JP6315850B2 - Near-infrared cut filter, near-infrared absorbing composition, photosensitive resin composition, cured film, compound, camera module, and camera module manufacturing method - Google Patents

Description

  The present invention relates to a near-infrared cut filter, a near-infrared absorbing composition, a photosensitive resin composition, a cured film, a compound, a camera module, and a method for manufacturing a camera module.

In recent years, CCDs and CMOS image sensors, which are solid-state imaging devices for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. Since the solid-state imaging device uses a silicon photodiode having sensitivity to near infrared rays in the light receiving portion thereof, it is necessary to correct visibility, and a near-infrared cut filter (hereinafter also referred to as IR cut filter) is required. Often used.
As a material for a near-infrared cut filter, Patent Document 1 discloses a metal compound as a copolymer of a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof and a compound having an ethylenically unsaturated bond. An infrared shielding film containing an added infrared shielding resin is disclosed.
On the other hand, Patent Document 2 discloses that protein detection is performed using a squarylium compound.
Patent Document 3 discloses a color filter using a squarylium compound.

JP 2010-134457 A US Patent Application Publication No. 2012/0276642 JP 2012-13945 A

In recent years, further improvement in image quality has been demanded in camera modules and the like. For this reason, development of a near-infrared cut filter having high visible light transmittance and excellent near-infrared light shielding properties is desired.
Therefore, an object of the present invention is to provide a near-infrared cut filter, a near-infrared absorbing composition, a photosensitive resin composition, a cured film, a compound, a camera module, and a camera module manufacturing method capable of obtaining a camera image with good image quality. Is to provide.

一般式（１）中、Ａ¹およびＡ²は、それぞれ独立に、アリール基、ヘテロ環基または下記一般式（２）で表される基であり、Ｒ¹は、ハロゲン原子を１個以上有するアルキル基、ハロゲン原子を１個以上有するアリール基、または、ハロゲン原子を１個以上有するヘテロ環基を表す；

一般式（２）中、Ｚ¹は、含窒素複素環を形成する非金属原子群を表し、Ｒ²は、アルキル基、アルケニル基またはアラルキル基を表し、ｄは、０または１を表し、波線は一般式（１）との連結手を表す。
＜４＞ 一般式（２）で表される基が、下記一般式（３）または（４）で表される、＜３＞に記載の近赤外線カットフィルタ；

一般式（３）および（４）中、Ｒ¹¹は、アルキル基、アルケニル基またはアラルキル基を表し、Ｒ¹²は、置換基を表し、ｍが２以上の場合は、Ｒ¹²同士は、連結して環を形成してもよく、Ｘは、窒素原子、または、ＣＲ¹³Ｒ¹⁴を表し、Ｒ¹³およびＲ¹⁴は、それぞれ独立に水素原子または置換基を表し、
ｍは、０〜４の整数を表し、波線は一般式（１）との連結手を表す。
＜５＞ 一般式（１）におけるＲ¹は、ハロゲン原子を１個以上有するアルキル基またはハロゲン原子を１個以上有するアリール基である、＜３＞または＜４＞に記載の近赤外線カットフィルタ。
＜６＞ 近赤外線吸収物質として銅化合物を含有し、銅化合物が、リン含有銅錯体、スルホン酸銅錯体およびカルボン酸銅錯体から選択される少なくとも１種である、＜１＞〜＜５＞のいずれかに記載の近赤外線カットフィルタ。
銅化合物が、リン含有銅錯体、スルホン酸銅錯体およびカルボン酸銅錯体から選択される少なくとも１種である、＜２＞に記載の近赤外線カットフィルタ。
＜７＞ 近赤外線吸収物質として、下記一般式（Ａ）で表される化合物を含有する、＜１＞〜＜６＞のいずれかに記載の近赤外線カットフィルタ；
一般式（Ａ）

一般式（Ａ）中、Ｚ¹およびＺ²は、それぞれ独立に、縮環してもよい５員または６員の含窒素複素環を形成する非金属原子群であり、Ｒ¹およびＲ²は、それぞれ独立に、脂肪族基または芳香族基を表し、Ｌ¹は、奇数個のメチンからなるメチン鎖を表し、ａおよびｂは、それぞれ独立に、０または１であり、
式中のＣｙで表される部位がカチオン部である場合、Ｘ¹はアニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位がアニオン部である場合、Ｘ¹はカチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位の電荷が分子内で中和されている場合、Ｘ¹は存在しない。
＜８＞ 膜厚が２００μｍ以下である、＜１＞〜＜７＞のいずれかに記載の近赤外線カットフィルタ。
＜９＞ 波長４００〜５７５ｎｍの範囲での光透過率が８５％以上である、＜１＞〜＜８＞のいずれかに記載の近赤外線カットフィルタ。
＜１０＞ 波長４５０〜５５０ｎｍの範囲での光透過率が９０％以上である、＜１＞〜＜９＞のいずれかに記載の近赤外線カットフィルタ。
＜１１＞ 波長７００〜１１００ｎｍの範囲での光透過率が２０％以下である、＜１＞〜＜１０＞のいずれかに記載の近赤外線カットフィルタ。
＜１２＞ 波長８００〜９００ｎｍの範囲での光透過率が１０％以下である、＜１＞〜＜１１＞のいずれかに記載の近赤外線カットフィルタ。
＜１３＞ 近赤外線吸収物質を含有し、膜厚３００μｍ以下の膜を形成したときの、波長４５０〜５５０ｎｍの範囲での光透過率が８５％以上であり、波長６８０ｎｍの光透過率が１０％以下である、近赤外線吸収組成物。
＜１４＞ 近赤外線吸収物質として、スルホン酸およびカルボン酸から選ばれる少なくとも１種を配位子とする銅錯体と、下記一般式（１）で表される化合物、および、下記一般式（Ａ）で表される化合物から選ばれる少なくとも１種の化合物とを含有する、＜１３＞に記載の近赤外線吸収組成物；

一般式（１）中、Ａ¹およびＡ²は、それぞれ独立に、アリール基、ヘテロ環基または下記一般式（２）で表される基であり、Ｒ¹は、ハロゲン原子を１個以上有するアルキル基、ハロゲン原子を１個以上有するアリール基、または、ハロゲン原子を１個以上有するヘテロ環基を表す；

一般式（２）中、Ｚ¹は、含窒素複素環を形成する非金属原子群を表し、Ｒ²は、アルキル基、アルケニル基またはアラルキル基を表し、ｄは、０または１を表し、波線は一般式（１）との連結手を表す；
一般式（Ａ）

一般式（Ａ）中、Ｚ¹およびＺ²は、それぞれ独立に、縮環してもよい５員または６員の含窒素複素環を形成する非金属原子群であり、Ｒ¹およびＲ²は、それぞれ独立に、脂肪族基または芳香族基を表し、Ｌ¹は、奇数個のメチンからなるメチン鎖を表し、ａおよびｂは、それぞれ独立に、０または１であり、
式中のＣｙで表される部位がカチオン部である場合、Ｘ¹はアニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位がアニオン部である場合、Ｘ¹はカチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位の電荷が分子内で中和されている場合、Ｘ¹は存在しない。
＜１５＞ 下記一般式（１）で表される化合物を含有する感光性樹脂組成物；

一般式（１）中、Ａ¹およびＡ²は、それぞれ独立に、アリール基、ヘテロ環基または下記一般式（２）で表される基であり、Ｒ¹は、ハロゲン原子を１個以上有するアルキル基、ハロゲン原子を１個以上有するアリール基、または、ハロゲン原子を１個以上有するヘテロ環基を表す；

一般式（２）中、Ｚ¹は、含窒素複素環を形成する非金属原子群を表し、Ｒ²は、アルキル基、アルケニル基またはアラルキル基を表し、ｄは、０または１を表し、波線は一般式（１）との連結手を表す。
＜１６＞ ＜１５＞に記載の感光性樹脂組成物を硬化してなる硬化膜。
＜１７＞ 下記一般式（１）で表される化合物；

一般式（１）中、Ａ¹およびＡ²は、それぞれ独立に、アリール基、ヘテロ環基または下記一般式（２）で表される基であり、
Ｒ¹は、ハロゲン原子を１個以上有するアルキル基、ハロゲン原子を１個以上有するアリール基、または、ハロゲン原子を１個以上有するヘテロ環基を表す；

一般式（２）中、Ｚ¹は、含窒素複素環を形成する非金属原子群を表し、Ｒ²は、アルキル基、アルケニル基またはアラルキル基を表し、ｄは、０または１を表し、波線は一般式（１）との連結手を表す。
＜１８＞ 固体撮像素子と、固体撮像素子の受光側に配置された＜１＞〜＜１２＞のいずれかに記載の近赤外線カットフィルタとを有するカメラモジュール。
＜１９＞ ＜１８＞に記載のカメラモジュールの製造方法であって、固体撮像素子の受光側において、＜１３＞または＜１４＞に記載の近赤外線吸収組成物を塗布することにより近赤外線カットフィルタを形成する工程を有する、カメラモジュールの製造方法。Specifically, the above problem has been solved by the following means <1>, preferably by means <2> to <18>.
<1> Contains a near-infrared absorbing material, has a film thickness of 300 μm or less, has a light transmittance of 85% or more in a wavelength range of 450 to 550 nm, and has a light transmittance of 10% or less at a wavelength of 680 nm. Near-infrared cut filter.
<2> The near-infrared absorbing material contains a first near-infrared absorbing material and a second near-infrared absorbing material, the first near-infrared absorbing material is a copper compound, and the second near-infrared absorbing material is The near-infrared cut filter according to <1>, which is a compound having a maximum absorption wavelength at a wavelength of 650 to 750 nm.
<3> The near-infrared cut filter according to <1> or <2>, which contains a compound represented by the following general formula (1) as a near-infrared absorbing substance;

In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), and R ¹ has one or more halogen atoms. An alkyl group, an aryl group having one or more halogen atoms, or a heterocyclic group having one or more halogen atoms;

In general formula (2), Z ¹ represents a nonmetallic atom group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, Represents a connecting hand with the general formula (1).
<4> The near-infrared cut filter according to <3>, wherein the group represented by the general formula (2) is represented by the following general formula (3) or (4);

In the general formulas (3) and (4), R ¹¹ represents an alkyl group, an alkenyl group or an aralkyl group, R ¹² represents a substituent, and when m is 2 or more, R ¹² are linked to each other. X may represent a nitrogen atom or CR ¹³ R ¹⁴ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent,
m represents an integer of 0 to 4, and the wavy line represents a connecting hand with the general formula (1).
<5> The near-infrared cut filter according to <3> or <4>, wherein R ¹ in the general formula (1) is an alkyl group having one or more halogen atoms or an aryl group having one or more halogen atoms.
<6> A copper compound is contained as a near-infrared absorbing material, and the copper compound is at least one selected from a phosphorus-containing copper complex, a sulfonic acid copper complex, and a carboxylic acid copper complex, from <1> to <5> The near infrared cut filter according to any one of the above.
The near-infrared cut filter according to <2>, wherein the copper compound is at least one selected from a phosphorus-containing copper complex, a sulfonic acid copper complex, and a carboxylic acid copper complex.
<7> The near-infrared cut filter according to any one of <1> to <6>, which contains a compound represented by the following general formula (A) as a near-infrared absorbing substance;
Formula (A)

In the general formula (A), Z ¹ and Z ² are each independently a nonmetallic atom group that forms a 5-membered or 6-membered nitrogen-containing heterocycle that may be condensed, and R ¹ and R ² are Each independently represents an aliphatic group or an aromatic group, L ¹ represents a methine chain composed of an odd number of methines, a and b are each independently 0 or 1,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents the number necessary for balancing the charge, and the site represented by Cy in the formula is an anion moiety. , X ¹ represents a cation, c represents a number necessary to balance the charge, and when the charge at the site represented by Cy in the formula is neutralized in the molecule, X ¹ Does not exist.
<8> The near-infrared cut filter according to any one of <1> to <7>, wherein the film thickness is 200 μm or less.
<9> The near-infrared cut filter according to any one of <1> to <8>, wherein the light transmittance in the wavelength range of 400 to 575 nm is 85% or more.
<10> The near-infrared cut filter according to any one of <1> to <9>, wherein the light transmittance in a wavelength range of 450 to 550 nm is 90% or more.
<11> The near-infrared cut filter according to any one of <1> to <10>, wherein the light transmittance in a wavelength range of 700 to 1100 nm is 20% or less.
<12> The near-infrared cut filter according to any one of <1> to <11>, wherein the light transmittance in a wavelength range of 800 to 900 nm is 10% or less.
<13> When a film having a film thickness of 300 μm or less containing a near-infrared absorbing substance is formed, the light transmittance in the wavelength range of 450 to 550 nm is 85% or more, and the light transmittance at a wavelength of 680 nm is 10%. The near-infrared absorption composition which is the following.
<14> As a near-infrared absorbing substance, a copper complex having at least one selected from sulfonic acid and carboxylic acid as a ligand, a compound represented by the following general formula (1), and the following general formula (A) The near-infrared absorbing composition according to <13>, comprising at least one compound selected from the compounds represented by:

In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), and R ¹ has one or more halogen atoms. An alkyl group, an aryl group having one or more halogen atoms, or a heterocyclic group having one or more halogen atoms;

In general formula (2), Z ¹ represents a nonmetallic atom group forming a nitrogen-containing heterocyclic ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, Represents a connecting hand with the general formula (1);
Formula (A)

In the general formula (A), Z ¹ and Z ² are each independently a nonmetallic atom group that forms a 5-membered or 6-membered nitrogen-containing heterocycle that may be condensed, and R ¹ and R ² are Each independently represents an aliphatic group or an aromatic group, L ¹ represents a methine chain composed of an odd number of methines, a and b are each independently 0 or 1,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents the number necessary for balancing the charge, and the site represented by Cy in the formula is an anion moiety. , X ¹ represents a cation, c represents a number necessary to balance the charge, and when the charge at the site represented by Cy in the formula is neutralized in the molecule, X ¹ Does not exist.
<15> A photosensitive resin composition containing a compound represented by the following general formula (1);

In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), and R ¹ has one or more halogen atoms. An alkyl group, an aryl group having one or more halogen atoms, or a heterocyclic group having one or more halogen atoms;

In general formula (2), Z ¹ represents a nonmetallic atom group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, Represents a connecting hand with the general formula (1).
<16> A cured film obtained by curing the photosensitive resin composition according to <15>.
<17> A compound represented by the following general formula (1);

In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2).
R ¹ represents an alkyl group having one or more halogen atoms, an aryl group having one or more halogen atoms, or a heterocyclic group having one or more halogen atoms;

In general formula (2), Z ¹ represents a nonmetallic atom group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, Represents a connecting hand with the general formula (1).
<18> A camera module having a solid-state imaging device and the near-infrared cut filter according to any one of <1> to <12> disposed on a light receiving side of the solid-state imaging device.
<19> The method for producing a camera module according to <18>, wherein the near-infrared cut filter is applied by applying the near-infrared absorbing composition according to <13> or <14> on the light receiving side of the solid-state imaging device. The manufacturing method of a camera module which has the process of forming.

