JP2007262323A - Near-infrared absorbing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near-infrared absorbing material with light resistance and the other physical properties compatible with each other. <P>SOLUTION: The near-infrared absorbing material comprises at least one of a singlet oxygen scavenger, a radical trapping agent and an antioxidant each represented by the general formula(I-1) or (I-2), and at least one compound 700 nm or longer in spectroscopic absorption maximum wavelength within the range of 400 to 1,600 nm in the form of its solution. In the general formula(I-1), R<SP>11</SP>is H, an aliphatic group, aromatic group, heterocyclic group bound through carbon atoms or a hydrolyzable protecting group; R<SP>12</SP>to R<SP>16</SP>are each H or a substituent; R<SP>21</SP>are each H, an acyl, sulfonyl, sulfinyl, oxyradical group or hydroxy group; Q is a nonmetal atom group necessary for forming a five- to seven-membered ring; and R<SP>22</SP>to R<SP>25</SP>are each H, an aliphatic roup, aromatic group or heterocyclic group bound through carbon atoms. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a near-infrared absorbing material, and more particularly, an important role in optoelectronics such as a near-infrared absorbing filter, a near-infrared absorbing colored resin composition, a liquid crystal display element, an optical card, an optical recording medium, and protective glasses. The present invention relates to a near-infrared absorbing material that satisfies both light resistance and other physical properties.

  Near-infrared absorbing dyes that do not substantially absorb visible light but absorb infrared rays are used in various optoelectronic products such as near-infrared absorbing filters. Depending on how they are used, they are exposed to high temperature, high humidity, or light irradiation conditions, and their decomposition sometimes becomes a problem. As a technique for improving resistance to these by changing the structure of the dye, for example, a naphthalocyanine dye having a specific structure (for example, Patent Documents 1 to 3) has been found to be good. It was difficult to achieve compatibility with other physical properties such as properties. In particular, suppression of light degradation of the phthalocyanine compound and other physical properties are desired (for example, Patent Document 4). Moreover, although the technique which suppresses decomposition | disassembly by light by using a near-infrared absorption pigment | dye and ultraviolet-ray absorption material together was known (for example, patent document 5, 6), the degree of the suppression is inadequate, and further light resistance, A technique for improving durability was desired.

Japanese Laid-Open Patent Publication No. 2-4685 JP-A-2-43269 JP-A-2-138382 Japanese Patent Laid-Open No. 11-152413 JP-A-10-77360 JP 2005-181966 A

  The object of the present invention is to play an important role in optoelectronics such as near-infrared absorbing filters, near-infrared absorbing colored resin compositions, liquid crystal display elements, optical cards, optical recording media, protective glasses, etc. It is to provide a near infrared ray absorbing material.

As a result of intensive studies, the present inventors have found that the above object of the present invention can be achieved by the following means.
(1) at least one of a singlet oxygen scavenger, a radical trap, and an antioxidant, and 2) at least one compound having a spectral absorption maximum wavelength in the range of 400 to 1600 nm in the solution of 700 nm or more. A near-infrared absorbing material characterized by containing.
(2) The near-infrared absorbing material according to (1), wherein at least one of the compounds in 1) is a compound represented by the following general formula (I-1) or (I-2) .

一般式（Ｉ−１）中、Ｒ¹¹は水素原子、脂肪族基、芳香族基、炭素原子で結合する複素環素又は加水分解可能な保護基を表し、Ｒ¹²〜Ｒ¹⁶は各々独立に水素原子又は置換基を表し、Ｒ¹¹とＲ¹²、Ｒ¹²とＲ¹³、Ｒ¹³とＲ¹⁴、Ｒ¹⁴とＲ¹⁵、Ｒ¹⁵とＲ¹⁶及びＲ¹⁶とＲ¹¹は互いに結合して環を形成してもよい。
一般式（Ｉ−２）中、Ｒ²¹は水素原子、脂肪族基、アシル基、スルホニル基、スルフィニル基、オキシラジカル基又はヒドロキシル基を表し、Ｑは５員、６員又は７員環を形成するのに必要な非金属原子群を表し、Ｒ²²〜Ｒ²⁵は各々独立に水素原子、脂肪族基、芳香族基又は炭素原子で結合する複素環基を表し、Ｒ²¹とＲ²²、Ｒ²²とＲ²³、Ｒ²⁴とＲ²⁵及びＲ²¹とＲ²⁴は互いに結合して環を形成してもよい。
（３）前記１）における化合物を２種以上含有することを特徴とする（１）又は（２）に記載の近赤外線吸収材料。
（４）さらに３）紫外線吸収剤及び蛍光増白剤の少なくとも１種を含有することを特徴とする（１）〜（３）のいずれか１項に記載の近赤外線吸収材料。
（５）前記３）における化合物が、溶液における２７０ｎｍ〜１６００ｎｍの範囲の分光吸収極大波長が４１０ｎｍ以下であることを特徴とする（４）に記載の近赤外線吸収材料。
（６）前記３）における化合物が、下記一般式（III−１）〜（III−９）のいずれかで表される化合物であることを特徴とする（４）又は（５）に記載の近赤外線吸収材料。

