) = 2, a compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (21) = 3, compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (21) = 6, compound in which R ¹ is all hydrogen atoms), DPCA -120 (a compound in which m = 2 in the formula, the number of groups represented by formula (21) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone modified structure can be used individually or in mixture of 2 or more types.
Examples of commercially available products such as polymerizable monomers include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and a hexafunctional acrylate having six pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd. There are DPCA-60, TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

<< Compound having epoxy group or oxetanyl group >>
The 3rd preferable aspect of this invention is an aspect containing the compound which has an epoxy group or an oxetanyl group as a polymeric compound. Specific examples of the compound having an epoxy group or oxetanyl group include a polymer having an epoxy group in the side chain, and a polymerizable monomer or oligomer having two or more epoxy groups in the molecule, and a bisphenol A type epoxy resin, Bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like can be mentioned. Moreover, a monofunctional or polyfunctional glycidyl ether compound is also mentioned, and a polyfunctional aliphatic glycidyl ether compound is preferable.
These compounds may be used as commercial products or can be obtained by introducing an epoxy group into the side chain of the polymer.

As a commercial item, description of Unexamined-Japanese-Patent No. 2012-155288 Paragraph 0191 etc. can be considered, and these content is integrated in this-application specification.
Moreover, as a commercial item, polyfunctional aliphatic glycidyl ether compounds, such as Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, Nagase ChemteX Co., Ltd. product), are mentioned. . Although these are low chlorine products, they are not low chlorine products, and EX-212, EX-214, EX-216, EX-321, EX-850, etc. can be used as well.
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER1031S, and the like are also included.
Furthermore, JER-157S65, JER-152, JER-154, JER-157S70, (Mitsubishi Chemical Corporation make) etc. are mentioned as a commercial item of a phenol novolak type epoxy resin.

Specific examples of the polymer having an oxetanyl group in the side chain and the polymerizable monomer or oligomer having two or more oxetanyl groups in the molecule include Aronoxetane OXT-121, OXT-221, OX-SQ, PNOX ( As described above, Toagosei Co., Ltd.) can be used.
The molecular weight is preferably 500 to 5000000, more preferably 1000 to 500000 in terms of weight average.
As the epoxy unsaturated compound, those having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether can be used, but preferred are unsaturated compounds having an alicyclic epoxy group. As such a thing, description of Unexamined-Japanese-Patent No. 2009-265518 Paragraph 0045 etc. can be considered, and these content is integrated in this-application specification.

The composition of the present invention may contain a polymer having a crosslinking group such as an unsaturated double bond, an epoxy group or an oxetanyl group. Specific examples include polymers (copolymers) having the following repeating units. As the polymer having the following repeating unit, a polymer having an epoxy group is preferred.

（式（３０）中、Ｒ¹は水素原子または有機基を表す。） << Compound having partial structure represented by formula (30) >>
The curable compound used in the present invention may have a partial structure represented by the following formula (30). This curable compound may have a crosslinking group such as an unsaturated double bond, an epoxy group or an oxetanyl group.

(In formula (30), R ¹ represents a hydrogen atom or an organic group.)

In formula (30), R ¹ represents a hydrogen atom or an organic group. Examples of the organic group include a hydrocarbon group, specifically, an alkyl group or an aryl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or these groups and a divalent group. What consists of a combination with these coupling groups is preferable.
Specific examples of such organic radicals, -OR ', - SR', or with these groups _{- (CH 2) m - (} m is an integer of from 1 to 10), an alkylene ring having 5 to 10 carbon atoms A combination of at least one of a group, —O—, —CO—, —COO— and —NH— is preferable. Here, R ′ is a hydrogen atom, a straight chain having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms (preferably a straight chain having 1 to 7 carbon atoms, 3 to 7 carbon atoms). A branched or cyclic alkyl group), an aryl group having 6 to 10 carbon atoms, or a group composed of a combination of an aryl group having 6 to 10 carbon atoms and an alkylene group having 1 to 10 carbon atoms.
In the above formula (30), R ¹ and C may be bonded to form a ring structure (heterocyclic structure). The hetero atom in the heterocyclic structure is a nitrogen atom in the above formula (30). The heterocyclic structure is preferably a 5- or 6-membered ring structure, and more preferably a 5-membered ring structure. The heterocyclic structure may be a condensed ring, but is preferably a single ring.
Specific examples of particularly preferable R ¹ include a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, —OR ′ (R ′ is a linear alkyl group having 1 to 5 carbon atoms), and — (CH ₂ ) _m —. (M is an integer of 1 to 10, preferably m is an integer of 1 to 5), and R ¹ and C in the above formula (30) are bonded to form a heterocyclic structure (preferably 5 members) Group which formed a ring structure).

The compound having the partial structure represented by the formula (30) is represented by (polymer main chain structure-partial structure of the above (30) -R ¹ ), or (A-partial structure of the above (30). -B) is preferable. Here, A is a linear alkyl group having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms. B is a combination of — (CH ₂ ) _m — (m is an integer of 1 to 10, preferably m is an integer of 1 to 5), the partial structure of the above (30), and a polymerizable group. It is a group.

（式（１−１）中、Ｒ⁴は水素原子またはメチル基を表し、Ｒ⁵およびＲ⁶はそれぞれ独立して水素原子または有機基を表す。式（１−２）中、Ｒ⁷は水素原子またはメチル基を表す。式（１−３）中、Ｌ¹は二価の連結基を表し、Ｒ⁸は水素原子または有機基を表す。式（１−４）中、Ｌ²およびＬ³はそれぞれ独立して二価の連結基を表し、Ｒ⁹およびＲ¹⁰はそれぞれ独立して水素原子または有機基を表す。式（１−５）中、Ｌ⁴は二価の連結基を表し、Ｒ¹¹〜Ｒ¹⁴はそれぞれ独立して水素原子または有機基を表す。） Examples of the compound having a partial structure represented by the above formula (30) include structures represented by any of the following formulas (1-1) to (1-5).

(In formula (1-1), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group. In formula (1-2), R ⁷ represents hydrogen. In formula (1-3), L ¹ represents a divalent linking group, R ⁸ represents a hydrogen atom or an organic group, and in formula (1-4), L ² and L ³ represent an atom or a methyl group. Each independently represents a divalent linking group, R ⁹ and R ¹⁰ each independently represents a hydrogen atom or an organic group, and in formula (1-5), L ⁴ represents a divalent linking group; R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or an organic group.)

In the above formula (1-1), R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group. As an organic group, it is synonymous with R < ¹ > in the said Formula (30), and its preferable range is also the same.
In the above formulas (1-3) to (1-5), L ^{1 to} L ⁴ each represent a divalent linking group. Examples of the divalent linking _{group, - (CH 2) m -} (m is an integer of from 1 to 10), a cyclic alkylene group having 5 to 10 carbon atoms, -O -, - CO -, - COO- , and -NH - at least preferably made of one of a combination _{of, - (CH 2) m -} (m is an integer of 1 to 8) is more preferably.
In the above formulas (1-3) to (1-5), R ^{8 to} R ¹⁴ each independently represents a hydrogen atom or an organic group. The organic group is preferably a hydrocarbon group, specifically an alkyl group or an alkenyl group.
The alkyl group may be substituted. Further, the alkyl group may be any of a chain, a branch, and a ring, but a linear or cyclic group is preferable. As an alkyl group, a C1-C10 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C6 alkyl group is more preferable.
Alkenyl groups may be substituted. As an alkenyl group, a C1-C10 alkenyl group is preferable, a C1-C4 alkenyl group is more preferable, and a vinyl group is especially preferable.
Examples of the substituent include a polymerizable group, a halogen atom, an alkyl group, a carboxylic ester group, a halogenated alkyl group, an alkoxy group, a methacryloyloxy group, an acryloyloxy group, an ether group, a sulfonyl group, a sulfide group, an amide group, Examples include an acyl group, a hydroxy group, and a carboxyl group. Among these substituents, a polymerizable group (for example, a vinyl group, a (meth) acryloyloxy group), a (meth) acryloyl group, an epoxy group, an aziridinyl group) is preferable, and a vinyl group is more preferable. )

Further, the compound having the partial structure represented by the above formula (30) may be a monomer or a polymer, but is preferably a polymer. That is, the compound having a partial structure represented by the above formula (30) is preferably a compound represented by the above formula (1-1) or the above formula (1-2).
Moreover, when the compound which has the partial structure shown by the said Formula (30) is a polymer, it is preferable to contain the said partial structure in the side chain of a polymer.

The molecular weight of the compound having the partial structure represented by the above formula (30) is preferably 50 to 1,000,000, more preferably 500 to 500,000. By setting it as such molecular weight, the effect of this invention can be achieved more effectively.
The content of the compound having the partial structure represented by the above (30) is preferably 5 to 80% by mass and more preferably 10 to 60% by mass in the composition of the present invention.

Specific examples of the compound having the partial structure represented by the above formula (30) include a compound having the following structure or the following exemplified compound, but are not limited thereto. In the present invention, in particular, the compound having a partial structure represented by the above formula (30) is preferably polyacrylamide.

Specific examples of the compound having the partial structure represented by the above formula (30) include water-soluble polymers. Preferred main chain structures include polyvinylpyrrolidone, poly (meth) acrylamide, polyamide, polyvinylpyrrolidone, and polyurethane. And polyurea. The water-soluble polymer may be a copolymer, and the copolymer may be a random copolymer.
As polyvinylpyrrolidone, trade names K-30, K-85, K-90, K-30W, K-85W, K-90W (manufactured by Nippon Shokubai Co., Ltd.) can be used.

  Examples of poly (meth) acrylamide include (meth) acrylamide polymers and copolymers. Specific examples of acrylamide include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide and the like can be mentioned. Corresponding methacrylamides can also be used in the same manner.

Examples of the water-soluble polyamide resin include a compound obtained by copolymerizing a polyamide resin and a hydrophilic compound. The derivative of the water-soluble polyamide resin is, for example, a compound in which water-soluble polyamide resin is used as a raw material and hydrogen of an amide bond (—CONH—) is substituted with a methoxymethyl group (—CH ₂ OCH ₃ ), A compound in which the structure of the amide bond is changed by substitution of an atom in the water-soluble polyamide resin molecule or addition reaction.
Examples of the polyamide resin include so-called “n-nylon” synthesized by polymerization of ω amino acid and so-called “n, m-nylon” synthesized by copolymerization of diamine and dicarboxylic acid. Among these, from the viewpoint of imparting hydrophilicity, a copolymer of diamine and dicarboxylic acid is preferable, and a reaction product of ε-caprolactam and dicarboxylic acid is more preferable.
Examples of hydrophilic compounds include hydrophilic nitrogen-containing cyclic compounds and polyalkylene glycols.
Here, the hydrophilic nitrogen-containing cyclic compound is a compound having a tertiary amine component in the side chain or main chain, and examples thereof include aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylaminoεcaprolactam and the like. .
On the other hand, in the compound in which the polyamide resin and the hydrophilic compound are copolymerized, at least one selected from the group consisting of, for example, a hydrophilic nitrogen-containing cyclic compound and a polyalkylene glycol is copolymerized in the main chain of the polyamide resin. Therefore, the hydrogen bond ability of the amide bond portion of the polyamide resin is larger than that of N-methoxymethylated nylon.
Among the compounds obtained by copolymerizing polyamide resin and hydrophilic compound, 1) reaction product of ε-caprolactam, hydrophilic nitrogen-containing cyclic compound and dicarboxylic acid, and 2) ε-caprolactam, polyalkylene glycol and dicarboxylic acid The reaction product with
These are commercially available, for example, from Toray Finetech Co., Ltd. under the trademark “AQ nylon”. A reaction product of ε-caprolactam, a hydrophilic nitrogen-containing cyclic compound, and dicarboxylic acid is available as AQ nylon A-90 manufactured by Toray Finetech Co., Ltd., and ε-caprolactam, polyalkylene glycol, and dicarboxylic acid The reaction product is available as AQ nylon P-70 manufactured by Toray Finetech Co., Ltd. AQ nylon A-90 P-70 P-95 T-70 (manufactured by Toray Industries, Inc.) can be used.

The molar ratio of the polymer containing the repeating unit having the partial structure represented by the formula (30) and the repeating unit having an epoxy group is preferably 10/90 to 90/10, and 30/70 to 70 / 30 is more preferable. The weight average molecular weight of the copolymer is preferably 3,000 to 1,000,000, and more preferably 5,000 to 200,000.
The content of the polymerizable compound in the composition of the present invention is preferably 1 to 90% by mass, more preferably 15 to 80% by mass, and still more preferably 40 to 75% by mass with respect to the total solid content excluding the solvent. .
Moreover, when using the polymer containing the repeating unit which has a crosslinking group as a polymeric compound, 10-75 mass% is preferable with respect to the total solid of the composition of this invention except a solvent, 20-65 mass%. Is more preferable, and 20-60 mass% is further more preferable.
Only one type of polymerizable compound or two or more types may be used, and in the case of two or more types, the total amount falls within the above range.

<Binder polymer>
The composition of the present invention may further contain a binder polymer in addition to the polymerizable compound, if necessary, for the purpose of improving the film properties. As the binder polymer, an alkali-soluble resin is preferably used. By containing an alkali-soluble resin, there is an effect in improving heat resistance and fine adjustment of coating properness.
As the alkali-soluble resin, paragraphs 0558 to 0571 of JP 2012-208494 A (corresponding to [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to and the contents thereof can be referred to. Is incorporated herein.
When the composition of this invention contains a binder polymer, it is preferable that content of a binder polymer is 1-80 mass% with respect to the total solid of a composition, and it is 5-50 mass%. More preferably, it is more preferably 7 to 30% by mass.

<Surfactant>
The composition of the present invention may contain a surfactant. Only one type of surfactant may be used, or two or more types may be combined. The addition amount of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.005 to 1.0% by mass, and still more preferably based on the solid content of the composition of the present invention. 0.01 to 0.1% by mass.
As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, the composition of the present invention contains at least one of a fluorine-based surfactant and a silicone-based surfactant, so that liquid properties (particularly fluidity) when prepared as a coating solution are further improved. . Thereby, the uniformity of coating thickness and the liquid-saving property are further improved.
That is, when a film is formed using a coating liquid to which a composition containing at least one of a fluorosurfactant and a silicone surfactant is applied, the interfacial tension between the coated surface and the coating liquid is reduced. Thereby, the wettability to the coated surface is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  3-40 mass% is suitable for the fluorine content rate in a fluorine-type surfactant, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the colored photosensitive composition.

