JP5601768B2 - Near-infrared absorbing composition, near-infrared absorbing coating material, and production method thereof - Google Patents

Description

The present invention, near-infrared absorbing composition relates near infrared absorbing coating and methods for their preparation, and more particularly high visible light transmittance and light resistance and near-infrared-absorbing composition having both moisture and heat resistance, the near infrared absorbing coating material And a manufacturing method thereof .

  Near-infrared absorbing dyes are used as optical filters as plasma display panels (PDP) and infrared cut films for CCDs and heat ray shielding films, and as light-to-heat conversion materials as write-once optical discs (CD-R) and flash fusion fixing materials. It is used as an information display material as security ink and invisible barcode ink. It is invisible in addition to having strong absorption in the near-infrared region, especially as a characteristic feature of near-infrared pigments. There is a high demand for invisibility. At the same time, high fastness is required as a performance required for all dyes.

Examples of dyes with excellent invisibility that have almost no absorption in the wavelength region of 400 nm to 700 nm include cyanine methine dyes and J-aggregates thereof, but long methine conjugated chains are flexible and absorb due to isomerization. Degradation due to changes in shape, reaction with heat, oxygen, and nucleophiles is likely to occur, and the fastness is low.
Highly robust near-infrared absorbing dyes with a rigid skeleton include vanadyl naphthalocyanine dyes marketed by Nippon Shokubai Co., Ltd. and quartertalylene dyes marketed by BASF Corp., but vanadyl phthalocyanine is invisible. Insufficient sex. Further, although quarterrylene has good invisibility in a molecular dispersion state such as a solution, when the concentration is increased, absorption occurs in the visible region due to association, the invisibility is lost, and the use form is limited.
As a dye that has excellent invisibility and covers the infrared region widely, there are diimonium dyes marketed by Nippon Kayaku Co., Ltd., etc., but they are easy to be reduced, their fastness is insufficient, and their usage is limited. Will be.
As described above, no near-infrared dye that achieves both invisibility and fastness has been put on the market, and the development of a near-infrared absorbing dye that achieves both of these performances is desired.

On the other hand, as an application example of near-infrared absorption dyes, Patent Document 1 or 2 discloses a film having a near-infrared absorption filter function by dissolving or dispersing an organic pigment together with an organic solvent and a binder resin and applying it to the film. Examples of fabrication are known.
However, this mode of use has the disadvantage that it has a large impact on the environment due to the use of an organic solvent. In addition, the manufacturing equipment needs to be explosion-proof equipment, which requires a large capital investment.

Further, a water-soluble dye as exemplified in Patent Document 3 or 4 is dissolved in water together with a water-soluble binder, specifically gelatin, and applied to the film to form a film having a near-infrared absorption filter function. It has been proposed to use it.
However, regarding water-soluble dyes that can be applied to a film without using a large amount of organic solvent, there has been a problem that durability, in particular, near-infrared absorptivity decreases under high temperature and high humidity.
Japanese Patent Laid-Open No. 11-231126 JP 2002-138203 A JP-A-11-109126 JP 2001-228324 A

An object of the present invention, while having a high invisibility and near infrared absorptivity, less negative environmental effects, the near-infrared-absorbing composition and a sufficient light resistance and moist heat resistance, the near infrared ray absorbing composition It is in providing the coating material to contain , the manufacturing method of this near-infrared absorption composition, and the manufacturing method of this near-infrared absorption coating material .

As a result of intensive studies, the present inventors have made the near-infrared absorbing compound decomposed by allowing the near-infrared absorbing compound to exist in a matrix made of a hydrophobic polymer (preferably an aqueous dispersion of an organic resin). It was found that the durability can be improved by suppressing. Further, it has been found that fastness can be improved by using a near-infrared absorbing compound in the form of dispersed fine particles. Furthermore, it discovered that the fastness of a coating film could be improved by performing heat drying when producing the coating film containing this near-infrared absorption composition. The present invention has been completed based on these findings.
The problems of the present invention have been solved by the following means.
<1> A near-infrared absorbing composition containing at least a near-infrared absorbing compound represented by the following general formula (1 ′) and a hydrophobic polymer.

(Wherein R ^1a and R ^1b may be the same or different and each independently represents an alkyl group, an aryl group or a heteroaryl group which may have a substituent selected from the following substituent group) R ² and R ³ each independently represents a hydrogen atom , cyano group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, carboxyl group or heterocyclic group , One is an electron-withdrawing group having a Hammett's σp value of 0.2 or more , and R ² and R ³ may combine to form a ring, where R ⁴ is a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl. Represents a group, a substituted boron or a metal atom, and may be covalently or coordinately bonded to R ^1a , R ^1b and / or R ^3. )
(Substituent group)
Alkyl group, alkenyl group, alkynyl group, aryl group, branched alkoxy group, aryloxy group, aromatic heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, Sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group , Heterocyclic group

（式中、Ｒ ^1a 及びＲ ^1b は同じであっても異なっても良く、各々独立にアルキル基、アリール基またはヘテロアリール基を表す。Ｒ ² 及びＲ ³ は各々独立に水素原子、シアノ基、アシル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アルキルスルホニル基、アリールスルホニル基、スルファモイル基、カルボキシル基またはヘテロ環基を表し、少なくとも一方はＨａｍｍｅｔｔのσｐ値が０．２以上の電子吸引性基であり、Ｒ ² 及びＲ ³ は結合して環を形成しても良い。Ｒ ⁴ は水素原子、アルキル基、アリール基、ヘテロアリール基、置換ホウ素または金属原子を表し、Ｒ ^1a 、Ｒ ^1b 及び／又はＲ ³ と共有結合もしくは配位結合しても良い。）
＜４＞前記Ｒ ^1a 及びＲ ^1b におけるアリール基が、下記置換基群から選択される置換基を有してもよいアリール基であることを特徴とする＜３＞項に記載の近赤外線吸収組成物。
〔置換基群〕
アルキル基、アルケニル基、アルキニル基、アリール基、分岐アルコキシ基、アリールオキシ基、芳香族ヘテロ環オキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、アシルアミノ基、アルコキシカルボニルアミノ基、スルホニルアミノ基、スルファモイル基、カルバモイル基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルホニル基、スルフィニル基、ウレイド基、ヒドロキシ基、メルカプト基、ハロゲン原子、シアノ基、スルホ基、カルボキシル基、ニトロ基、ヘテロ環基
＜５＞前記Ｒ ^４ が置換ホウ素であることを特徴とする＜１＞〜＜４＞のいずれか１項に記載の近赤外線吸収組成物。
＜６＞前記近赤外線吸収化合物が、分散剤で分散され、水性分散微粒子状態で存在することを特徴とする＜１＞〜＜５＞のいずれか１項に記載の近赤外線吸収組成物。
＜７＞前記疎水性ポリマーが、有機樹脂の水性分散物を形成してなることを特徴とする＜１＞〜＜６＞のいずれか１項に記載の近赤外線吸収組成物。
<2> The near-infrared absorbing composition according to <1>, wherein the near-infrared absorbing compound is present in an aqueous dispersed fine particle state.
<3> A near-infrared absorbing composition containing at least a near-infrared absorbing compound represented by the following general formula (1) and a hydrophobic polymer,
The near-infrared absorbing compound is present in the form of an aqueous dispersion fine particle;
A near-infrared absorbing composition, wherein the fine particles have a volume average particle diameter of 10 nm to 250 nm.

(In the formula, R ^1a and R ^1b may be the same or different and each independently represents an alkyl group, an aryl group or a heteroaryl group. R ² and R ³ each independently represent a hydrogen atom, a cyano group, Represents an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a carboxyl group, or a heterocyclic group, at least one of which is an electron-withdrawing group having a Hammett σp value of 0.2 or more R ² and R ³ may combine to form a ring, and R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a substituted boron or a metal atom, and R ^1a , R ^1b and And / or R ³ may be covalently bonded or coordinated.)
<4> The near-infrared absorbing composition according to <3 >, wherein the aryl group in R ^1a and R ^1b is an aryl group which may have a substituent selected from the following substituent group: object.
(Substituent group)
Alkyl group, alkenyl group, alkynyl group, aryl group, branched alkoxy group, aryloxy group, aromatic heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, Sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group , Heterocyclic group
<5> The near-infrared absorbing composition according to any one of <1> to <4>, wherein R ⁴ is substituted boron.
<6> The near-infrared absorbing composition according to any one of <1> to <5>, wherein the near-infrared absorbing compound is dispersed in a dispersant and is present in an aqueous dispersed fine particle state.
< 7 > The near-infrared absorbing composition according to any one of <1> to < 6 > , wherein the hydrophobic polymer forms an aqueous dispersion of an organic resin.