In general formula (I-1), R ¹¹ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group bonded by a carbon atom or a hydrolyzable protecting group, and R ^{12 to} R ¹⁶ are each independently Represents a hydrogen atom or a substituent, and R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ^16, and R ¹⁶ and R ¹¹ are bonded to each other to form a ring. It may be formed.
In the general formula (I-2), R ²¹ represents a hydrogen atom, an aliphatic group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy radical group or a hydroxyl group, and Q forms a 5-membered, 6-membered or 7-membered ring. R ^{22 to} R ²⁵ each independently represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom, and R ²¹ and R ²² , R ²² and R ²³ , R ²⁴ and R ²⁵ and R ²¹ and R ²⁴ may be bonded to each other to form a ring.
(3) The near-infrared absorbing material according to (1) or (2), comprising two or more compounds in 1) above.
(4) Further, 3) The near-infrared absorbing material according to any one of (1) to (3), further comprising at least one of an ultraviolet absorber and a fluorescent brightening agent.
(5) The near-infrared absorbing material according to (4), wherein the compound in 3) above has a spectral absorption maximum wavelength in the range of 270 nm to 1600 nm in the solution of 410 nm or less.
(6) The compound according to (4) or (5), wherein the compound in 3) is a compound represented by any one of the following general formulas (III-1) to (III-9): Infrared absorbing material.

In the formula, R ^{311 to} R ³¹⁴ , R ^{321 to} R ³⁶⁶ , R ^{371 to} R ³⁷⁸ , R ^{381 to} R ³⁸⁴ , R ^{386 to} R ³⁸⁹ , and R ^{391 to} R ⁴⁰⁰ each independently represent a hydrogen atom or a substituent. ^R315 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom. R ³⁷⁹ , R ³⁸⁰ and R ³⁸⁵ represent a substituent. X ³⁴¹ represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom. n ₃₇₉ and n ₃₈₀ each independently represents an integer of 0 to 4, when n ₃₇₉ and n ₃₈₀ is 2 or more, plural R ³⁷⁹ and R ³⁸⁰ may be the same or different. n ₃₈₅ represents an integer of 0 to 6, and when n ₃₈₅ is 2 or more, a plurality of R ³⁸⁵ may be the same or different.
Here, groups adjacent to each other may be bonded to each other to form a ring.
(7) The near-infrared absorbing material according to any one of (4) to (6), comprising two or more compounds in 3) above.
(8) The near-infrared absorbing material according to any one of (1) to (7), wherein the spectral absorption maximum wavelength in 2) is 780 nm or more.
(9) The near-infrared absorbing material according to any one of (1) to (8), wherein the compound in 2) is a compound represented by the following general formula (II-1).

In General Formula (II-1), R ^{211 to} R ²¹⁴ , R ^{221 to} R ²²⁴ , R ^{231 to} R ²³⁴ , and R ^{241 to} R ²⁴⁴ each independently represent a hydrogen atom or a substituent, and among these groups, Adjacent groups may be bonded to each other to form a ring. M ²¹¹ represents two atoms selected from the group consisting of a hydrogen atom and a monovalent metal atom, a divalent metal atom, or a divalent substituted metal atom including a trivalent or tetravalent metal atom.