Specifically, surfactants described in paragraph 0552 of JP2012-208494A (corresponding US Patent Application Publication No. 2012/0235099 [0678]) and the like are mentioned as the fluorine-based surfactant, These contents are incorporated herein.
Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene Examples thereof include oxypropylene block copolymers, acetylene glycol surfactants, and acetylene polyoxyethylene oxide. These can be used alone or in combination of two or more.
Specific product names include Surfinol 61, 82, 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, 504, CT-111, CT- 121, CT-131, CT-136, CT-141, CT-151, CT-171, CT-324, DF-37, DF-58, DF-75, DF-110D, DF-210, GA, OP- 340, PSA-204, PSA-216, PSA-336, SE, SE-F, TG, GA, Dinol 604 (Nippon Chemical Co., Ltd. and Air Products & Chemicals), Orphine A, B, AK-02, CT -151W, E1004, E1010, P, SPC, STG, Y, 32W, PD 001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, SK-14, AE-3 (Nisshin Chemical Co., Ltd.) acetylenol E00, E13T, E40, E60, E81, E100, E200 (all trade names, Kawaken Fine Chemical) (Manufactured by Co., Ltd.). Of these, Olfine E1010 is preferable.
In addition, specific examples of nonionic surfactants include nonionic surfactants described in paragraph 0553 of JP2012-208494A (corresponding to [0679] of the corresponding US Patent Application Publication No. 2012/0235099). The contents of which are incorporated herein by reference.
Specific examples of the cationic surfactant include a cationic surfactant described in paragraph 0554 of JP2012-208494A (corresponding to [0680] of the corresponding US Patent Application Publication No. 2012/0235099). The contents of which are incorporated herein by reference.
Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

  Examples of the silicone surfactant include silicone surfactants described in paragraph 0556 of JP2012-208494A (corresponding to [0682] of the corresponding US Patent Application Publication No. 2012/0235099). The contents of which are incorporated herein by reference. In addition, “Toray Silicone SF8410”, “Same SF8427”, “Same SH8400”, “ST80PA”, “ST83PA”, “ST86PA” manufactured by Toray Dow Corning Co., Ltd., “TSF-400” manufactured by Momentive Performance Materials, Inc. “TSF-401”, “TSF-410”, “TSF-4446” “KP321”, “KP323”, “KP324”, “KP340”, etc. manufactured by Shin-Etsu Silicone Co., Ltd. are also exemplified.

<Polymerization initiator>
The composition of the present invention may contain a polymerization initiator. The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound by light, heat, or both, and can be appropriately selected according to the purpose. It is preferable that When polymerization is initiated by light, those having photosensitivity to visible light from the ultraviolet region are preferred.
Moreover, when starting superposition | polymerization with a heat | fever, the polymerization initiator decomposed | disassembled at 150-250 degreeC is preferable.

The polymerization initiator that can be used in the present invention is preferably a compound having at least an aromatic group, such as an acylphosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, and a ketal derivative. Compounds, thioxanthone compounds, oxime compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, benzoin ether compounds, ketal derivative compounds, metallocene compounds, etc. Onium salt compounds, organoboron salt compounds, disulfone compounds, thiol compounds, and the like.
Specific examples of the acetophenone compound, the trihalomethyl compound, the hexaarylbiimidazole compound, and the oxime compound include Japanese Patent Application Laid-Open No. 2012-208494, paragraphs 0506 to 0510 (corresponding to US 2012/0235099 corresponding specification). [0622-0628]) and the like can be taken into account, the contents of which are incorporated herein.

Further, it can also be suitably used for the cyclic oxime compounds described in JP 2007-231000 A (corresponding US Patent Application Publication No. 2011/0123929) and JP 2007-322744 A.
In addition, an oxime compound having a specific substituent shown in Japanese Patent Application Laid-Open No. 2007-26979 (corresponding US Patent Application Publication No. 2010/0104976) and Japanese Patent Application Laid-Open No. 2009-191061 (corresponding US Patent Application Publication). No. 2009/023085) and oxime compounds having a thioaryl group.
Japanese Patent Application Laid-Open No. 2012-208494, paragraph 0513 (corresponding to US Patent Application Publication No. 2012/235099 [0632]) and the following formulas (OX-1), (OX-2) or (OX-3) The description of the compound can be referred to and the contents thereof are incorporated herein.
Specific examples of oxime compounds that can be suitably used include paragraphs 0090 to 0106 of JP-A-2009-191061 (paragraph 0393 of the corresponding US Patent Application Publication No. 2009/023085) and JP-A-2012-032556. The descriptions in Japanese Laid-Open Patent Publication No. 0054, Japanese Patent Laid-Open No. 2012-122045, Paragraph 0054, and the like can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, an oxime compound, an acetophenone compound, or an acylphosphine compound is preferable. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969, an acylphosphine oxide initiator described in Japanese Patent No. 4225898, and the oxime initiator described above, As the oxime initiator, compounds described in JP-A No. 2001-233842 can also be used.
As the oxime compound, commercially available products IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can be used. As the acetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Japan Ltd.) can be used. As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF Japan Ltd.) can be used.
The content of the polymerization initiator is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, and particularly preferably 0.1 to 15% by mass with respect to the solid content of the composition of the present invention. preferable. Only one type of polymerization initiator may be used, or two or more types may be used, and in the case of two or more types, the total amount falls within the above range.

<Other ingredients>
Examples of other components that can be used in combination with the composition of the present invention include a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, and a plasticizer. Furthermore, adhesion promoters to the substrate surface and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, A chain transfer agent or the like) may be used in combination.
By appropriately containing these components, properties such as stability and film physical properties of the target near-infrared absorption filter can be adjusted.
These components include, for example, paragraph number 0183 of JP2012-003225A (corresponding US Patent Application Publication No. 2013/0034812), paragraph number 0101-0102, paragraph number 0103 of JP2008-250074. 0104, paragraph numbers 0107 to 0109, paragraph numbers 0159 to 0184 of JP 2013-195480 A, and the like can be referred to, and the contents thereof are incorporated in the present specification.

<Preparation and use of near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention can be prepared by mixing the above components.
In preparing the composition, the components constituting the composition may be blended together, or may be blended sequentially after each component is dissolved and dispersed in an organic solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending.
In the present invention, it is preferable to filter 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, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. Filter. Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The filter has a pore diameter of preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, still more preferably 0.2 to 1.5 μm, and still more preferably 0.3 to 0.7 μm. By setting it within this range, it becomes possible to reliably remove fine foreign matters such as impurities and aggregates contained in the composition while suppressing filtration clogging.
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. When filtering two or more times by combining different filters, it is preferable that the second and subsequent hole diameters are the same or larger than the first filtering hole diameter. 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., Ltd. .
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. By setting it as this range, a foreign material can be removed with the component particles contained in the composition remaining.

Although the use of the near-infrared absorptive composition of this invention is not specifically limited, The near-infrared cut filter (for example, near-infrared cut filter with respect to a wafer level lens) in the light-receiving side of a solid-state image sensor, the back surface side (light reception) of a solid-state image sensor And a near infrared cut filter on the light receiving side of the solid-state image sensor. Moreover, it is preferable to apply | coat the near-infrared absorptive composition of this invention directly on a solid-state image sensor, and to form a coating film.
The viscosity of the near-infrared absorbing composition of the present invention is preferably in the range of 1 mPa · s to 3000 mPa · s, more preferably 10 mPa · s to 2000 mPa · s when an infrared cut layer is formed by coating. It is the following ranges, More preferably, it is the range of 100 mPa * s or more and 1500 mPa * s or less.

Since the composition of this invention can be supplied in the state which can be apply | coated, a near-infrared cut filter can be easily formed in the desired member and position of a solid-state image sensor.
The near-infrared cut filter obtained using the composition of the present invention preferably has a light transmittance satisfying at least one of the following (1) to (9), and the following (1) to (8) It is more preferable to satisfy all the conditions (1), and it is even more preferable to satisfy all the conditions (1) to (9).
(1) The light transmittance at a wavelength of 400 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(2) The light transmittance at a wavelength of 450 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(3) The light transmittance at a wavelength of 500 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(4) The light transmittance at a wavelength of 550 nm is preferably 80% or more, more preferably 90% or more, still more preferably 92% or more, and particularly preferably 95% or more.
(5) The light transmittance at a wavelength of 700 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(6) The light transmittance at a wavelength of 750 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(7) The light transmittance at a wavelength of 800 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(8) The light transmittance at a wavelength of 850 nm is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, and particularly preferably 5% or less.
(9) The light transmittance at a wavelength of 900 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
Moreover, it is preferable that the light transmittance of the near-infrared cut filter has a light transmittance of 95% or more in the entire wavelength range of 450 to 500 nm.
Although the near-infrared cut filter can be appropriately selected according to the purpose, the film thickness is preferably 300 μm or less, more preferably 250 μm or less, further preferably 200 μm or less, and 100 μm or less. It is particularly preferred. The lower limit of the film thickness is, for example, preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more. According to the composition of this invention, since it has high near-infrared shielding, the film thickness of a near-infrared cut filter can be made thin.
The near-infrared cut filter has a film thickness of 300 μm or less, and preferably has a light transmittance of 85% or more in the entire range of wavelengths from 400 to 550 nm, more preferably 90% or more. Further, the light transmittance at at least one point in the wavelength range of 700 to 800 nm is preferably 20% or less, and the light transmittance in the entire range of wavelength 700 to 800 nm is more preferably 20% or less. . According to the present invention, it is possible to provide a near-infrared cut filter that can secure a wide range of visible light with high transmittance and has high near-infrared shielding properties.
The near-infrared cut filter is used for lenses having a function of absorbing / cutting near-infrared rays (camera lenses such as digital cameras, mobile phones, and in-vehicle cameras, optical lenses such as f-θ lenses, pickup lenses) and semiconductor light receiving elements. Optical filters, near-infrared absorbing films and near-infrared absorbing plates that block heat rays for energy saving, agricultural coatings for selective use of sunlight, recording media that use near-infrared absorbing heat, and electronic equipment And photographic near-infrared filters, protective glasses, sunglasses, heat ray blocking films, optical character reading recording, confidential document copy prevention, electrophotographic photoreceptors, laser welding, and the like. It is also useful as a noise cut filter for CCD cameras and a filter for CMOS image sensors.

The present invention has a step of forming a film by applying (preferably a dropping method, coating or printing) the near-infrared absorbing composition of the present invention on the light-receiving side of a solid-state imaging device, and a near-infrared step. The present invention also relates to a method for manufacturing a cut filter. About a film thickness, laminated structure, etc., it can select suitably according to the objective.
The support to which the composition of the present invention is applied may be a transparent substrate made of glass or the like, a solid-state imaging device, a separate substrate provided on the light receiving side of the solid-state imaging device, or a solid substrate. It may be a layer such as a flattening layer provided on the light receiving side of the image sensor.
The method for forming the near-infrared cut filter can be carried out by using, for example, a dropping method (drop casting), a spin coater, a slit spin coater, a slit coater, screen printing, applicator application, or the like. In the case of the dropping method (drop casting), it is preferable to form a dropping region of the near-infrared absorbing composition having a photoresist as a partition on a glass substrate so as to obtain a uniform film with a predetermined film thickness. In addition, a film thickness can adjust the dripping amount and solid content concentration of a composition, and the area of a dripping area | region.
In addition, the drying conditions of the coating film vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 seconds to 150 ° C. for about 30 seconds to 15 minutes.

The method for forming a near-infrared cut filter using the near-infrared absorbing composition of the present invention may include other steps. Other processes are not particularly limited and may be appropriately selected depending on the purpose. For example, a surface treatment process of a substrate, a preheating process (prebaking process), a curing process, a postheating process (postbaking process) ) And the like.
<Pre-heating process / Post-heating process>
The heating temperature in the preheating step and the postheating step is usually 80 ° C to 200 ° C, and preferably 90 ° C to 150 ° C. The heating time in the preheating step and the postheating step is usually 30 seconds to 240 seconds, and preferably 60 seconds to 180 seconds.
<Curing process>
The curing process is a process of curing the formed film as necessary, and the mechanical strength of the near-infrared cut filter is improved by performing this process.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably. Here, in the present invention, “exposure” is used to include not only light of various wavelengths but also irradiation of radiation such as electron beams and X-rays.
The exposure is preferably performed by irradiation of radiation, and as the radiation that can be used for the exposure, ultraviolet rays such as electron beams, KrF, ArF, g rays, h rays, i rays and visible light are particularly preferably used.
As an exposure method. Examples include stepper exposure and exposure with a high-pressure mercury lamp.
Exposure is more preferably 5~3000mJ / cm ² is preferably ^{10~2000mJ / cm 2, 50~1000mJ / cm} 2 is particularly preferred.
Examples of the entire surface exposure processing method include a method of exposing the entire surface of the formed film. When the near-infrared absorbing composition contains a polymerizable compound, curing of the polymerization component in the film formed from the composition is promoted by overall exposure, the curing of the film further proceeds, mechanical strength, Durability is improved.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.
Moreover, as a method of the whole surface heat treatment, a method of heating the entire surface of the formed film can be given. By heating the entire surface, the film strength of the pattern is increased.
The heating temperature in the entire surface heating is preferably 120 ° C to 250 ° C, and more preferably 160 ° C to 220 ° C. When the heating temperature is 120 ° C. or higher, the film strength is improved by the heat treatment, and when the heating temperature is 250 ° C. or lower, the components in the film are decomposed and the film quality is prevented from becoming weak and brittle.
The heating time in the entire surface heating is preferably 3 minutes to 180 minutes, and more preferably 5 minutes to 120 minutes.
There is no restriction | limiting in particular as an apparatus which performs whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

The camera module of the present invention is a camera module having a solid-state image sensor and a near-infrared cut filter disposed on the light-receiving side of the solid-state image sensor, and the near-infrared cut filter is the above-described near-infrared cut filter.
The method for manufacturing a camera module according to the present invention is a method for manufacturing a camera module having a solid-state imaging device and a near-infrared cut filter disposed on the light-receiving side of the solid-state imaging device, on the light-receiving side of the solid-state imaging device. And a step of forming a film by applying the near-infrared absorbing composition of the present invention described above.