According to the present invention, there are provided a near-infrared cut filter, a near-infrared absorbing composition, a photosensitive resin composition, a cured film, a compound, a camera module, and a camera module manufacturing method capable of obtaining a camera image with good image quality. It became possible to do.
Moreover, providing the near-infrared cut filter which is excellent in heat resistance by containing the compound represented by General formula (1) and / or the compound represented by General formula (A) as a near-infrared absorber. it can.

It is a schematic sectional drawing which shows the structure of the camera module which has a near-infrared cut off filter based on embodiment of this invention. It is a schematic sectional drawing which shows an example of the near-infrared cut filter periphery part in a camera module. It is a schematic sectional drawing which shows an example of the near-infrared cut filter periphery part in a camera module. It is a schematic sectional drawing which shows an example of the near-infrared cut filter periphery part in a camera module. It is a figure which shows the absorption spectrum (DMSO) of compound I-17. It is a spectrum figure which shows the light transmittance of the film | membrane obtained using the photosensitive resin composition of Example 1. FIG. It is a spectrum figure which shows the light transmittance of the film | membrane obtained using the photosensitive resin composition of the comparative example 1. It is a spectrum figure which shows the light transmittance of the film | membrane obtained using the photosensitive resin composition of the comparative example 2.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “monomer” are synonymous. 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, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In the 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 as well as a group (atomic group) having no substituent. is there.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
Near-infrared light refers to light (electromagnetic waves) having a wavelength region of 700 to 2500 nm.
In this specification, solid content means solid content in 25 degreeC.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID × 15.0 cm) can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.

一般式（１）中、Ａ¹およびＡ²は、それぞれ独立に、アリール基、ヘテロ環基または下記一般式（２）で表される基であり、Ｒ¹は、ハロゲン原子を１個以上有するアルキル基、ハロゲン原子を１個以上有するアリール基、または、ハロゲン原子を１個以上有するヘテロ環基を表す。

一般式（２）中、Ｚ¹は、含窒素複素環を形成する非金属原子群を表し、Ｒ²は、アルキル基、アルケニル基またはアラルキル基を表し、ｄは、０または１を表し、波線は一般式（１）との連結手を表す。<Near-infrared absorbing composition>
The near infrared ray absorbing composition of the present invention contains a near infrared ray absorbing substance. The near-infrared absorbing material preferably contains a compound having a maximum absorption wavelength at a wavelength of 650 to 750 nm, more preferably contains a cyanine compound, a pyrrolopyrrole compound, and a squarylium compound, and is represented by the following general formula (1). And at least one compound selected from the compounds represented by the following general formula (A) is more preferable, and a compound represented by the following general formula (1) is particularly preferable. .
<< Near-infrared absorbing material >>
<<< Compound Represented by Formula (1) >>>

In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), and R ¹ has one or more halogen atoms. An alkyl group, an aryl group having one or more halogen atoms, or a heterocyclic group having one or more halogen atoms is represented.

In general formula (2), Z ¹ represents a nonmetallic atom group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, Represents a connecting hand with the general formula (1).

R ¹ in the general formula (1) represents an alkyl group having one or more halogen atoms, an aryl group having one or more halogen atoms, or a heterocyclic group having one or more halogen atoms, and one halogen atom An alkyl group having one or more halogen atoms is more preferable, and an alkyl group having one or more halogen atoms is more preferable.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable. In the fluorine atom, the nucleophilicity of the adjacent anion is lowered (in other words, the stability of the anion is increased) by the action of electron withdrawing. Therefore, for example, in the case of a fluorine atom, it is considered that the compound represented by the general formula (1) is hardly decomposed by an anion during heating, and heat resistance is particularly improved. Moreover, since the nucleophilicity of an anion falls, so that there are many fluorine atoms, it is thought that heat resistance improves further.
The number of halogen atoms contained in R ¹ is 1 or more, and 50% or more of the hydrogen atoms bonded to the carbon atoms of the group represented by R ¹ (alkyl group, aryl group, heterocyclic group) are substituted with halogen atoms. Preferably 80% or more, more preferably 100%.
1-20 are preferable, as for carbon number of an alkyl group, 1-15 are more preferable, 1-8 are still more preferable, and 1-3 are especially preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
6-48 are preferable, as for carbon number of an aryl group, 6-24 are more preferable, and 6 is more preferable.
The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, and more preferably a single ring or a condensed ring having 2 to 4 condensations. Examples of the hetero atom contained in the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of heteroatoms is preferably 1 to 3, and more preferably 1 or 2.
R ¹ is preferably a perfluoroalkyl group or a perfluoroaryl group, and particularly preferably a perfluoroalkyl group. The perfluoroalkyl group means a group in which all hydrogen atoms bonded to carbon atoms constituting the alkyl group are substituted with fluorine atoms. The perfluoroaryl group means a group in which all hydrogen atoms bonded to carbon atoms constituting the aryl group are substituted with fluorine atoms.

A ¹ and A ² in the general formula (1) each independently represent an aryl group, a heterocyclic group or a group represented by the general formula (2), and a group represented by the general formula (2) is preferable.
The number of carbon atoms of the aryl group represented by A ¹ and A ² is preferably 6-48, more preferably 6 to 24, 6 to 12 are particularly preferred. Specific examples include a phenyl group and a naphthyl group. When the aryl group has a substituent, the carbon number of the aryl group means the number excluding the carbon number of the substituent.
The heterocyclic group represented by A ¹ and A ² is preferably a 5-membered ring or a 6-membered ring. In addition, the heterocyclic group is preferably a single ring or a condensed ring, 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, a single ring or a condensed ring. A condensed ring having 2 or 3 is more preferable. As a hetero atom contained in a heterocyclic group, a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, and a nitrogen atom and a sulfur atom are preferable. 1-3 are preferable and, as for the number of heteroatoms, 1-2 are more preferable. Specific examples include a heterocyclic group derived from a monocyclic or polycyclic aromatic ring such as a 5-membered or 6-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom.
The aryl group and heterocyclic group may have a substituent. Examples of the substituent include those shown below.

A halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom);
A linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl);
A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms such as cyclohexyl and cyclopentyl, and a multicycloalkyl group such as a bicycloalkyl group (preferably having 5 to 30 carbon atoms). Substituted or unsubstituted bicycloalkyl groups such as, for example, polycyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl) and tricycloalkyl groups A group having a structure, preferably a monocyclic cycloalkyl group or a bicycloalkyl group, and a monocyclic cycloalkyl group is particularly preferred);
A linear or branched alkenyl group (a linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl);
A cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycycloalkenyl group such as A bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2, 2] Oct-2-en-4-yl) and tricycloalkenyl groups, and monocyclic cycloalkenyl groups are particularly preferred).
An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group);
An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl);
Heterocyclic group (preferably a 5- or 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably a ring-constituting atom is a carbon atom A heterocyclic group selected from a nitrogen atom and a sulfur atom and having at least one heteroatom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5- or 6-membered member having 3 to 30 carbon atoms Aromatic heterocyclic groups such as 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl);
A cyano group;
A hydroxyl group;
A nitro group;
Carboxyl group;
An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy);
An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms such as phenoxy, 2-methylphenoxy, 2,4-di-t-amylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy);
A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy);
Heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, wherein the heterocyclic part is preferably the heterocyclic part described above for the heterocyclic group, for example, 1-phenyltetrazole -5-oxy, 2-tetrahydropyranyloxy);
An acyloxy group (preferably a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, Stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy);
A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di -N-octylaminocarbonyloxy, Nn-octylcarbamoyloxy);
An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy);
Aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy );
An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms); And, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino);
An acylamino group (preferably a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, Lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino);
Aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino) ;
Alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl -Methoxycarbonylamino);
Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) ;
Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonyl amino);
An alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methylsulfonylamino, butyl Sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino);
A mercapto group;
An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio);
An arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio);
Heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, and the heterocyclic portion is preferably the heterocyclic portion described above for the heterocyclic group, for example, 2-benzothiazolyl Luthio, 1-phenyltetrazol-5-ylthio);
Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl);
A sulfo group;
An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl);
An alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl);
Acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl , Stearoyl, benzoyl, pn-octyloxyphenylcarbonyl);
Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl) ;
An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl);
A carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methyl Sulfonyl) carbamoyl)
An aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocyclic portion is described in the above heterocyclic group) The heterocycle moiety is preferred), for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo);
An imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, such as N-succinimide and N-phthalimide);
A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino);
A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl);
A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy);
A phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino);
Examples thereof include a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as trimethylsilyl, t-butyldimethylsilyl, and phenyldimethylsilyl).

The substituent that the aryl group and heterocyclic group may have is preferably a halogen atom, an alkyl group, a hydroxy group, an amino group, or an acylamino group.
The halogen atom is preferably a chlorine atom.
1-20 are preferable, as for carbon number of an alkyl group, 1-10 are more preferable, 1-5 are still more preferable, and 1-4 are the most preferable. The alkyl group is preferably linear or branched.
The amino group is preferably a group represented by —NR ¹⁰⁰ R ¹⁰¹ . R ¹⁰⁰ and R ¹⁰¹ each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, 1-10 are still more preferable, and 1-8 are especially preferable. The alkyl group is preferably linear or branched, and more preferably linear.
The acylamino group is preferably a group represented by —NR ¹⁰² —C (═O) —R ¹⁰³ . ^R102 represents a hydrogen atom or an alkyl group, and preferably a hydrogen atom. R ¹⁰³ represents an alkyl group. R ¹⁰² and R ¹⁰³ carbon atoms of the alkyl group represented by is preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5, 1 to 4 are particularly preferred.
When the aryl group and the heterocyclic group have two or more substituents, the plurality of substituents may be the same or different.

一般式（２）中、Ｚ¹は、含窒素複素環を形成する非金属原子群を表し、Ｒ²は、アルキル基、アルケニル基またはアラルキル基を表し、ｄは、０または１を表し、波線は一般式（１）との連結手を表す。Next, the group represented by the general formula (2) represented by A ¹ and A ² will be described.

In general formula (2), Z ¹ represents a nonmetallic atom group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, Represents a connecting hand with the general formula (1).

In the general formula (2), R ² represents an alkyl group, an alkenyl group or an aralkyl group, and is preferably an alkyl group.
1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, 1-12 are still more preferable, and 2-8 are especially preferable.
2-30 are preferable, as for carbon number of an alkenyl group, 2-20 are more preferable, and 2-12 are still more preferable.
The alkyl group and the alkenyl group may be linear, branched or cyclic, and are preferably linear or branched.
7-30 are preferable and, as for carbon number of an aralkyl group, 7-20 are more preferable.

In the general formula (2), the nitrogen-containing heterocycle formed by Z ¹ is preferably a 5-membered ring or a 6-membered ring. The nitrogen-containing heterocycle is preferably a monocycle or a condensed ring, preferably a monocycle or a condensed ring having 2 to 8 condensations, more preferably a single ring or a condensed ring having 2 to 4 condensations, and a condensation number of 2 Or the condensed ring of 3 is more preferable. The nitrogen-containing heterocyclic ring may contain a sulfur atom in addition to the nitrogen atom. Moreover, the nitrogen-containing heterocycle may have a substituent. As a substituent, the substituent which the aryl group or heterocyclic group mentioned above may have is mentioned, The preferable range is also the same. For example, a halogen atom, an alkyl group, a hydroxy group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-12 are still more preferable. The alkyl group is preferably linear or branched.

一般式（３）および（４）中、Ｒ¹¹は、アルキル基、アルケニル基またはアラルキル基を表し、Ｒ¹²は、置換基を表し、ｍが２以上の場合は、Ｒ¹²同士は、連結して環を形成してもよく、Ｘは、窒素原子、または、ＣＲ¹³Ｒ¹⁴を表し、Ｒ¹³およびＲ¹⁴は、それぞれ独立に水素原子または置換基を表し、ｍは、０〜４の整数を表し、波線は一般式（１）との連結手を表す。The group represented by the general formula (2) is preferably a group represented by the following general formula (3) or (4).

In the general formulas (3) and (4), R ¹¹ represents an alkyl group, an alkenyl group or an aralkyl group, R ¹² represents a substituent, and when m is 2 or more, R ¹² are linked to each other. And X may represent a nitrogen atom or CR ¹³ R ¹⁴ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent, and m is an integer of 0 to 4 The wavy line represents a connecting hand with the general formula (1).

R ¹¹ in the general formulas (3) and (4) has the same meaning as R ² in the general formula (2), and the preferred range is also the same.
R ¹² in the general formulas (3) and (4) represents a substituent. As a substituent, the substituent which the aryl group or heterocyclic group mentioned above may have is mentioned, The preferable range is also the same. For example, a halogen atom, an alkyl group, a hydroxy group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-12 are still more preferable. The alkyl group is preferably linear or branched.
When m is 2 or more, R ¹² may be linked to form a ring. Examples of the ring include an alicyclic ring (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. The ring may be monocyclic or multicyclic. When the substituents are linked to form a ring, the linking group is a group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. They can be linked by a divalent linking group selected from the above. For example, it is preferable that R ¹² are connected to each other to form a benzene ring.
X in the general formula (3) represents a nitrogen atom or CR ¹³ R ¹⁴ , and R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent. Examples of the substituent include the substituents that the above-described aryl group or heterocyclic group may have. For example, an alkyl group etc. are mentioned. 1-20 are preferable, as for carbon number of an alkyl group, 1-10 are more preferable, 1-5 are still more preferable, 1-3 are especially preferable, and 1 is the most preferable. The alkyl group is preferably linear or branched, and particularly preferably linear.
m represents an integer of 0 to 4, and 0 to 2 is preferable.

The molecular weight of the compound represented by the general formula (1) is preferably 100 to 2,000, and more preferably 150 to 1,000.
The compound represented by the general formula (1) preferably has a maximum absorption wavelength at a wavelength of 600 to 800 nm, more preferably a maximum absorption wavelength at 600 to 750 nm, and a maximum absorption wavelength at 650 to 750 nm. Is more preferable.
Specific examples of the compound represented by the general formula (1) include the following compounds, but are not limited thereto. In the following, R ¹ , A ¹ and A ² each correspond to the general formula (1). The wavy lines in the group shown in A ¹ and A ² represents a linking position to the general formula (1).

It is preferable that the near-infrared absorption composition of this invention contains 5-90 mass% of compounds represented by General formula (1) with respect to the total solid of a near-infrared absorption composition. The lower limit is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is preferably 85% by mass or less, and more preferably 80% by mass or less.
Moreover, it is preferable to contain 0.01-50 mass parts of compounds represented by General formula (1) with respect to 100 mass parts of copper compounds mentioned later. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.
By setting it as such a range, it is possible to obtain a near-infrared cut filter that can cut infrared rays in a desired range with good cutting. For example, a near-infrared cut filter having spectral characteristics with a film thickness of 300 μm or less, a light transmittance in the wavelength range of 450 to 550 nm of 85% or more, and a light transmittance of wavelength 680 nm of 10% or less can be obtained. .