  According to the present invention, near-infrared absorbing filter, near-infrared absorbing colored resin composition, liquid crystal display device, optical card, optical recording medium, protective glasses, etc. Infrared absorbing materials can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
The present invention relates to 1) at least one of a singlet oxygen scavenger, a radical trap agent and an antioxidant, and 2) at least one compound having a spectral absorption maximum wavelength in a range of 400 to 1600 nm in a solution of 700 nm or more. Is a near-infrared absorbing material.
In the present invention, it is preferable to further contain 3) at least one of an ultraviolet absorber and an optical brightener, and these compounds have a spectral absorption maximum wavelength in the range of 270 nm to 1600 nm in the solution of 410 nm or less. Is preferred.

<Spectral absorption maximum wavelength>
Hereinafter, the spectral absorption maximum wavelength will be described.
The spectral absorption maximum wavelength is defined by an absorption spectrum in a solution, and any solvent may be used as long as the compound dissolves therein. These solvents may be organic or inorganic solvents, water, or a mixed solvent thereof. In the present invention, as long as the solvent and temperature at which the compound dissolves, the spectral absorption maximum wavelength under any condition may be within the range defined by the present invention.
Examples of the organic solvent include amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (for example, sulfolane), sulfoxide solvents (for example, dimethyl sulfoxide). Ureido solvents (eg tetramethylurea), ether solvents (eg dioxane, tetrahydrofuran, cyclopentylmethyl ether), ketone solvents (eg acetone, cyclohexanone), hydrocarbon solvents (eg toluene, xylene, n-decane), Halogen solvents (eg tetrachloroethane, chlorobenzene, chloronaphthalene), alcohol solvents (eg methanol, ethanol, isopropyl alcohol, ethylene glycol, cyclohexanol, phenol), pyridi Solvent (eg pyridine, γ-picoline, 2,6-lutidine), ester solvent (eg ethyl acetate, butyl acetate), carboxylic acid solvent (eg acetic acid, propionic acid), nitrile solvent (eg acetonitrile), sulfone An acid solvent (for example, methanesulfonic acid) and an amine solvent (for example, triethylamine, tributylamine) can be mentioned, and examples of the inorganic solvent include sulfuric acid and phosphoric acid.

Of these solvents, the amide solvent, the sulfone solvent, the sulfoxide solvent, the ureido solvent, the ether solvent, the ketone solvent, and the halogen solvent are preferably used at the maximum spectral absorption wavelength of the compound defined in 3) above. A solvent, an alcohol solvent, an ester solvent, and a nitrile solvent, particularly preferably ethyl acetate or N, N-dimethylformamide, while at the maximum spectral absorption wavelength of the compound defined in 2) above. Preferably an amide solvent, a sulfone solvent, a sulfoxide solvent, a ureido solvent, an ether solvent, a hydrocarbon solvent, a halogen solvent, a sulfonic acid solvent, and sulfuric acid, particularly preferably tetrahydrofuran or sulfuric acid. .
The concentration of the compound for measuring the spectral absorption maximum wavelength may be a concentration at which the spectral absorption maximum wavelength can be confirmed, and is preferably in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻² (mol / l). The temperature is not particularly limited, but is preferably 0 ° C. to 80 ° C., and room temperature (25 ° C.) is most preferable if there is no problem with the solubility of the compound.

  As a measuring instrument, a normal spectral absorption measuring device (for example, U-4100 spectrophotometer manufactured by Hitachi High-Technologies Corporation) can be used.

<Group in the present invention>
Here, before entering description of a compound, it demonstrates in detail regarding the group in this invention.
In this specification, an aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The alkyl group may have a branch or may form a ring. The number of carbon atoms in the alkyl group is preferably 1-20, and more preferably 1-18. The alkyl part of the substituted alkyl group is the same as the above alkyl group. The alkenyl group may have a branch or may form a ring. The alkenyl group has preferably 2 to 20 carbon atoms, and more preferably 2 to 18 carbon atoms. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. The alkynyl group may have a branch or may form a ring. The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 18 carbon atoms. The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. The alkyl part of the aralkyl group and the substituted aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group and the substituted aralkyl group is the same as the following aryl group.