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.
The camera module 10 includes, for example, a solid-state imaging device 11, a planarization layer 12 provided on the solid-state imaging device 11, a near-infrared cut filter 13, and an imaging lens 14 disposed in the internal space above the near-infrared cut filter. A lens holder 15.
In the camera module 10, incident light hν from 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 element portion 16 of the solid-state imaging element 11. .
The solid-state image sensor 11 has, for example, an image sensor section 16, an interlayer insulating film (not shown), a base layer (not shown), a color filter 17, an overcoat (not shown) on the main surface of a silicon substrate as a base. ), The micro lens 18 is provided in this order. The color filter 17 (red color filter, green color filter, blue color filter) and the microlens 18 are respectively arranged so as to correspond to the imaging element unit 16.
Further, instead of providing the near-infrared cut filter 13 on the surface of the flattening layer 12, the surface of the microlens 18, between the base layer and the color filter 17, or between the color filter 17 and the overcoat, The form in which the infrared cut filter 13 is provided may be sufficient. For example, the near-infrared cut filter 13 may be provided at a position within 2 mm (more preferably within 1 mm) from the surface of the microlens. If it is provided at this position, the process of forming the near infrared cut filter can be simplified, and unnecessary near infrared rays to the microlens can be sufficiently cut, so that the near infrared shielding property can be further improved.
The near-infrared cut filter of the present invention can be subjected to a solder reflow process. By manufacturing the camera module through the solder reflow process, it is possible to automatically mount electronic component mounting boards, etc. that need to be soldered, making the productivity significantly higher than when not using the solder reflow process. Can be improved. Furthermore, since it can be performed automatically, the cost can be reduced. When subjected to a solder reflow process, the infrared cut filter is exposed to a temperature of about 250 to 270 ° C., so that the infrared cut filter can withstand the solder reflow process (hereinafter also referred to as “solder reflow resistance”). It is preferable to have.
In the specification of the present application, “having solder reflow resistance” refers to retaining characteristics as an infrared cut filter before and after heating at 200 ° C. for 10 minutes. More preferably, the characteristics are maintained before and after heating at 230 ° C. for 10 minutes. More preferably, the characteristics are maintained before and after heating at 250 ° C. for 3 minutes. If it does not have solder reflow resistance, when it is kept under the above conditions, the infrared absorption ability of the infrared cut filter may be reduced, or the function as a film may be insufficient.
The present invention also relates to a method for manufacturing a camera module, including a reflow process. Since the near-infrared cut filter of the present invention maintains the near-infrared absorption ability even if there is a reflow process, it does not impair the characteristics of a small, lightweight and high-performance camera module.

2 to 4 are schematic cross-sectional views showing an example of the vicinity of the near-infrared cut filter in the camera module.
As shown in FIG. 2, the camera module includes a solid-state imaging device 11, a planarization layer 12, an ultraviolet / infrared light reflection film 19, a transparent substrate 20, a near infrared absorption layer 21, and an antireflection layer 22. May be included in this order.
The ultraviolet / infrared light reflection film 19 has an effect of imparting or enhancing the function of a near-infrared cut filter. For example, paragraphs 0033 to 0039 of Japanese Patent Application Laid-Open No. 2013-68688 can be referred to. Incorporated in the description.
The transparent substrate 20 transmits light having a wavelength in the visible region. For example, paragraphs 0026 to 0032 of JP2013-68688A can be referred to, and the contents thereof are incorporated in the present specification.
The near-infrared absorbing layer 21 can be formed by applying the above-described near-infrared absorbing composition of the present invention.
The antireflection layer 22 has a function of improving the transmittance by preventing reflection of light incident on the near-infrared cut filter and efficiently using incident light. For example, JP 2013-68688 A Paragraph 0040, which is incorporated herein by reference.
As shown in FIG. 3, the camera module includes a solid-state imaging device 11, a near infrared absorption layer 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 absorption layer 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.
Moreover, as a solid-state image sensor, it can also be set as the structure of the image sensor concerning the 1st-14th embodiment described after the 0049 column of international publication WO14 / 061188 pamphlet.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass.

<Synthesis example>
Compounds A1-1 to A1-3, A1-6, A1-7, A1-9, A1-15, A1-26, and compounds A2-1, A2-33, A2-35, A2-37 are used as reagents. Commercially available from Tokyo Kasei, Wako Pure Chemicals, or Aldrich, they were used as they were without further purification.

三ツ口フラスコに、窒素雰囲気下、２，６−ジブロモピリジン １４．２４ｇ、ヨウ化銅（Ｉ）０．６１ｇ、テトラヒドロフラン（市販脱水溶媒）１８０ｍＬを導入し、０℃に冷却した。ここに、ｔｅｒｔ−ブチルマグネシウムクロリドの１．０Ｍテトラヒドロフラン溶液を７０ｍＬ滴下し、室温で１時間撹拌した。飽和塩化アンモニウム水溶液１００ｍＬ、酢酸エチル１００ｍＬを加え、抽出・分液により得られた有機層を濃縮して得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶媒：ヘキサン）で精製することにより、２−ブロモ−６−ｔｅｒｔ−ブチルピリジンを１０ｇ得た。
続いて、三ツ口フラスコに、窒素雰囲気下、上で合成した２−ブロモ−６−ｔｅｒｔ−ブチルピリジン３．６５ｇ、テトラヒドロフラン（市販脱水溶媒）５０ｍＬを導入し、−７８℃に冷却した。ここに、ｎ−ブチルリチウムの１．６Ｍヘキサン溶液を１０．０ｍＬ滴下し、−７８℃で３０分間撹拌した。ここに、砕いたドライアイスを大過剰量ゆっくりと加え、室温で２時間撹拌した。水１００ｍＬ、酢酸エチル５０ｍＬを加え、抽出・分液により水層（ｐＨ〜１１）を回収した。この水層に対して、濃塩酸を少しずつ加えてｐＨ〜２とし、酢酸エチル５０ｍＬで３回抽出して得られた有機層を濃縮することにより、化合物Ａ１−４を２ｇ得た。 Synthesis example of compound A1-4

Under a nitrogen atmosphere, 14.24 g of 2,6-dibromopyridine, 0.61 g of copper (I) iodide, and 180 mL of tetrahydrofuran (commercial dehydrating solvent) were introduced into a three-necked flask and cooled to 0 ° C. 70 mL of 1.0M tetrahydrofuran solution of tert-butylmagnesium chloride was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. A crude product obtained by adding 100 mL of a saturated aqueous ammonium chloride solution and 100 mL of ethyl acetate and concentrating the organic layer obtained by extraction / separation is purified by silica gel column chromatography (solvent: hexane) to give 2- 10 g of bromo-6-tert-butylpyridine was obtained.
Subsequently, 3.65 g of 2-bromo-6-tert-butylpyridine synthesized above and 50 mL of tetrahydrofuran (commercially available dehydrated solvent) were introduced into a three-necked flask under a nitrogen atmosphere and cooled to -78 ° C. Here, 10.0 mL of 1.6M hexane solution of n-butyllithium was dropped, and the mixture was stirred at −78 ° C. for 30 minutes. A large excess of crushed dry ice was slowly added thereto, and the mixture was stirred at room temperature for 2 hours. 100 mL of water and 50 mL of ethyl acetate were added, and the aqueous layer (pH˜11) was recovered by extraction and liquid separation. Concentrated hydrochloric acid was gradually added to the aqueous layer to adjust the pH to 2, and the organic layer obtained by extracting three times with 50 mL of ethyl acetate was concentrated to obtain 2 g of Compound A1-4.

Synthesis Example of Compound A1-5 Compound A1-5 was synthesized in the same manner as Compound A1-4 using 2-ethylhexylmagnesium bromide instead of tert-butylmagnesium chloride.

フラスコに、２−シアノピリミジン０．１０ｇ、１２質量％水酸化ナトリウム水溶液１３ｍＬを加え、７０℃で３０分間撹拌した。１Ｎ希塩酸を少しずつ加えてｐＨ〜３とし、酢酸エチル１０ｍＬで３回抽出して得られた有機層を濃縮することにより、化合物Ａ１−８を０．１０ｇ得た。 Synthesis example of compound A1-8

To the flask, 0.10 g of 2-cyanopyrimidine and 13 mL of a 12% by mass aqueous sodium hydroxide solution were added and stirred at 70 ° C. for 30 minutes. 1N diluted hydrochloric acid was added little by little to adjust the pH to 3, and the organic layer obtained by extracting three times with 10 mL of ethyl acetate was concentrated to obtain 0.10 g of Compound A1-8.

三ツ口フラスコに、窒素雰囲気下、チアゾール８．５ｇ、テトラヒドロフラン（市販脱水溶媒）１５０ｍＬを導入し、−７８℃に冷却した。ここに、ｎ−ブチルリチウムの１．６Ｍヘキサン溶液を６０ｍＬ滴下し、−７８℃で３０分間撹拌した。ここに、砕いたドライアイスを大過剰量ゆっくりと加え、室温で２時間撹拌した。水１００ｍＬ、酢酸エチル５０ｍＬを加え、抽出・分液により水層（ｐＨ〜１１）を回収した。この水層に対して、濃塩酸を少しずつ加えてｐＨ〜２とし、酢酸エチル５０ｍＬで３回抽出して得られた有機層を濃縮することにより、化合物Ａ１−１０を１２ｇ得た。 Synthesis Example of Compound A1-10

In a three-necked flask, 8.5 g of thiazole and 150 mL of tetrahydrofuran (commercial dehydration solvent) were introduced under a nitrogen atmosphere and cooled to -78 ° C. Here, 60 mL of 1.6M hexane solution of n-butyllithium was dropped, and the mixture was stirred at −78 ° C. for 30 minutes. A large excess of crushed dry ice was slowly added thereto, and the mixture was stirred at room temperature for 2 hours. 100 mL of water and 50 mL of ethyl acetate were added, and the aqueous layer (pH˜11) was recovered by extraction and liquid separation. Concentrated hydrochloric acid was gradually added to this aqueous layer to adjust the pH to 2, and the organic layer obtained by extracting three times with 50 mL of ethyl acetate was concentrated to obtain 12 g of Compound A1-10.

三ツ口フラスコに、窒素雰囲気下、ピラゾール−３−カルボン酸エチル３．０ｇ、ヨウ化カリウム３．５５ｇ、炭酸カリウム４．４４ｇ、１−ブロモブタン４．４０ｇ、アセトン４８ｍＬを加え、１０時間加熱還流した。室温に冷却後、濾過により不溶物を除去し、濾液を濃縮して得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶媒：ヘキサン／酢酸エチル）で精製することにより、１−ブチルピラゾール−３−カルボン酸エチルを２．８ｇ得た。
フラスコに上記生成物を０．３９ｇ、エタノール３ｍＬを加え、室温で撹拌しながら水０．０５ｇ、ｔｅｒｔ−ブトキシカリウム０．２２ｇを加えた後、７０℃で３０分間撹拌した。これを減圧濃縮して得られた固体は対応するカルボン酸カリウムであり、これをそのまま銅錯体化に用いた。 Synthesis Example of Compound A1-11

Under a nitrogen atmosphere, 3.0 g of ethyl pyrazole-3-carboxylate, 3.55 g of potassium iodide, 4.44 g of potassium carbonate, 4.40 g of 1-bromobutane and 48 mL of acetone were added to a three-necked flask and heated under reflux for 10 hours. After cooling to room temperature, insoluble matters were removed by filtration, and the filtrate was concentrated, and the resulting crude product was purified by silica gel column chromatography (solvent: hexane / ethyl acetate) to give 1-butylpyrazole-3- 2.8 g of ethyl carboxylate was obtained.
To the flask, 0.39 g of the above product and 3 mL of ethanol were added, 0.05 g of water and 0.22 g of tert-butoxypotassium were added while stirring at room temperature, and the mixture was stirred at 70 ° C. for 30 minutes. The solid obtained by concentrating this under reduced pressure was the corresponding potassium carboxylate, which was directly used for copper complexation.

三ツ口フラスコに、窒素雰囲気下、ピラゾール−３−カルボン酸エチル３．０ｇ、２−ブロモ−２−メチルプロパン４．４０ｇ、ジメチルホルムアミド４８ｍＬを加え、７２時間加熱還流した。室温に冷却後、濾過により不溶物を除去し、濾液を濃縮して得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶媒：ヘキサン／酢酸エチル）で精製することにより、１−ｔｅｒｔ−ブチル−ピラゾール−３−カルボン酸エチルを０．８ｇ得た。
化合物Ａ１−１１と同様の方法によりエステルを加水分解し、化合物Ａ１−１２を得た。 Synthesis Example of Compound A1-12

Under a nitrogen atmosphere, 3.0 g of ethyl pyrazole-3-carboxylate, 4.40 g of 2-bromo-2-methylpropane, and 48 mL of dimethylformamide were added to a three-necked flask, and the mixture was heated to reflux for 72 hours. After cooling to room temperature, insoluble matters were removed by filtration, and the filtrate was concentrated, and the resulting crude product was purified by silica gel column chromatography (solvent: hexane / ethyl acetate) to give 1-tert-butyl-pyrazole. 0.8 g of ethyl -3-carboxylate was obtained.
The ester was hydrolyzed in the same manner as for compound A1-11 to give compound A1-12.

三ツ口フラスコに、窒素雰囲気下、ピラゾール−３−カルボン酸５．５ｇ、１−アダマンタノール７．５ｇ、リン酸１００ｍＬ、酢酸２５ｍＬを加え、６０℃で７時間半撹拌した。室温に冷却後、水２００ｍＬを加えて析出した白色固体を濾過により回収した。この白色固体に、水３００ｍＬ、酢酸エチル１００ｍＬを加えて、室温で撹拌しながら、５０質量％水酸化ナトリウム水溶液をｐＨ〜１２になるまで加えた。抽出・分液により水層を回収し、酢酸エチル１００ｍＬで４回洗浄した。この水層に対して、濃塩酸を少しずつ加えてｐＨ〜２とすると白色固体が析出し、この白色固体を濾過し、水で洗浄することにより、１−（１−アダマンチル）ピラゾール−３−カルボン酸を３．９ｇ得た。 Synthesis example of compound A1-13

Under a nitrogen atmosphere, 5.5 g of pyrazole-3-carboxylic acid, 7.5 g of 1-adamantanol, 100 mL of phosphoric acid, and 25 mL of acetic acid were added to a three-necked flask, and the mixture was stirred at 60 ° C. for 7 and a half hours. After cooling to room temperature, 200 mL of water was added and the precipitated white solid was collected by filtration. To this white solid, 300 mL of water and 100 mL of ethyl acetate were added, and a 50% by mass aqueous sodium hydroxide solution was added to pH˜12 while stirring at room temperature. The aqueous layer was recovered by extraction and liquid separation, and washed 4 times with 100 mL of ethyl acetate. When concentrated hydrochloric acid is gradually added to the aqueous layer to adjust the pH to 2, a white solid is precipitated. The white solid is filtered and washed with water to give 1- (1-adamantyl) pyrazole-3- 3.9 g of carboxylic acid was obtained.