一般式（Ａ）中、Ｚ¹およびＺ²は、それぞれ独立に、縮環してもよい５員または６員の含窒素複素環を形成する非金属原子群であり、Ｒ¹およびＲ²は、それぞれ独立に、脂肪族基または芳香族基を表し、Ｌ¹は、奇数個のメチンからなるメチン鎖を表し、ａおよびｂは、それぞれ独立に、０または１であり、
式中のＣｙで表される部位がカチオン部である場合、Ｘ¹はアニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位がアニオン部である場合、Ｘ¹はカチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位の電荷が分子内で中和されている場合、Ｘ¹は存在しない。<<< Compound represented by formula (A) >>>
Formula (A)

In the general formula (A), Z ¹ and Z ² are each independently a nonmetallic atom group that forms a 5-membered or 6-membered nitrogen-containing heterocycle that may be condensed, and R ¹ and R ² are Each independently represents an aliphatic group or an aromatic group, L ¹ represents a methine chain composed of an odd number of methines, a and b are each independently 0 or 1,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents the number necessary for balancing the charge, and the site represented by Cy in the formula is an anion moiety. , X ¹ represents a cation, c represents a number necessary to balance the charge, and when the charge at the site represented by Cy in the formula is neutralized in the molecule, X ¹ Does not exist.

In the general formula (A), Z ¹ and Z ² each independently represent a nonmetallic atom group that forms a 5-membered or 6-membered nitrogen-containing heterocyclic ring that may be condensed.
The nitrogen-containing heterocycle may be condensed with another heterocycle, aromatic ring or aliphatic ring. The nitrogen-containing heterocycle is preferably a 5-membered ring. More preferably, a 5-membered nitrogen-containing heterocycle is condensed with a benzene ring or a naphthalene ring. Specific examples of the nitrogen-containing heterocycle include an oxazole ring, an isoxazole ring, a benzoxazole ring, a naphthoxazole ring, an oxazolocarbazole ring, an oxazodibenzobenzofuran ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, an indolenine ring, Examples include benzoindolenin ring, imidazole ring, benzimidazole ring, naphthimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, furopyrrole ring, indolizine ring, imidazoquinoxaline ring, quinoxaline ring, quinoline ring, indolenine ring Benzoindolenine ring, benzoxazole ring, benzothiazole ring and benzimidazole ring are preferable, and indolenine ring, benzothiazole ring and benzimidazole ring are particularly preferable.

The nitrogen-containing heterocyclic ring and the ring condensed thereto may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an aliphatic group, an aromatic group, a heterocyclic group, —OR ¹⁰ , —COR ¹¹ , —COOR ¹² , —OCOR ¹³ , —NR ¹⁴ R ¹⁵ , —NHCOR. ¹⁶ , —CONR ¹⁷ R ¹⁸ , —NHCONR ¹⁹ R ²⁰ , —NHCOOR ²¹ , —SR ²² , —SO ₂ R ²³ , —SO ₂ OR ²⁴ , —NHSO ₂ R ²⁵ or —SO ₂ NR ²⁶ R ²⁷ . R ^{10 to} R ²⁷ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. When R ^{12 of} —COOR ¹² is hydrogen (that is, a carboxyl group), a hydrogen atom may be dissociated (that is, a carbonate group) or may be in a salt state. When R ^{24 of} —SO ₂ OR ²⁴ is a hydrogen atom (ie, a sulfo group), the hydrogen atom may be dissociated (ie, a sulfonate group) or may be in a salt state.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Aliphatic groups include alkyl groups, alkenyl groups, alkynyl groups, and aralkyl groups. These groups may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, and an amino group. A carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may have a hydrogen atom dissociated or a salt state.

The alkyl group may be cyclic or linear. The chain alkyl group may have a branch. 1-20 are preferable, as for carbon number of an alkyl group, 1-12 are more preferable, and 1-8 are the most preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a cyclopropyl group, a cyclohexyl group, and a 2-ethylhexyl group. Examples of substituted alkyl groups include 2-hydroxyethyl, 2-carboxyethyl, 2-methoxyethyl, 2-diethylaminoethyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl and Examples include 4-sulfobutyl group.
The alkenyl group may be cyclic or chain-like. The chain alkenyl group may have a branching group. 2-20 are preferable, as for carbon number of an alkenyl group, 2-12 are more preferable, and 2-8 are the most preferable. Examples of the alkenyl group include vinyl group, allyl group, 1-propenyl group, 2-butenyl group, 2-pentenyl group and 2-hexenyl group.
The alkynyl group may be cyclic or chain-like. The chain alkynyl group may have a branching group. 2-20 are preferable, as for carbon number of an alkynyl group, 2-12 are more preferable, and 2-8 are the most preferable. Examples of alkynyl groups include ethynyl and 2-propynyl groups.
The alkyl part of the aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group is the same as the aryl group described later. Examples of aralkyl groups include benzyl and phenethyl.

In the present invention, the aromatic group includes an aryl group. The aryl group may have a substituent. As a substituent, the substituent which the aliphatic group mentioned above may have is mentioned, The preferable range is also the same.
6-25 are preferable, as for carbon number of an aryl group, 6-15 are more preferable, and 6-10 are the most preferable. Examples of the aryl group include a phenyl group and a naphthyl group. As the aryl group having a substituent, 4-carboxyphenyl group, 4-acetamidophenyl group, 3-methanesulfonamidophenyl group, 4-methoxyphenyl group, 3-carboxyphenyl group, 3,5-dicarboxyphenyl group, Examples include 4-methanesulfonamidophenyl group and 4-butanesulfonamidophenyl group.

In the present invention, the heterocyclic group may have a substituent. As a substituent, the substituent which the aliphatic group mentioned above may have is mentioned, The preferable range is also the same.
The heterocyclic ring of the heterocyclic group is preferably a 5- or 6-membered ring. The heterocycle may be a single ring or a condensed ring. Examples of heterocycles include pyridine ring, piperidine ring, furan ring group, furfuran ring, thiophene ring, pyrrole ring, quinoline ring, morpholine ring, indole ring, imidazole ring, pyrazole ring, carbazole ring, phenothiazine ring, phenoxazine ring , Indoline ring, thiazole ring, pyrazine ring, thiadiazine ring, benzoquinoline ring and thiadiazole ring.

In the general formula (A), R ¹ and R ² each independently represents an aliphatic group or an aromatic group. Examples of the aliphatic group include an alkyl group, an alkenyl group, an alkynyl group, and an aralkyl group. Aromatic groups include aryl groups. As the alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group, those described above for the substituent can be used, and preferred ranges are also the same. The alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, and an amino group. A carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may have a hydrogen atom dissociated or a salt state.

In the formula (A), L ¹ represents a methine chain composed of an odd number of methines. L ¹ is preferably a methine chain composed of 3, 5 or 7 methine groups.
The methine group may have a substituent. The methine group having a substituent is preferably a central (meso-position) methine group. Specific examples of the substituent are the same as the substituent that the nitrogen-containing heterocycle of Z ¹ and Z ² may have. Further, two substituents of the methine chain may be bonded to form a 5- or 6-membered ring.

In the general formula (1), a and b are each independently 0 or 1. Both a and b are preferably 0. When a and b are both 0, general formula (1) is expressed as follows.

式（１Ａ）および（１Ｂ）中、Ｒ^1A、Ｒ^2A、Ｒ^1BおよびＲ^2Bは、それぞれ独立に、アルキル基、アルケニル基、アルキニル基、アラルキル基またはアリール基を表し、
Ｌ^1AおよびＬ^1Bは、それぞれ独立に奇数個のメチンからなるメチン鎖を表し、
Ｙ¹およびＹ²は、各々独立に−Ｓ−、−Ｏ−、−ＮＲ^X1−または−ＣＲ^X2Ｒ^X3−を表し、
Ｒ^X1、Ｒ^X2およびＲ^X3は、各々独立に水素原子またはアルキル基を表し、
Ｖ^1A、Ｖ^2A、Ｖ^1BおよびＶ^2Bは、それぞれ独立に、ハロゲン原子、シアノ基、ニトロ基、アルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基、ヘテロアリール基、−ＯＲ¹⁰、−ＣＯＲ¹¹、−ＣＯＯＲ¹²、−ＯＣＯＲ¹³、−ＮＲ¹⁴Ｒ¹⁵、−ＮＨＣＯＲ¹⁶、−ＣＯＮＲ¹⁷Ｒ¹⁸、−ＮＨＣＯＮＲ¹⁹Ｒ²⁰、−ＮＨＣＯＯＲ²¹、−ＳＲ²²、−ＳＯ₂Ｒ²³、−ＳＯ₂ＯＲ²⁴、−ＮＨＳＯ₂Ｒ²⁵または−ＳＯ₂ＮＲ²⁶Ｒ²⁷を表し、Ｖ^1A、Ｖ^2A、Ｖ^1BおよびＶ^2Bは、縮合環を形成していてもよく、
Ｒ¹⁰〜Ｒ²⁷は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基または複素環基を表し、
−ＣＯＯＲ¹²のＲ¹²が水素の場合および−ＳＯ₂ＯＲ²⁴のＲ²⁴が水素原子の場合は、水素原子が解離しても、塩の状態であってもよく、
ｍ１およびｍ２は、それぞれ独立に０〜４を表し、
式中のＣｙで表される部位がカチオン部である場合、Ｘ¹はアニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、
式中のＣｙで表される部位がアニオン部である場合、Ｘ¹はカチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、
式中のＣｙで表される部位の電荷が分子内で中和されている場合、Ｘ¹は存在しない。In the formula (A), if moiety represented by Cy in the formula is a cation portion, X ¹ is an anion, c is represents a number necessary to balance the charge. Examples of anions include halide ions (Cl ⁻ , Br ⁻ , I ⁻ ), p-toluenesulfonate ions, ethyl sulfate ions, PF ₆ ⁻ , BF ₄ ⁻ or ClO ₄ ⁻ , tris (halogenoalkylsulfonyl) methide anions ( For example, (CF ₃ SO ₂ ) ₃ C ⁻ ), di (halogenoalkylsulfonyl) imide anion (for example, (CF ₃ SO ₂ ) ₂ N ⁻ ), tetracyanoborate anion and the like can be mentioned.
In the formula (A), if moiety represented by Cy in the formula is an anion portion, X ¹ represents a cation, c is represents a number necessary to balance the charge. Examples of the cation include alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ etc.), alkaline earth metal ions (Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Sr ²⁺ etc.), transition metal ions (Ag ⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ²⁺ ), other metal ions (such as Al ³⁺ ), ammonium ion, triethylammonium ion, tributylammonium ion, pyridinium ion, tetrabutylammonium Ion, guanidinium ion, tetramethylguanidinium ion, diazabicycloundecenium and the like. As the cation, Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , and diazabicycloundecenium are preferable.
In the general formula (A), when the charge at the site represented by Cy in the formula is neutralized in the molecule, X ¹ does not exist.
The compound represented by the general formula (A) is also preferably a compound represented by the following (1A) or (1B), and more preferably a compound represented by the following (1B).

In formulas (1A) and (1B), R ^1A , R ^2A , R ^1B and R ^2B each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,
L ^1A and L ^1B each independently represent a methine chain composed of an odd number of methines;
Y ¹ and Y ² each independently represent —S—, —O—, —NR ^X1 — or —CR ^X2 R ^X3 —
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group,
V ^1A , V ^2A , V ^1B and V ^2B are each independently a halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heteroaryl group, —OR ¹⁰ , — ^{COR 11, -COOR 12, -OCOR 13} , -NR 14 R 15, -NHCOR 16, -CONR 17 R 18, -NHCONR 19 R 20, -NHCOOR 21, -SR 22, -SO 2 R 23, -SO 2 Represents OR ²⁴ , —NHSO ₂ R ²⁵ or —SO ₂ NR ²⁶ R ²⁷ , and V ^1A , V ^2A , V ^1B and V ^2B may form a condensed ring;
R ^{10 to} R ²⁷ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group,
When R ^{12 of} —COOR ¹² is hydrogen and R ^{24 of} —SO ₂ OR ²⁴ is a hydrogen atom, the hydrogen atom may be dissociated or in a salt state.
m1 and m2 each independently represent 0 to 4,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents a number necessary to balance the charge,
When the site represented by Cy in the formula is an anion moiety, X ¹ represents a cation, c represents a number necessary for balancing the charge,
When the charge at the site represented by Cy in the formula is neutralized in the molecule, X ¹ does not exist.

The groups represented by R ^1A , R ^2A , R ^1B and R ^2B are synonymous with the alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group described for R ¹ and R ² in formula (A), and are preferable. The range is the same. These groups may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, and an amino group. A carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may have a hydrogen atom dissociated or a salt state.
When R ^1A , R ^2A , R ^1B and R ^2B represent an alkyl group, it is more preferably a linear alkyl group.
Y ¹ and Y ² are each independently -S -, - O -, - NR X1 - or -CR ^X2 R ^X3 - represents, -NR ^X1 - is preferred.
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. 1-10 are preferable, as for carbon number of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear. The alkyl group is particularly preferably a methyl group or an ethyl group.
L ^1A and L ^1B have the same meaning as L ^{1 in} formula (A), and the preferred range is also the same.
The groups represented by V ^1A , V ^2A , V ^1B and V ^2B are synonymous with the ranges described for the substituents that the nitrogen-containing heterocycle of Z ¹ and Z ² in formula (A) may have, and are preferable. The range is the same.
m1 and m2 each independently represent 0 to 4, with 0 to 2 being preferred.
The anion and cation represented by X ¹ have the same meaning as the range described for X ¹ in formula (A), and the preferred range is also the same.

Specific examples of the compound represented by formula (A) are shown below. In the following tables, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, Bn represents a benzyl group, Ph represents a phenyl group, and PRS represents C ₃ H ₆ SO ^{3. -} represents, BUS represents C ₄ H ₉ SO ^3-.

  The compound represented by the general formula (A) is “Heterocyclic Compounds Cyanine Dies and Related Compounds” by FM Harmer. John Wiley & Sons-New York, London, 1964, and DM Starmer, "Heterocyclic Compounds-Special Topics in. Heterocyclic Chemistry in Heterocyclic Chemistry in Heterocyclic Chemistry ”, Chapter 18, Section 14, 482-515, John Wiley & Sons, New York, London, 1977,“ Rods Chemistry of Carbon Compounds (Rodd) ”. 's Chemistry of Carbon Compounds) "2nd. Ed. vol. IV, part B, 1977, Chapter 15, pages 369-422, published by Elsevier Science Publishing Company Inc., New York, JP-A-6-313939 and JP-A-5- It can be easily synthesized with reference to Japanese Patent No. 88293.

<<< Solid dispersion >>>>
The compound represented by the general formula (1) and the compound represented by the general formula (A) (hereinafter also referred to as a dye compound) include compounds that form an aggregate only by being dissolved in water. It is preferable that gelatin or a salt (eg, barium chloride, potassium chloride, sodium chloride, calcium chloride) is added to the aqueous solution of the dye compound to form an aggregate. A method of adding gelatin to an aqueous solution of a dye compound is more preferable.
The aggregate of the dye compound can also be formed as a solid fine particle dispersion of the dye compound. For solid dispersion, for example, “Pigment Dispersion Technology-Surface Treatment and Use of Dispersing Agents and Evaluation of Dispersibility-” published by Technical Information Association, “Encyclopedia of Pigments” published by Asakura Shoten Co., Ltd. Is described in detail in “Latest“ pigment dispersion ”practical know-how / examples”. In order to obtain a solid fine particle dispersion, a known disperser can be used. Examples of the disperser include a ball mill, a vibrating ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill, and a roller mill. The disperser is described in JP-A-52-92716 and WO88 / 074794. A vertical or horizontal medium disperser is preferred.
Dispersion may be carried out in the presence of a suitable solvent (eg, water, alcohol, cyclohexanone, 2-methoxy-1-methylethyl acetate). It is preferable to use a surfactant. As the surfactant, an anionic surfactant (described in JP-A No. 52-92716 and International Patent No. 88/074794) is preferably used. If necessary, an anionic polymer, a nonionic surfactant, or a cationic surfactant may be used.
After the dye compound is dissolved in an appropriate solvent, a poor solvent may be added to obtain a fine powder. In this case, the above surfactant may be used. Alternatively, it may be dissolved by adjusting the pH, and then the pH may be changed to precipitate pigment microcrystals. This microcrystal is also an association of the dye compound. When the dye compound in the associated state is fine particles (or microcrystals), the average particle size is 1000 μm or less, preferably 0.001 μm to 100 μm, more preferably 0.005 μm to 50 μm.