（式中、Ｒ ^1a 及びＲ ^1b は同じであっても異なっても良く、各々独立にアルキル基、アリール基またはヘテロアリール基を表す。Ｒ ² 及びＲ ³ は各々独立に水素原子、シアノ基、アシル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アルキルスルホニル基、アリールスルホニル基、スルファモイル基、カルボキシル基またはヘテロ環基を表し、少なくとも一方はＨａｍｍｅｔｔのσｐ値が０．２以上の電子吸引性基であり、Ｒ ² 及びＲ ³ は結合して環を形成しても良い。Ｒ ⁴ は水素原子、アルキル基、アリール基、ヘテロアリール基、置換ホウ素、金属原子を表し、Ｒ ^1a 、Ｒ ^1b 及び／又はＲ ³ と共有結合もしくは配位結合しても良い。）
［製造工程］
［１］上記近赤外線吸収化合物を水中で分散して水性分散液を得る工程
［２］前記工程で得た近赤外線吸収化合物微粒子の水性分散液に疎水性ポリマーの水性分散物を添加する工程
＜１２＞前記Ｒ ^1a 及びＲ ^1b におけるアリール基が、下記置換基群から選択される置換基を有してもよいアリール基であることを特徴とする＜１１＞項に記載の近赤外線吸収組成物の製造方法。
〔置換基群〕
アルキル基、アルケニル基、アルキニル基、アリール基、分岐アルコキシ基、アリールオキシ基、芳香族ヘテロ環オキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、アシルアミノ基、アルコキシカルボニルアミノ基、スルホニルアミノ基、スルファモイル基、カルバモイル基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルホニル基、スルフィニル基、ウレイド基、ヒドロキシ基、メルカプト基、ハロゲン原子、シアノ基、スルホ基、カルボキシル基、ニトロ基、ヘテロ環基
＜１３＞前記Ｒ ^４ が置換ホウ素であることを特徴とする＜１１＞または＜１２＞項に記載の近赤外線吸収組成物の製造方法。
＜１４＞前記近赤外線吸収化合物を、分散剤で分散し、前記近赤外線吸収組成物中に水性分散微粒子状態で存在することを特徴とする＜１１＞〜＜１３＞のいずれか１項に記載の近赤外線吸収組成物の製造方法。
＜１５＞前記微粒子の体積平均粒子径が１０ｎｍ以上２５０ｎｍ以下であることを特徴とする＜１１＞〜＜１４＞のいずれか１項に記載の近赤外線吸収組成物の製造方法。
＜１６＞前記疎水性ポリマーが、アクリル樹脂またはウレタン樹脂を含有することを特徴とする＜１１＞〜＜１５＞のいずれか１項に記載の近赤外線吸収組成物の製造方法。
＜１７＞支持体上に、＜１１＞〜＜１６＞のいずれか１項に記載の製造方法により得た近赤外線吸収組成物を用いて近赤外線吸収層を形成する工程を有し、該工程において、加熱乾燥を行うことを特徴とする近赤外線吸収塗布物の製造方法。
＜１８＞前記赤外線吸収塗布物の可視光線の吸収率が３０％以下であることを特徴とする＜１７＞項に記載の近赤外線吸収塗布物の製造方法。
< 8 > The near-infrared absorbing composition according to any one of <1> to < 7 >, wherein the hydrophobic polymer contains an acrylic resin or a urethane resin.
< 9 > A near-infrared absorbing coated material comprising a near-infrared absorbing layer formed using the near-infrared absorbing composition according to any one of <1> to < 8 > on a support. .
< 10 > The near-infrared absorbing coated article according to < 9 >, wherein the visible light absorption is 30% or less.
< 11 > A method for producing a near-infrared absorbing composition comprising at least a near-infrared absorbing compound and a hydrophobic polymer,
The near-infrared absorbing compound is a compound represented by the following general formula (1),
A method for producing a near-infrared absorbing composition comprising at least the following steps [1] and [2].

(In the formula, R ^1a and R ^1b may be the same or different and each independently represents an alkyl group, an aryl group or a heteroaryl group. R ² and R ³ each independently represent a hydrogen atom, a cyano group, Represents an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a carboxyl group, or a heterocyclic group, at least one of which is an electron-withdrawing group having a Hammett σp value of 0.2 or more R ² and R ³ may combine to form a ring, and R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a substituted boron, a metal atom, R ^1a , R ^1b and And / or R ³ may be covalently bonded or coordinated.)
[Manufacturing process]
[1] A step of obtaining an aqueous dispersion by dispersing the near-infrared absorbing compound in water.
[2] A step of adding an aqueous dispersion of a hydrophobic polymer to an aqueous dispersion of near-infrared absorbing compound fine particles obtained in the above step
<12> The near-infrared absorbing composition according to <11 >, wherein the aryl group in R ^1a and R ^1b is an aryl group which may have a substituent selected from the following substituent group: Manufacturing method.
(Substituent group)
Alkyl group, alkenyl group, alkynyl group, aryl group, branched alkoxy group, aryloxy group, aromatic heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, Sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group , Heterocyclic group
<13> The method for producing a near-infrared absorbing composition according to <11> or <12 >, wherein R ⁴ is substituted boron.
<14> The <11> to <13>, wherein the near-infrared absorbing compound is dispersed with a dispersant and is present in an aqueous dispersed fine particle state in the near-infrared absorbing composition. Of manufacturing a near infrared ray absorbing composition.
<15> The method for producing a near-infrared absorbing composition according to any one of <11> to <14>, wherein the fine particles have a volume average particle diameter of 10 nm to 250 nm.
<16> The method for producing a near-infrared absorbing composition according to any one of <11> to <15>, wherein the hydrophobic polymer contains an acrylic resin or a urethane resin.
<17> A step of forming a near-infrared absorbing layer using the near-infrared absorbing composition obtained by the production method according to any one of <11> to <16> on a support, The method for producing a near-infrared-absorbing coated article, wherein the drying is performed by heating.
<18> The method for producing a near-infrared-absorbing coating according to <17>, wherein the infrared-absorbing coating has a visible light absorptivity of 30% or less.

The near-infrared absorbing composition of the present invention has high invisibility and near-infrared absorbing ability, has little adverse effect on the environment, has sufficient light resistance and moist heat resistance, and includes the near-infrared absorbing composition. Things can be provided.
Further, the near-infrared absorbing composition of the present invention uses an aqueous dispersion of the near-infrared absorbing compound and the hydrophobic polymer, so that complicated equipment such as an organic solvent-based coating equipment is required for coating. do not do. In addition, the use of an organic solvent can be remarkably reduced, or it can be produced without using it at all, and the environmental load can be reduced as compared with organic solvent-based coating.
Moreover, the near-infrared absorption coating material of this invention can suppress the fall of the near-infrared absorptivity after a preservation | save under high temperature and high humidity, and the fall of the near-infrared absorptivity by light.
Furthermore, the near-infrared absorbing coated product of the present invention can provide an optical filter excellent in durability at a low cost.

  The near-infrared absorbing composition of the present invention is characterized by containing at least a near-infrared absorbing compound represented by the general formula (1) and a hydrophobic polymer. Further, other materials may be included as appropriate. By allowing the near-infrared absorbing compound to be present in the matrix made of the hydrophobic polymer, it is possible to constitute a highly robust near-infrared absorbing composition by suppressing decomposition of the near-infrared absorbing compound.

(I) Near-infrared absorbing compound Hereinafter, the near-infrared absorbing compound represented by the general formula (1) will be described.

(In the formula, R ^1a and R ^1b may be the same or different and each independently represents an alkyl group, an aryl group or a heteroaryl group. R ² and R ³ each independently represents a hydrogen atom or a substituent. And at least one is an electron-withdrawing group, and R ² and R ³ may combine to form a ring, and R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a substituted boron, or a metal atom. And R ^1a , R ^1b and / or R ³ may be covalently bonded or coordinated.)

In general formula (1), the alkyl group represented by R ^1a and R ^1b is preferably 1 to 30 carbon atoms (in the present invention, “A to B” is used to mean “A or more and B or less”. ), More preferably an alkyl group having 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl. , Cyclopropyl, cyclopentyl, cyclohexyl and the like.
Moreover, as an aryl group represented by R ^{< 1a>} , R ^<1b >, Preferably it is C6-C30, More preferably, it is C6-C20, Most preferably, it is a C6-C12 aryl group, for example, phenyl, o-methylphenyl, p-methylphenyl, biphenyl, naphthyl, anthranyl, phenanthryl and the like can be mentioned.
The heteroaryl group represented by R ^1a and R ^1b is preferably a heteroaryl group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of the hetero atom include a nitrogen atom, an oxygen atom, It is a sulfur atom. Specific examples include imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, benzthiazolyl, naphthothiazolyl, benzoxazolyl, m-carbazolyl, azepinyl and the like.
R ^1a and R ^1b in the general formula (1) may be the same as or different from each other.