三ツ口フラスコに、窒素雰囲気下、ピルビン酸４．４ｇ、シクロペンチルメチルエーテル１０ｍＬを加え、室温で撹拌した。ここにアニリン４．７ｇを滴下し、１０分間撹拌した後、０℃に冷却して析出した固体を濾過により回収することで化合物Ａ１−１４を３．６ｇ得た。 Synthesis Example of Compound A1-14

Under a nitrogen atmosphere, 4.4 g of pyruvic acid and 10 mL of cyclopentyl methyl ether were added to a three-necked flask and stirred at room temperature. The aniline 4.7g was dripped here, and after stirring for 10 minutes, 3.6g of compound A1-14 was obtained by collect | recovering the solid which precipitated by cooling to 0 degreeC by filtration.

三ツ口フラスコに、窒素雰囲気下、２，６−ジアセチルピリジン１６．３ｇ、テトラヒドロフラン（市販脱水溶媒）１６０ｍＬを導入し、０℃に冷却した。ここに、メチルマグネシウムブロミドｎ−ブチルリチウムの３Ｍジエチルエーテル溶液を３３ｍＬ滴下し、室温で３時間撹拌した。飽和塩化アンモニウム水溶液１００ｍＬ、酢酸エチル１００ｍＬを加え、抽出・分液により得られた有機層を濃縮することにより、化合物Ａ１−１６を１９．５ｇ得た。 Synthesis example of compound A1-16

Into a three-necked flask, 16.3 g of 2,6-diacetylpyridine and 160 mL of tetrahydrofuran (commercial dehydration solvent) were introduced under a nitrogen atmosphere and cooled to 0 ° C. Here, 33 mL of 3M diethyl ether solution of methylmagnesium bromide n-butyllithium was dropped, and the mixture was stirred at room temperature for 3 hours. 19.5 g of compound A1-16 was obtained by adding 100 mL of saturated aqueous ammonium chloride solution and 100 mL of ethyl acetate and concentrating the organic layer obtained by extraction and liquid separation.

三ツ口フラスコに、窒素雰囲気下、ピコリン酸２．４６ｇ、トリフルオロメタンスルホンアミド３．０ｇ、Ｎ，Ｎ−ジメチルアミノピリジン（ＤＭＡＰ）３．６６ｇ、ジメチルホルムアミド１５０ｍＬを加えて、室温で撹拌した。ここに、１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミド塩酸塩（ＥＤＣＩ）５．７３ｇを加え、室温で４時間撹拌した。水１００ｍＬ、酢酸エチル１００ｍＬを加え、抽出・分液により水層を回収し、ここに濃塩酸を少しずつ加えてｐＨ〜２とした。酢酸エチル１００ｍＬを加え、抽出・分液により得られた有機層を濃縮することにより、化合物Ａ１−１７を１．５６ｇ得た。 Synthesis Example of Compound A1-17

Under a nitrogen atmosphere, 2.46 g of picolinic acid, 3.0 g of trifluoromethanesulfonamide, 3.66 g of N, N-dimethylaminopyridine (DMAP), and 150 mL of dimethylformamide were added to a three-necked flask and stirred at room temperature. To this, 5.73 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI) was added and stirred at room temperature for 4 hours. 100 mL of water and 100 mL of ethyl acetate were added, and the aqueous layer was recovered by extraction / separation, and concentrated hydrochloric acid was added little by little to adjust the pH to 2. Ethyl acetate 100mL was added and the organic layer obtained by extraction and liquid separation was concentrated, and 1.56g of compound A1-17 was obtained.

三ツ口フラスコに、窒素雰囲気下、ｔｅｒｔ−ブトキシカリウム１１．２０ｇ、トルエン１００ｍＬを加え、０℃に冷却した。ここに酢酸エチル５．３０ｇを滴下した後、ジピコリン酸ジメチル９．７５ｇを導入し、室温で２時間撹拌した。飽和塩化アンモニウム水溶液２００ｍＬを加え、抽出・分液して得られた有機層を濃縮し、２Ｎ希塩酸５０ｍＬを加え、８０℃で２時間撹拌した。酢酸エチル５０ｍＬを加え、抽出・分液して得られた有機層を濃縮して得られた粗生成物を熱水で２回再結晶することにより、化合物Ａ１−１８を１０ｇ得た。 Synthesis example of compound A1-18

Under a nitrogen atmosphere, 11.20 g of potassium tert-butoxy and 100 mL of toluene were added to a three-necked flask and cooled to 0 ° C. 5.30 g of ethyl acetate was added dropwise thereto, and then 9.75 g of dimethyl dipicolinate was introduced and stirred at room temperature for 2 hours. 200 mL of saturated aqueous ammonium chloride solution was added, the organic layer obtained by extraction and liquid separation was concentrated, 50 mL of 2N dilute hydrochloric acid was added, and the mixture was stirred at 80 ° C. for 2 hours. 10 g of compound A1-18 was obtained by adding 50 mL of ethyl acetate and recrystallizing the crude product obtained by concentrating the organic layer obtained by extraction and liquid separation twice with hot water.

三ツ口フラスコに、窒素雰囲気下、ＷＯ２００６０９８５０５号パンフレットに記載の方法で合成した２，２−ビス（６−ブロモー２−ピリジル）プロパン５．６ｇ、テトラヒドロフラン（市販脱水溶媒）１５０ｍＬを導入し、−７８℃に冷却した。ここに、ｎ−ブチルリチウムの１．６Ｍヘキサン溶液を２０ｍＬ滴下し、−７８℃で３０分間撹拌した。ここに、砕いたドライアイスを大過剰量ゆっくりと加え、室温で２時間撹拌した。水１００ｍＬ、酢酸エチル５０ｍＬを加え、抽出・分液により水層（ｐＨ〜１１）を回収した。この水層に対して、濃塩酸を少しずつ加えてｐＨ〜２とし、酢酸エチル５０ｍＬで３回抽出して得られた有機層を濃縮することにより、化合物Ａ１−１９を４．２ｇ得た。 Synthesis example of compound A1-19

Into a three-necked flask, 5.6 g of 2,2-bis (6-bromo-2-pyridyl) propane synthesized by the method described in the pamphlet of WO2006098505 and 150 mL of tetrahydrofuran (commercial dehydration solvent) were introduced under a nitrogen atmosphere, and −78 ° C. Cooled to. Here, 20 mL of 1.6 M hexane solution of n-butyllithium was dropped, and the mixture was stirred at −78 ° C. for 30 minutes. A large excess of crushed dry ice was slowly added thereto, and the mixture was stirred at room temperature for 2 hours. 100 mL of water and 50 mL of ethyl acetate were added, and the aqueous layer (pH˜11) was recovered by extraction and liquid separation. Concentrated hydrochloric acid was gradually added to this aqueous layer to adjust the pH to 2, and the organic layer obtained by extracting three times with 50 mL of ethyl acetate was concentrated to obtain 4.2 g of Compound A1-19.

Synthesis Example of Compound A1-20 Org. Chem. It was synthesized by the method described in 1970, 35, 4114.

Synthesis Example of Compound A1-21 Instead of ethyl pyrazole-3-carboxylate, diethyl pyrazole-3-phosphonate synthesized by the method described in Tetrahedron 1999, 55, 14791 was used, and p-toluenesulfone was substituted for 1-bromobutane. Synthesized in the same manner as for compound A1-14 using methyl acid.

三ツ口フラスコに、窒素雰囲気下、２，６−ジメチル−４−ヘプタノール２０ｇ、ピリジン５０ｍＬを導入し、室温で撹拌した。ここにｐ−トルエンスルホニルクロリド５５ｇを導入し、室温で終夜撹拌した。２規定の希塩酸１００ｍＬ，酢酸エチル１００ｍＬを加え、抽出・分液した。更に、水相に酢酸エチル１００ｍＬを加えて、抽出・分液する操作を２回行い、計３回の分液操作で得られた有機相を合わせ、これに２規定の希塩酸１００ｍＬを加えて抽出・分液する操作を２回行った。さらに、有機相に飽和塩化ナトリウム水溶液１００ｍＬを加えて抽出・分液して得られた有機相を濃縮することで、対応するトシラートを４２ｇ得た。
このトシラートを３−ブロモペンタンの代わりに用いることで、化合物Ａ１−２２と同様の方法で化合物Ａ１−２３を合成した。
化合物Ａ１−２４の合成例
２，６−ジメチル−４−ヘプタノールの代わりに２，６，８−トリメチル−４−ノナノールを用いて、化合物Ａ１−２３と同様の方法で合成した。
化合物Ａ１−２７の合成例
チアゾールの代わりに４，５−ジメチルチアゾールを用い、化合物Ａ１−１０と同様の方法で合成した。
化合物Ａ１−２８の合成例

三ツ口フラスコに、窒素雰囲気下、フェニルボロン酸１．００ｇ、６−ブロモピリジン−２−カルボン酸１．００ｇ、炭酸カリウム１．３８ｇ、テトラヒドロフランと水の５：１の混合溶媒５０ｍＬを導入し、室温で冷却した。ここに、テトラキス(トリフェニルホスフィン)パラジウム０．５５ｇを導入し、４時間加熱還流した。室温に冷却後、水４０ｍＬ、酢酸エチル４０ｍＬを導入し、抽出・分液により得られた水相に酢酸エチル２０ｍＬを導入し、抽出・分液した。得られた水相（ｐＨ１１）にｐＨ４になるまで希塩酸を導入した。析出した固体を濾過により回収することで、化合物Ａ１−２８を０．０７ｇ得た。
化合物Ａ１−２９の合成例

三ツ口フラスコに、窒素雰囲気下、２，６−ジメチルフェニルボロン酸０．９０ｇ、６−ブロモピリジン−２−カルボン酸メチル０．９２ｇ、リン酸カリウム１．９２ｇ、トルエン３０ｍＬを導入し、室温で冷却した。ここに、トリシクロヘキシルホスフィン０．１３ｇ、酢酸パラジウム０．１０ｇを導入し、１００度で終夜撹拌した。室温に冷却後、飽和塩化アンモニウム水溶液３０ｍＬ、酢酸エチル４０ｍＬを導入し、抽出・分液した。これにより得られた有機相を濃縮して得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶媒：ヘキサン／酢酸エチル）で精製することにより、化合物Ａ１−２９のメチルエステル体を０．４５ｇ得た。
このエステルを、化合物Ａ１−１１と同様の方法により加水分解し、化合物Ａ１−２９を得た。
化合物Ａ１−３０の合成例

三ツ口フラスコに、窒素雰囲気下、ジイソピロピルアミン１３．２ｇ、テトラヒドロフラン（市販脱水溶媒）２００ｍＬを導入し、−７８℃に冷却した。ここに、ｎ−ブチルリチウムの１．６Ｍヘキサン溶液を６４．０ｍＬ滴下し、−７８℃で１０分間撹拌した。ここに、２−ブロモ−６−メチルピリジン６．０ｇを滴下し、−７８℃で３０分間撹拌した。ここに、ヨードエタン１５．９７ｇを滴下した後、室温まで徐々に昇温した。室温にて１時間撹拌後、飽和塩化アンモニウム水溶液１００ｍＬを導入し、抽出・分液した。水相に酢酸エチル１００ｍＬを導入して抽出・分液する操作を２回行い、最初の分液と合わせて計３回の分液操作で得られた有機相を合わせ、濃縮して得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶媒：ヘキサン／酢酸エチル）で精製することにより、２−ブロモ−６−（３−ペンチル）ピリジンを７．２ｇ得た。この化合物を、化合物Ａ１−４の合成法と同様の方法により、化合物Ａ１−３０へと変換した。
化合物Ａ１−３１の合成例

三ツ口フラスコに、窒素雰囲気下、ジイソピロピルアミン１３．０ｇ、テトラヒドロフラン（市販脱水溶媒）２００ｍＬを導入し、−７８℃に冷却した。ここに、ｎ−ブチルリチウムの１．６Ｍヘキサン溶液を８０．０ｍＬ滴下し、−７８℃で１５分間撹拌した。ここに、２−ブロモ−６−メチルピリジン２０ｇを滴下し、−７８℃で３０分間撹拌した。ここに、１−ブロモ−２−メチルプロパン１７．７ｇを滴下した後、室温まで徐々に昇温した。室温にて１時間撹拌後、飽和塩化アンモニウム水溶液１００ｍＬを導入し、抽出・分液した。水相に酢酸エチル１５０ｍＬを導入して抽出・分液した。計２回の分液操作で得られた有機相を合わせ、濃縮して得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶媒：ヘキサン／酢酸エチル）で精製することにより、２−ブロモ−６−（３−メチルブチル）ピリジンを１８．８ｇ得た。この化合物を、化合物Ａ１−４の合成法と同様の方法により、化合物Ａ１−３１へと変換した。
化合物Ａ１−３２の合成例

国際公開公報２００７１４８７３８記載の方法で、２，６−ジブロモ−４−トリフルオロメチルピリジンを合成した。この化合物１．７３ｇを三ツ口フラスコに導入し、窒素雰囲気下、塩化鉄（ＩＩＩ）０．４０ｇ、テトラヒドロフラン３０ｍＬを導入し、室温で撹拌した。ここに、メチルマグネシウムブロミドの３Ｍジエチルエーテル溶液を２ｍＬ滴下し、室温で１時間半撹拌した。飽和塩化アンモニウム水溶液３０ｍＬ、酢酸エチル３０ｍＬを加え、抽出・分液により得られた有機層を濃縮して得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶媒：ヘキサン）で精製することにより、２−ブロモ−６−メチル−４−トリフルオロメチルピリジンを０．１８ｇ得た。この化合物を、化合物Ａ１−４の合成法と同様の方法により、化合物Ａ１−３２へと変換した。
化合物Ａ１−３３の合成例