  The substituent of the substituted alkyl group, the substituent of the substituted alkenyl group, the substituent of the substituted alkynyl group, or the substituent of the alkyl part of the substituted aralkyl group includes a halogen atom (for example, chlorine atom, bromine atom, iodine atom), alkyl Group [Represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 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, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl) and tricyclo structures with more ring structures It is intended to free. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They include alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted groups having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] Transfected-2-en-4-yl) are intended to encompass. 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), a heterocyclic group (preferably 5 or 6 A monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably a 5- or 6-membered aromatic having 3 to 30 carbon atoms For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably having 1 to 30 carbon atoms) Substituted or unsubstituted alkoxy groups 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, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoyl Aminophenoxy), silyloxy groups (preferably silyloxy groups having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy groups (preferably substituted or unsubstituted groups having 2 to 30 carbon atoms) Heterocyclic oxy group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, carbon number 6 to 30 substituted or unsubstituted arylcarbonyloxy groups For example, 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), alkoxycarbonyloxy group (preferably, carbon number) 2 to 30 substituted or unsubstituted alkoxycarbonyloxy groups such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarboni A ruoxy 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 anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms) Groups such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino groups (preferably substituted with 1 to 30 carbon atoms) Or unsubstituted aminocarbonylamino, such as carb Ylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonyl Amino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) Carbonylamino groups such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), sulfamoylamino groups (preferably Is a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl or arylsulfonylamino A group (preferably a substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2, 3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), 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, for example, Phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyltetrazole -5-ylthio), a 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-dimethyl Sulfamoyl, N-acetylsulfamoyl, N-benzo Rusulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl or arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms) Arylsulfinyl groups 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, and substitution having 4 to 30 carbon atoms Or a heterocyclic carbonyl group bonded to a carbonyl group with an unsubstituted carbon atom, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2- Furylcarbonyl), aryloxyca Bonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl A 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 having 1 to 30 carbon atoms) Substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) 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, such as phenylazo, p-chlorophenylazo, 5- Ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, For example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphini ), A phosphinyloxy group (preferably having 2 to 30 carbon atoms) A substituted or unsubstituted phosphinyloxy group, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphine having 2 to 30 carbon atoms) A ruamino group such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as trimethylsilyl, t-butyldimethylsilyl, Phenyldimethylsilyl) and the like.

  Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

  Examples of the substituent of the aryl moiety of the substituted aralkyl group include the substituents of the following substituted aryl group.

In the present specification, the aromatic group means an aryl group and a substituted aryl group. These aromatic groups may be condensed with an aliphatic ring, another aromatic ring or a heterocyclic ring. The number of carbon atoms in the aromatic group is preferably 6 to 40, more preferably 6 to 30, and still more preferably 6 to 20. Among them, the aryl group is preferably a phenyl group or naphthyl group which may have a substituent, and particularly preferably a phenyl group which may have a substituent.
Examples of the substituent of the substituted aryl group include those listed above as “substituent of substituted alkyl group, substituent of substituted alkenyl group, substituent of substituted alkynyl group, or substituent of alkyl moiety of substituted aralkyl group”. It is done.

In the present specification, a heterocyclic group contains at least one heteroatom as a ring-constituting atom, and may be either saturated or unsaturated, and may be an aromatic ring, or another ring. Even if it forms a condensed ring, it may have a substituent. The number of ring members is preferably a 4-8 membered ring.
In the present invention, it preferably contains an aromatic 5-membered or 6-membered saturated or unsaturated heterocyclic ring. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. Heterocyclic heteroatoms include B, N, O, S, Se and Te. Among them, N, O and S are preferable as the hetero atom of the heterocyclic ring. The heterocyclic ring preferably has a valence (monovalence) in which the carbon atom is free (the heterocyclic group is bonded at the carbon atom). The number of carbon atoms of a preferable heterocyclic group is 1-40, More preferably, it is 1-30, More preferably, it is 1-20. Saturated heterocycles include pyrrolidine, morpholine, 2-bora-1,3-dioxolane and 1,3-thiazolidine rings. Unsaturated heterocycles include imidazole, thiazole, benzothiazole, benzoxazole, benzotriazole, benzoselenazole, pyridine, pyrimidine and quinoline rings. The heterocyclic group may have a substituent. Examples of the substituent include the above-mentioned “substituent of substituted alkyl group, substituent of substituted alkenyl group, substituent of substituted alkynyl group, or alkyl of substituted aralkyl group”. Partial substituents ".