R ² and R ³ each independently represent a hydrogen atom or a substituent, at least one of which is an electron-withdrawing group, and R ² and R ³ may combine to form a ring. Examples of the substituent include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably carbon number). 2-10, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably carbon number). 2-10, for example, propargyl, 3-pentynyl, etc.), aryl group (preferably having 6 carbon atoms) 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, biphenyl, naphthyl, anthranyl, phenanthryl, etc.), amino group (preferably carbon Number 0 to 30, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, including alkylamino group, arylamino group and heterocyclic amino group, such as amino, methylamino, dimethylamino, diethylamino , Dibenzylamino, diphenylamino, ditolylamino, etc.), an alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms such as methoxy, Ethoxy, butoxy, 2-ethylhexyloxy, etc.), ants Ruoxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.) An aromatic heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy and the like. ),

An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group ( Preferably it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and the like, and an aryloxycarbonyl group (preferably having a carbon number). 7 to 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl, and acyloxy groups (preferably 2 to 30 carbon atoms, more preferably carbon atoms). 2 to 20, particularly preferably 2 to 10 carbon atoms, for example, acetoxy, benzoyloxy An acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino). An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms such as methoxycarbonylamino), aryloxycarbonylamino group (Preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino), sulfonylamino group (preferably 1 carbon atom) To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, Methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl groups (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methyl And carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, Methylthio, ethylthio, etc.), ants Ruthio group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenylthio and the like. ),

Aromatic heterocyclic thio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolyl And sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl). ), Sulfinyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.) A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, Ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example diethyl phosphorus Acid amide, phenylphosphoric acid amide, etc.), hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxam An acid group, a sulfino group, a hydrazino group, an imino group, a heterocyclic group (preferably having a carbon number of 1 to 30, more preferably a carbon number of 1 to 12, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, Specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, ben Oxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, Examples thereof include trimethylsilyl and triphenylsilyl). These substituents may be further substituted.

The electron-withdrawing group represented by R ² or R ³ preferably represents an electron-withdrawing group having a Hammett σp value (sigma para value) of 0.2 or more. For example, a cyano group, an acyl group, an alkyloxycarbonyl group Aryloxycarbonyl group, sulfamoyl group, sulfinyl group, heterocyclic group and the like. These electron withdrawing groups may be further substituted.

  Hammett's substituent constant σ value will be described. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σp value and σm value, and these values can be found in many general books. For example, J. et al. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Areas of Chemistry”, No. 122, 96-103, 1979 (Nankodo), Chem. Rev. 1991, 91, 165-195. The substituent having Hammett's substituent constant σp value of 0.2 or more in the present invention is an electron-attracting group. The σp value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more.

Specific examples include a cyano group (0.66), a carboxyl group (—COOH: 0.45), an alkoxycarbonyl group (—COOMe: 0.45), an aryloxycarbonyl group (—COOPh: 0.44), and a carbamoyl group (—CONH ₂ : 0.36). , An alkylcarbonyl group (—COMe: 0.50), an arylcarbonyl group (—COPh: 0.43), an alkylsulfonyl group (—SO ₂ Me: 0.72), an arylsulfonyl group (—SO ₂ Ph: 0.68), and the like. In the present specification, Me represents a methyl group, and Ph represents a phenyl group. The values in parentheses are the σp values of typical substituents in Chem. Rev. 1991, Vol. 91, pp. 165-195.

Further, when R ² and R ³ are combined to form a ring, a 5- to 7-membered ring (preferably a 5- to 6-membered ring) is formed, and the formed ring is usually a merocyanine dye and an acidic nucleus. Are preferably used, and specific examples thereof include the following.
(A) 1,3-dicarbonyl nucleus: For example, 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6- Zeon etc.
(B) pyrazolinone nucleus: for example 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazoyl) -3-methyl-2 -Pyrazolin-5-one and the like.
(C) Isoxazolinone nucleus: For example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one and the like.
(D) Oxindole nucleus: For example, 1-alkyl-2,3-dihydro-2-oxindole and the like.
(E) 2,4,6-triketohexahydropyrimidine nucleus: for example, barbituric acid or 2-thiobarbituric acid and its derivatives. Examples of the derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl, 1,3-diphenyl, 1,3-diaryl compounds such as 1,3-di (p-chlorophenyl) and 1,3-di (p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, Examples include 1,3-di (2-pyridyl) 1,3-diheterocyclic substituents and the like.
(F) 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and its derivatives. Examples of the derivatives include 3-alkylrhodanine such as 3-methylrhodanine, 3-ethylrhodanine and 3-allylrhodanine, 3-arylrhodanine such as 3-phenylrhodanine, and 3- (2-pyridyl) rhodanine. And the like.
(G) 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazoledione nucleus: for example, 3-ethyl-2-thio-2,4-oxazolidinedione and the like.
(H) Tianaphthenone nucleus: For example, 3 (2H) -thianaphthenone-1,1-dioxide and the like.
(I) 2-thio-2,5-thiozolidinedione nucleus: For example, 3-ethyl-2-thio-2,5-thiazolidinedione and the like.
(J) 2,4-thiozolidinedione nucleus: For example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione and the like.
(K) Thiazolin-4-one nucleus: For example, 4-thiazolinone, 2-ethyl-4-thiazolinone and the like.
(L) 4-thiazolidinone nucleus: for example, 2-ethylmercapto-5-thiazoline-4-one, 2-alkylphenylamino-5-thiazoline-4-one, and the like.
(M) 2,4-imidazolidinedione (hydantoin) nucleus: for example, 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, etc.
(N) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione Such.
(O) Imidazolin-5-one nucleus: For example, 2-propylmercapto-2-imidazolin-5-one and the like.
(P) 3,5-pyrazolidinedione nucleus: for example, 1,2-diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione, and the like.
(Q) Benzothiophen-3-one nucleus: for example, benzothiophen-3-one, oxobenzothiophen-3-one, dioxobenzothiophen-3-one and the like.
(R) Indanone nucleus: For example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, 3,3-dimethyl-1-indanone, and the like.

Note that the σp values of R ² and R ^{3 in} the case of forming a ring cannot be defined, but in the present invention, it is considered that R ² and R ³ are each substituted with a partial structure of the ring. In this case, the σp value is defined. For example, when a 1,3-indandione ring is formed, it is considered that R ² and R ³ are each substituted with a benzoyl group.

The ring formed by combining R ² and R ³ is preferably a 1,3-dicarbonyl nucleus, a pyrazolinone nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body), 2- Thio-2,4-thiazolidinedione nucleus, 2-thio-2,4-oxazolidinedione nucleus, 2-thio-2,5-thiazolidinedione nucleus, 2,4-thiazolidinedione nucleus, 2,4-imidazolidinedione nucleus 2-thio-2,4-imidazolidinedione nucleus, 2-imidazolin-5-one nucleus, 3,5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus, or indanone nucleus, more preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine nucleus (including thioketone body), 3,5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus Or the Indanone nucleus.

R ³ is particularly preferably a heterocycle.
Two R ² in the general formula (1) may be the same or different from each other, and two R ³ may be the same or different from each other.

The alkyl group, aryl group, and heteroaryl group represented by R ⁴ have the same meanings as the substituents described for R ^1a and R ^1b , and the preferred ranges are also the same. The substituent of the substituted boron represented by R ⁴ has the same meaning as the substituent described above for R ² and R ³ , and is preferably an alkyl group, an aryl group, or a heteroaryl group. The metal atom represented by R ⁴ is preferably a transition metal, magnesium, aluminum, calcium, barium, zinc, or tin, and more preferably aluminum, zinc, tin, vanadium, iron, cobalt, nickel, copper Palladium, iridium, or platinum, particularly preferably aluminum, zinc, vanadium, iron, copper, palladium, iridium, or platinum.
R ⁴ may be covalently bonded or coordinated to R ^1a , R ^1b and / or R ³ .
Two R ⁴ in the general formula (1) may be the same as or different from each other.

  The compound represented by the general formula (1) is preferably a near-infrared absorbing compound represented by any of the following general formulas (2), (3), or (4).

(In the formula, Z ^1a and Z ^1b each independently represent an atomic group that forms an aryl ring or a heteroaryl ring. R ^5a and R ^5b each independently represent an aryl group having 6 to 20 carbon atoms, or 4 to 20 carbon atoms. Heteroaryl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, a carboxyl group, a carbamoyl group having 1 to 20 carbon atoms, a halogen atom, or cyano Any one of the groups, R ^5a or R ^5b and Z ^1a or Z ^1b may combine to form a condensed ring, R ²² and R ²³ each independently represent a cyano group, Represents an acyl group having 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl or arylsulfinyl group having 1 to 10 carbon atoms, or a nitrogen-containing heteroaryl group having 3 to 20 carbon atoms, or R ²² and R ²³ are bonded Cyclic acid .R ⁴ representing the nuclei of hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, a metal atom, or a halogen atom as a substituent, the carbon number This represents a substituted boron having an alkyl group of 1 to 10, an aryl group of 6 to 20 carbon atoms, or a heteroaryl group of 4 to 20 carbon atoms, and may have a covalent bond or a coordinate bond with R ²³ . The compound may further have a substituent.)