三ツ口フラスコに、窒素雰囲気下、化合物Ａ１−３１を１．４４ｇ、トリフルオロメタンスルホンアミド１．１１ｇ、４−ジメチルアミノピリジン１．３７ｇ、ジメチルホルムアミド２０ｍＬを導入し、室温で終夜撹拌した。ここに水１００ｍＬを導入し、室温で撹拌しながらｐＨ１になるまで濃塩酸を加えた。析出した固体を濾過により回収し、これをメタノールで再結晶することにより、化合物Ａ１−３３を１．５ｇ得た。
化合物Ａ１−３４の合成例

上記スキームに従い、化合物Ａ１−３３と同様の方法で合成した。
化合物Ａ１−３５の合成例

Ｅｕｒ．Ｊ．Ｍｅｄ．Ｃｈｅｍ．２０１０，４５，１２２５の文献記載の方法により合成したパーフルオロブタンスルホンアミドを用い、上記スキームに従い、化合物Ａ１−３３と同様の方法で合成した。
化合物Ａ１−３６の合成例
化合物Ａ１−３１の代わりに化合物Ａ１−３０を用い、化合物Ａ１−３３と同様の方法で合成した。
化合物Ａ１−３７の合成例
化合物Ａ１−３１の代わりに化合物Ａ１−１１を用い、化合物Ａ１−３３と同様の方法で合成した。
化合物Ａ１−３８の合成例
化合物Ａ１−３１の代わりに化合物Ａ１−２２を用い、化合物Ａ１−３３と同様の方法で合成した。
化合物Ａ１−３９の合成例
化合物Ａ１−３１の代わりに化合物Ａ１−１２を用い、化合物Ａ１−３３と同様の方法で合成した。
化合物Ａ１−４０の合成例
トリフルオロメタンスルホンアミドの代わりにメタンスルホンアミドを用い、化合物Ａ１−３８と同様の方法で合成した。
化合物Ａ１−４１の合成例
トリフルオロメタンスルホンアミドの代わりにｏ−トルエンスルホンアミドを用い、化合物Ａ１−３８と同様の方法で合成した。
化合物Ａ１−４２の合成例
化合物Ａ１−３１の代わりに化合物Ａ１−２７を用い、化合物Ａ１−３３と同様の方法で合成した。 Synthesis Example of Compound A1-22 Synthesis was performed in the same manner as for Compound A1-11, using 3-bromopentane instead of 1-bromobutane and cesium carbonate instead of potassium carbonate.
Synthesis Example of Compound A1-23

Under a nitrogen atmosphere, 20 g of 2,6-dimethyl-4-heptanol and 50 mL of pyridine were introduced into a three-necked flask and stirred at room temperature. Here, 55 g of p-toluenesulfonyl chloride was introduced and stirred at room temperature overnight. 2N diluted hydrochloric acid (100 mL) and ethyl acetate (100 mL) were added, and the mixture was extracted and separated. Further, 100 mL of ethyl acetate was added to the aqueous phase, and extraction and liquid separation were performed twice. The organic phases obtained by the liquid separation operation were combined three times, and 100 mL of 2N dilute hydrochloric acid was added thereto for extraction. -The liquid separation operation was performed twice. Furthermore, the organic phase obtained by adding 100 mL of saturated sodium chloride aqueous solution to an organic phase, extracting and liquid-separating was concentrated, and 42 g of corresponding tosylate was obtained.
Compound A1-23 was synthesized in the same manner as Compound A1-22 by using this tosylate instead of 3-bromopentane.
Synthesis Example of Compound A1-24 Compound A1-24 was synthesized in the same manner as Compound A1-23 using 2,6,8-trimethyl-4-nonanol instead of 2,6-dimethyl-4-heptanol.
Synthesis Example of Compound A1-27 4,5-dimethylthiazole was used in place of thiazole and was synthesized in the same manner as compound A1-10.
Synthesis Example of Compound A1-28

In a three-necked flask, under a nitrogen atmosphere, 1.00 g of phenylboronic acid, 1.00 g of 6-bromopyridine-2-carboxylic acid, 1.38 g of potassium carbonate, 50 mL of a mixed solvent of 5: 1 tetrahydrofuran and water were introduced at room temperature. It was cooled with. The tetrakis (triphenylphosphine) palladium 0.55g was introduce | transduced here, and it heated and refluxed for 4 hours. After cooling to room temperature, 40 mL of water and 40 mL of ethyl acetate were introduced, and 20 mL of ethyl acetate was introduced into the aqueous phase obtained by extraction / separation, followed by extraction / separation. Dilute hydrochloric acid was introduced into the obtained aqueous phase (pH 11) until pH 4 was reached. 0.07g of compound A1-28 was obtained by collect | recovering the depositing solid by filtration.
Synthesis example of compound A1-29

Into a three-necked flask, 0.90 g of 2,6-dimethylphenylboronic acid, 0.92 g of methyl 6-bromopyridine-2-carboxylate, 1.92 g of potassium phosphate and 30 mL of toluene were introduced under a nitrogen atmosphere and cooled at room temperature. did. To this, 0.13 g of tricyclohexylphosphine and 0.10 g of palladium acetate were introduced, and the mixture was stirred at 100 degrees overnight. After cooling to room temperature, 30 mL of saturated ammonium chloride aqueous solution and 40 mL of ethyl acetate were introduced, followed by extraction and liquid separation. The crude product obtained by concentrating the organic phase thus obtained was purified by silica gel column chromatography (solvent: hexane / ethyl acetate) to obtain 0.45 g of a methyl ester of Compound A1-29. .
This ester was hydrolyzed in the same manner as for compound A1-11 to give compound A1-29.
Synthesis Example of Compound A1-30

In a three-necked flask, 13.2 g of diisopropylpyramine and 200 mL of tetrahydrofuran (commercially available dehydrated solvent) were introduced under a nitrogen atmosphere and cooled to -78 ° C. Here, 64.0 mL of 1.6 M hexane solution of n-butyllithium was dropped, and the mixture was stirred at −78 ° C. for 10 minutes. To this, 6.0 g of 2-bromo-6-methylpyridine was added dropwise and stirred at -78 ° C for 30 minutes. Here, 15.97 g of iodoethane was dropped, and then the temperature was gradually raised to room temperature. After stirring at room temperature for 1 hour, 100 mL of saturated aqueous ammonium chloride solution was introduced, followed by extraction and liquid separation. Extraction and liquid separation were performed twice by introducing 100 mL of ethyl acetate into the aqueous phase, and the organic phases obtained by the liquid separation operation three times in total with the first liquid separation were combined and concentrated. The crude product was purified by silica gel column chromatography (solvent: hexane / ethyl acetate) to obtain 7.2 g of 2-bromo-6- (3-pentyl) pyridine. This compound was converted to compound A1-30 by the same method as the synthesis method of compound A1-4.
Synthesis example of compound A1-31

Under a nitrogen atmosphere, 13.0 g of diisopropylpyramine and 200 mL of tetrahydrofuran (commercially available dehydrated solvent) were introduced into a three-necked flask and cooled to -78 ° C. Here, 80.0 mL of 1.6 M hexane solution of n-butyllithium was dropped, and the mixture was stirred at −78 ° C. for 15 minutes. To this, 20 g of 2-bromo-6-methylpyridine was added dropwise and stirred at -78 ° C for 30 minutes. Here, 17.7 g of 1-bromo-2-methylpropane was dropped, and then the temperature was gradually raised to room temperature. After stirring at room temperature for 1 hour, 100 mL of saturated aqueous ammonium chloride solution was introduced, followed by extraction and liquid separation. 150 mL of ethyl acetate was introduced into the aqueous phase for extraction and liquid separation. By combining the organic phases obtained by the liquid separation operation twice in total and concentrating the crude product obtained by silica gel column chromatography (solvent: hexane / ethyl acetate), 2-bromo-6- 18.8 g of (3-methylbutyl) pyridine was obtained. This compound was converted to compound A1-31 by the same method as the synthesis method of compound A1-4.
Synthesis example of compound A1-32

2,6-dibromo-4-trifluoromethylpyridine was synthesized by the method described in International Publication No. WO 2008878738. 1.73 g of this compound was introduced into a three-necked flask, and 0.40 g of iron (III) chloride and 30 mL of tetrahydrofuran were introduced under a nitrogen atmosphere and stirred at room temperature. 2 mL of a 3M diethyl ether solution of methylmagnesium bromide was added dropwise thereto, and the mixture was stirred at room temperature for 1.5 hours. A crude product obtained by adding 30 mL of a saturated aqueous ammonium chloride solution and 30 mL of ethyl acetate and concentrating the organic layer obtained by extraction / separation was purified by silica gel column chromatography (solvent: hexane) to give 2- 0.18 g of bromo-6-methyl-4-trifluoromethylpyridine was obtained. This compound was converted to compound A1-32 by the same method as the synthesis method of compound A1-4.
Synthesis example of compound A1-33

Under a nitrogen atmosphere, 1.44 g of Compound A1-31, 1.11 g of trifluoromethanesulfonamide, 1.37 g of 4-dimethylaminopyridine, and 20 mL of dimethylformamide were introduced into a three-necked flask and stirred overnight at room temperature. 100 mL of water was introduced here, and concentrated hydrochloric acid was added until pH 1 while stirring at room temperature. The precipitated solid was collected by filtration and recrystallized from methanol to obtain 1.5 g of Compound A1-33.
Synthesis example of compound A1-34

According to the said scheme, it synthesize | combined by the method similar to compound A1-33.
Synthesis example of compound A1-35

Eur. J. et al. Med. Chem. Using perfluorobutanesulfonamide synthesized by the method described in the literature of 2010, 45, 1225, the compound was synthesized in the same manner as compound A1-33 according to the above scheme.
Synthesis Example of Compound A1-36 Compound A1-30 was used instead of compound A1-31, and compound A1-33 was synthesized in the same manner as compound A1-33.
Synthesis Example of Compound A1-37 Compound A1-11 was used instead of compound A1-31, and compound A1-33 was synthesized in the same manner as compound A1-33.
Synthesis Example of Compound A1-38 Compound A1-22 was used instead of compound A1-31, and compound A1-33 was synthesized in the same manner as compound A1-33.
Synthesis Example of Compound A1-39 Compound A1-12 was used instead of compound A1-31, and compound A1-33 was synthesized in the same manner as compound A1-33.
Synthesis Example of Compound A1-40 The compound A1-40 was synthesized in the same manner as Compound A1-38, using methanesulfonamide instead of trifluoromethanesulfonamide.
Synthesis Example of Compound A1-41 Compound o1-toluenesulfonamide was used instead of trifluoromethanesulfonamide and was synthesized in the same manner as compound A1-38.
Synthesis Example of Compound A1-42 Compound A1-27 was used in place of compound A1-31, and synthesis was performed in the same manner as for compound A1-33.

Ｊ．Ｏｒｇ．Ｃｈｅｍ．１９８９，５４，３６２５に記載の方法で合成した２−（２−メチル−１，３−ジオキサン−２−イル）エタノールを用い、化合物Ａ２−３と同様の方法でブロモ酢酸と反応させて得られた生成物を、濃塩酸中８０℃で２時間加熱還流させることにより、アセタール脱保護を行った。脱保護反応液は、飽和炭酸水素ナトリウム水溶液に滴下して中和し、酢酸エチルで抽出・分液して得られた有機層を濃縮することで化合物Ａ２−１０が得られた。 Synthesis Example of Compound A2-3 In a three-necked flask, 13.0 g of 2-ethylhexanol and 200 mL of tetrahydrofuran (commercial dehydration solvent) were introduced in a nitrogen atmosphere and cooled to 0 ° C. To this, 4.0 g of sodium hydride (60% dispersion) was introduced and stirred at 0 ° C. for 30 minutes. Bromoacetic acid 15.0g was dripped here, and it stirred at room temperature for 5 hours. 200 mL of saturated ammonium chloride and 100 mL of ethyl acetate were added, and the organic layer obtained by extraction and liquid separation was concentrated to obtain 18.4 g of Compound A2-3.
Synthesis Example of Compound A2-4 The compound A2-4 was synthesized in the same manner as Compound A2-3 using tert-butyl alcohol instead of 2-ethylhexanol.
Synthesis Example of Compound A2-7 Diethylene glycol monoethyl ether was used instead of 2-ethylhexanol and was synthesized in the same manner as Compound A2-3.
Synthesis Example of Compound A2-10

J. et al. Org. Chem. Obtained by reacting with bromoacetic acid in the same manner as compound A2-3 using 2- (2-methyl-1,3-dioxan-2-yl) ethanol synthesized by the method described in 1989, 54, 3625. The acetal deprotection was performed by heating and refluxing the obtained product in concentrated hydrochloric acid at 80 ° C. for 2 hours. The deprotection reaction solution was dropped into a saturated aqueous sodium hydrogen carbonate solution to neutralize, and the organic layer obtained by extraction and liquid separation with ethyl acetate was concentrated to obtain Compound A2-10.

三ツ口フラスコにβ−プロピオラクトン７．２ｇ、メタノール１００ｍＬを導入し、室温で撹拌しながら、ナトリウムメトキシド（２８％メタノール溶液）を１９．３ｇを滴下し、５０℃で２時間加熱還流した。室温に冷却後、ブロモ酢酸１３．９ｇを滴化し、５時間加熱還流した。飽和塩化アンモニウム２００ｍＬ、酢酸エチル１００ｍＬを加え、抽出・分液して得られた有機層を濃縮することにより、化合物Ａ２−１２を１２．４ｇ得た。 Synthesis example of compound A2-12

Into a three-necked flask, 7.2 g of β-propiolactone and 100 mL of methanol were introduced. While stirring at room temperature, 19.3 g of sodium methoxide (28% methanol solution) was added dropwise, and the mixture was heated to reflux at 50 ° C. for 2 hours. After cooling to room temperature, 13.9 g of bromoacetic acid was added dropwise and heated to reflux for 5 hours. 12.4 g of compound A2-12 was obtained by adding 200 mL of saturated ammonium chloride and 100 mL of ethyl acetate, and concentrating the organic layer obtained by extraction and liquid separation.