<Singlet oxygen scavenger, radical trap agent and antioxidant>
The near-infrared absorbing material of the present invention contains at least one of a singlet oxygen scavenger, a radical trap agent, and an antioxidant. These compounds may be any compounds that can capture singlet oxygen, trap radicals, and prevent oxidation. For example, Seesorb 612 NH (Cipro Corp.), Irgastab 2002 (Ciba Geigy Corp.) )), Etc., hindered amine compounds such as Tinuvin 744 (Ciba Geigy), phenol compounds such as Irganox 1076 (Ciba Geigy), and amines such as Sumizer 9A (Sumitomo Chemical Co., Ltd.) Compounds, sulfur compounds such as Sumilizer TPM (Sumitomo Chemical Co., Ltd.), phosphorus compounds such as Sumilizer TPPR (Sumitomo Chemical Co., Ltd.), etc., and these may be used alone or in combination. It can also be used in combination with the UV absorbers described below Kill. The use amount of these compounds is preferably 0.01 to 10 moles, more preferably 0.05 to 7 moles, based on 1 mole of the compound defined in 2) above. More preferably, it is 0.1-5 mol, Most preferably, it is 0.1-2 mol.

  The compound in 1) is preferably a compound represented by the following general formula (I-1) or (I-2).

In general formula (I-1), R ¹¹ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group bonded by a carbon atom or a hydrolyzable protecting group, and R ^{12 to} R ¹⁶ are each independently Represents a hydrogen atom or a substituent, and R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ^16, and R ¹⁶ and R ¹¹ are bonded to each other to form a ring. It may be formed.
In the general formula (I-2), R ²¹ represents a hydrogen atom, an aliphatic group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy radical group or a hydroxyl group, and Q forms a 5-membered, 6-membered or 7-membered ring. R ^{22 to} R ²⁵ each independently represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom, and R ²¹ and R ²² , R ²² and R ²³ , R ²⁴ and R ²⁵ and R ²¹ and R ²⁴ may be bonded to each other to form a ring.

Here, the hydrolyzable protecting group for R ¹¹ in the general formula (I-1) is preferably a silyl group, a phosphate group or a group represented by the following general formula (IV).
Formula (IV)
R ¹¹¹ -Y ¹¹¹ -Z ¹¹¹ -
In the formula, R ¹¹¹ represents an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom, and Y ¹¹¹ represents a single bond, —O—, —S—, —N (R ¹¹² ) —, —C—. Or it represents those combined. Here, R ¹¹² represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, acyl group or sulfonyl group bonded by a carbon atom. Z ¹¹¹ represents —CO— or SO ₂ —.
R ¹¹ is preferably a hydrogen atom, an aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a heterocyclic group bonded with carbon atoms having 2 to 20 carbon atoms, or water having 1 to 20 carbon atoms. A decomposable protecting group, more preferably a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms, and a hydrolyzable protecting group having 1 to 10 carbon atoms, still more preferably a hydrogen atom and 1 to 8 carbon atoms. A hydrolyzable protecting group connected by an aliphatic group, a silyl group having 1 to 10 carbon atoms, a phosphate ester group having 1 to 10 carbon atoms, or a carbonyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom , A hydrolyzable protecting group linked by an aliphatic group having 1 to 4 carbon atoms, a silyl group having 3 to 6 carbon atoms, a phosphate ester group having 2 to 8 carbon atoms, or a carbonyl group having 1 to 8 carbon atoms. More preferably, a hydrogen atom, a trimethylsilyl group, dimethylphosphoric acid Ester group, diethyl phosphoric acid ester group, a benzoyl group or acetyl group, most preferably a hydrogen atom.

R ^{12 to} R ¹⁶ are preferably hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyl. Oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto Group, alkylthio group, arylthio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxy group Sicarbonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, more preferably hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group Cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, alkylthio group, arylthio group, An acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a silyl group, and more preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an acyloxy group, an acyl group. Amino group, carbamoyloxy group, an alkylthio group, more preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an acylamino group, and most preferably a hydrogen atom or an alkyl group. Moreover, it is preferable that one or both of R ¹² and R ¹⁶ is a tertiary alkyl group.