(In the formula, R ^31a and R ^31b each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms. R ³² represents a cyano group or a carbon atom. Represents an acyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl or arylsulfinyl group having 1 to 10 carbon atoms, or a nitrogen-containing heteroaryl group having 3 to 10 carbon atoms R ⁶ and R ⁷ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a heteroaryl group having 4 to 10 carbon atoms, and R ⁶ and R ⁷ are bonded to form a ring. The ring to be formed is an alicyclic ring having 5 to 10 carbon atoms, an aryl ring having 6 to 10 carbon atoms, or a heteroaryl ring having 3 to 10 carbon atoms, wherein R ⁸ and R ⁹ are each independently carbon. An alkyl group having 1 to 10 carbon atoms and 1 to 10 carbon atoms Represents an alkoxy group, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 10 carbon atoms, X represents an oxygen atom, a sulfur atom, -NR-, -CRR'-, and R and R 'represent hydrogen Represents an atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.)

(In the formula, R ^41a and R ^41b represent different groups, and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. R ⁴² represents cyano. group represents an acyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, alkylsulfinyl or arylsulfinyl group having 1 to 10 carbon atoms, or a nitrogen-containing heteroaryl group having 3 to 10 carbon atoms .Z ² Represents an atomic group that forms a nitrogen-containing hetero 5 or 6-membered ring with —C═N—, and the nitrogen-containing hetero ring includes a pyrazole ring, a thiazole ring, an oxazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, and a triazole. A ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a benzo-fused ring or a naphtho-fused ring thereof, or a complex of these condensed rings, and R ⁴⁴ represents a hydrogen atom. Children, alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, heteroaryl groups having 4 to 20 carbon atoms, metal atoms, or halogen atoms as substituents, alkyl groups having 1 to 10 carbon atoms, carbon This represents a substituted boron having an aryl group of 6 to 20 or a heteroaryl group of 4 to 20 carbon atoms, and may have a covalent bond or a coordinate bond with the nitrogen-containing heterocycle formed by Z ² . The compound may further have a substituent.)

The general formula (2) will be described.
In the general formula (2), Z ^1a and Z ^1b each independently represent an atomic group that forms an aryl ring or a heteroaryl ring. The aryl ring and heteroaryl ring formed are synonymous with the aryl group and heteroaryl group described as the substituents for R ² and R ³ in the general formula (1), and the preferred ranges are also the same. Z ^1a and Z ^1b are preferably the same.
R ^5a and R ^5b are each independently an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, It represents any one of 20 alkoxycarbonyl groups, carboxyl groups, carbamoyl groups having 1 to 20 carbon atoms, halogen atoms, or cyano groups. Specific examples are synonymous with the examples described for R ² and R ³ in the general formula (1), and preferred ranges are also the same. R ^5a and R ^5b are preferably the same.
R ^5a or R ^5b and Z ^1a or Z ^1b may combine to form a condensed ring, and examples of the condensed ring include a naphthyl ring and a quinoline ring.
By introducing a group represented by R ^5a or R ^5b into the aryl ring or heteroaryl ring formed by Z ^1a or Z ^1b , invisibility can be greatly improved.

R ²² and R ²³ are each independently a cyano group, an acyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl or arylsulfinyl group having 1 to 10 carbon atoms, or 3 to 20 carbon atoms. It represents a nitrogen-containing heteroaryl group, or R ²² and R ²³ are combined to represent a cyclic acidic nucleus. Specifically, it is synonymous with the example demonstrated by R < ² > and R < ³ > in the said General formula (1), and its preferable range is also the same. R ⁴ has the same meaning as R ⁴ in the general formula (1), and the preferred range is also the same. R ⁴ may have a covalent bond or a coordinate bond with R ²³ .

The compound represented by the general formula (2) may further have a substituent, and the substituent is synonymous with the substituents of R ² and R ³ , and the preferred range is also the same.

As a preferable combination in the general formula (2), Z ^1a and Z ^1b each independently form a benzene ring or a pyridine ring, and R ^5a and R ^5b each independently represent an alkyl group, an alkoxy group, a halogen atom, a cyano group. R ²² and R ²³ are each independently a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, or a cyclic acidic nucleus in which R ²² and R ²³ are bonded, and R ⁴ is a hydrogen atom, a substituted boron, This is the case of transition metal atoms, magnesium, aluminum, calcium, barium, zinc, and tin. As a particularly preferred combination, Z ^1a and Z ^1b together form a benzene ring, R ^5a and R ^5b are both an alkyl group, a halogen atom, or a cyano group, and R ²² and R ²³ are each independently a nitrogen-containing heterocycle. A combination of a cyclic group and a cyano group or an alkoxycarbonyl group, or a cyclic acidic nucleus in which R ²² and R ²³ are bonded, and R ⁴ is a hydrogen atom, substituted boron, aluminum, zinc, vanadium, iron, copper, palladium, iridium This is the case of platinum.

The general formula (3) will be described.
In General Formula (3), R ^31a and R ^31b each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms, specifically, These are synonymous with the examples described for R ^1a and R ^1b in the general formula (1), and the preferred ranges are also the same. R ^31a and R ^31b are preferably the same.
R ³² is a cyano group, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl or arylsulfinyl group having 1 to 10 carbon atoms, or a nitrogen-containing heteroaryl group having 3 to 10 carbon atoms. it is the same as examples of R ² in the formula (1), and preferred ranges are also the same.

R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a heteroaryl group having 4 to 10 carbon atoms. (1) have the same meanings as examples of the substituents of R ² and R ³ in the preferred range is also the same. R ⁶ and R ⁷ may combine to form a ring, and the ring formed is an alicyclic ring having 5 to 10 carbon atoms, an aryl ring having 6 to 10 carbon atoms, or a heteroaryl ring having 3 to 10 carbon atoms. Preferred examples include a benzene ring, naphthalene ring, and pyridine ring.
By introducing a 5-membered nitrogen-containing heterocycle substituted with R ⁶ and R ⁷ and further forming a boron complex, an infrared absorbing dye that achieves both high fastness and high invisibility can be realized.

R ⁸ and R ⁹ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 10 carbon atoms. to are the same as examples of the substituents R ² and R ³ in the general formula (1), and preferred ranges are also the same.
X represents an oxygen atom, a sulfur atom, -NR-, or -CRR'-. R and R ′ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. .

As a preferable combination in the general formula (3), R ^31a and R ^31b are each independently an alkyl group having 1 to 10 carbon atoms, a benzene ring or a pyridine ring, R ³² is a cyano group, an alkoxycarbonyl group, R ⁶ and R ⁷ are bonded to form a benzene ring or a pyridine ring, a pyrazine ring, a pyrimidine ring, and R ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, In this case, X is an oxygen atom, a sulfur atom, -NR-, -CRR'-, and R and R 'are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. As a particularly preferred combination, R ^31a and R ^31b are both an alkyl group having 1 to 10 carbon atoms or a benzene ring, R ³² is a cyano group, and R ⁶ and R ⁷ are bonded to form a benzene ring or a pyridine ring. And R ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a naphthyl group, and X is oxygen or sulfur.

The general formula (4) will be described.
In the general formula (4), R ^41a and R ^{41b each} represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. It is synonymous with the example ^demonstrated by R ^{< 1a>} and R ^<1b> in Formula (1), and its preferable range is also the same. However, R ^41a and R ^41b represent different groups.
R ⁴² is a cyano group, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl or arylsulfinyl group having 1 to 10 carbon atoms, or a nitrogen-containing heteroaryl group having 3 to 10 carbon atoms. it is the same as examples of R ² in the formula (1), and preferred ranges are also the same.
Z ² represents an atomic group that forms a nitrogen-containing hetero 5 or 6-membered ring with —C═N—, and the nitrogen-containing hetero ring includes a pyrazole ring, a thiazole ring, an oxazole ring, an imidazole ring, an oxadiazole ring, and a thiadiazole ring. , A triazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a benzo condensed ring or a naphth condensed ring, or a complex of these condensed rings.
R ⁴⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, a halogen atom as a metal atom or a substituent, and an alkyl having 1 to 10 carbon atoms. Represents a substituted boron having a group, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 4 to 20 carbon atoms, and may have a covalent bond or a coordinate bond with the nitrogen-containing heterocycle formed by Z ^2. .
By introducing different groups represented by R ^41a and R ^41b and introducing a nitrogen-containing hetero 5- or 6-membered ring formed by Z ² with —C═N—, high robustness and high invisibility are obtained. High dispersibility and high organic solvent solubility can be imparted.

As a preferable combination in the general formula (4), R ^41a and R ^41b are each independently an alkyl group having 1 to 10 carbon atoms, a benzene ring or a pyridine ring, and R ⁴² is a cyano group and having 1 to 10 carbon atoms. An alkyl or arylsulfinyl group, an alkoxycarbonyl group, and Z ² together with —C═N— is a thiazole ring, an oxazole ring, an imidazole ring, a thiadiazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, or a benzo-condensation thereof. This is a case where a ring or a naphtho condensed ring is formed, and R ⁴⁴ is a hydrogen atom, a substituted boron, a transition metal atom, magnesium, aluminum, calcium, barium, zinc, or tin. As a particularly preferred combination, R ^41a and R ^41b each independently represents an alkyl group having 1 to 10 carbon atoms or a benzene ring, R ⁴² represents a cyano group, Z ² together with —C═N— represents a thiazole ring, oxazole A ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, or a benzo condensed ring or a naphth condensed ring thereof, R ⁴⁴ is a hydrogen atom, a substituted boron (as a substituent, an alkyl group having 1 to 10 carbon atoms, A benzene ring, a pyridine ring, or a thiophene ring), aluminum, zinc, vanadium, iron, copper, palladium, iridium, or platinum.