Synthesis Example of Compound A2-13 The compound A2-13 was synthesized in the same manner as Compound A2-3 using 2,2,2-trifluoroethanol instead of 2-ethylhexanol.
Synthesis Example of Compound A2-18 Compound A2-18 was synthesized in the same manner as Compound A2-3 using methyl salicylate instead of 2-ethylhexanol.
Synthesis Example of Compound A2-19 Synthesis was performed in the same manner as Compound A2-3 using tetrahydropyran-2-methanol instead of 2-ethylhexanol.
Synthesis Example of Compound A2-21 Synthesis was performed in the same manner as Compound A2-3 using tetrahydrofurfuryl alcohol in place of 2-ethylhexanol.
Synthesis Example of Compound A2-22 The compound A2-22 was synthesized in the same manner as Compound A2-3 using furfuryl alcohol instead of 2-ethylhexanol.
The synthesis example of compound A2-23 It synthesize | combined by the method of Polymer 2013,54,2924.
Synthesis Example of Compound A2-24 Synthesis was performed in the same manner as Compound A2-3 using 3-buten-1-ol instead of 2-ethylhexanol.
Synthesis Example of Compound A2-28 The compound A2-28 was synthesized in the same manner as Compound A2-3 using 1,6-heptadien-4-ol instead of 2-ethylhexanol.

三ツ口フラスコに２−ブロモプロピオン酸１５．３ｇ、メタノール１００ｍＬを導入し、室温で撹拌しながら、ナトリウムメトキシド（２８％メタノール溶液）を１９．３ｇを滴下し、５０℃で１２時間加熱還流した。反応液を減圧濃縮し、１Ｎ希塩酸１００ｍＬ、酢酸エチル１００ｍＬを加え、抽出・分液して得られた有機層を濃縮することにより、化合物Ａ２−１２を１０．４ｇ得た。 Synthesis example of compound A2-29

To a three-necked flask, 15.3 g of 2-bromopropionic acid and 100 mL of methanol were introduced, and 19.3 g of sodium methoxide (28% methanol solution) was added dropwise with stirring at room temperature, and the mixture was heated to reflux at 50 ° C. for 12 hours. The reaction solution was concentrated under reduced pressure, 100 mL of 1N diluted hydrochloric acid and 100 mL of ethyl acetate were added, and the organic layer obtained by extraction and liquid separation was concentrated to obtain 10.4 g of compound A2-12.

Synthesis Example of Compound A2-31 Am. Chem. Soc. 1948, 70, 1157.
Synthesis Example of Compound A2-34 Instead of 2-bromopropionic acid, J.P. Org. Chem. 1957, 23, 1785. Using bromofluoroacetic acid synthesized by the method described in 1), the compound was synthesized in the same manner as compound A2-29.

三ツ口フラスコに、窒素雰囲気下、テトラヒドロピラン−２−メタノール２５．０ｇ、アセトニトリル３７５ｇを導入し、室温で撹拌しながら２，２，６，６−テトラメチルピペリジン １−オキシル（ＴＥＭＰＯ）２．４ｇ、ｐＨ６．８リン酸バッファー３７５ｇ、亜塩素酸ナトリウム３８．９ｇをこの順序で導入した。ここに、次亜塩素酸ナトリウムの４質量％水溶液２００．３ｇをゆっくり滴下した後、４０℃で６時間撹拌した。室温に冷却後、飽和炭酸水素ナトリウム水溶液７００ｍＬ、亜硫酸ナトリウム６８ｇを導入した。酢酸エチルで３回洗浄し（４００ｍＬ，３００ｍＬ，３００ｍＬ）、濃塩酸をｐＨ〜２までゆっくり加えた。酢酸エチルで３回抽出・分液して（３００ｍＬ×３）得られた有機層を水３００ｍＬ、続いて、飽和塩化ナトリウム水溶液３００ｍＬで洗浄し、減圧濃縮することにより、化合物２−３６を２２．３ｇ得た。 Synthesis example of compound A2-36

Into a three-necked flask, 25.0 g of tetrahydropyran-2-methanol and 375 g of acetonitrile were introduced under a nitrogen atmosphere, and 2.4 g of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) was stirred at room temperature. 375 g of pH 6.8 phosphate buffer and 38.9 g of sodium chlorite were introduced in this order. To this, 200.3 g of a 4% by mass aqueous solution of sodium hypochlorite was slowly added dropwise, followed by stirring at 40 ° C. for 6 hours. After cooling to room temperature, 700 mL of a saturated aqueous sodium hydrogen carbonate solution and 68 g of sodium sulfite were introduced. Wash three times with ethyl acetate (400 mL, 300 mL, 300 mL) and slowly add concentrated hydrochloric acid to pH˜2. The organic layer obtained by extraction and liquid separation three times with ethyl acetate (300 mL × 3) was washed with 300 mL of water, followed by 300 mL of a saturated aqueous solution of sodium chloride, and concentrated under reduced pressure to give compound 2-36 as 22.2. 3 g was obtained.

三ツ口フラスコに、窒素雰囲気下、エチレングリコール１２．４ｇ、テトラヒドロフラン（市販脱水溶媒）２００ｍＬを導入し、０℃に冷却した。ここに水素化ナトリウム（６０％ディスパージョン）１６．０ｇを導入し、０℃で３０分間撹拌した。ここにブロモ酢酸５５．６ｇを滴下し、室温で５時間撹拌した。飽和塩化アンモニウム２００ｍＬ、酢酸エチル１００ｍＬを加え、抽出・分液して得られた有機層を濃縮することにより、化合物Ａ２−３を３２．４ｇ得た。 Synthesis example of compound A2-40

Under a nitrogen atmosphere, 12.4 g of ethylene glycol and 200 mL of tetrahydrofuran (commercial dehydration solvent) were introduced into a three-necked flask and cooled to 0 ° C. 16.0 g of sodium hydride (60% dispersion) was introduced here and stirred at 0 ° C. for 30 minutes. Bromoacetic acid 55.6g was dripped here, and it stirred at room temperature for 5 hours. 200 mL of saturated ammonium chloride and 100 mL of ethyl acetate were added, and the organic layer obtained by extraction and liquid separation was concentrated to obtain 32.4 g of Compound A2-3.

Synthesis Example of Compound A2-41 Synthesis was performed in the same manner as for Compound A2-40 using diethylene glycol instead of ethylene glycol.
Synthesis Example of Compound A2-42 The compound A2-42 was synthesized in the same manner as Compound A2-40 using 2,2-diethyl-1,3-propanediol instead of ethylene glycol.
Synthesis Example of Compound A2-44 The compound A2-44 was synthesized in the same manner as Compound A2-40 using cis-1,2-cyclohexanediol instead of ethylene glycol.

＜硬化性化合物＞
ＫＡＹＡＲＡＤ ＤＰＨＡ：（日本化薬社製、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートとの混合物）
ＪＥＲ１５７Ｓ６５：（三菱化学社製、特殊ノボラック型エポキシ樹脂）
ＫＡＹＡＲＡＤ Ｄ−３２０：（日本化薬社製、ジペンタエリスリトールテトラアクリレート）
Ｍ−５１０：（東亞合成社製、多塩基酸変性アクリルオリゴマー）
Ｍ−５２０：（東亞合成社製、多塩基酸変性アクリルオリゴマー）
ＤＰＣＡ−６０：（日本化薬社製、ペンチレンオキシ鎖を６個有する６官能アクリレート）
＜溶剤＞
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート In this example, the following abbreviations were adopted.
<Compound (A)>
Compounds A1-1 to A1-42: represent the above-described compounds A1-1 to A1-42.
Compounds A2-1 to A2-44: Represents the following compounds.

<Curable compound>
KAYARAD DPHA: (Nippon Kayaku Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
JER157S65: (Mitsubishi Chemical Corporation, special novolac type epoxy resin)
KAYARAD D-320: (Nippon Kayaku Co., Ltd., dipentaerythritol tetraacrylate)
M-510: (manufactured by Toagosei Co., Ltd., polybasic acid-modified acrylic oligomer)
M-520: (manufactured by Toagosei Co., Ltd., polybasic acid-modified acrylic oligomer)
DPCA-60: (Nippon Kayaku Co., Ltd., 6-functional acrylate having 6 pentyleneoxy chains)
<Solvent>
PGMEA: Propylene glycol monomethyl ether acetate

<Synthesis of copper complex>
(Synthesis of copper complex 1-1)
The sodium salt of Compound A1-1 (814 mg, 2.97 mmol) was dissolved in 50 ml of water. After the temperature of this solution was raised to 50 ° C., an aqueous solution (50 ml) of copper sulfate pentahydrate (739 mg, 2.97 mmol) was added dropwise and reacted at 50 ° C. for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, and the precipitated solid was collected by filtration to obtain copper complex 1-1 (1.00 g).

(Synthesis of copper complex 1-2 to 1-55)
Copper complexes 1-2 to 1-55 were obtained by a method according to the synthesis method of copper complex 1-1.

(Synthesis of copper complex 2-1)
Compound A2-1 (886 mg, 9.84 mmol) was dissolved in 20 ml of methanol. After the temperature of this solution was raised to 50 ° C., a methanol solution (160 ml) of copper hydroxide (449 mg, 4.60 mmol) was added dropwise and reacted at 50 ° C. for 2 hours. After completion of the reaction, the copper complex 2-1 (1.00 g) was obtained by distilling off the water and the solvent generated in the evaporator.

(Synthesis of copper complex 2-2 to 2-26)
Copper complexes 2-2 to 2-26 were obtained by a method according to the synthesis method of copper complex 2-1.
(Synthesis of Copper Complex 2-27)
The sodium salt of compound A2-3 (1.00 g, 4.76 mmol) was dissolved in 20 ml of methanol, heated to 50 ° C., and then a solution of copper sulfate pentahydrate (0.73 g, 2.92 mmol) in methanol (20 ml). ) Was added dropwise. After heating at 50 ° C. for 1 hour, the reaction solution was cooled to 5 ° C. in an ice-water bath, and the reaction solution was filtered. The filtrate was concentrated with an evaporator to obtain copper complex 2-27 (1.14 g).

２００ｍＬフラスコに、２，６−ビス（ブロモメチル)ピリジン（東京化成製）４．０ｇ、ジメチルアミンの３３％エタノール溶液（アルドリッチ製）３０ｍＬを導入し、室温で３時間撹拌した後、室温で２日間静置した。析出する白色固体（ジメチルアミン臭化水素塩）を濾過により除去し、濾液を減圧し濃縮して得られた粗生成物を、飽和炭酸水素ナトリウム水溶液と酢酸エチルを用いて分液し、得られた有機相を無水硫酸ナトリウムにより予備乾燥した後に減圧濃縮することにより、化合物Ａ３−２３を１．０ｇ得た。

１０ｍＬフラスコに、化合物Ａ３−２３を３８ｍｇ、メタノールを１ｍＬ加え、室温で撹拌しながら、塩化銅（ＩＩ）二水和物（和光純薬製）３４ｍｇを導入し、１０分間撹拌した。得られた青色溶液を減圧乾固することにより、銅錯体Ｃｕ３−６ａを緑色固体として得た。 (Synthesis example of copper complex Cu3-6a)

Into a 200 mL flask, 4.0 g of 2,6-bis (bromomethyl) pyridine (manufactured by Tokyo Chemical Industry) and 30 mL of 33% ethanol solution of dimethylamine (manufactured by Aldrich) were introduced, stirred at room temperature for 3 hours, and then at room temperature for 2 days. Left to stand. The precipitated white solid (dimethylamine hydrobromide) was removed by filtration, and the filtrate was concentrated under reduced pressure. The resulting crude product was separated using a saturated aqueous sodium bicarbonate solution and ethyl acetate. The organic phase was pre-dried with anhydrous sodium sulfate and concentrated under reduced pressure to obtain 1.0 g of Compound A3-23.

To a 10 mL flask, 38 mg of compound A3-23 and 1 mL of methanol were added, and while stirring at room temperature, 34 mg of copper (II) chloride dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was introduced and stirred for 10 minutes. The obtained blue solution was dried under reduced pressure to obtain copper complex Cu3-6a as a green solid.

上記スキームに従い、銅錯体Ｃｕ３−６ａと同様の方法で合成した。 (Synthesis example of copper complex Cu3-7a)

According to the said scheme, it synthesize | combined by the method similar to copper complex Cu3-6a.

(Synthesis example of copper complex Cu3-10a)
Compound A3-43 was synthesized by the method described in the literature (J. Organomet. Chem. 2009, 694, 2636) and copper complexed by the same method as copper complex Cu3-6a.
(Synthesis example of copper complex Cu3-15a)
Compound A3-52 was synthesized by the method described in the literature (Tetrahedron 1998, 54, 2365) and copper complexed by the same method as copper complex Cu3-6a.
(Synthesis example of copper complex Cu3-16a)
Compound A3-54 is commercially available from Tokyo Chemical Industry and was copper-complexed in the same manner as copper complex Cu3-6a.

３００ｍＬフラスコに、ビス（２−ピリジルメチル)アミン１９．９ｇ、トリエチルアミン１３．３ｇ、テトラヒドロフラン１５０ｍＬを導入し、室温で撹拌した。水冷しながら２−エチルヘキサノイルクロリド１６．５ｇを滴下し、室温で３時間撹拌した。水と酢酸エチルを用いて分液し、得られた有機相を無水硫酸マグネシウムにより予備乾燥した後に減圧濃縮した。この粗生成物をシリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン／酢酸エチル）により精製することで化合物Ａ３−１３５を１０ｇ得た。得られた化合物Ａ３−１３５を用い、銅錯体Ｃｕ３−６ａと同様の方法で銅錯体化した。 (Synthesis example of copper complex Cu3-35a)

Into a 300 mL flask, 19.9 g of bis (2-pyridylmethyl) amine, 13.3 g of triethylamine, and 150 mL of tetrahydrofuran were introduced and stirred at room temperature. While cooling with water, 16.5 g of 2-ethylhexanoyl chloride was added dropwise and stirred at room temperature for 3 hours. Liquid separation was performed using water and ethyl acetate, and the obtained organic phase was pre-dried with anhydrous magnesium sulfate and then concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate) to obtain 10 g of Compound A3-135. The obtained compound A3-135 was used to form a copper complex in the same manner as the copper complex Cu3-6a.