In general formula (I-2), R ²¹ is preferably a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, an oxy radical group, or a hydroxyl group, more preferably a hydrogen atom, An alkyl group having 1 to 3 carbon atoms, an acyl group having 2 to 7 carbon atoms, an oxy radical group or a hydroxyl group, more preferably a hydrogen atom, an acetyl group, an oxy radical group or a hydroxyl group, most preferably a hydrogen atom. It is.
R ^{22 to} R ²⁵ are preferably a hydrogen atom or an aliphatic group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, still more preferably a hydrogen atom or 1 carbon atom. Is an alkyl group of ˜2, most preferably R ^{22 to} R ²⁵ are all methyl groups.
Q is preferably a nonmetallic atom group necessary for forming a 5- to 7-membered ring having at least one oxygen atom, sulfur atom or nitrogen atom as a ring-constituting atom, and more preferable as a ring-constituting heteroatom. Is an oxygen atom or a nitrogen atom, more preferably a nitrogen atom. The number of ring members is preferably a 5- to 7-membered ring, more preferably a 6-membered ring. Most preferred is when Q forms a piperidine ring.

  Specific examples of the compound defined in 1) of the present invention are shown below, but the present invention is not limited to these.

  These compounds are described in British Patent Nos. 1,326,889, 1,354,313, 1,410,846, U.S. Pat. Nos. 3,336,135 and 4,268,593. Nos. 4,558,131 and 4,584,265, Japanese Patent Publication Nos. 51-1420 and 52-6523, Japanese Patent Publication Nos. 58-114036 and 59. No. 5246, No. 61-73152, No. 61-86750, No. 61-90155, No. 61-90156, No. 61-172246, etc., or the like. It can be synthesized by the method.

<Compound whose spectral absorption maximum wavelength in the range of 400 to 1600 nm in the solution is 700 nm or more>
The near-infrared absorbing material of the present invention contains at least one compound having a spectral absorption maximum wavelength in the range of 400 to 1600 nm in the solution of 700 nm or more. This compound functions as a near-infrared absorber and an infrared absorber in the present invention. The spectral absorption maximum wavelength is preferably 730 nm or more, more preferably 760 nm or more, and particularly preferably 780 nm or more from the viewpoint of so-called “invisibility” that it is not felt by human eyes. .
Examples of the compound having a spectral absorption maximum wavelength in the range of 400 to 1600 nm in the solution of 700 nm or more include, for example, phthalocyanine compounds, cyanine compounds, squarylium compounds, diimonium compounds, polymethine compounds, azomethine compounds, oxonol compounds, croconium compounds, and dithiol metal complex compounds. Is mentioned. Examples thereof include those described in JP-A No. 2000-281919, JP-A No. 10-180947, and JP-A No. 2003-139946.
Of these, preferred are phthalocyanine compounds, cyanine compounds, squarylium compounds, diimonium compounds, polymethine compounds, oxonol compounds and croconium compounds, more preferred are phthalocyanine compounds, cyanine compounds, diimonium compounds, oxonol compounds and croconium compounds, and even more preferred. A phthalocyanine compound, a diimonium compound, an oxonol compound, and a croconium compound, more preferably a phthalocyanine compound, a diimonium compound, and an oxonol compound, and most preferably a phthalocyanine compound.

  A preferable compound as these compounds is represented by the following general formula (II-1).

In the general formula (II-1), R ^{211 to} R ²¹⁴ , R ^{221 to} R ²²⁴ , R ^{231 to} R ²³⁴ , and R ^{241 to} R ²⁴⁴ each independently represent a hydrogen atom or a substituent, Adjacent groups may be bonded to each other to form a ring. M ²¹¹ represents two atoms selected from the group consisting of a hydrogen atom and a monovalent metal atom, a divalent metal atom, or a divalent substituted metal atom including a trivalent or tetravalent metal atom.