Conventionally known resins and surfactants can be added for the purpose of improving the dispersibility of the dye compound. Examples of commercially available products include phthalocyanine derivatives (commercial products: EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Zeneca); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid type (Co) polymer polyflow no. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic interfaces such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Activator: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (above Morishita Sangyo Co., Ltd.), Disperse 6, polymer dispersants such as Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by Sannopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 Various Solsperse dispersants (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.).
As the surfactant, a known one can be appropriately selected and used, and examples thereof include a cationic surfactant, a fluorine surfactant, and a polymer dispersant.
In addition, the graft copolymer having a specific acid amide group-containing monomer and a quaternary ammonium salt monomer residue in the main chain described in JP-A-10-254133 has an excellent effect of finely dispersing the dye compound. Since it has, it can use preferably. By using the graft copolymer, it is possible to finely disperse the pigment while reducing energy and time consumption, and the dispersed pigment may agglomerate or settle even over time. Long-term dispersion stability can be maintained. The above resins may be used alone or in combination of two or more. The amount of the resin added is preferably about 1 to 150 parts by mass with respect to 100 parts by mass of the dye compound.

<<< Copper compound >>>
The near-infrared absorbing composition of the present invention preferably further contains a copper compound as an infrared absorbing material. A copper compound having a maximum absorption wavelength within a wavelength range of 700 nm to 1000 nm (near infrared region) can be preferably used.
The copper in the copper compound is preferably monovalent or divalent copper, and more preferably divalent copper.
The copper content in the copper compound is preferably 2 to 40% by mass, more preferably 5 to 40% by mass.
The copper compound may be a copper compound other than a copper complex or a copper complex, but is preferably a copper complex. As the copper compound, 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. 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 copper salt is preferably a monovalent or divalent copper salt, more preferably a divalent copper salt.

  In the present invention, a copper compound obtained by reacting a compound having an acid group with a copper component is preferably used. More preferred are copper compounds obtained by reacting a compound containing at least one of a sulfonic acid group, a carboxylic acid group, a phosphinic acid group, and a phosphoric acid group with a copper component (hereinafter, these compounds are referred to as a sulfonic acid copper compound, a carboxylic acid group, respectively). An acid copper compound, a copper phosphinate compound, and a copper phosphate compound), a copper sulfonate compound, a copper carboxylate compound and a copper phosphate compound are more preferable, and a copper sulfonate compound and a copper carboxylate compound are more preferable.

As a copper compound, what is represented by a following formula (A) is preferable.
Cu (L) _n1・ (X) _n2 Formula (A)
In the above formula (A), 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 preferably has a group having a lone electron 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.

  When the copper compound is a copper complex, the ligand is coordinated to the central metal copper. A copper complex can be obtained by mixing and reacting a compound serving as a ligand or a salt thereof with a copper component. Therefore, if the near-infrared absorbing composition contains copper and a ligand, it is predicted that a copper complex is formed in the composition.

As a compound used as a ligand or its salt, an organic acid compound or its salt etc. are mentioned suitably, for example. Organic acid compounds or salts thereof include phosphoric acid, phosphoric acid ester, phosphonic acid, phosphonic acid ester, phosphinic acid, substituted phosphinic acid, sulfonic acid, carboxylic acid, carbonyl (ester, ketone), amine, amide, sulfonamide, Examples thereof include compounds having urethane, urea, alcohol, thiol and the like. Among these, phosphoric acid, phosphoric acid ester, phosphonic acid, phosphonic acid ester, phosphinic acid, substituted phosphinic acid, sulfonic acid, and carboxylic acid are preferable, and phosphoric acid ester, phosphonic acid ester, substituted phosphinic acid, sulfonic acid, and carboxylic acid Is more preferable.
The compound serving as a ligand or a salt thereof is preferably represented by the following general formula (i).

（一般式（ｉ）中、Ｒ¹はｎ価の有機基を表し、Ｘ¹は酸基を表し、ｎは１〜６の整数を表す。）
一般式（ｉ）中、Ｒ¹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、アルキル基、ハロゲン原子（好ましくはフッ素原子）、重合性基（例えば、ビニル基、（メタ）アクリロイル基、エポキシ基、オキセタン基など）、スルホン酸基、カルボン酸基、リン原子を含有する酸基、カルボン酸エステル基（例えば−ＣＯ₂ＣＨ₃）、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）等が挙げられる。炭化水素基が置換基を有する場合、さらに置換基を有していてもよく、置換基としてはアルキル基、上記重合性基、ハロゲン原子等が挙げられる。
炭化水素基が１価の場合、アルキル基、アルケニル基またはアリール基が好ましく、アリール基がより好ましい。炭化水素基が２価の場合、アルキレン基、アリーレン基、オキシアルキレン基が好ましく、アリーレン基がより好ましい。炭化水素基が３価以上の場合には、上記１価の炭化水素基または２価の炭化水素基に対応するものが好ましい。
アルキル基及びアルキレン基は、直鎖状、分岐状または環状のいずれであってもよい。直鎖状のアルキル基及びアルキレン基の炭素数は、１〜２０が好ましく、１〜１２がより好ましく、１〜８がさらに好ましい。分岐状のアルキル基及びアルキレン基の炭素数は、３〜２０が好ましく、３〜１２がより好ましく、３〜８がさらに好ましい。環状のアルキル基及びアルキレン基は、単環、多環のいずれであってもよい。環状のアルキル基及びアルキレン基の炭素数は、３〜２０が好ましく、４〜１０がより好ましく、６〜１０がさらに好ましい。
アルケニル基及びアルケニレン基の炭素数は、２〜１０が好ましく、２〜８がより好ましく、２〜４がさらに好ましい。
アリール基及びアリーレン基の炭素数は、６〜１８が好ましく、６〜１４がより好ましく、６〜１０がさらに好ましい。
一般式（ｉ）中、Ｘ¹は、スルホン酸基、カルボン酸基およびリン原子を含有する酸基のうちの少なくとも１つが好ましい。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、スルホン酸基およびカルボン酸基を有するものが好ましい。
一般式（ｉ）中、ｎ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、７０〜１０００が好ましく、７０〜５００がより好ましい。

(In general formula (i), R ¹ represents an n-valent organic group, X ¹ represents an acid group, and n represents an integer of 1 to 6.)
In general formula (i), R ¹ 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. Examples of the substituent include an alkyl group, a halogen atom (preferably a fluorine atom), a polymerizable group (for example, a vinyl group, a (meth) acryloyl group, an epoxy group, An oxetane group), a sulfonic acid group, a carboxylic acid group, an acid group containing a phosphorus atom, a carboxylic acid ester group (for example, —CO ₂ CH ₃ ), a hydroxyl group, an alkoxy group (for example, a methoxy group), an amino group, a carbamoyl group, Examples thereof include a carbamoyloxy group and a halogenated alkyl group (for example, a fluoroalkyl group and a chloroalkyl group). When the hydrocarbon group has a substituent, the hydrocarbon group may further have a substituent, and examples of the substituent include an alkyl group, the polymerizable group, and a halogen atom.
When the hydrocarbon group is monovalent, an alkyl group, an alkenyl group or an aryl group is preferable, and an aryl group is more preferable. When the hydrocarbon group is divalent, an alkylene group, an arylene group, or an oxyalkylene group is preferable, and an arylene group is more preferable. When the hydrocarbon group is trivalent or higher, those corresponding to the monovalent hydrocarbon group or divalent hydrocarbon group are preferred.
The alkyl group and the alkylene group may be linear, branched or cyclic. 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 and alkenylene group, 2-8 are more preferable, and 2-4 are more preferable.
6-18 are preferable, as for carbon number of an aryl group and an arylene group, 6-14 are more preferable, and 6-10 are more preferable.
In general formula (i), X ¹ is preferably at least one of an acid group containing a sulfonic acid group, a carboxylic acid group and a phosphorus atom. X ¹ may be one kind or two or more kinds, but is preferably two kinds or more, and preferably has a sulfonic acid group and a carboxylic acid group.
In general formula (i), n 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), 70-1000 are preferable and 70-500 are more preferable.

Preferable embodiments of the compound containing an acid group or a salt thereof include (1) a compound having at least one of a sulfonic acid group, a carboxylic acid group and an acid group containing a phosphorus atom, more preferably ( 2) An embodiment having two or more acid groups, more preferably (3) an embodiment having a sulfonic acid group and a carboxylic acid group. In these embodiments, since the structure of the copper complex is more easily distorted, the color value can be further improved, and the infrared absorption ability, which is the ability to absorb near infrared rays, is more effectively exhibited. Furthermore, the color value can be further improved by using a compound having a sulfonic acid group and a carboxylic acid group.
Hereinafter, the copper compound and the compound forming the ligand will be described in detail.

<<<<< Phosphorus-Containing Copper Complex >>>>
The phosphorus-containing copper complex is not particularly limited as long as it has a ligand containing a phosphorus compound, but a copper phosphate complex, a phosphate ester copper complex, a phosphonate copper complex, a phosphonate copper complex, a phosphine An acid copper complex and a substituted phosphinic acid copper complex are preferable, and a phosphoric acid ester copper complex, a phosphonic acid ester copper complex, and a substituted phosphinic acid copper complex are more preferable.

<<<<<<< Phosphate Copper Complex >>>>>>
The phosphate ester copper complex has copper as a central metal and a phosphate ester compound as a ligand. As the phosphate ester compound forming the ligand, a compound represented by the following formula (B) is more preferable.
_{(HO) n -P (= O} ) - (OR 2) 3-n Formula (B)
In the above formula (B), R ² represents an organic group, and n represents 1 or 2.
Wherein R ² represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 1 to 18 carbon atoms, or an alkenyl group having 1 to 18 carbon atoms, or —OR ² Represents a polyoxyalkyl group having 4 to 100 carbon atoms, a (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms, or a (meth) acryloyl polyoxyalkyl group having 4 to 100 carbon atoms, and n is 1 or 2)
When n is 1, R ² may be the same or different.

  Specific examples of the phosphoric ester compound include, for example, paragraphs 0020 to 0025 of JP2013-253224A (paragraphs 0020 to 0025 of pamphlet of international publication WO2013 / 168824), paragraph 0041 of JP2001-354945A, and the like. To 0045 (corresponding to US Patent Application Publication No. 2003/0160217 [0059]), the contents of which are incorporated herein by reference.

（式（Ｅ）中、Ｒ³、Ｒ⁴は、各々独立に、１価の有機基を示す。）
式（Ｅ）で表される化合物およびその塩は、銅に配位する配位子として作用する。<<<<<<< Phosphonate Copper Complex >>>>>>
The phosphonate copper complex has copper as a central metal and a phosphonate ester compound as a ligand. As the phosphonate compound forming the ligand, a compound represented by the following formula (E) is more preferable.

(In formula (E), R ³ and R ⁴ each independently represents a monovalent organic group.)
The compound represented by the formula (E) and a salt thereof act as a ligand coordinated to copper.

R ³ and R ⁴ in the formula (E) each independently represent a monovalent organic group. Specific examples of the monovalent organic group include, but are not limited to, a linear, branched, or cyclic alkyl group, alkenyl group, aryl group, and heteroaryl group. Here, these groups are divalent linking groups (for example, alkylene group, cycloalkylene group, arylene group, heteroarylene group, -O-, -S-, -CO-, -COO-, -OCO). A group via —, —SO ₂ —, —NR— (wherein R is a hydrogen atom or an alkyl group) may be used. The monovalent organic group may have a substituent.
1-20 are preferable, as for carbon number with a linear or branched alkyl group, 1-10 are more preferable, and 1-8 are more preferable.
The cyclic alkyl group may be monocyclic or polycyclic. 3-20 are preferable, as for carbon number of a cyclic | annular alkyl group, 4-10 are more preferable, and 6-10 are more preferable.
6-18 are preferable, as for carbon number of an aryl group, 6-14 are more preferable, and 6-10 are more preferable.
The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl 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. Specifically, a heteroaryl group derived from a monocyclic or polycyclic aromatic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom is used. Examples of the heteroaryl ring in the heteroaryl group include an 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, quinazoline ring, cinolin ring , Pteridine ring, carbazole ring, carboline ring, phenanthrine ring, acridine ring, perimidine ring, phenanthroline ring, phthalazine ring, phenazazine ring, phenoxazine ring, and furazane ring.
Examples of the substituent that the monovalent organic group may have include an alkyl group, a polymerizable group (for example, a vinyl group, a (meth) acryloyl group, an epoxy group, and an oxetane group), a halogen atom, a carboxyl group, and a carboxyl group. Examples include acid ester groups (for example, —CO ₂ CH _{3 and the} like), hydroxyl groups, amide groups, halogenated alkyl groups (for example, fluoroalkyl groups and chloroalkyl groups) and the like. Moreover, as a substituent, the substituent which R < ¹ > in general formula (i) mentioned above may have is also mentioned.
The divalent linking group alkylene group, arylene group, or heteroarylene group is derived by removing one hydrogen atom from the above-mentioned linear, branched, or cyclic alkyl group, aryl group, or heteroaryl group. And a divalent linking group.
The molecular weight of the phosphonic acid ester copper complex represented by the formula (E) is preferably 200 to 1000, more preferably 250 to 750, and still more preferably 300 to 500.

（式（Ｆ）中、Ｒ³およびＲ⁴は、各々独立に、１価の有機基を示す。「＊」は、銅と配位結合する部位を示す。）
式（Ｆ）中、Ｒ³およびＲ⁴は、式（Ｅ）中におけるＲ³およびＲ⁴と同義であり、好ましい範囲も同様である。
ホスホン酸エステル銅錯体の具体例を以下に示す。

The phosphonate copper complex preferably has a structure represented by the following formula (F).

(In formula (F), R ³ and R ⁴ each independently represents a monovalent organic group. “*” Represents a site that coordinates to copper.)
Wherein (F), R ³ and R ⁴ have the same meanings as R ³ and R ⁴ in the formula (E), and preferred ranges are also the same.
Specific examples of the phosphonate copper complex are shown below.

（式（Ｇ）中、Ｒ⁵およびＲ⁶は、各々独立に、１価の有機基を示す。）<<<<<<< Substituted copper phosphinate complex >>>>
The substituted phosphinic acid copper complex has copper as a central metal and a substituted phosphinic acid compound as a ligand. As the substituted phosphinic acid compound forming the ligand, a compound represented by the following formula (G) is preferable.

(In formula (G), R ⁵ and R ⁶ each independently represents a monovalent organic group.)