安息香酸銅（関東化学製）１モルに対して２モルのリン酸ジフェニル（東京化成製）を加え、アセトン中室温で３時間撹拌した後、ヘキサンを加えることで、ビス（リン酸ジフェニル）銅（ＩＩ）が得られる。これをメタノールに溶解させ、１モルの化合物Ａ３−２（東京化成製）を加え、１０分間撹拌した。得られた青色溶液を減圧乾固することにより、銅錯体Ｃｕ３−５６ａを得た。 (Synthesis example of copper complex Cu3-56a)

2 mol of diphenyl phosphate (manufactured by Tokyo Chemical Industry) is added to 1 mol of copper benzoate (manufactured by Kanto Chemical Co., Inc.) and stirred for 3 hours at room temperature in acetone, and then hexane is added to add bis (diphenyl phosphate) copper. (II) is obtained. This was dissolved in methanol, 1 mol of compound A3-2 (manufactured by Tokyo Chemical Industry) was added, and the mixture was stirred for 10 minutes. Copper complex Cu3-56a was obtained by drying the obtained blue solution under reduced pressure.

(Synthesis example of copper complex Cu3-63a)
It synthesize | combined by the method similar to copper complex Cu3-35a using copper acetate (II) monohydrate (made by Wako Purechemical) instead of copper chloride (II) dihydrate.

１００ｍＬフラスコに、酢酸銅（ＩＩ）一水和物（和光純薬製）１．９９ｇ、化合物Ａ３−５９（和光純薬製）１．６７ｇ、メタノール２０ｍＬを導入し、１０分間加熱還流した。ここに化合物ＡＡ２−１５（東京化成製）１．８４ｇを加え、更に１０分間加熱還流した。溶媒を５ｍＬ程度まで減圧濃縮し、水を２０ｍＬ加えることで析出した固体を濾過により改修し、銅錯体Ｃｕ４−３６ａを青色固体として得た。 (Synthesis example of copper complex Cu4-36a)

Into a 100 mL flask were introduced 1.99 g of copper (II) acetate monohydrate (manufactured by Wako Pure Chemical Industries), 1.67 g of compound A3-59 (manufactured by Wako Pure Chemical Industries), and 20 mL of methanol, and the mixture was heated to reflux for 10 minutes. The compound AA2-15 (product made from Tokyo Chemical Industry) 1.84g was added here, and also it heat-refluxed for 10 minutes. The solvent was concentrated under reduced pressure to about 5 mL, and the solid precipitated by adding 20 mL of water was modified by filtration to obtain copper complex Cu4-36a as a blue solid.

２００ｍＬフラスコに、４−メチルチアゾール（東京化成製）５．０ｇ、酢酸銅（無水）（和光純薬製）１．８３ｇ、トルエン１００ｍＬを加え、１２時間加熱還流した。室温に冷却後、水を加えて析出物を濾別した後、濾液に酢酸エチルを加えて分液・抽出した。得られた有機相を無水硫酸マグネシウムで予備乾燥し、減圧濃縮して得られた褐色の粗生成物（微量の原料を含有）を、メタノールで再結晶することにより、化合物ＡＡ２−２２を淡黄色固体として得た。この化合物を用いて、銅錯体Ｃｕ４−３６ａと同様の方法で錯体化した。 (Synthesis example of copper complex Cu4-39a)

To a 200 mL flask, 5.0 g of 4-methylthiazole (manufactured by Tokyo Chemical Industry), 1.83 g of copper acetate (anhydrous) (manufactured by Wako Pure Chemical Industries) and 100 mL of toluene were added, and the mixture was heated to reflux for 12 hours. After cooling to room temperature, water was added and the precipitate was filtered off, and then ethyl acetate was added to the filtrate for liquid separation and extraction. The obtained organic phase was pre-dried with anhydrous magnesium sulfate and concentrated under reduced pressure, and the brown crude product (containing a small amount of raw material) was recrystallized from methanol to give compound AA2-22 to a pale yellow color. Obtained as a solid. Using this compound, it was complexed in the same manner as copper complex Cu4-36a.

５００ｍＬ三ツ口フラスコに、窒素雰囲気下、３，５−ジメチルピラゾール（東京化成製）１０ｇ、ジメチルスルホキシド６０ｍＬを加え、撹拌する。ここに水酸化カリウム（和光純薬製）２３．３ｇを少しずつ加え、６０度で１時間撹拌した。ここに、ジメチルスルホキシド４０ｍＬに溶解させたジブロモメタン（和光純薬製）９ｇを滴下し、６０度で４時間撹拌した。室温に冷却後、水２００ｍＬを滴下し、クロロホルムで抽出後、水、飽和食塩水で洗浄して得られた有機相を減圧濃縮することにより、化合物ＡＡ２−３２を白色固体として得た。この化合物を用いて、銅錯体Ｃｕ４−３６ａと同様の方法で錯体化した。 (Synthesis example of copper complex Cu4-45a)

To a 500 mL three-necked flask, 10 g of 3,5-dimethylpyrazole (manufactured by Tokyo Chemical Industry) and 60 mL of dimethyl sulfoxide are added and stirred under a nitrogen atmosphere. To this was added 23.3 g of potassium hydroxide (manufactured by Wako Pure Chemical Industries) little by little, and the mixture was stirred at 60 degrees for 1 hour. 9 g of dibromomethane (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 40 mL of dimethyl sulfoxide was added dropwise thereto and stirred at 60 degrees for 4 hours. After cooling to room temperature, 200 mL of water was added dropwise, extracted with chloroform, washed with water and saturated brine, and concentrated under reduced pressure to give Compound AA2-32 as a white solid. Using this compound, it was complexed in the same manner as copper complex Cu4-36a.

１００ｍＬフラスコに、化合物Ａ２−３２を０．２０ｇ、酢酸銅（ＩＩ）一水和物（和光純薬製）０．１９ｇ、メタノール１０ｍＬを加え、撹拌しながら室温から４０度に昇温して３０分間撹拌した。徐々に溶解して青色溶液となったら、化合物Ａ３−９６（東京化成製）０．１５ｇと５０重量％水酸化ナトリウム水溶液０．１６ｇを溶解させたメタノール溶液１０ｍＬを滴下した。ゆっくりと析出した青白色固体を濾過により回収し、銅錯体Ｃｕ４−４９ａを０．１６ｇ得た。 (Synthesis example of copper complex Cu4-49a)

To a 100 mL flask were added 0.20 g of compound A2-32, 0.19 g of copper (II) acetate monohydrate (manufactured by Wako Pure Chemical Industries), and 10 mL of methanol, and the temperature was raised from room temperature to 40 degrees with stirring. Stir for minutes. When the solution was gradually dissolved to give a blue solution, 10 mL of a methanol solution in which 0.15 g of Compound A3-96 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.16 g of 50 wt% aqueous sodium hydroxide solution were dissolved was added dropwise. The pale white solid that slowly precipitated was collected by filtration to obtain 0.16 g of copper complex Cu4-49a.

(Synthesis example of copper complex Cu4-52a)
The compound A3-103, which is commercially available from Tokyo Chemical Industry as keridamic acid monohydrate, was used and synthesized in the same manner as the copper complex Cu4-49a.
(Synthesis example of copper complex Cu4-62a)
In the same manner as compound AA2-32 using 3,5-diisopropylpyrazole (manufactured by Tokyo Chemical Industry) instead of 3,5-dimethylpyrazole and 2-chloromethylpyridine hydrochloride (manufactured by Tokyo Chemical Industry) instead of dibromomethane. The synthesized compound AA2-26 was complexed in the same manner as the copper complex Cu4-36a.
(Synthesis example of copper complex Cu4-63a)
The compound AA2-28 commercially available from Tokyo Chemical Industry was used and synthesized in the same manner as the copper complex Cu4-36a.

１００ｍＬフラスコに、ビス（２−ピリジルメチル）アミン（東京化成製）１．９９ｇ、エタノール２０ｍＬ、トリエチルアミン１．０１ｇを加え、室温で撹拌しながらブロモ酢酸（関東化学製）１．４９ｇを滴下した後、５時間加熱還流した。室温に冷却後、反応液を減圧濃縮して得られた粗生成物に酢酸エチルを加えて析出した固体をメタノールで分散洗浄し、濾過により化合物Ａ４−１２１を０．５ｇ得た。この化合物を用い、銅錯体Ｃｕ５−１ａと同様の方法で錯体化した。
（銅錯体Ｃｕ５−７２ａの合成例）
メタノール中で化合物Ａ４−１（東京化成製）と塩化銅（ＩＩ）二水和物（和光純薬製）を１：１のモル比で混合し、１０分間撹拌した反応液を減圧乾固させることで銅錯体Ｃｕ５−１ａを得た。
銅錯体Ｃｕ５−１ａを水に溶解させ、撹拌しながら過剰量の飽和テトラフルオロホウ酸ナトリウム（和光純薬製）水溶液を加えた。析出固体を濾過により回収し、銅錯体Ｃｕ５−７２ａを得た。
（銅錯体Ｃｕ５−８２ａの合成例）
銅錯体Ｃｕ５−１ａの代わりに化合物Ａ４−６２（アルドリッチ製）、テトラフルオロホウ酸ナトリウムの代わりテトラキス（ペンタフルオロフェニル）ホウ酸リチウム（東京化成製）を用いて、Ｃｕ５−７２ａと同様の方法で合成した。
（銅錯体Ｃｕ５−８３ａの合成例）
化合物Ａ４−６３（東京化成製）を用いて、銅錯体Ｃｕ５−８２ａと同様の方法で合成した。
（銅錯体Ｃｕ５−９２ａの合成例）
テトラフルオロホウ酸ナトリウムの代わりビス(トリフルオロメタンスルホン)イミドリチウムを用いてＣｕ５−７２ａと同様の方法で、銅錯体Ｃｕ５−９２ａを合成した。
（銅錯体Ｃｕ５−９５ａの合成例）
化合物Ａ４−６３（東京化成製）を用いて、銅錯体Ｃｕ５−９２ａと同様の方法で合成した。 (Synthesis example of copper complex Cu5-37a)

After adding 1.99 g of bis (2-pyridylmethyl) amine (manufactured by Tokyo Chemical Industry), 20 mL of ethanol and 1.01 g of triethylamine to a 100 mL flask, 1.49 g of bromoacetic acid (manufactured by Kanto Chemical) was added dropwise with stirring at room temperature. Heated to reflux for 5 hours. After cooling to room temperature, ethyl acetate was added to the crude product obtained by concentrating the reaction solution under reduced pressure, the precipitated solid was dispersed and washed with methanol, and 0.5 g of compound A4-121 was obtained by filtration. Using this compound, it was complexed in the same manner as copper complex Cu5-1a.
(Synthesis example of copper complex Cu5-72a)
Compound A4-1 (manufactured by Tokyo Chemical Industry Co., Ltd.) and copper (II) chloride dihydrate (manufactured by Wako Pure Chemical Industries) are mixed at a molar ratio of 1: 1 in methanol, and the reaction solution stirred for 10 minutes is dried under reduced pressure. Thus, a copper complex Cu5-1a was obtained.
Copper complex Cu5-1a was dissolved in water, and an excess amount of a saturated aqueous solution of sodium tetrafluoroborate (manufactured by Wako Pure Chemical Industries, Ltd.) was added with stirring. The precipitated solid was collected by filtration to obtain a copper complex Cu5-72a.
(Synthesis example of copper complex Cu5-82a)
In the same manner as Cu5-72a, using Compound A4-62 (manufactured by Aldrich) instead of copper complex Cu5-1a and tetrakis (pentafluorophenyl) lithium borate (manufactured by Tokyo Chemical Industry) instead of sodium tetrafluoroborate Synthesized.
(Synthesis example of copper complex Cu5-83a)
It synthesize | combined by the method similar to copper complex Cu5-82a using compound A4-63 (product made from Tokyo Chemical Industry).
(Synthesis example of copper complex Cu5-92a)
Copper complex Cu5-92a was synthesized in the same manner as Cu5-72a using bis (trifluoromethanesulfone) imide lithium instead of sodium tetrafluoroborate.
(Synthesis example of copper complex Cu5-95a)
It synthesize | combined by the method similar to copper complex Cu5-92a using compound A4-63 (product made from Tokyo Chemical Industry).

<Evaluation of near-infrared absorbing composition>
<< Preparation of near-infrared absorbing composition >>
(Example 1-1)
The following compound was mixed and the near-infrared absorptive composition of Example 1-1 was prepared.
The copper complex 1-1 20 parts by mass KAYARAD DPHA 20 parts by mass JER157S65 20 parts by mass PGMEA 120 parts by mass Except for changing the copper complex 1-1 to copper complexes 1-2 to 1-55, Example 1-1 and The near-infrared absorptive composition of each Example was prepared by setting it as the same composition.

(Example 2-1)
The following compound was mixed and the near-infrared absorptive composition of Example 2-1 was prepared.
Copper complex 2-1 20 parts by mass KAYARAD DPHA 20 parts by mass JER157S65 20 parts by mass PGMEA 120 parts by mass Copper complex 2-1 is converted to copper complex 2-2 to 2-27, copper acetate (anhydrous) or copper p-toluenesulfonate The near-infrared absorptive composition of each Example and the comparative example was prepared by setting it as the composition similar to Example 2-1 except having changed into.