Examples of the substituent represented by R ^{211 to} R ²¹⁴ , R ^{221 to} R ²²⁴ , R ^{231 to} R ²³⁴ , and R ^{241 to} R ²⁴⁴ include the substituents of the above substituted alkyl groups, the substituents of the substituted alkenyl groups, and the substituted alkynyls. And a substituent of the alkyl part of the substituted aralkyl group, preferably a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy Group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, Sulfamoylamino group, alkyl or aryl Sulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, Imido group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, more preferably halogen atom, alkyl group, aryl group, cyano group, hydroxyl group, nitro group, carboxyl group, Alkoxy, aryloxy, silyloxy, heterocyclic oxy, acyloxy, carbamoyloxy, amino, acylamino, aminocarbonylamino, alkoxycarbonylamino, aryloxycal Nylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, carbamoyl group , Imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, more preferably halogen atom, alkyl group, aryl group, hydroxyl group, alkoxy group, aryloxy group, amino group Group, mercapto group, alkylthio group, arylthio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, more preferably halogen atom, alkyl group, aryl group, An alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group, more preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number An aryloxy group having 6 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an arylthio group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, carbon An alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, and an arylthio group having 6 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, An aryloxy group having 6 to 8 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and an arylthio group having 6 to 8 carbon atoms, and most preferably an alkoxy group having 1 to 4 carbon atoms. A.
It is also preferable that R ²¹² and R ²¹³ , R ²²² and R ²²³ , R ²³² and R ^233, and R ²⁴² and R ²⁴³ are bonded to each other to form a condensed benzene ring.

M ²¹¹ is preferably 2 hydrogen atoms, 2 Li ⁺ , 2 Na ⁺ , 2 K ⁺ , 2 Rb ⁺ , 2 Cs ⁺ and Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Ti ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ²⁺ , Ru ²⁺ , Rh ²⁺ , Pd ²⁺ , Pt ²⁺ , Ba ²⁺ , Cd ²⁺ , Hg ²⁺ , Pb ²⁺ , Sn ²⁺ , Al—Cl, Al—Br, Al—F, Al—I, Ga—Cl, Ga—F, Ga—I, Ga—Br, In -Cl, In-Br, In- I, In-F, Tl-Cl, Tl-Br, Tl-I, Tl-F, Mn-OH, Fe-Cl, Ru-Cl, CrCl 2, SiCl 2, SiBr _{2, SiF 2, SiI 2,} ZrCl 2, GeCl 2, GeBr 2, GeI 2, GeF 2, SnCl 2, SnBr 2, SnI 2, SnF 2, TiCl 2, TiBr 2, _{iF 2, Si (OH) 2} , Ge (OH) 2, Zr (OH) 2, Mn (OH) 2, Sn (OH) 2, TiR 2, CrR 2, SiR 2, SnR 2, GeR 2, Si ( OR) ₂ , Sn (OR) ₂ , Ge (OR) ₂ , Ti (OR) ₂ , Cr (OR) ₂ , Sn (SR) ₂ , Ge (SR) ₂ [R represents an aliphatic group, an aromatic group. VO, MnO, TiO, more preferably 2 hydrogen atoms, 2 Li ⁺ , 2 Na ⁺ , 2 K ⁺ , 2 Rb ⁺ and Be ²⁺ , Mg ^{2 +} , Ca ²⁺ , Ti ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ²⁺ , Ru ²⁺ , Rh ²⁺ , Pd ²⁺ , Pt ²⁺ , ^{Ba 2+, Sn 2+, Al-} Cl, Al-Br, Ga-Cl, Ga-F, Ga-I, Ga-Br, In-Cl, In-Br, Tl-Cl, Tl-Br, Mn- OH, F e-Cl, Ru-Cl, CrCl ₂ , SiCl ₂ , SiBr ₂ , ZrCl ₂ , GeCl ₂ , GeBr ₂ , SnCl ₂ , SnBr ₂ , TiCl ₂ , TiBr ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , SnR ₂ , GeR ₂ , Si (OR) ₂ , Sn (OR) ₂ , Ge (OR) ₂ , Ti (OR) ₂ , Cr (OR) ₂ , Sn (SR) ₂ , Ge (SR) ₂ [R represents an aliphatic group or an aromatic group], VO, MnO or TiO, more preferably 2 Hydrogen atoms, 2 Li ⁺ , 2 Na ⁺ , 2 K ⁺ , and Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Ti ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ^{2 +, Ni 2+, Cu 2+,} Zn 2+, Ru 2+, Rh 2+, Pd 2+, Pt 2+, Ba 2+, Sn 2+, Al- l, Ga-Cl, In- Cl, Tl-Cl, Mn-OH, Fe-Cl, Ru-Cl, CrCl 2, SiCl 2, ZrCl 2, GeCl 2, TiCl 2, Si (OH) 2, Ge (OH ) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , GeR ₂ , Si (OR) ₂ , Ge (OR) ₂ , Ti (OR) ₂ , Cr (OR) ₂ [R represents an aliphatic group or an aromatic group], VO, MnO, or TiO. Further preferred M ²¹¹ is two hydrogen atoms, Mn ²⁺ , VO, Zn ²⁺ or Cu ²⁺ , most preferably VO, Zn ²⁺ or Cu ²⁺ .