  Specific examples of the compound (dye compound) represented by any one of the general formulas (1) to (4) are shown below, but the present invention is not limited to the following specific examples.

Next, a method for synthesizing the compound represented by any one of the general formulas (1) to (4) will be described.
The compound represented by any one of the general formulas (1) to (4) may be obtained by condensing an active methylene compound with a corresponding diketopyrrolopyrrole compound and, in some cases, further reacting with boron or a metal. Can be synthesized. The diketopyrrolopyrrole compound can be synthesized by the method described in “High Performance Pigments”, Wiley-VCH, 2002, pages 160 to 163. More specific examples include US Pat. No. 5,969. No. 154, and Japanese Patent Laid-Open No. 9-323993. In addition, the condensation reaction between the diketopyrrolopyrrole compound and the active methylene compound and the subsequent boronation can be synthesized in accordance with the non-patent document, Angelwante Chemie International Edition of English, Vol. 46, pages 3750-3653 (2007). Boronating reagents are described in J. Org. Med. Chem. It can be synthesized with reference to Volume 3, pages 356 to 360 (1976). For example, bromocatechol borane can be purchased from Tokyo Chemical Industry Co., Ltd. and used.

The compound represented by any one of the general formulas (1) to (4) is not particularly limited, but preferably has an absorption maximum at 700 to 1050 nm, more preferably 700 to 1000 nm. The compound represented by any one of the general formulas (1) to (4) preferably selectively absorbs infrared rays having a wavelength of 700 nm to 1000 nm.
In addition, the compound represented by any one of the general formulas (1) to (4) has a molar extinction coefficient ε that is not particularly limited, but is preferably 50,000 to 300,000, and more preferably 100,000. ~ 250,000.

  The compound represented by any one of the general formulas (1) to (4) can be preferably used as an IR dye. Since it is invisible, the color of the compound is preferably transparent, but may be slightly colored green or gray.

  In the near-infrared absorbing composition of the present invention, the content of the near-infrared absorbing compound is preferably 5% by mass or more based on the solid content of the transparent resin (binder) in order to effectively obtain the infrared shielding effect. 10 mass% or more is preferable. In order to maintain the physical properties of the transparent resin, the amount of the infrared absorbing dye is preferably suppressed to 50% by mass or less.

The near-infrared absorbing compound in the near-infrared absorbing layer is preferably used in the form of aqueous dispersed fine particles.
Here, the aqueous dispersed fine particles refer to fine particles dispersed in water as a dispersion medium.
When the near-infrared absorbing compound is used in the form of aqueous dispersed fine particles, the compounds in the fine particles are associated with each other, so that high light resistance and wet heat resistance can be imparted to the near-infrared absorbing layer.

  When producing the aqueous dispersed fine particles of the near infrared absorbing compound, the quality of dispersion may be improved by using a surfactant and a dispersant. Examples of the surfactant include anionic, nonionic, cationic and amphoteric surfactants. Any surfactant may be used, but an anionic or nonionic surfactant is used. Is preferred. Examples of the anionic surfactant include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, and polyoxyethylene alkyls. Examples thereof include ether sulfate, polyoxyethylene alkylaryl ether sulfate, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester and the like.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin. Examples include fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, fluorine-based resins, and silicon-based resins.

  Examples of the dispersing apparatus for producing the aqueous dispersed fine particles include a ball mill, a sand mill, a bead mill, a roll mill, a jet mill, a paint shaker, an attritor, an ultrasonic disperser, and a disper.

The volume average particle diameter of the fine particles is preferably 10 nm or more and 250 nm or less, and more preferably 20 nm or more and 200 nm or less. The volume average particle diameter of the fine particles refers to the particle diameter of the fine particles themselves or, in the case where an additive such as a dispersant is attached to the fine particles, the particle diameter to which the additive is attached.
In the present invention, a nanotrac UPA particle size analyzer (UPA-EX150, trade name, manufactured by Nikkiso Co., Ltd.) can be used as a device for measuring the volume average particle diameter of fine particles. The measurement is performed according to a predetermined measurement method by placing 3 ml of the fine particle dispersion in a measurement cell. As parameters input at the time of measurement, ink viscosity is used as the viscosity, and fine particle density is used as the density of the dispersed particles.

When the volume average particle diameter of the particles in the pigment dispersion is less than 10 nm, there are cases where the storage stability cannot be ensured, while when it exceeds 250 nm, the optical density may be lowered.

(Ii) Hydrophobic polymer The near-infrared absorbing composition of the present invention is characterized by containing at least a hydrophobic polymer as described above.
The said hydrophobic polymer used for the near-infrared absorption composition of this invention may be used individually by 1 type, and may mix and use 2 or more types as needed.

Although there is no restriction | limiting in particular in the molecular weight of the said hydrophobic polymer used for the near-infrared absorption composition of this invention, Usually, the thing of about 3000-1 million is preferable at a weight average molecular weight. When the weight average molecular weight is less than 3,000, the strength of the coating layer may be insufficient, and when the weight average molecular weight exceeds 1,000,000, the coated surface may be poor.
The hydrophobic polymer used in the present invention is an aqueous organic resin (polymer) in which a hydrophobic organic resin (polymer) is dispersed in a dispersion medium whose main component is water (sometimes referred to as a solvent in this specification). It is preferable to form a dispersion.
The content of water contained in the solvent is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and still more preferably 70 to 100% by mass. As the solvent other than water, a solvent having solubility in water such as alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran and butyl cellosolve is preferably used.
In the near-infrared absorbing composition of the present invention, the content of the hydrophobic polymer (preferably the content of the aqueous dispersion of the polymer) is preferably 0.2 to 10 g / m ² . In the case of less than 0.2 g / m ^2, the film strength of the near infrared absorbing layer and the adhesion to the support may be weakened when forming a near infrared absorbing coated material described later, and if it exceeds 10 g / m ^2. There may be a problem of applicability, unevenness, and haze increase under high temperature and high humidity.
As the hydrophobic organic resin (polymer), various polymers such as acrylic resin, vinyl resin, polyurethane resin, and polyester resin can be used. However, only water-soluble polymers (gelatin, polyvinyl alcohol, carboxymethyl cellulose, etc.) cannot be used as a binder in the present invention. When only a water-soluble polymer is used as a binder, there is a problem that a near-infrared absorbing compound under high temperature and high humidity is decomposed. When a water-soluble polymer is contained in the near-infrared absorbing layer, an aqueous dispersion of the polymer needs to be present in the same layer, and the aqueous dispersion preferably has a solid content of 0.2 to 10 g / m ^2. In the case where a water-soluble polymer is added, the amount is preferably 0.2 g / m ² or less.
From the viewpoint of improving the adhesion of the organic resin (polymer) layer to the support when forming a near-infrared absorbing coating to be described later, a curing agent (for example, a carbodiimide compound) is added to the near-infrared absorbing composition of the present invention. It may be contained and cured by the curing agent when forming a near infrared absorbing coated material described later. In the present invention, from the viewpoint of maintaining a good working environment and preventing air pollution, the polymer and the curing agent such as a carbodiimide compound are preferably used in the form of an aqueous dispersion in the form of an emulsion.
The polymer preferably contains a crosslinkable group of any of a methylol group, a hydroxyl group, a carboxyl group, and an amino group so that a crosslinking reaction with a curing agent such as a carbodiimide compound is possible. Among these, a hydroxyl group and a carboxyl group are more preferable, and a carboxyl group is particularly preferable. The content of the crosslinkable group such as a hydroxyl group and a carboxyl group in the polymer is preferably 0.0001 to 1 equivalent / kg, particularly preferably 0.001 to 1 equivalent / kg.

  Acrylic resins include acrylic acid esters such as acrylic acid and alkyl acrylate, acrylamide, acrylonitrile, methacrylic acid esters such as methacrylic acid and alkyl methacrylate, and homopolymers of any monomer of methacrylamide and methacrylonitrile. Or the copolymer obtained by superposition | polymerization of 2 or more types of these monomers can be mentioned. Among these, homopolymers of monomers of acrylic acid esters such as alkyl acrylates and methacrylic acid esters such as alkyl methacrylates, or copolymers obtained by polymerization of two or more of these monomers preferable. For example, mention may be made of homopolymers of monomers of acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 6 carbon atoms, or copolymers obtained by polymerization of two or more of these monomers. it can. The acrylic resin has the above composition as a main component and, for example, partially uses a monomer having any group of a methylol group, a hydroxyl group, a carboxyl group, and an amino group so that a crosslinking reaction with a carbodiimide compound is possible. The resulting polymer.