<< Production of near-infrared cut filter >>
A photoresist was applied on a glass substrate and patterned by lithography to form a partition wall of the photoresist to form a dripping region of the near infrared absorbing composition. 3 ml of each of the near infrared ray absorbing compositions prepared in Examples and Comparative Examples was dropped. The substrate with the coating film was dried at room temperature for 24 hours, and then the coating film thickness was evaluated. The film thickness was 192 μm.
<< Near-infrared shielding evaluation >>
The transmittance of the obtained near-infrared cut filter at a wavelength of 800 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Near-infrared shielding was evaluated according to the following criteria.
A: Transmittance at 800 nm ≦ 5%
B: 5% <800 nm transmittance ≦ 7%
C: 7% <800 nm transmittance ≦ 10%
D: 10% <800 nm transmittance

<< Heat resistance evaluation >>
The obtained near-infrared cut filter was left at 200 ° C. for 5 minutes. Before and after the heat resistance test, the maximum absorbance (Absλmax) at a wavelength of 700 to 1400 nm and the minimum absorbance (Absλmin) at a wavelength of 400 to 700 nm of the near-infrared cut filter are measured with a spectrophotometer U-4100. (Abstract of Hitachi High-Technologies) was used to determine the absorbance ratio represented by “Absλmax / Absλmin”.
Absorbance ratio change rate represented by | ((absorbance ratio before test−absorbance ratio after test) / absorbance ratio before test) × 100 | (%) was evaluated according to the following criteria. The results are shown in the table below.
A: Absorbance ratio change rate ≦ 2%
B: 2% <absorbance ratio change rate ≦ 4%
C: 4% <absorbance ratio change rate ≦ 7%
D: 7% <Change rate of absorbance ratio << Evaluation of water absorption >>
The sufficiently dried copper complex powder was allowed to stand for 5 hours at 25 ° C. and a relative humidity of 95% (water absorption test). Based on the mass before the water absorption test, the mass increase rate of the copper complex powder after the water absorption test was calculated and evaluated according to the following criteria.
A1: 0 ≦ mass increase rate ≦ 3%
A2: 3% <mass increase rate ≦ 10%
B: 10% <mass increase rate ≦ 25%
C: 25% <mass increase rate ≦ 60%
D: 60% <mass increase rate

As is clear from the above table, it was found that the near-infrared absorbing compositions of the examples can increase the shielding property in the near-infrared region even when a cured film is formed. Furthermore, it was found that the near-infrared cut filters of the examples all have a light transmittance of 80% or more at a wavelength of 550 nm, and can improve the transparency in the visible light region and the shielding property in the near-infrared region. . Moreover, the near-infrared cut filter of an Example can confirm that the light transmittance in the wavelength range of 450-550 nm is 85% or more, and the light transmittance in the wavelength range of 800-900 nm is 20% or less. It was. It was also found that the near-infrared cut filter of the example can secure a wide range of visible light with high transmittance and is excellent in spectral characteristics. On the other hand, the near-infrared absorptive composition of the comparative example is difficult to achieve both transparency in the visible light region and shielding in the near-infrared region when used as a cured film, as compared to the examples. I understood.
Moreover, as for the copper complex used in the Example, all the water absorption evaluations were C or more evaluation. In particular, the copper complexes used in Examples 1-1 to 1-55, Examples 2-1 to 2-18, 2-21, and 2-24 to 2-27 all have a water absorption evaluation of B or higher. there were. The copper complex using the compound (A1-22) has a water absorption evaluation of A1, and was confirmed to be particularly excellent.
Examples 1-1, 1-2, 1-12, 1-13, 1-22 1-24, 1-26, 1-30, 1-31, 1-35, 1-36 and 1-38 The transmittance in the visible light region in the solution state was particularly good.
Examples 1-1, 1-2, 1-12, 1-13, 1-22 1-24, 1-26, 1-30, 1-31, 1-35, 1-36 and 1-38 It was found that the near-infrared absorbing composition was particularly excellent in light transmittance at 400 to 500 nm and had a light transmittance of 90% or more.
The near-infrared cut filters obtained using the near-infrared absorbing compositions of Examples 1-13, 1-22, and 1-23 were found to have particularly good transmittance in the visible light region.
On the other hand, the copper acetate (anhydrous) used in Comparative Example 2-1 did not have good transparency in the visible light region. The copper p-toluenesulfonate used in Comparative Example 2-2 was not good in water absorption evaluation.

  Moreover, in the near-infrared absorptive compositions of Examples 1-1 to 1-55 and Examples 2-1 to 2-27, 20 parts by mass of a polymerizable compound (KAYARAD DPHA) were added in an equivalent amount of KAYARAD D-320, M. A near-infrared cut filter can be obtained in the same manner as those except that it is changed to -510, M-520 or DPCA-60. Even these near-infrared cut filters can increase the transparency in the visible light region and the shielding property in the near-infrared region when used as a cured film.

Moreover, in the near-infrared absorptive compositions of Examples 1-1 to 1-55 and Examples 2-1 to 2-27, 20 parts by mass of a polymerizable compound (KAYARAD DPHA) were added in an equivalent amount to KAYARAD D-310, D. -330, DPCA-20, DPCA-30, DPCA-120 (above, Nippon Kayaku Co., Ltd.), M-305, M-460 (manufactured by Toa Gosei), A-TMMT (manufactured by Shin-Nakamura Chemical), SR- A near-infrared cut filter is obtained in the same manner as those described above except that it is changed to 494 (manufactured by Sartomer), Denacor EX-212L (manufactured by Nagase ChemteX Corporation) or JER-157S65 (manufactured by Mitsubishi Chemical Corporation). be able to. Even with these near-infrared cut filters, the same excellent effects as those of the near-infrared cut filter of Example 2-1 can be obtained.
Moreover, in the near-infrared absorptive composition of Examples 1-1 to 1-55 and Examples 2-1 to 2-27, the content of the copper complex with respect to the total solid content of the composition is 15% by mass, 20% by mass, Even when the content is 30% by mass or 40% by mass, excellent near-infrared light shielding ability can be obtained similarly to those.
Moreover, in the near-infrared absorptive compositions of Examples 1-1 to 1-55 and Examples 2-1 to 2-27, the content of the solvent (PGMEA) is 10% by mass, 20% by mass, 30% by mass or 40%. Even in the case of mass%, excellent coating properties can be obtained in the same manner as those near-infrared absorbing compositions.
Moreover, in the near-infrared absorptive compositions of Examples 1-1 to 1-55 and Examples 2-1 to 2-27, after preparation of each composition, DFA421 NXEY (0.45 μm nylon filter) manufactured by Nippon Pole was used. The same effect can be obtained when filtration is performed.

(Example 3-1)
The following compound was mixed and the near-infrared absorptive composition of Example 3-1 was prepared.
Copper complex Cu3-6a 20 parts by mass KAYARAD DPHA 20 parts by mass JER157S65 20 parts by mass PGMEA 120 parts by mass Except for changing the copper complex Cu3-6a to the copper complex shown in the following table, the same as Example 3-1 The near-infrared absorptive composition of each Example was prepared by setting it as a composition.

<Production of near-infrared cut filter>
A near-infrared cut filter was produced using the near-infrared absorbing composition.
A photoresist was applied on a glass substrate and patterned by lithography to form a partition wall of the photoresist to form a dripping region of the near infrared absorbing composition. 3 ml of each near-infrared absorbing composition was dropped on the dropping region on the glass substrate and dried by standing at room temperature for 24 hours. When the film thickness of the coating film after drying was evaluated, the film thickness was 100 μm.

<< Maximum absorption wavelength of copper complex and measurement of molar extinction coefficient at maximum absorption wavelength >>
Each copper complex was dissolved in a solvent described in the following table to prepare a solution having a concentration of 1 g / L. Next, the absorption spectrum of the solution in which the copper complex was dissolved was measured using UV-1800 manufactured by Shimadzu Corporation. The maximum absorption wavelength, the molar extinction coefficient and the gram extinction coefficient at the maximum absorption wavelength, and the molar extinction coefficient at 800 nm. And the Gram extinction coefficient was measured. In the table, DMF represents N, N-dimethylformamide, and MFG represents propylene glycol monomethyl ether.

<< Near-infrared shielding evaluation >>
The transmittance at a wavelength of 800 nm in the near-infrared cut filter obtained as described above was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Near-infrared shielding was evaluated according to the following criteria. The results are shown in the table below.
A: Transmittance at 800 nm ≦ 5%
B: 5% <800 nm transmittance ≦ 25%
C: Transmittance of 25% <800 nm

<< Visible light transmittance evaluation >>
The transmittance at a wavelength of 550 nm in the near-infrared cut filter obtained as described above was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Visible light transmittance was evaluated according to the following criteria. The results are shown in the table below.
A: 85% ≦ transmittance at wavelength 550 nm B: 45 ≦ transmittance at wavelength 550 nm <85%
C: Transmittance <45% at a wavelength of 550 nm

上記表に示すように、上記表から明らかなとおり、実施例で使用した銅錯体は吸水率評価が良好であった。また、実施例の近赤外線吸収性組成物は、硬化膜としたときにも近赤外線領域での遮蔽性を高くできることがわかった。更には、可視光透過性も良好であった。 << Water absorption >>
The mass increase rate of the copper complex powder after the water absorption test was calculated according to the method described above, and evaluated according to the above criteria.

As shown in the above table, as is clear from the above table, the copper complex used in the examples had a good water absorption evaluation. Moreover, it turned out that the near-infrared absorptive composition of an Example can make the shielding property in a near-infrared area | region high when it is set as a cured film. Furthermore, the visible light transmittance was also good.

Moreover, in the near-infrared absorptive composition of Examples 3-1 to 3-23, 20 mass parts of polymerizable compounds (KAYARAD DPHA) were used in an equal amount of KAYARAD D-320, M-510, M-520 or DPCA-60. A near-infrared cut filter can be obtained in the same manner as that except for the above. Even these near-infrared cut filters can increase the transparency in the visible light region and the shielding property in the near-infrared region when used as a cured film.
Moreover, in the near-infrared absorptive composition of Examples 3-1 to 3-23, 20 mass parts of polymerizable compounds (KAYARAD DPHA) were used in equal amounts of KAYARAD D-310, D-330, DPCA-20, DPCA-30. , DPCA-120 (Nippon Kayaku Co., Ltd.), M-305, M-460 (Toa Gosei), A-TMMT (Shin Nakamura Chemical), SR-494 (Sartomer), Denacol EX- A near-infrared cut filter can be obtained in the same manner as above except that it is changed to 212L (manufactured by Nagase ChemteX Corporation) or JER-157S65 (manufactured by Mitsubishi Chemical Corporation).
Moreover, in the near-infrared absorptive composition of Examples 3-1 to 3-23, when the content of the copper complex with respect to the total solid content of the composition is 15% by mass, 20% by mass, 30% by mass, or 40% by mass However, excellent near-infrared light shielding ability can be obtained in the same manner as those.
Further, in the near-infrared absorbing compositions of Examples 3-1 to 3-23, even when the content of the solvent (PGMEA) is 10% by mass, 20% by mass, 30% by mass or 40% by mass, As with the infrared absorbing composition, excellent coating properties can be obtained.
Moreover, in the near-infrared absorptive composition of Examples 3-1 to 3-23, also when it filters using DFA421NXEY (0.45 micrometer nylon filter) made from Japan Pole after preparation of each composition, the same effect Is obtained.

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 Image sensor part, 17 Color filter, 18 Micro lens, 19 Ultraviolet / infrared light reflection film, 20 transparent substrate, 21 near-infrared absorbing layer, 22 antireflection layer

Claims (17)

The near-infrared absorptive composition containing the copper complex whose increase rate of the mass on the basis of before leaving it to stand at 25 degreeC and 95% of relative humidity for 5 hours is less than 25%. The copper complex includes a compound (A) having a coordination site coordinated by an anion and a coordination atom coordinated by a lone pair, and two or more coordination atoms coordinated by a lone pair The near-infrared absorptive composition of Claim 1 which is a copper complex which makes 1 or more types of compounds chosen from the compound (B) to have as a ligand. The near copper according to claim 1, wherein the copper complex is a copper complex having a compound (A) having a coordination site coordinated by an anion and a coordination atom coordinated by an unshared electron pair as a ligand. Infrared absorbing composition. The near-infrared absorbing composition according to claim 2, wherein the copper complex has a 5-membered ring and / or a 6-membered ring formed of copper and the compound forming the ligand. 5. The method according to claim 2, wherein the anion is an oxygen anion, a nitrogen anion, or a sulfur anion, and the coordination atom coordinated by the lone pair is an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. The near-infrared absorptive composition of Claim 1. The near-infrared absorptivity according to any one of claims 2 to 5, wherein the compound (A) has 1 to 3 atoms connecting an anion and a coordination atom coordinated by a lone pair. Composition. The near-infrared absorptive composition of any one of Claims 2-6 whose molecular weight of the compound which makes the said ligand is 50-1000. The compound constituting the ligand is a compound containing a 5-membered ring or a 6-membered ring, and the coordination atom coordinated by the lone pair is an atom constituting a 5-membered ring or a 6-membered ring. The near-infrared absorptive composition of any one of 2-7. The near-infrared absorptive composition of any one of Claims 2-8 whose coordinating | ligand atom coordinated by the said lone pair is a nitrogen atom. The near-infrared absorptive composition of Claim 9 in which the atom adjacent to the said nitrogen atom is a carbon atom, and the said carbon atom has a substituent. The near-infrared absorbing composition according to any one of claims 2 to 7, wherein the compound (A) is represented by the formula (I);

In formula (I), X ¹ represents a group containing a coordination site coordinated with the anion; Y ¹ represents a nitrogen atom or a phosphorus atom, and constitutes a 4- to 7-membered ring together with an adjacent carbon atom. R ^X1 represents a substituent, and n1 represents an integer of 0 to 6. Wherein in formula (I), the ring formed together with the carbon atom to which Y ¹ is adjacent is an aromatic ring, near-infrared absorbing composition of claim 11. The coordination site coordinated with the anion is at least one selected from the following group (AN):
Group (AN)

A coordination atom coordinated by the unshared electron pair is included in the ring, or included in at least one partial structure selected from the following group (UE):
Group (UE)

The wavy line is the bonding position with the atomic group constituting the compound (A),
X represents N or CR, R and R ¹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and R ² each independently represents a hydrogen atom. Represents an alkyl group, alkenyl 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 near-infrared absorptive composition of any one of 2-7. The near-infrared absorptive composition according to any one of claims 2 to 7, wherein the compound (A) is represented by the following general formula (IV):
X ¹ -L ¹ -Y ¹ formula (IV)
In general formula (IV), X ¹ represents a coordination site coordinated with at least one anion selected from the following group (AN):
Group (AN)

Y ¹ is a ring containing a coordinating atom coordinated by the lone pair, or a moiety containing a coordinating atom coordinated by at least one lone pair selected from the following group (UE) Representing the structure,
Group (UE)

The wavy line is the bonding position with the atomic group constituting the compound (A),
X represents N or CR, R and R ¹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and R ² each independently represents a hydrogen atom. Represents an alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, amino group or acyl group, L ¹ Represents a single bond or a divalent linking group. The near-infrared absorptive composition of any one of Claims 1-14 which further contains a sclerosing | hardenable compound and a solvent. The near-infrared cut filter formed by hardening | curing the near-infrared absorptive composition of any one of Claims 1-15. It is a camera module which has a solid-state image sensor and the near-infrared cut filter arrange | positioned at the light-receiving side of the said solid-state image sensor, Comprising: The said near-infrared cut filter is a near infrared ray of any one of Claims 1-15. A camera module, which is a near-infrared cut filter formed by curing an absorbent composition.

Images