The compound represented by the formula (G) and a salt thereof act as a ligand coordinated to copper.
In formula (G), R ⁵ and R ⁶ each independently represents a monovalent organic group. Although it does not specifically limit as a specific monovalent organic group, The same thing as the monovalent organic group demonstrated by R < ³ >, R < ⁴ > in Formula (E) mentioned above is mentioned, A preferable range is also the same. .
50-750 are preferable, as for the molecular weight of the substituted phosphinic acid compound represented by Formula (G), 50-500 are more preferable, and 80-300 are more preferable.

（式（Ｈ）中、Ｒ⁵およびＲ⁶は、各々独立に、１価の有機基を示す。「＊」は、銅と配位結合する部位を示す。）
式（Ｈ）中、Ｒ⁵およびＲ⁶は、式（Ｇ）中におけるＲ⁵およびＲ⁶と同義であり、好ましい範囲も同様である。
置換ホスフィン酸銅錯体の具体例を以下に示す。The substituted copper phosphinate complex used in the present invention preferably contains a structure represented by the following formula (H).

(In formula (H), R ⁵ and R ⁶ each independently represents a monovalent organic group. “*” Represents a site that coordinates to copper.)
Wherein (H), R ⁵ and R ⁶ has the same meaning as R ⁵ and R ⁶ in the formula (G), and preferred ranges are also the same.
Specific examples of the substituted phosphinic acid copper complex are shown below.

A phosphorus-containing copper complex can be obtained by reacting a copper component with a phosphorus-containing compound (for example, a phosphate ester, a phosphonate ester, a substituted phosphinic acid, or the like) serving as a ligand or a salt thereof.
As the copper component, 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 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 benzoate, and copper (meth) acrylate are more preferable.
A phosphorus containing compound is compoundable with reference to a well-known method, for example.
For example, the phosphate ester compound can be obtained by reacting 2-hydroxyethyl methacrylate, phenyl phosphate ester and 1,3,5-triisopropylsulfonic acid chloride in a pyridine solvent.
As the salt of the phosphorus-containing compound, for example, a metal salt is preferable, and specific examples include sodium salt, potassium salt, magnesium salt, calcium salt, borate and the like.
The reaction ratio for reacting the copper component with the phosphorus-containing compound or salt thereof is preferably 1: 1.5 to 1: 4 in terms of molar ratio.
Moreover, it is preferable that the reaction conditions at the time of making a copper component, a phosphorus containing compound, or its salt react are 20-50 degreeC, for 0.5 hour or more, for example.

The maximum absorption wavelength of the phosphorus-containing copper complex is preferably in the range of 700 to 1000 nm, more preferably in the range of 720 to 890 nm, and still more preferably in the range of 730 to 880 nm. The maximum absorption wavelength can be measured using, for example, Cary 5000 UV-Vis-NIR (Spectrophotometer manufactured by Agilent Technologies).
The phosphorus-containing copper complex preferably has a gram absorbance of 0.04 or more (g / mL), more preferably 0.06 or more (g / mL), and 0.08 or more (g / mL). More preferably,
Gram absorbance can be calculated using, for example, a Cary 5000 UV-Vis-NIR (Spectrophotometer manufactured by Agilent Technologies).

（式（Ｉ）中、Ｒ⁷は１価の有機基を表す。）<<<<< Copper sulfonate complex >>>>
The sulfonic acid copper complex has copper as a central metal and a sulfonic acid compound as a ligand.
As the sulfonic acid compound as a ligand, a compound represented by the following formula (I) is more preferable.

(In the formula (I), R ⁷ represents a monovalent organic group.)

The sulfonic acid represented by the formula (I) and a salt thereof act as a ligand coordinated to copper.
Specific examples of the monovalent organic group represented by R ^{7 in} the general formula (I) include a hydrocarbon group. Specific examples include linear, branched or cyclic alkyl groups, alkenyl groups, and aryl groups. The group can be mentioned. These groups are divalent linking groups (for example, linear or branched alkylene groups, cyclic alkylene groups (cyclic alkylene groups), arylene groups, -O-, -S-, -CO-,- A group via COO—, —OCO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group, etc.) may be used.
The carbon number of the linear alkyl group, the branched alkyl group, the cyclic alkyl group, the alkenyl group and the aryl group is the same as that described for R ¹ in the general formula (i) described above, and the preferred range is also the same. It is.
The monovalent organic group may have a substituent, and examples of the substituent include a substituent that the monovalent organic group represented by R ³ and R ^{4 in} the above-described formula (E) may have. Can be mentioned. Examples of the substituent that the linear alkyl group and the branched alkyl group may have include at least one of a halogen atom, a polymerizable group, and a carboxylic acid group. Examples of the substituent that the aryl group may have include at least one of an alkyl group, an alkoxy group, a halogenated alkyl group, a halogen atom, a polymerizable group, a sulfonic acid group, a carboxylic acid group, and a methyl carboxylate group. And at least one of a sulfonic acid group and a carboxylic acid group is preferred.
As the linear or branched alkylene group, cyclic alkylene group, or arylene group that is a divalent linking group, one hydrogen atom is removed from the linear, branched, or cyclic alkyl group or aryl group described above. And a divalent linking group derived from the above.
Examples of the substituent that the monovalent organic group may have include the substituent that the monovalent organic group represented by R ³ and R ^{4 in} the above-described formula (E) may have.
Examples of the substituent that R ⁷ may have when it is a linear alkyl group or a branched alkyl group include at least one of a halogen atom, a polymerizable group, and a carboxylic acid group. Examples of the substituent that may be present when R ⁷ is an aryl group include an alkyl group, an alkoxy group, a halogenated alkyl group, a halogen atom, a polymerizable group, a sulfonic acid group, a carboxylic acid group, and a carboxylic acid methyl group. And at least one of a sulfonic acid group and a carboxylic acid group is preferable.
The molecular weight of the sulfonic acid compound represented by the formula (I) is preferably 80 to 750, more preferably 80 to 600, and still more preferably 80 to 450.

（式（Ｊ）中、Ｒ⁸は、１価の有機基を示す。「＊」は、銅と配位結合する部位を示す。）
式（Ｊ）中、Ｒ⁸は、式（Ｉ）中におけるＲ⁷と同義であり、好ましい範囲も同様である。
スルホン酸銅錯体の具体例を以下に示す。The copper sulfonate complex preferably has a structure represented by the following formula (J).

(In formula (J), R ⁸ represents a monovalent organic group. “*” Represents a site that coordinates to copper.)
In formula (J), R ⁸ has the same meaning as R ⁷ in formula (I), and the preferred range is also the same.
Specific examples of the copper sulfonate complex are shown below.

The sulfonic acid copper complex can be obtained by reacting a copper component with a sulfonic acid compound or a salt thereof as a ligand.
As a copper component, it is synonymous with the phosphorus containing copper complex mentioned above, and its preferable range is also the same.
A commercially available sulfonic acid can also be used for a sulfonic acid compound, and it can also synthesize | combine it with reference to a well-known method.
As a salt of a sulfonic acid compound, for example, a metal salt is preferable, and specific examples thereof include a sodium salt and a potassium salt.
As a reaction ratio at the time of making a copper component, a sulfonic acid compound, or its salt react, 1: 1.5-1: 4 are preferable by molar ratio. At this time, the sulfonic acid compound or a salt thereof may be one kind or two or more kinds.
The reaction conditions for reacting the copper component with the sulfonic acid compound or a salt thereof are, for example, 20 to 50 ° C. and preferably 0.5 hours or longer.
The maximum absorption wavelength and gram absorbance of the copper sulfonate complex are synonymous with the phosphorus-containing copper complex described above, and the preferred range is also the same.

<< other copper compounds >>
As a copper compound used by this invention, you may use the copper compound which makes a carboxylic acid a ligand other than what was mentioned above. As the carboxylic acid, for example, a compound represented by the following formula (K) is preferable.

（式（Ｋ）中、Ｒ¹は１価の有機基を表す。）
式（Ｋ）中、Ｒ¹は１価の有機基を表す。１価の有機基としては、特に限定されないが、例えば、一般式（Ｉ）中の１価の有機基Ｒ⁷と同義であってもよく、その好ましい範囲も同様であってもよい。
カルボン酸の具体例としては、例えば、特開２０１３−２５３２２４号公報の段落００２９（対応する国際公開ＷＯ２０１３／１６８８２４号パンフレットの段落００２９）の記載を参酌でき、これらの内容は本願明細書に組み込まれる。

(In formula (K), R ¹ represents a monovalent organic group.)
In formula (K), R ¹ represents a monovalent organic group. The monovalent organic group is not particularly limited, for example, the general formula (I) may be synonymous with the monovalent organic group R ⁷ in, or may be also the same preferred ranges thereof.
As specific examples of the carboxylic acid, for example, the description of paragraph 0029 of JP2013-253224A (corresponding to paragraph 0029 of WO2013 / 168824 pamphlet) can be referred to, and the contents thereof are incorporated in the present specification. .

<<<<< Polymer type copper compound >>>>
In the present invention, a polymer-type copper compound obtained by a reaction between a polymer containing an acid group or a salt thereof and a copper component can be used as the copper compound.
This copper compound is, for example, a polymer containing an acid group ion site and a polymer copper complex containing a copper ion. The polymer copper complex has an acid group ion site in the side chain of the polymer, the acid group ion site is bonded to copper (for example, coordination bond), and a cross-linked structure is formed between the side chains starting from copper. ing. Heat resistance can be improved by using a polymer copper complex.
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.
The acid group possessed by the polymer containing an acid group or a salt thereof is not particularly limited as long as it can react with the copper component described above, but is preferably one that coordinates with the copper component. 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 salt of the acid group include a metal atom such as sodium (particularly an alkali metal atom), an atomic group such as tetrabutylammonium. 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.

（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。）
式（Ａ１−１）中、Ｒ¹は水素原子であることが好ましい。
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。
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。<<<<<< First Embodiment of Polymer Containing 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 formula (A1-1), R ¹ is preferably a hydrogen atom.
In 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—, A group consisting of —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NX— (X represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a combination thereof; Can be 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 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 is a hydrogen atom or an alkali. A 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、式（Ａ１−１）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。
式（Ａ１−１）で表される構成単位を含む重合体が、他の構成単位（好ましくは式（Ａ１−２）で表される構成単位）を含む場合、式（Ａ１−１）で表される構成単位と式（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 formula (A1-1). 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 formula (A1-1) contains another structural unit (preferably a structural unit represented by the formula (A1-2)), the polymer is represented by the formula (A1-1). The molar ratio of the structural unit to be represented and the structural unit represented by the formula (A1-2) is preferably 95: 5 to 20:80, and more preferably 90:10 to 40:60.

<<<<<< Second Embodiment of Polymer Containing Acid Group or Salt thereof >>>>
As the polymer type copper compound, 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 referred to as an aromatic group-containing polymer). ) And a copper component of a polymer obtained by a reaction with 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.
6-20 are preferable, as for carbon number of an aromatic hydrocarbon 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 for carbon number of an aromatic heterocyclic group, 2-30 are preferable. The aromatic heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The aromatic heterocyclic group 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. Examples of the hetero atom contained in the aromatic heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom or an oxygen atom is preferable.
When the aromatic hydrocarbon group or aromatic heterocyclic group has a substituent T, the substituent T includes an alkyl group or a polymerizable group (preferably a polymerizable group containing a carbon-carbon double bond). ), 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 , An acyl group, a hydroxy group, a carboxyl group, an 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: 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: Polymer having main chain structure represented by (—O—Ph—Ph—O—Ph—SO ₂ —Ph—) Polyetherketone polymer: (—O—Ph—O—Ph—C (═O ) Polymer having main chain structure represented by -Ph-) Polyphenylene ether polymer: Polymer having main chain structure represented by (-Ph-O-, -Ph-S-) Polyphenylene polymer : (- Ph-) polymer 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-O-C (= O) -O-) Polymer having a chain structure 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, (- Polymers having a main chain structure represented by Ph-C (= O) O-) Examples of polyethersulfone-based polymers, polysulfone-based polymers, and polyetherketone-based polymers include JP-A-2006-310068. The main chain structure described in paragraph 0022 of the publication and paragraph 0028 of JP-A-2008-27890 can be referred to, 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または芳香族ヘテロ環基を表し、Ｙ¹は単結合又は２価の連結基を表し、Ｘ¹は酸基又はその塩を表す。）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 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. .)

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 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 composed of a combination of these. 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. 1-20 are preferable, as for carbon number of a linear alkylene group, 1-10 are more preferable, and 1-6 are more preferable. 3-20 are preferable, as for carbon number of a branched alkylene group, 3-10 are more preferable, and 3-6 are more preferable. The cyclic alkylene group may be monocyclic or polycyclic. 3-20 are preferable, as for carbon number of a cyclic | annular alkylene group, 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) described above 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, 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 formula (A1-3), the acid group represented by X ¹ or a salt thereof is synonymous with the acid group or the salt thereof described above, 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 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.

<< Sub-near-infrared absorbing material >>
The near-infrared absorbing composition of the present invention may further contain a sub-infrared absorbing material different from the above-described near-infrared absorbing material in addition to the above-mentioned near-infrared absorbing material. When the near-infrared absorbing composition of the present invention further contains a sub-near-infrared absorbing material, when the film having a film thickness of 300 μm or less is formed, the light transmittance in the entire range of wavelengths from 450 to 550 nm is further improved. An excellent composition can be provided. In addition, it is possible to provide a near-infrared cut filter having a high light-shielding property (near-infrared shielding property) in the near-infrared region and a high light-transmitting property (visible light transmittance) in the visible light region.

As the near-infrared absorbing material, a metal oxide is preferable. The metal oxide is preferably a metal oxide having a maximum absorption wavelength in the wavelength range of 800 to 2000 nm. For example, cesium tungsten oxide (CsWO _x ), quartz (SiO ₂ ), magnetite (Fe ₃ O ₄ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), zirconia (ZrO ₂ ), spinel (MgAl ₂ O ₄₎ ) And the like, and cesium tungsten oxide is preferable.
Tungsten oxide compounds have high absorption for infrared rays (especially light having a wavelength of about 800 to 1200 nm) (that is, high light shielding properties (shielding properties) for infrared rays) and low absorption for visible light. It is a shielding material. Therefore, when the near-infrared absorptive composition of the present invention contains a tungsten compound, the light shielding property (infrared shielding property) in the infrared region is high, and the light transmitting property (visible light transmittance) in the visible light region is high. A near infrared cut filter can be manufactured.

The tungsten oxide compound is more preferably a tungsten oxide compound represented by the following general formula (composition formula) (I).
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 represented by 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, alkali metals are preferable, Rb or Cs is more preferable, and Cs is particularly 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.
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, etc., and Cs _0.33 WO ₃ Alternatively, Rb _0.33 WO ₃ is preferable, and Cs _0.33 WO ₃ is more preferable.

  The metal oxide is preferably fine particles. The average particle diameter of the metal oxide fine particles is preferably 800 nm or less, more preferably 400 nm or less, and even more 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 the translucency in the visible light region can be further improved. From the viewpoint of avoiding light scattering, the average particle diameter of the metal oxide is preferably as small as possible. However, the average particle diameter of the metal oxide is preferably 1 nm or more for reasons such as ease of handling during production.