  Examples of the vinyl resin include polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl methyl ether, polyolefin, ethylene / butadiene copolymer, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, vinyl chloride / ( A meth) acrylic acid ester copolymer and an ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / (meth) acrylic acid ester copolymer) can be mentioned. Among these, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl polymer, polyolefin, ethylene / butadiene copolymer and ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / acrylic acid ester copolymer). Is preferred. The vinyl resin can be crosslinked with a carbodiimide compound so that, for example, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl methyl ether, and polyvinyl acetate leave a vinyl alcohol unit in the polymer. Thus, the polymer having a hydroxyl group is used, and the other polymer is, for example, a crosslinkable polymer by partially using a monomer having any of a methylol group, a hydroxyl group, a carboxyl group, and an amino group.

  Examples of the polyurethane resin include polyhydroxy compounds (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), aliphatic polyester polyols obtained by reaction of polyhydroxy compounds and polybasic acids, polyether polyols (eg, Polyurethane derived from poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol), polycarbonate-based polyol, and polyethylene terephthalate polyol, or a mixture thereof and polyisocyanate can be given. In the polyurethane resin, for example, the hydroxyl group remaining unreacted after the reaction between polyol and polyisocyanate can be used as a functional group capable of crosslinking reaction with a carbodiimide compound.

  As said polyester resin, the polymer obtained by reaction of a polyhydroxy compound (for example, ethylene glycol, propylene glycol, glycerol, trimethylol propane) and a polybasic acid is mentioned generally. In the above-mentioned polyester resin, for example, the hydroxyl group and carboxyl group remaining unreacted after the reaction between the polyol and the polybasic acid can be used as a functional group capable of crosslinking reaction with the carbodiimide compound. Of course, a third component having a functional group such as a hydroxyl group may be added.

  Among the above polymers, acrylic resins and polyurethane resins are preferable, and polyurethane resins are particularly preferable.

  Incidentally, the dispersion state of the aqueous dispersion of the polymer may be one in which the polymer is emulsified in a dispersion medium, emulsion polymerized, micelle-dispersed, or partially hydrophilic in the polymer molecule. Any one having a simple structure may be used. In addition, about the polymer aqueous dispersion (or simply referred to as the aqueous dispersion) in the present invention, “synthetic resin emulsion (Hiraku Okuda, Hiroshi Inagaki, published by Kobunshi Shuppankai (1978))”, “application of synthetic latex ( Sugimura Takaaki, Kataoka Ikuo, Suzuki Junichi, edited by Kasahara Keiji, published by Kobunshi Publishing Co., Ltd. (1993)), “Synthetic Latex Chemistry (written by Soichi Muroi, published by Kobunshi Publishing Co., Ltd. (1970))”, etc. Yes. The average particle size of the dispersed particles is preferably 1 to 50000 nm, more preferably about 5 to 1000 nm. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.

In addition, as the aqueous dispersion, the following commercially available polymers may be used.
Superflex 830, 460, 870, 420, 420NS (Polyurethane made by Daiichi Kogyo Seiyaku), Bondick 1370NS, 1320NS, Hydran Hw140SF, WLS201, WLS202, WLS213 (Polyurethane made by Dainippon Ink & Chemicals), Olester UD350, UD500, UD600 (Mitsui Chemicals Polyurethane), Neoletz R972, R966, R9660 (Enomoto Kasei Polyurethane), Finetex Es650, Es2200 (Dainippon Ink Chemicals Polyester), Bironal MD1100, MD1400, MD1480 (Toyobo Polyester), Julimer ET325 ET410, AT-613, SEK301 (Nippon Pure Chemicals Acrylic), Boncoat AN117, AN226 (Dai Nippon Ink Industrial acrylic), Luckstar DS616, DS807 (Dainippon Ink & Chemicals styrene-butadiene rubber), Nippon LX110, LX206, LX426, LX433 (Nippon Zeon styrene-butadiene rubber), Nippon LX513, LX1551, LX550, LX1571 ( Zeon Nippon Acrylonitrile-Butadiene Rubber) (all trade names).

(Iii) Coating film Hereinafter, the near-infrared absorbing coating material of the present invention (hereinafter sometimes referred to as a near-infrared absorbing coating film) will be described.
The near-infrared absorbing coating film of the present invention is prepared by preparing the near-infrared absorbing composition containing the near-infrared absorbing compound and the aqueous dispersion of the polymer, and applying the near-infrared absorbing composition on a support. It can produce by forming the near-infrared absorption layer which becomes.
As a method for applying the near infrared absorbing layer, for example, a dip coating method, a roller coating method, a spray coating method, a gravure coating method, a bar coating method, a die coating method, or the like can be selected. These coating methods can perform continuous processing, and are more productive than batch-type vapor deposition methods. Also, a spin coating method that can form a thin and uniform coating film can be employed.
The support (for example, a plastic film such as polyester) carrying the coating layer may be any of before successive biaxial stretching, before simultaneous biaxial stretching, after uniaxial stretching and before re-stretching, or after biaxial stretching. . The surface of the plastic support to which the coating solution is applied is preferably subjected to surface treatment such as ultraviolet irradiation treatment, corona discharge treatment, glow discharge treatment, etc. in advance.
Two or more near infrared absorption layers may be provided. The film thickness of the near-infrared absorbing layer is preferably 0.1 μm or more in order to effectively obtain the near-infrared shielding effect per layer, the solvent during film formation hardly remains, and film formation operability is easy. In view of the above, it is preferably 10 μm or less, particularly preferably 0.3 to 3 μm.

  When producing the near-infrared absorbing coating film of the present invention, it is preferable to heat and dry after coating. By heat drying, the polymers are fused to each other, and the light resistance and heat-and-moisture resistance of the coating film can be improved. Although there is no restriction | limiting in particular as heat drying conditions, Specifically, 100-150 degreeC and 1-10 minutes are preferable, and 100-130 degreeC and 1-5 minutes are more preferable.

When an optical filter is produced by coating the near-infrared absorbing coating film of the present invention on a transparent support, a plastic film, a plastic plate, a glass plate, or the like can be used as the support.
Examples of the raw material for the plastic film and plastic plate include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, EVA; polyvinyl chloride, Vinyl resins such as polyvinylidene chloride; polyether ether ketone (PEEK), polysulfone (PSF), polyether sulfone (PES), polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC) Etc. can be used.
In the present invention, the plastic film is preferably a polyethylene terephthalate film or triacetyl cellulose (TAC) from the viewpoints of transparency, heat resistance, ease of handling, and price.

For applications where transparency is required, such as near infrared absorption filters for displays, it is preferable that the support is highly transparent. In this case, the total visible light transmittance of the plastic film or plastic plate is preferably 70 to 100%, more preferably 85 to 100%, and particularly preferably 90 to 100%. Moreover, in this invention, what was colored to such an extent that the objective of this invention is not disturbed can also be used as the said plastic film and a plastic board.
The plastic film and plastic plate in the present invention can be used as a single layer, but can also be used as a multilayer film in which two or more layers are combined.

  When a glass plate is used as the support in the present invention, the type thereof is not particularly limited. However, when used as an application of an electromagnetic wave shielding film for display, it is preferable to use tempered glass having a tempered layer on the surface. There is a high possibility that tempered glass can prevent breakage compared to glass that has not been tempered. Furthermore, the tempered glass obtained by the air cooling method is preferable from the viewpoint of safety because even if it is broken, the crushed pieces are small and the end face is not sharp.

The near infrared absorption coating material of the present invention preferably has an absorptance in the near infrared region of 50% or more, more preferably 70% or more. Moreover, it is preferable that the absorptivity of visible region (450 nm-650 nm) is 30% or less (preferably 20-0%).
Here, the absorptance is a value representing the absorbance at the measurement wavelength as a percentage when the absorbance at λmax is 100%.

(Iv) Other functional layers Further functionality may be imparted to the near-infrared absorbing coating film of the present invention as required. Alternatively, a functional layer having functionality may be provided separately from the near-infrared absorbing layer. This functional layer can have various specifications for each application. For example, as an electromagnetic shielding material for a display, an antireflection layer provided with an antireflection function by adjusting a refractive index or a film thickness, a non-glare layer or an antiglare layer (both have a glare prevention function), a specific wavelength region Layers that have a color tone adjustment function that absorbs visible light, antifouling layers that have the ability to easily remove dirt such as fingerprints, hard-coat layers that are difficult to scratch, layers that have an impact absorption function, and glass scattering when glass is broken A layer having a prevention function or the like can be provided. These functional layers may be provided on the opposite surface across the silver salt-containing layer and the support, or may be provided on the same surface side.

(Anti-reflection and anti-glare properties)
The translucent electromagnetic wave shielding film has anti-reflection (AR: anti-reflection) properties to suppress external light reflection, or anti-glare (AG: anti-glare) properties to prevent the reflection of mirror images, or both characteristics. It is preferable to provide any of the antireflection antiglare (ARAG) properties provided.
With these performances, it is possible to prevent the display screen from becoming difficult to see due to the reflection of a lighting fixture or the like. Further, by reducing the visible light reflectance of the film surface, not only the reflection can be prevented but also the contrast and the like can be improved. When the functional film having antireflection properties and antiglare properties is attached to the translucent electromagnetic wave shielding film, the visible light reflectance is preferably 2% or less, more preferably 1.3% or less, and still more preferably Is 0.8% or less.