Metal oxides are commercially available. When the metal oxide is, for example, a tungsten oxide compound, the tungsten oxide compound can be obtained by a method in which the tungsten compound is heat-treated in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent No. 4096205). .
The tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.
The near-infrared absorbing composition of the present invention may not contain a sub-near infrared absorbing substance, but when it contains a sub-infrared absorbing substance, the content thereof is the near-infrared absorbing composition of the present invention. The total solid content is preferably 20 to 85% by mass, more preferably 30 to 80% by mass, and even more preferably 40 to 75% by mass.
Moreover, 1 type may be sufficient as a sub near-infrared absorber, and 2 or more types can also be used for it. When using 2 or more types, it is preferable that a total amount is the said range.

<< Curable compound >>
The composition of the present invention may contain a curable compound. The curable compound may be a compound having a polymerizable group (hereinafter sometimes referred to as “polymerizable compound”) or a non-polymerizable compound such as a binder. The curable compound may be in any chemical form such as a monomer, an oligomer, a prepolymer, or a polymer. Examples of the curable compound include paragraphs 0070 to 0191 in JP-A-2014-41318 (paragraphs 0071 to 0192 in pamphlet of international publication WO 2014/017669), paragraphs 0045 to 0216 in JP-A-2014-32380, and the like. Which is incorporated herein by reference.
As the curable compound, a polymerizable compound is preferable. For example, the compound containing an ethylenically unsaturated bond, cyclic ether (epoxy, oxetane) etc. is mentioned. As the ethylenically unsaturated bond, a vinyl group, a styryl group, a (meth) acryloyl group, and an allyl group are preferable.
Specific 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, polyfunctional Epoxy resin and the like.
The curable 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. Although the number of functional groups is not particularly limited, 2 to 8 functions are preferable, and 3 to 6 functions are more preferable.
When the near-infrared absorbing composition of the present invention contains a curable compound, the content of the curable compound is preferably 1 to 80% by mass with respect to the total solid content excluding the solvent. The lower limit is preferably 5% by mass or more, and more preferably 7% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less.
Only one type of curable compound may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.

<<< Compound containing an ethylenically unsaturated bond >>>
As examples of the compound containing an ethylenically unsaturated bond, the description in paragraphs 0033 to 0034 of JP2013-253224A can be referred to, the contents of which are incorporated herein.
Examples of the compound containing an ethylenically unsaturated bond include ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available product, KAYARAD D). -330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D- 310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available products are KAYARAD DPHA; Nippon Kayaku Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and these No (meta) acrylic Yl group ethylene glycol, structures through a propylene glycol residue are preferable. These oligomer types can also be used.
Moreover, description of the polymeric compound of Paragraph 0034-0038 of Unexamined-Japanese-Patent No. 2013-253224 can be referred, This content is integrated in this specification.
Moreover, the polymerizable monomer etc. as described in Unexamined-Japanese-Patent No. 2012-208494 Paragraph 0477 ([0585] of corresponding US Patent application publication 2012/0235099) are mentioned, The content of these is integrated in this-application specification. It is.
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 compound containing an ethylenically unsaturated bond, 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. If the compound containing an ethylenically unsaturated bond has an unreacted carboxyl group as in the case of a mixture as described above, it can be used as it is. An acid group may be introduced by reacting a hydroxyl group of a compound 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.

The compound containing an ethylenically unsaturated bond 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 added to an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group by reacting is preferred, 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 kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid value as the entire polyfunctional monomer is adjusted to fall within the above range.

<<< Compound having epoxy group or oxetanyl group >>>
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.
The weight average molecular weight is preferably 500 to 5000000, and more preferably 1000 to 500000.
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, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Chemical Industries, Ltd.) ), Cyclo-P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (above, manufactured by Daicel Chemical Industries, Ltd.) and the like.
Furthermore, JER-157S65, JER-152, JER-154, JER-157S70 (above, Mitsubishi Chemical Corporation) 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 Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (and more Toagosei Co., Ltd.) can be used.
As the compound having an epoxy group, 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 compound containing an epoxy group or oxetanyl group may contain a polymer having an epoxy group or oxetanyl group as a repeating unit. Specific examples include polymers (copolymers) having the following repeating units.

<<< Other curable compounds >>>
Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone modified structure as a sclerosing | hardenable compound.
As the polyfunctional monomer having a caprolactone-modified structure, the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated herein.
Such a polyfunctional monomer having a caprolactone-modified structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (paragraphs 0083 to 0085 of JP 2014-041318 A). In the formulas (1) to (3), m = 1, the number of groups represented by the formula (2) = 2, a compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, Number of groups represented by formula (2) = 3, compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, Compounds in which R ¹ is all hydrogen atoms), DPCA-120 (a compound in which m = 2, the number of groups represented by formula (2) = 6, and R ¹ is all hydrogen atoms), etc. Can do.
Polyfunctional monomers having a caprolactone-modified structure can be used alone or in admixture of two or more.
Examples of commercially available products include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd. And TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

（式（３０）中、Ｒ¹は水素原子または有機基を表す。）The curable compound 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.

Specific examples of the compound having the partial structure represented by the above formula (30) include compounds having the following structures or the following exemplified compounds, 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. The water-soluble polymer is preferably a water-soluble polyamide resin.

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. 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.

<< Polymerization initiator >>
The near infrared ray absorbing composition of the present invention may contain a polymerization initiator. 0.01-30 mass% is preferable, as for content of a polymerization initiator, 0.1-20 mass% is more preferable, and 0.1-15 mass% is especially preferable. Only one type of polymerization initiator may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably in the above range.
The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound by light or heat, or both, and can be appropriately selected according to the purpose.
When the polymerizable compound is polymerized by light, a photopolymerization initiator is preferred. The photopolymerization initiator preferably has photosensitivity to visible light from the ultraviolet region.
Further, when the polymerization of the polymerizable compound is initiated by heat, a thermal polymerization initiator is preferable. The thermal polymerization initiator is preferably one that decomposes at 150 to 250 ° C.

The polymerization initiator is preferably a compound having at least an aromatic group. For example, an acylphosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, a ketal derivative compound, a thioxanthone compound, Oxium compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, metallocene compounds and other onium salt compounds, organic boron salt compounds, disulfone compounds, thiols Compound etc. are mentioned.
As the polymerization initiator, the description in paragraphs 0218 to 0251 of JP-A-2014-41318 (paragraphs 0220 to 0253 in the corresponding international publication WO 2014/017669) can be referred to, and the contents thereof are incorporated in the present specification. .

Examples of oxime compounds include IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), and Adeka Arcles NCI-831. (ADEKA), Adeka Arkles NCI-930 (ADEKA), etc. can be used.
As the acetophenone-based initiator, commercially available products such as IRGACURE-907, IRGACURE-369, IRGACURE-379 (trade names: all manufactured by BASF Japan Ltd.) and the like 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.
In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP 2013-164471 A ( C-3). This content is incorporated herein.

<< Alkali-soluble resin >>
The near-infrared absorbing composition of the present invention may contain an alkali-soluble resin. By blending the alkali-soluble resin, a desired pattern can be formed by alkali development.
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred. As the alkali-soluble resin, paragraphs 0558 to 0571 of JP2012-208494A (corresponding to [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to and the contents thereof can be referred to. Is incorporated herein.
When the near-infrared absorbing composition of the present invention contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 1% by mass or more in the total solid content of the near-infrared absorbing composition of the present invention. It can also be made into mass% or more, can be made into 5 mass% or more, and can also be made into 10 mass% or more. Moreover, content of alkali-soluble resin can also be 80 mass% or less in the total solid of the composition of this invention, can also be 65 mass% or less, and can also be 60 mass% or less. It can also be made into 15 mass% or less.
In addition, it cannot be overemphasized that it can also be set as the aspect which does not contain alkali-soluble resin, when not forming a pattern by alkali image development using the near-infrared absorption composition of this invention.

<< Surfactant >>
The near infrared ray absorbing 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. 0.0001-2 mass% is preferable with respect to solid content of the near-infrared absorption composition of this invention, content of surfactant is more preferable 0.005-1.0 mass%, 0.01- 0.1 mass% is still more preferable.
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 near-infrared absorbing composition of the present invention preferably contains at least one of a fluorine-based surfactant and a silicone-based surfactant. According to this, the liquid characteristics (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and the liquid-saving property are further improved.
That is, when the near-infrared absorbing composition contains at least one of a fluorine-based surfactant and a silicone-based surfactant, the interfacial tension between the surface to be coated and the coating liquid decreases, and the surface to be coated becomes wet. The coating property of the coating liquid on the surface to be coated is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

3-40 mass% is preferable, as for the fluorine content rate in a fluorochemical surfactant, 5-30 mass% is more preferable, and 7-25 mass% is still more preferable. 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 near-infrared absorbing composition.
Specific examples of the fluorosurfactant include the surfactants described in paragraphs 0060 to 0064 of JP 2014-41318 A (paragraphs 0060 to 0064 of the corresponding international publication WO 2014/17669 pamphlet) and the like. These contents are incorporated herein.

上記の化合物の重量平均分子量は、例えば、１４，０００である。Commercially available fluorosurfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, R30, F-437, F-475, F-479, F-482, F-554, F-780, F-781 (above, DIC) Manufactured by Co., Ltd.), FLORARD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).
The following compounds are also exemplified as the fluorosurfactant used in the present invention.

The weight average molecular weight of the above compound is, for example, 14,000.

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- 01, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, SK-14, AE-3 (all Nissin 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.

<< Solvent >>
The near infrared ray absorbing composition of the present invention may contain a solvent. The solvent is not particularly limited and may be appropriately selected depending on the purpose as long as each component can be uniformly dissolved or dispersed. For example, water or an organic solvent can be used.
Preferable examples of the organic solvent include alcohols, ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and the like. These may be used alone or in combination of two or more. When two or more solvents are used in combination, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, A mixed solution composed of two or more selected from ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate is preferable.
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 the corresponding US Patent Application Publication No. 2012/0235099). 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.
As the solvent, it is preferable to use at least one selected from cyclohexanone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, butyl acetate, ethyl lactate and propylene glycol monomethyl ether.
The amount of the solvent in the near-infrared absorbing composition of the present invention is preferably such that the total solid content of the near-infrared absorbing composition of the present invention is 5 to 90% by mass, and is 10 to 80% by mass. Is more preferable, and the amount which becomes 20-75 mass% is still more preferable.

<Polymerization inhibitor>
The near-infrared absorbing composition of the present invention may contain a small amount of a polymerization inhibitor in order to prevent unnecessary reaction of the curable compound during the production or storage of the composition.
As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like are mentioned, and p-methoxyphenol is preferred.
When the near-infrared absorbing composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 5% by mass with respect to the total solid content of the near-infrared absorbing composition of the present invention. Is preferred.

<< Other ingredients >>
The near-infrared absorbing composition of the present invention may be used by appropriately selecting other components depending on the purpose, as long as the effects of the present invention are not impaired.
Examples of other components that can be used in combination include a dispersant, a sensitizer, a crosslinking agent (crosslinking agent aqueous solution), acetic anhydride, a silane compound, a curing accelerator, a filler, 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.
These components include, for example, paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding US Patent Application Publication No. 2013/0034812 [0237] to [0309]), JP2008-250074A. Paragraph Nos. 0101 to 0102, Paragraph Nos. 0103 to 0104 of JP 2008-250074, Paragraphs 0107 to 0109 of JP 2008-250074, Paragraphs 0159 to 0184 of JP 2013-195480, etc. The contents of which are incorporated herein by reference.
By appropriately containing these components, properties such as stability and film physical properties of the target near-infrared cut filter can be adjusted.

<Preparation and use of near-infrared absorbing composition>
Since the near-infrared absorbing composition of the present invention can be made into a liquid, for example, a near-infrared cut filter can be easily produced by applying the near-infrared absorbing composition of the present invention to a substrate and drying it. it can.
The infrared absorbing composition is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. If a filter is conventionally used for the filtration use etc., it can be used without being specifically limited. For example, fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon-6 and nylon-6,6, polyolefin resin such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. Filter. Among these materials, polypropylene (including high density polypropylene) is preferable.
The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 2.5 μm, and still more preferably 0.01 to 1.5 μm. By setting the pore diameter of the filter in the above range, it is possible to reliably remove fine foreign matters.
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 pore sizes be larger than the pore size of the first filtering. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co. .
As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is preferably 0.5 to 7.0 μm, more preferably 2.5 to 7.0 μm, and even more preferably 4.5 to 6.0 μm. By setting the pore size of the filter in the above range, foreign substances that obstruct the preparation of a uniform and smooth light-shielding composition are removed in a subsequent step while leaving the component particles contained in the composition mixture. be able to.
For example, after the filtering by the first filter, another component may be added and the second filtering may be performed.
For example, when the infrared absorbing layer is formed by coating, the viscosity of the infrared absorbing composition is preferably in the range of 1 to 3000 mPa · s. The lower limit is preferably 10 mPa · s or more, and more preferably 100 mPa · s or more. The upper limit is preferably 2000 mPa · s or less, and more preferably 1500 mPa · s or less.
The viscosity of the near-infrared absorbing composition of the present invention is preferably 1 to 3000 mPa · s, more preferably 10 to 2000 mPa · s, and more preferably 100 to 1500 mPa · s when a near-infrared cut filter is formed by coating. Is more preferable.
The near-infrared absorbing composition of the present invention is for a near-infrared cut filter on the light-receiving side of a solid-state imaging device, and when forming a near-infrared cut filter by coating, from the viewpoint of thick film formability and uniform coatability, 10 to 3000 mPa · s is preferable, 500 to 1500 mPa · s is more preferable, and 700 to 1400 mPa · s is still more preferable.
Although the total solid content of the near-infrared absorptive composition of this invention is changed by the apply | coating method, it is preferable that it is 1-50 mass%, it is more preferable that it is 1-30 mass%, and 10-30 mass. % Is more preferable.

  Although the use of the near-infrared absorptive composition of this invention is not specifically limited, It can use preferably for formation of a near-infrared cut filter etc. For example, it is preferable for a near-infrared cut filter (for example, for a near-infrared cut filter for a wafer level lens) on the light-receiving side of a solid-state image sensor, a near-infrared cut filter on the back side (the side opposite to the light-receiving side) of the solid-state image sensor Can be used. In particular, it can be preferably used as a near-infrared cut filter on the light receiving side of the solid-state imaging device.

<Near-infrared cut filter>
Next, the near infrared cut filter of the present invention will be described.
The near-infrared cut filter of the present invention is formed by curing the above-described near-infrared absorbing composition of the present invention.

Next, the near infrared cut filter of the present invention will be described.
The near-infrared cut filter of the present invention contains a near-infrared absorbing material, has a film thickness of 300 μm or less, a light transmittance in the wavelength range of 450 to 550 nm of 85% or more, and a light transmittance of wavelength 680 nm of 10%. It has the following spectral characteristics.
In the near-infrared cut filter of the present invention, the light transmittance preferably satisfies at least one of the following conditions (1) to (10), and particularly preferably satisfies all the conditions.
(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 680 nm is preferably 10% or less, more preferably 8% or less, further preferably 6% or less, and particularly preferably 5% or less.
(6) 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.
(7) 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.
(8) 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.
(9) The light transmittance at a wavelength of 850 nm is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
(10) 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.