The functional film as described above can be formed by providing a functional layer having antireflection properties and antiglare properties on a suitable transparent substrate.
As the antireflection layer, for example, a fluorine-based transparent polymer resin, magnesium fluoride, a silicon-based resin, a thin film of silicon oxide, or the like formed as a single layer with an optical film thickness of, for example, a quarter wavelength, a different refractive index, It may be formed of a multi-layered laminate of thin films of inorganic compounds such as metal oxides, fluorides, silicides, nitrides, sulfides, or organic compounds such as silicon resins, acrylic resins, and fluorine resins. it can.

The antiglare layer can be formed from a layer having a minute uneven surface state of about 0.1 μm to 10 μm. Specifically, acrylic, silicon-based resin, melamine-based resin, urethane-based resin, alkyd-based resin, fluorine-based resin and other thermosetting or photo-curable resins, silica, organosilicon compounds, melamine, acrylic, etc. It is possible to form by coating and curing an ink in which particles of the inorganic compound or organic compound are dispersed.
The average particle size of the particles is preferably about 1 to 40 μm.
The antiglare layer can also be formed by applying the thermosetting or photocurable resin and pressing and curing a mold having a desired gloss value or surface state.
When the antiglare layer is provided, the haze of the translucent electromagnetic wave shielding film is preferably 0.5% or more and 20% or less, more preferably 1% or more and 10% or less. If the haze is too small, the antiglare property is insufficient, and if the haze is too large, the transmitted image sharpness tends to be low.

(Hard coat property)
In order to add scratch resistance to the near-infrared absorbing filter, it is also preferable that the functional film has a hard coat property. Examples of the hard coat layer include acrylic resins, silicon resins, melamine resins, urethane resins, alkyd resins, thermosetting resins such as fluorinated resins, and photocurable resins. There is no particular limitation. The thickness of the hard coat layer is preferably about 1 to 50 μm. When the antireflection layer and / or the antiglare layer is formed on the hard coat layer, a functional film having scratch resistance, antireflection property and / or antiglare property is preferably obtained.
The surface hardness of the translucent electromagnetic wave shielding film to which hard coat properties are imparted is preferably a pencil hardness according to JIS (K-5400) of at least H, more preferably 2H, and even more preferably 3H or more. .
In the present invention, it is preferable to have at least one of an electromagnetic wave shielding layer, a hard coat layer, an antireflection layer and an antiglare layer on the opposite side of the near infrared absorption layer with the transparent support interposed therebetween. That is, a near-infrared absorption layer is first formed on one surface of the transparent support. Thereafter, at least one of an electromagnetic wave shielding layer, a hard coat layer, an antireflection layer and an antiglare layer is formed on the other surface of the transparent support. It is preferable to form all these layers.

(Anti-fouling property)
It is preferable that the near-infrared absorbing filter has antifouling property because it can prevent fingerprints and the like and can be easily removed when they are attached.
The functional film having antifouling properties can be obtained, for example, by applying a compound having antifouling properties on a transparent substrate. The compound having antifouling property may be a compound having non-wetting properties with respect to water and / or fats and oils, and examples thereof include fluorine compounds and silicon compounds. Specific examples of the fluorine compound include trade name OPTOOL (manufactured by Daikin), and examples of the silicon compound include trade name Takata Quantum (manufactured by Nippon Oil & Fats Co., Ltd.).

(UV-cutting property)
The near-infrared absorbing filter is preferably imparted with UV-cutting properties for the purpose of preventing deterioration of a dye and a transparent substrate described later. The functional film having ultraviolet cut-off property can be formed by a method in which the transparent substrate itself contains an ultraviolet absorber or by providing an ultraviolet absorbing layer on the transparent substrate.
As the ultraviolet ray cutting ability necessary for protecting the dye, the transmittance in the ultraviolet region shorter than the wavelength of 380 nm is 20% or less, preferably 10% or less, more preferably 5% or less. A functional film having ultraviolet cut-off properties can be obtained by forming a layer containing an ultraviolet absorber or an inorganic compound that reflects or absorbs ultraviolet rays on a transparent substrate. Conventionally known UV absorbers such as benzotriazoles and benzophenones can be used, and their types and concentrations are dispersibility / solubility in the medium to be dispersed or dissolved, absorption wavelength / absorption coefficient, thickness of the medium. It is determined from the above and is not particularly limited.

In addition, it is preferable that the functional film which has ultraviolet cut-off property has little absorption of visible light region, and does not remarkably reduce visible light transmittance, or exhibit colors, such as yellow.
Moreover, when the layer containing the pigment | dye mentioned later is formed in the functional film, it is preferable that the layer which has ultraviolet-cut property exists outside the layer.

  As described in detail above, the infrared-absorbing composition of the present invention and the coating film using the same are radiated from the display as a filter for plasma display, for example, without significantly impairing the brightness of the plasma display. It can be used as an optical filter that can efficiently cut near-infrared rays in the vicinity of 800-1000 nm, prevent adverse effects on wavelengths used by remote control of peripheral electronic devices, transmission optical communication, etc., and prevent their malfunction. . Or the near-infrared absorption filter excellent in light resistance and heat-and-moisture resistance can be provided with low environmental load and low cost.

  Hereinafter, the present invention will be described in more detail with reference to 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 should not be construed as being limited by the specific examples shown below.

Synthesis example 1
[Preparation of Exemplified Compound (D-17)]
Exemplified compound (D-17) was prepared according to the following scheme.

  First, a diketopyrrolopyrrole compound (DPP) was synthesized according to a method described in US Pat. No. 5,969,154 using 4- (2-ethylhexyloxy) benzonitrile as a raw material.

3 grams (1 molar equivalent) of a diketopyrrolopyrrole compound and 1.6 grams (2.5 molar equivalent) of pyridine acetonitrile are stirred in 60 mL of toluene, and 6.5 grams of phosphorus oxychloride (8 molar equivalents) are added. Heated to reflux for hours. After cooling to room temperature (25 ° C.), 50 mL of chloroform and 20 mL of water were added, and the mixture was further stirred for 30 minutes. The organic layer was taken out by a liquid separation operation and washed with an aqueous sodium hydrogen carbonate solution, and then the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (solvent chloroform) and recrystallized using chloroform / acetonitrile solvent to obtain 3.3 g of the target compound (D-17) in a yield of 70%. It was.
¹ H-NMR (CDCl ₃ ): δ 0.9-1.0 (m, 12H), 1.35-1.6 (m, 16H), 1.8 (m, 2H), 3.95 (d, 4H), 7.1 (d, 4H), 7.4-7.5 (m, 4H), 7.7 (d, 4H), 7.75 (d, 2H), 8.0 (d, 2H) )

Synthesis example 2
[Preparation of Exemplary Compound (D-10)]
Exemplified compound (D-10) was prepared according to the above scheme.
Titanium chloride (0.9 mL, 3 molar equivalents) was added to a toluene solution (1.2 M) of diphenylborinic acid 2-aminomethyl ester (1.4 g, 3 molar equivalents) and stirred for 30 minutes at an external temperature of 100 ° C. did. Next, the toluene compound liquid (0.2M) of exemplary compound (D-17) (2.3g) was added, and also it stirred on heating-reflux conditions for 2 hours. When the mixture was cooled to room temperature and methanol was added, crystals were precipitated. The crystals were separated by filtration and recrystallized from chloroform / methanol to obtain 3.0 g of Exemplified Compound (D-10) in a yield of 93%.
λmax was 779 nm in chloroform. The molar absorption coefficient was 2.06 × 10 ⁵ dm ³ / mol · cm in chloroform.
¹ H-NMR (CDCl ₃ ): δ 0.9-1.0 (m, 12H), 1.35-1.6 (m, 16H), 1.8 (m, 2H), 3.85 (d, 4H), 6.45 (s, 8H), 7.0 (d, 4H), 7.15 (m12H), 7.2 (m, 2H), 7.25 (m, 4H + 4H), 7.5 ( m, 2H)

Synthesis example 3
[Preparation of exemplary compound (D-28)]
Exemplified compound (D-28) was prepared in the same manner as described above except that the raw materials were changed. ¹ H-NMR whose structure has been identified is shown.
Exemplary compound (D-28)
¹ H-NMR (CDCl ₃ ): 1.9 (s, 6H), 6.65 (d, 2H), 6.7-6.8 (m, 6H), 6.95 (m, 8H), 7 0.0-7.1 (m, 4H), 7.25-7.35 (m, 12H), 7.5 (m, 2H), 7.85 (d, 2H)
λmax was 752 nm in chloroform. The molar absorption coefficient was 1.53 × 10 ⁵ dm ³ / mol · cm in chloroform.
In addition, the solution absorption spectrum of exemplary compound (D-10) and (D-17) is shown in FIG.
It was found that the exemplified compounds (D-10), (D-17) and (D-28) are all excellent in near-infrared light absorption, have a small absorption at 400 to 500 nm, and are further excellent in invisibility.

Example 1
(Production of aqueous dispersed fine particles of near-infrared absorbing compound)
Water was added to the near-infrared absorbing compound and dispersant of the types and parts by mass shown in Table 1 below to make 500 parts by mass. To this was further added 500 parts by mass of 0.1 mmφ zirconia beads, followed by treatment at 300 rpm for 5 hours with a planetary ball mill to prepare an aqueous dispersion composed of fine particles.
Thereafter, beads were separated from the aqueous dispersion by filtration to obtain aqueous dispersions A-1 to A-5. The particle size of the fine particles in the aqueous dispersion A was measured with a Nanotrac UPA particle size analyzer (UPA-EX150, trade name, manufactured by Nikkiso Co., Ltd.). The average particle size is shown in Table 1 below.

(Preparation of near infrared absorption film)
Polyethylene terephthalate (PET) was added to aqueous dispersions A-1 to A-5 by adding the types of polymers shown in Table 2 below, adjusting the concentration by adding pure water to the coating stock solution with a total of 100 parts by mass. It was applied to the plate. Furthermore, the coating film was dried by the drying method shown in Table 2 below, and near-infrared absorbing films B-1 to B-17 were produced. The coating solution concentration was adjusted by measuring the absorption spectrum of the obtained film so that the optical density at λmax of the near-infrared absorbing compound was 1.5.
FIG. 2 shows an absorption spectrum of the near-infrared absorbing film B-4.
As is apparent from FIG. 2, λmax was 848 nm, and good infrared light absorptivity was obtained. It can also be seen that the film has almost no absorption at 400 to 700 nm and has excellent invisibility.

(Light resistance test)
The obtained near-infrared absorbing films B-1 to B-17 were each irradiated with a 220,000 lux xenon lamp for 72 hours. The absorbance at the spectral maximum absorption wavelength of the near-infrared absorbing films B-1 to B-17 was measured, the residual ratio to that before light irradiation was determined, and the light resistance was evaluated. The results are shown in Table 2 below.

(Moisture and heat resistance test)
Each of the obtained near-infrared absorbing films B-1 to B-17 was placed in a wet heat tester at 60 ° C. and 90% RT for 120 hours. The absorbance at the spectral maximum absorption wavelength of each near-infrared absorbing film B-1 to B-17 was measured, the residual ratio to that before the wet heat test was determined, and the wet heat resistance was evaluated. The results are shown in Table 2 below.

  As is apparent from Table 2, the near-infrared absorbing films B-3 to B-6, B-8, B-9, B-11, B-12, B-14, B-15, B-17 of the present invention. Both exhibited good light resistance and wet heat resistance. In particular, the near-infrared absorbing films B-4, B-12, and B-15 obtained by heating and drying (130 ° C. for 5 minutes) using a binder made of a urethane resin all have extremely high light resistance and moisture and heat resistance. showed that.

  As a result of the above, the near-infrared absorbing composition of the present invention and the near-infrared absorbing film obtained thereby have excellent characteristics of having good near-infrared absorptivity and invisibility as well as high light resistance and moist heat resistance. It can be seen that it can be applied as an optical filter or an information recording material.

FIG. 1 shows the solution absorption spectra of Exemplified Compounds D-10 and D-28. FIG. 2 shows an absorption spectrum of the near-infrared absorbing film B-4 produced in Example 1.

Claims (18)

A near-infrared absorbing composition containing at least a near-infrared absorbing compound represented by the following general formula (1 ′) and a hydrophobic polymer.

(Wherein R ^1a and R ^1b may be the same or different and each independently represents an alkyl group, an aryl group or a heteroaryl group which may have a substituent selected from the following substituent group) R ² and R ³ each independently represents a hydrogen atom , cyano group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, carboxyl group or heterocyclic group , One is an electron-withdrawing group having a Hammett's σp value of 0.2 or more , and R ² and R ³ may combine to form a ring, where R ⁴ is a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl. Represents a group, a substituted boron or a metal atom, and may be covalently or coordinately bonded to R ^1a , R ^1b and / or R ^3. )
(Substituent group)
Alkyl group, alkenyl group, alkynyl group, aryl group, branched alkoxy group, aryloxy group, aromatic heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, Sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group , Heterocyclic group   The near-infrared absorbing composition according to claim 1, wherein the near-infrared absorbing compound is present in an aqueous dispersed fine particle state. A near-infrared absorbing composition containing at least a near-infrared absorbing compound represented by the following general formula (1) and a hydrophobic polymer,
The near-infrared absorbing compound is present in the form of an aqueous dispersion fine particle;
A near-infrared absorbing composition, wherein the fine particles have a volume average particle diameter of 10 nm to 250 nm.

(Wherein R ^1a And R ^1b May be the same or different and each independently represents an alkyl group, an aryl group or a heteroaryl group. R ² And R ^Three Each independently represents a hydrogen atom, a cyano group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a carboxyl group or a heterocyclic group, at least one of which is a Hammett σp value Is an electron withdrawing group of 0.2 or more, and R ² And R ^Three May combine to form a ring. R ^Four Represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a substituted boron or a metal atom, and R ^1a , R ^1b And / or R ^Three And may be covalently bonded or coordinately bonded. ) R ^1a And R ^1b The near-infrared absorbing composition according to claim 3, wherein the aryl group in is an aryl group which may have a substituent selected from the following substituent group.
(Substituent group)
Alkyl group, alkenyl group, alkynyl group, aryl group, branched alkoxy group, aryloxy group, aromatic heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, Sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group , Heterocyclic group R ⁴ Is a substituted boron, The near-infrared absorption composition of any one of Claims 1-4 characterized by the above-mentioned. The near-infrared absorbing composition according to any one of claims 1 to 5, wherein the near-infrared absorbing compound is dispersed with a dispersant and is present in an aqueous dispersed fine particle state. Wherein the hydrophobic polymer is, near-infrared absorbing composition according to any one of claims 1-6, characterized by comprising forming an aqueous dispersion of organic resin. The near-infrared absorbing composition according to any one of claims 1 to 7 , wherein the hydrophobic polymer contains an acrylic resin or a urethane resin. It has a near-infrared absorption layer formed using the near-infrared absorption composition of any one of Claims 1-8 on a support body, The near-infrared absorption coating material characterized by the above-mentioned. The near-infrared absorbing coating material according to claim 9 , wherein the visible light absorption rate is 30% or less. A method for producing a near-infrared absorbing composition comprising at least a near-infrared absorbing compound and a hydrophobic polymer,
The near-infrared absorbing compound is a compound represented by the following general formula (1),
A method for producing a near-infrared absorbing composition comprising at least the following steps [1] and [2].

(Wherein R ^1a And R ^1b May be the same or different and each independently represents an alkyl group, an aryl group or a heteroaryl group. R ² And R ^Three Each independently represents a hydrogen atom, a cyano group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a carboxyl group or a heterocyclic group, at least one of which is a Hammett σp value Is an electron withdrawing group of 0.2 or more, and R ² And R ^Three May combine to form a ring. R ^Four Represents a hydrogen atom, alkyl group, aryl group, heteroaryl group, substituted boron, metal atom, R ^1a , R ^1b And / or R ^Three And may be covalently bonded or coordinately bonded. )
[Manufacturing process]
[1] A step of obtaining an aqueous dispersion by dispersing the near-infrared absorbing compound in water.
[2] A step of adding an aqueous dispersion of a hydrophobic polymer to an aqueous dispersion of near-infrared absorbing compound fine particles obtained in the above step R ^1a And R ^1b The method for producing a near-infrared absorbing composition according to claim 11, wherein the aryl group in is an aryl group which may have a substituent selected from the following substituent group.
(Substituent group)
Alkyl group, alkenyl group, alkynyl group, aryl group, branched alkoxy group, aryloxy group, aromatic heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, Sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group , Heterocyclic group R ⁴ Is a substituted boron, The manufacturing method of the near-infrared absorption composition of Claim 11 or 12 characterized by the above-mentioned. The near-infrared absorbing composition according to any one of claims 11 to 13, wherein the near-infrared absorbing compound is dispersed with a dispersant and is present in an aqueous dispersed fine particle state in the near-infrared absorbing composition. Manufacturing method. The method for producing a near-infrared absorbing composition according to claim 11, wherein a volume average particle diameter of the fine particles is 10 nm or more and 250 nm or less. The said hydrophobic polymer contains an acrylic resin or a urethane resin, The manufacturing method of the near-infrared absorption composition of any one of Claims 11-15 characterized by the above-mentioned. It has the process of forming a near-infrared absorption layer using the near-infrared absorption composition obtained by the manufacturing method of any one of Claims 11-16 on a support body, In this process, heat drying is carried out. A method for producing a near-infrared-absorbing coated product, comprising: 18. The method for producing a near-infrared absorbing coating material according to claim 17, wherein the visible light absorptivity of the infrared absorbing coating material is 30% or less.

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