Although the film thickness of the near-infrared cut filter of this invention can be suitably adjusted according to the objective, 300 micrometers or less are preferable, 200 micrometers or less are more preferable, and 100 micrometers or less are especially preferable. The lower limit of the film thickness of the near-infrared cut filter of the present invention is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, and more preferably 4 μm or more.
The near-infrared cut filter of the present invention has a film thickness of 300 μm or less and a light transmittance in the wavelength range of 400 to 550 nm of 85% or more, preferably 90% or more.
In the near-infrared cut filter of the present invention, the light transmittance at a wavelength of 680 nm is 10% or less, and preferably 8% or less.
The near-infrared cut filter of the present invention has a film thickness of 300 μm or less, and preferably has a light transmittance of 20% or less in a range of at least one wavelength of 700 to 1100 nm. More preferably, the light transmittance is 20% or less.
The near-infrared cut filter of the present invention preferably has a film thickness of 300 μm or less and a light transmittance of 10% or less at at least one point in the wavelength range of 800 to 900 nm, and has a wavelength range of 800 to 900 nm. More preferably, the light transmittance is 10% 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 of the present invention has a function of absorbing / cutting near-infrared rays (a lens for a camera such as a digital camera, a mobile phone, or an in-vehicle camera, an optical lens such as an f-θ lens, a pickup lens) and a semiconductor light receiving device. Optical filters for elements, near-infrared absorbing films and near-infrared absorbing plates that block heat rays for energy saving, agricultural coating agents for selective use of sunlight, recording media that use near-infrared absorbing heat, Used for electronic devices and photographic near infrared filters, protective glasses, sunglasses, heat ray blocking films, optical character reading and recording, confidential document copy prevention, electrophotographic photoreceptors, laser welding, and the like. It is also useful as a noise cut filter for CCD cameras and a filter for CMOS image sensors.

<Method for manufacturing near-infrared cut filter>
The near-infrared cut filter of the present invention is produced through a step of forming a film by applying (preferably a dropping method, coating or printing) the near-infrared absorbing composition of the present invention to a support, and a step of drying the film. it can. About a film thickness, laminated structure, etc., it can select suitably according to the objective. Further, a step of forming a pattern may be performed.
In the step of forming a film, for example, the near-infrared absorbing composition of the present invention is applied to a support using a dropping method (drop cast), a spin coater, a slit spin coater, a slit coater, screen printing, applicator application, etc. Can be implemented. 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 the support so that a uniform film can be obtained 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. There is no restriction | limiting in particular as thickness of the film | membrane after drying, According to the objective, it can select suitably. As thickness of a film | membrane, 1 micrometer-500 micrometers are preferable, for example, 1 micrometer-300 micrometers are more preferable, and 1 micrometer-200 micrometers are especially preferable. In the present invention, even in the case where such a thin film is used, the near-infrared light shielding property can be maintained.
The support may be a transparent substrate made of glass or the like. Moreover, a solid-state image sensor may be sufficient. Moreover, another board | substrate provided in the light-receiving side of the solid-state image sensor may be sufficient. Further, it may be a layer such as a flattening layer provided on the light receiving side of the solid-state imaging device.
In the step of drying the membrane, the drying conditions vary depending on each component, the type of solvent, the use ratio, etc., but are about 60 seconds to 150 ° C. for about 30 seconds to 15 minutes.
As a pattern forming step, for example, a step of applying the near infrared absorbing composition of the present invention on a support to form a film-like composition layer, a step of exposing the composition layer in a pattern, And a method including a step of forming a pattern by developing and removing an unexposed portion. As a pattern forming step, a pattern may be formed by a photolithography method, or a pattern may be formed by a dry etching method.
In the manufacturing method of the near-infrared cut filter, other steps may be included. There is no restriction | limiting in particular as another process, According to the objective, it can select suitably. For example, the surface treatment process of a base material, a pre-heating process (pre-baking process), a hardening process, a post-heating process (post-baking process), etc. are mentioned.

<< Pre-heating process / Post-heating process >>
The heating temperature in the preheating step and the postheating step is preferably 80 to 200 ° C, more preferably 90 ° C to 150 ° C. The heating time in the preheating step and the postheating step is preferably 30 to 240 seconds, more preferably 60 to 180 seconds.
<< Curing treatment 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 a 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.
Examples of the exposure method 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.
120-250 degreeC is preferable and the heating temperature in a whole surface heating has more preferable 160-220 degreeC. 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 to 180 minutes, and more preferably 5 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.

<Camera module and camera module manufacturing method>
The camera module of the present invention includes a solid-state image sensor and a near-infrared cut filter arranged on the light receiving side of the solid-state image sensor.
The method for manufacturing a camera module according to the present invention is a method for manufacturing 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 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 is disposed, for example, above the solid-state image sensor 11, the flattening layer 12 provided on the main surface side (light-receiving side) of the solid-state image sensor, the near-infrared cut filter 13, and the near-infrared cut filter. A lens holder 15 having an imaging lens 14 in the internal space.
In the camera module 10, incident light hν from the outside passes through the imaging lens 14, the near-infrared cut filter 13, and the planarizing layer 12 in order, and then reaches the imaging device portion of the solid-state imaging device 11.
The solid-state image sensor 11 has, for example, an image sensor 16, an interlayer insulating film (not shown), a base layer (not shown), a color filter 17, and an overcoat (not shown) on the main surface of a silicon substrate as a base. The microlens 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 image sensor 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 blocking 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 used in the solder reflow process, the near-infrared cut filter is exposed to a temperature of about 250 to 270 ° C. Therefore, the near-infrared cut filter is also referred to as heat resistance that can withstand the solder reflow process (hereinafter also referred to as “solder reflow resistance”). ).
In this specification, “having solder reflow resistance” means that the characteristics as a near-infrared cut filter are maintained 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, the infrared absorption ability of the near-infrared cut filter may decrease or the function as a film may be insufficient when held under the above conditions.
The present invention also relates to a method for manufacturing a camera module, including a reflow process. 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 base material 20, and a near infrared absorption layer (near infrared cut filter) 21. And an antireflection layer 22 in this order.
The ultraviolet / infrared light reflection film 19 has an effect of imparting or enhancing the function of a near-infrared cut filter. For example, paragraphs 0033 to 0039 of 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 (near infrared cut filter) 21, an antireflection layer 22, a planarization layer 12, an antireflection layer 22, and a transparent substrate. The material 20 and the ultraviolet / infrared light reflection film 19 may be provided in this order.
As shown in FIG. 4, the camera module includes a solid-state imaging device 11, a near infrared absorption layer (near infrared cut filter) 21, an ultraviolet / infrared light reflection film 19, a planarization layer 12, and an antireflection layer 22. And you may have the transparent base material 20 and the reflection preventing layer 22 in this order.

<Compound>
Next, the compound of the present invention will be described.
The compound of this invention is a compound represented by General formula (1) demonstrated in the near-infrared absorptive substance of the near-infrared absorptive composition of this invention, The suitable range is also the same as the range mentioned above.
In the compound of the present invention, since the group represented by R ¹ contains a halogen atom, the detailed reason is not known, but the heat resistance and light resistance can be improved. Moreover, the transmittance in the wavelength range of 650 to 750 nm can be further reduced. In particular, heat resistance can be further improved by incorporating fluorine atoms as halogen atoms. Since the nucleophilicity of the adjacent anion decreases (in other words, the stability of the anion increases) due to the electron-attracting action of the fluorine atom, the compound represented by the general formula (1) is formed by the anion during heating. It is thought that it becomes difficult to be decomposed and heat resistance is improved. And as the number of fluorine atoms increases, the nucleophilicity of the anion decreases, so that the heat resistance is considered to improve.
In the chloroform solution, the compound of the present invention preferably has a maximum absorption wavelength at 600 to 800 nm, more preferably has a maximum absorption wavelength at 600 to 750 nm, and more preferably has a maximum absorption wavelength at 650 to 750 nm. preferable.
The compound of the present invention can be preferably used for forming, for example, a near infrared cut filter that shields light having a wavelength of 600 to 800 nm. It can also be used as a near-infrared absorption filter for solid-state imaging devices such as plasma display panels (PDP) and CCDs, an optical filter for heat ray shielding films, a light-to-heat conversion material for write-once optical discs (CD-R) and flash fusion fixing materials. Can do. It can also be used as an information display material in security ink or invisible barcode ink.

<Photosensitive resin composition>
Next, the photosensitive resin composition of the present invention will be described.
The photosensitive resin composition of this invention is a composition containing the compound represented by General formula (1) demonstrated in the near-infrared absorber of the near-infrared absorptive composition of this invention. The compound represented by general formula (1) is synonymous with the compound represented by general formula (1) described above, and the preferred range is also the same.
Moreover, the photosensitive resin composition of this invention may contain other components other than the compound represented by General formula (1) demonstrated with the near-infrared absorptive composition mentioned above, and the hardening mentioned above. It is preferable to contain a functional compound. The cured film obtained by curing the photosensitive resin composition of the present invention can be used for a near infrared cut filter and the like.

  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. In the following, DMSO is an abbreviation for dimethyl sulfoxide.

原料１は、文献（Ｈｅｌｖｅｔｉｃａ Ｃｈｉｍｉｃａ Ａｃｔａ、第８８巻、第１１３５−１１４３ページ、２００５年）に記載の方法に従い合成した。
原料１ ０．４ｇと、トリフルオロスルホインアミド（東京化成品）０．２１ｇを、クロロホルム２０ｍｌに溶解させ、トリエチルアミン ０．１ｇと触媒量のジメチルアミノピリジンを添加した。攪拌下、加熱還流を３日間行い、冷却後、得られた粗結晶をろ別し、シリカゲルクロマトグラフィー（溶離液クロロホルム、メタノール）にて精製して、目的化合物（青色固体）Ｉ−１７を得た。収率は５５％であった。
ＮＭＲ （４００ＭＨｚ、ＤＭＳＯ−ｄ６）；δ１．３０（ｔ、６Ｈ）、４．２２（ｄ、４Ｈ）、４．９０（ｓ、２Ｈ）、７．１８（ｄ、２Ｈ）、７．３０（ｔ、２Ｈ）、７．３８（ｄ、２Ｈ）、７．８５（ｄ、２Ｈ）
吸収スペクトル（ＤＭＳＯ）を図５に示す。極大吸収波長は６７０ｎｍであった。(Synthesis Example 1) Synthesis of Compound I-17

The raw material 1 was synthesize | combined according to the method as described in literature (Helvetica Chimica Acta, a volume 88, 1135-1143 pages, 2005).
0.4 g of raw material 1 and 0.21 g of trifluorosulfoinamide (Tokyo Chemicals) were dissolved in 20 ml of chloroform, and 0.1 g of triethylamine and a catalytic amount of dimethylaminopyridine were added. Under stirring, heating under reflux is carried out for 3 days. After cooling, the resulting crude crystals are filtered off and purified by silica gel chromatography (eluent chloroform, methanol) to obtain the target compound (blue solid) I-17. It was. The yield was 55%.
NMR (400 MHz, DMSO-d6); δ 1.30 (t, 6H), 4.22 (d, 4H), 4.90 (s, 2H), 7.18 (d, 2H), 7.30 (t 2H), 7.38 (d, 2H), 7.85 (d, 2H)
The absorption spectrum (DMSO) is shown in FIG. The maximum absorption wavelength was 670 nm.

合成例１にならって、化合物Ｉ−２１を合成した。
ＮＭＲ （４００ＭＨｚ、ＤＭＳＯ−ｄ６）；δ１．３０（ｔ、６Ｈ）、４．５０（ｄ、４Ｈ）、４．９５（ｓ、２Ｈ）、７．４０（ｄ、２Ｈ）、７．５２（ｄ、２Ｈ）、７．７０（ｓ、２Ｈ）
吸収スペクトル（ＤＭＳＯ） 極大吸収波長６７０ｎｍ。(Synthesis Example 2) Synthesis of Compound I-21

Following Synthesis Example 1, Compound I-21 was synthesized.
NMR (400 MHz, DMSO-d6); δ 1.30 (t, 6H), 4.50 (d, 4H), 4.95 (s, 2H), 7.40 (d, 2H), 7.52 (d 2H), 7.70 (s, 2H)
Absorption spectrum (DMSO) Maximum absorption wavelength 670 nm.

合成例１にならって、化合物Ｉ−２２を合成した。
ＮＭＲ （４００ＭＨｚ、ＤＭＳＯ−ｄ６）；δ１．２３（ｔ、６Ｈ）、４．３０（ｄ、４Ｈ）、４．７０（ｓ、２Ｈ）、７．２０（ｄ、２Ｈ）、７．５８（ｔ、２Ｈ）、７．９０（ｄ、２Ｈ）、８．０５（ｄ、２Ｈ)，８．２０（ｄ、２Ｈ）
吸収スペクトル（ＤＭＳＯ） 極大吸収波長７００ｎｍ。Synthesis Example 3 Synthesis of Compound I-22

According to Synthesis Example 1, compound I-22 was synthesized.
NMR (400 MHz, DMSO-d6); δ 1.23 (t, 6H), 4.30 (d, 4H), 4.70 (s, 2H), 7.20 (d, 2H), 7.58 (t 2H), 7.90 (d, 2H), 8.05 (d, 2H), 8.20 (d, 2H)
Absorption spectrum (DMSO) Maximum absorption wavelength 700 nm.

<Preparation of photosensitive resin composition>
1.98 parts by mass of the alkali-soluble resin shown below, 1.69 parts by mass of the compounds shown in Table 6, and 0.19 mass of A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) as the polymerizable compound. Part, IRGACURE OXE 01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], manufactured by BASF Japan Ltd.) as a photopolymerization initiator 0.09 Part by mass: 0.01 part by mass of p-methoxyphenol as a polymerization inhibitor, and 1.0% propylene glycol monomethyl ether acetate (PGMEA) solution of MegaFac F781 (manufactured by DIC Corporation) as a fluorosurfactant After mixing and stirring 0.76 parts by mass and 4.53 parts by mass of PGMEA as a solvent, a nylon filter having a pore size of 0.5 μm (Nippon Pole Co., Ltd.) And a photosensitive resin composition was prepared.

比較化合物１：下記構造

比較化合物２：下記構造（Chemical Communication、第49巻、第4764ページ、2013年記載の化合物）

Alkali-soluble resin: The following structure (Mw: 14000, acid value 30 mgKOH / g)

Comparative compound 1: the following structure

Comparative Compound 2: The following structure (compound described in Chemical Communication, 49, 4764, 2013)

Each photosensitive resin composition was apply | coated to the glass substrate using the spin coater (made by Mikasa Co., Ltd.), and the coating film was formed. The thickness of the coating film was adjusted so that the film thickness (average thickness) was 0.8 μm. Next, the coating film was subjected to a heat treatment for 120 seconds using a 100 ° C. hot plate.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), 365 nm wavelength light was exposed at 1000 mJ / cm ² .

<Heat resistance>
After heating the obtained film at 200 ° C. for 5 minutes, the ΔEab value of the color difference before and after the heat resistance test was measured with a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). A smaller ΔEab value indicates better heat resistance.
The ΔEab value is a value obtained from the following color difference formula based on the CIE 1976 (L *, a *, b *) space color system (Japanese Color Society edited by New Color Science Handbook (Showa 60) p.266). .
ΔEab = {(ΔL *) ² + (Δa *) ² + (Δb *) ² } ^1/2
<< Criteria >>
5: ΔEab value <3
4: 3 ≦ ΔEab value <5
3: 5 ≦ ΔEab value <10
2: 10 ≦ ΔEab value <20
1: 20 ≦ ΔEab value <light resistance>
The resulting film was irradiated with 10,000 lux light through a UV cut filter with an Xe lamp for 10 hours, and then the color difference before and after the light resistance test was measured with a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). The ΔEab value was measured.
<< Criteria >>
5: ΔEab value <3
4: 3 ≦ ΔEab value <5
3: 5 ≦ ΔEab value <10
2: 10 ≦ ΔEab value <20
1: 20 ≦ ΔEab value

From the said result, the photosensitive resin composition of Examples 1-3 which used the compound of this invention was excellent in heat resistance and light resistance.
On the other hand, the photosensitive resin compositions of Comparative Examples 1 and 2 that did not contain the compound of the present invention were inferior in heat resistance.

The photosensitive resin compositions of Example 1 and Comparative Examples 1 and 2 were applied to a glass substrate using a spin coater (Mikasa Co., Ltd.) to form a coating film. The thickness of the coating film was adjusted so that the film thickness (average thickness) was 0.8 μm. Next, the coating film was subjected to a heat treatment (Prebake) for 120 seconds using a hot plate at 100 ° C.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), 365 nm wavelength light was exposed at 1000 mJ / cm ² .
The exposed film was heated at 130 ° C. or 200 ° C. for 5 minutes, or at 200 ° C. for 5 minutes, respectively.
After the prebake heat treatment, after prebake, and further heating at 130 ° C. or 200 ° C. for 5 minutes, the light transmittance in the wavelength range of 400 to 1000 nm is measured with an ultraviolet-visible near-infrared spectrophotometer U-4100. Measurement was performed using Hitachi High-Tech (ref. Glass substrate).
The results are shown in FIGS. FIG. 6 is a spectrum diagram showing the light transmittance of a film obtained using the photosensitive resin composition of Example 1, and FIG. 7 was obtained using the photosensitive resin composition of Comparative Example 1. FIG. 8 is a spectrum diagram showing the light transmittance of the film, and FIG. 8 is a spectrum diagram showing the light transmittance of the film obtained using the photosensitive resin composition of Comparative Example 3. 6 to 8, “Prebake” is a spectrum diagram of a film that has been prebaked only, and “130C” is a spectrum of a film that has been further heated at 130 ° C. for 5 minutes after the prebake. “200C” is a spectrum diagram of a film after prebake and further heated at 200 ° C. for 5 minutes.
As shown in FIG. 6, it can be seen that the photosensitive resin composition of the present invention sufficiently absorbs light having a wavelength of 700 nm, for example. Moreover, even if it heats at 200 degreeC, it turns out that the change of an absorption spectrum is small and it is excellent in heat resistance.
On the other hand, the photosensitive composition of Comparative Example 1 has low solubility of Comparative Compound 1 in a solvent, and as shown in FIG. 7, it could not absorb light having a wavelength of 700 nm. Moreover, heat resistance was low, and absorption was lost by heating at 130 ° C. or higher.
Further, as shown in FIG. 8, the photosensitive composition of Comparative Example 2 gave an H-association peak in the vicinity of a wavelength of 600 nm, and the absorption at a wavelength of 700 nm was small. In addition, the peaks around 680 nm and 600 nm fluctuated during heating.

化合物２を１．７ｇと、化合物３を３．０ｇとを、無水酢酸１０ｍｌに加え、１２０℃で１時間加熱攪拌した。その後、反応溶液に酢酸エチルを加え、析出した固体をろ別し、得られたろ物に化合物２を１．７ｇ、ジアザビシクロウンデセン０．５ｍｌ、アセトニトリル６０ｍｌを加え、室温で３時間攪拌し、析出物をろ過で得た。続いて得られた固体０．４ｇをメタノール１００ｍｌに溶かし、酢酸ナトリウムを０．５ｇ加え、室温で２時間攪拌した後、得られた固体をろ過することで、目的物Ｃ−１５を得た。収率は４５％であり、極大吸収波長は、ジメチルスルホキシド（ＤＭＳＯ）中で６２２ｎｍであった。Synthesis Example 4 Synthesis of Compound C-15

1.7 g of compound 2 and 3.0 g of compound 3 were added to 10 ml of acetic anhydride, and the mixture was heated and stirred at 120 ° C. for 1 hour. Thereafter, ethyl acetate was added to the reaction solution, the precipitated solid was filtered off, and 1.7 g of compound 2, 0.5 ml of diazabicycloundecene and 60 ml of acetonitrile were added to the obtained filtrate, and the mixture was stirred at room temperature for 3 hours. The precipitate was obtained by filtration. Subsequently, 0.4 g of the obtained solid was dissolved in 100 ml of methanol, 0.5 g of sodium acetate was added, the mixture was stirred at room temperature for 2 hours, and then the obtained solid was filtered to obtain a target product C-15. The yield was 45%, and the maximum absorption wavelength was 622 nm in dimethyl sulfoxide (DMSO).

上記結果より、化合物Ｃ−１５は、耐熱性および耐光性に優れていた。<Evaluation of heat resistance and light resistance>
In 69.5 parts by mass of ion-exchanged water, 0.5 part by mass of Compound C-15 was dissolved, and 30.0 parts by mass of a 10% by mass aqueous solution of gelatin was added and stirred to prepare a resin composition.
The obtained resin composition was applied to a glass substrate using a spin coater (Mikasa Co., Ltd.) to form a coating film. The thickness of the coating film was adjusted to 0.2 μm. Next, the coating film was subjected to heat treatment for 120 seconds using a 100 ° C. hot plate.
Table 7 shows the results of heat resistance and light resistance tests performed on the obtained film in the same manner as in Example 1.

From the above results, Compound C-15 was excellent in heat resistance and light resistance.

<Synthesis of copper complex>
<< Synthesis of Polymer A-1 >>
Polyethersulfone (manufactured by BASF, Ultrason E6020P) (5.0 g) was dissolved in 46 g of sulfuric acid, and 16.83 g of chlorosulfonic acid was added dropwise at room temperature under a nitrogen stream. After reacting at room temperature for 48 hours, the reaction solution was dropped into 1 L of a hexane / ethyl acetate (1/1) mixture cooled with ice water. The supernatant was removed and the resulting precipitate was dissolved in methanol. The obtained solution was dropped into 0.5 L of ethyl acetate, and the resulting precipitate was collected by filtration. 4.9g of polymer A-1 was obtained by drying the obtained solid under reduced pressure. The sulfonic acid group content (meq / g) in the polymer was calculated by neutralization titration. Further, the weight average molecular weight (Mw) was measured by gel permeation chromatography.

硬化性化合物Ａ：下記化合物（Ｍｗ：２４，０００）

界面活性剤Ａ：オルフィンＥ１０１０（日信化学工業株式会社製）

銅錯体Ａは、以下のようにして合成した。
スルホフタル酸５３．１％水溶液（１３．４９ｇ，２９．１ｍｍｏｌ）をメタノール５０ｍＬに溶かし、この溶液を５０℃に昇温した後、水酸化銅（２．８４ｇ，２９．１ｍｍｏｌ）を加え５０℃で２時間反応させた。反応終了後、エバポレータにて溶剤及び発生した水を留去することで銅錯体Ａ（８．５７ｇ）を得た。<< Synthesis of Copper Complex Cu-1 >>
To 20 g of 20% aqueous solution of polymer A-1, 556 mg of copper hydroxide was added and stirred at room temperature for 3 hours to dissolve the copper hydroxide. As a result, an aqueous solution of a copper complex (hereinafter also referred to as engineering plastic copper complex) Cu-1 was obtained.
<Preparation of near-infrared absorbing composition>
The following components were mixed in the blending amounts described below to prepare a near-infrared absorbing composition 1.
・ Copper complex A (copper complex having the following sulfophthalic acid as a ligand)
-Engineering plastic copper complex Cu-1: 30 parts by mass-Compound I-17: 3 parts by mass-The following curable compound A: 70 parts by mass-The following surfactant A: 0.4 parts by mass-Solvent (water): 50 Part by mass / solvent (PGMEA): 50 parts by mass

Curing compound A: the following compound (Mw: 24,000)

Surfactant A: Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.)

Copper complex A was synthesized as follows.
A 53.1% aqueous solution of sulfophthalic acid (13.49 g, 29.1 mmol) was dissolved in 50 mL of methanol, and the temperature of this solution was raised to 50 ° C. Then, copper hydroxide (2.84 g, 29.1 mmol) was added, The reaction was performed for 2 hours. After completion of the reaction, the solvent and generated water were distilled off with an evaporator to obtain a copper complex A (8.57 g).

<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 near-infrared absorptive composition 1 was dripped. 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 191 μm. It was found that the obtained near-infrared cut filter had a transmittance of 90% or more in the entire wavelength range of 400 to 550 nm and a transmittance of 10% or less at a wavelength of 680 nm.

  Even when compound I-17 is changed to compound I-21, I-22 or compound C-15 in the preparation of the near infrared absorbing composition, the near infrared absorbing cut filter using the near infrared absorbing composition 1 The same excellent effect was obtained. Further, even when Compound I-17 is changed to D-1 to D-139 described in paragraphs 0049 and after of JP-A-2009-263614, a near-infrared absorption cut using the near-infrared absorbing composition 1 is used. The same effect as the filter was obtained.

Even when the copper complex A is changed to a copper complex (17 species) having the following sulfonic acid compound as a ligand in the preparation of the near infrared absorbing composition, the near infrared absorption using the near infrared absorbing composition 1 is used. As with the cut filter, an excellent effect was obtained.

  In the preparation of the near-infrared absorbing composition, 5 parts by mass of a polymerizable compound was further added. The following compounds were used as the polymerizable compound. KAYARAD D-330, D-320, D-310, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (above, Nippon Kayaku Co., Ltd.), M-305, M-510, M -520, M-460 (manufactured by Toa Gosei), A-TMMT (manufactured by Shin-Nakamura Chemical), SR-494 (manufactured by Sartomer), Denacol EX-212L (manufactured by Nagase ChemteX Corporation), JER-157S65 (Mitsubishi) (Chemical Co., Ltd.). Even in these cases, excellent effects were obtained in the same manner as the near-infrared cut filter using the near-infrared absorbing composition 1.

  In the preparation of the near-infrared absorbing composition, the surfactant A is selected from Megafac F171 (manufactured by DIC Corporation), Surfinol 61 (manufactured by Nissin Chemical Co., Ltd.) or Tore Silicone SF8410 (Toray Dow Corning Corporation). Even when it was changed to “made”, an excellent effect was obtained in the same manner as the near-infrared cut filter using the near-infrared absorbing composition 1.

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, 17 Color filter, 18 Micro lens, 19 Ultraviolet / infrared light reflection film, 20 Transparent substrate, 21 Near infrared absorbing layer, 22 Antireflection layer

Claims (17)

A near-infrared cut containing a near-infrared absorbing material, having a film thickness of 300 μm or less, a light transmittance in the wavelength range of 450 to 550 nm of 85% or more, and a light transmittance of wavelength 680 nm of 10% or less. A filter,
The near-infrared absorbing material contains a compound represented by the following general formula (1); a near-infrared cut filter;

In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), and R ¹ has one or more halogen atoms. An alkyl group, an aryl group having one or more halogen atoms, or a heterocyclic group having one or more halogen atoms;

In general formula (2), Z ¹ represents a nonmetallic atom group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, Represents a connecting hand with the general formula (1). The near-infrared cut filter according to claim 1, wherein the group represented by the general formula (2) is represented by the following general formula (3) or the general formula (4);

In the general formulas (3) and (4), R ¹¹ represents an alkyl group, an alkenyl group or an aralkyl group, R ¹² represents a substituent, and when m is 2 or more, R ¹² are linked to each other. X may represent a nitrogen atom or CR ¹³ R ¹⁴ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent,
m represents an integer of 0 to 4, and the wavy line represents a connecting hand with the general formula (1). The near-infrared cut filter according to claim 1 or 2, wherein R ¹ in the general formula (1) is an alkyl group having one or more halogen atoms or an aryl group having one or more halogen atoms. Containing a copper compound as the near infrared absorbing material, wherein the copper compound is at least one selected from phosphorus-containing copper complexes, copper sulfonate complex and copper carboxylate complexes, either of claims 1-3 1 The near-infrared cut filter according to item. The near-infrared cut filter according to claim 4 , wherein the copper compound includes a polymer-type copper compound obtained by a reaction between a polymer containing an acid group or a salt thereof and a copper component. Thickness is 200μm or less, the near-infrared cut filter according to any one of claims 1-5. The near-infrared cut filter according to any one of claims 1 to 6 , wherein the light transmittance in a wavelength range of 400 to 575 nm is 85% or more. The near-infrared cut filter according to any one of claims 1 to 7 , wherein light transmittance in a wavelength range of 450 to 550 nm is 90% or more. The near-infrared cut filter according to any one of claims 1 to 8 , wherein the light transmittance in a wavelength range of 700 to 1100 nm is 20% or less. The near-infrared cut filter according to any one of claims 1 to 9 , wherein light transmittance in a wavelength range of 800 to 900 nm is 10% or less. When a film containing a near-infrared absorbing material and having a film thickness of 300 μm or less is formed, the light transmittance in the wavelength range of 450 to 550 nm is 85% or more, and the light transmittance at a wavelength of 680 nm is 10% or less. A near-infrared absorbing composition,
As the near-infrared absorbing substance, a near-infrared absorbing composition containing a compound represented by the following general formula (1);

In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), and R ¹ has one or more halogen atoms. An alkyl group, an aryl group having one or more halogen atoms, or a heterocyclic group having one or more halogen atoms;

In general formula (2), Z ¹ represents a nonmetallic atom group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, Represents a connecting hand with the general formula (1). Furthermore, the near-infrared absorption composition of Claim 11 containing the copper complex which uses at least 1 sort (s) chosen from a sulfonic acid and carboxylic acid as a ligand as the said near-infrared absorption substance. A photosensitive resin composition containing a compound represented by the following general formula (1);

In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), and R ¹ has one or more halogen atoms. An alkyl group, an aryl group having one or more halogen atoms, or a heterocyclic group having one or more halogen atoms;

In general formula (2), Z ¹ represents a nonmetallic atom group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, Represents a connecting hand with the general formula (1). A cured film obtained by curing the photosensitive resin composition according to claim 13 . A compound represented by the following general formula (1);

In the general formula (1), A ¹ and A ² are each independently an aryl group, a heterocyclic group or a group represented by the following general formula (2), and R ¹ has one or more halogen atoms. An alkyl group, an aryl group having one or more halogen atoms, or a heterocyclic group having one or more halogen atoms;

In general formula (2), Z ¹ represents a nonmetallic atom group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, Represents a connecting hand with the general formula (1). The camera module which has a solid-state image sensor and the near-infrared cut off filter of any one of Claims 1-10 arrange | positioned at the light-receiving side of the said solid-state image sensor. 17. The method of manufacturing a camera module according to claim 16 , wherein a step of forming a near-infrared cut filter by applying the near-infrared absorbing composition according to claim 11 or 12 on the light receiving side of the solid-state imaging device. A method for manufacturing a camera module.

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