  Specific examples of the compound defined in the above 2) are shown below, but the present invention is not limited thereto.

  The above compound can be easily synthesized by the method described in Chemistry-A. European Journal, Vol. 9, 5123-5134 (issued in 2003) or a method analogous thereto. For example, a phthalocyanine having a metal at the center can be directly synthesized from the corresponding phthalic acid or a derivative thereof (an acid anhydride, diamide, dinitrile, etc.) in the presence of a metal compound. At this time, it is preferable that a catalyst (for example, ammonium molybdate) and urea coexist. Alternatively, after synthesizing a metal compound of phthalocyanine once using a lithium compound, it can be synthesized using a metal compound as described later, and this method is particularly preferred for synthesizing a metal compound of naphthalocyanine. More specifically, the ratio of the raw materials when using a metal compound of phthalocyanine and a metal compound is preferably 0.1 to 10 mol of metal compound with respect to 1 mol of the metal compound of phthalocyanine, Preferably it is 0.5-5 mol, More preferably, it is 1-3 mol. As the metal compound, inorganic and organic metal compounds can be used, for example, halides (eg, chlorinated products, brominated products), sulfates, nitrates, cyanides, acetates, metal acetylacetonates, etc., preferably chlorides. Products, sulfates, cyanides, and acetates, more preferably chlorides and acetates, and most preferably acetates.

  Solvents used in the reaction are, for example, amide solvents (eg, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (eg, sulfolane), sulfoxide solvents (eg, dimethyl sulfoxide). , Ether solvents (eg dioxane, cyclopentyl methyl ether), ketone solvents (eg acetone, cyclohexanone), hydrocarbon solvents (eg toluene, xylene), halogen solvents (eg tetrachloroethane, chlorobenzene), alcohol solvents (eg 1-butanol, ethylene glycol, cyclohexanol) and pyridine solvents (for example, pyridine, γ-picoline, 2,6-lutidine) are used alone or in combination. Of these, amide solvents, sulfone solvents, ether solvents, hydrocarbon solvents, halogen solvents, pyridine solvents are preferred, and sulfone solvents, ether solvents, hydrocarbon solvents, halogen solvents are more preferred. More preferred are ether solvents, hydrocarbon solvents, halogen solvents, more preferred are halogen solvents, and chlorobenzene is most preferred. The reaction temperature is -30 to 250 ° C, preferably 0 to 200 ° C, more preferably 20 to 150 ° C, still more preferably 50 to 100 ° C, and the reaction time is 5 minutes to 30 hours.

<Ultraviolet absorber and fluorescent brightener>
In the present invention, it is preferable to further contain 3) at least one of an ultraviolet absorber and an optical brightener. These compounds preferably have a spectral absorption characteristic of a compound having a spectral absorption maximum wavelength in a range of 270 to 1600 nm in a solution of 470 nm or less, more preferably 430 nm or less, still more preferably 410 nm or less, and most preferably 380 nm or less. It is. As the chemical structural formula, compounds represented by any of the following general formulas (III-1) to (III-9) are preferable.

  The compounds represented by the general formulas (III-1) to (III-9) are described below.

In the formula, R ^{311 to} R ³¹⁴ , R ^{321 to} R ³⁶⁶ , R ^{371 to} R ³⁷⁸ , R ^{381 to} R ³⁸⁴ , R ^{386 to} R ³⁸⁹ , and R ^{391 to} R ⁴⁰⁰ each independently represent a hydrogen atom or a substituent. ^R315 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom. R ³⁷⁹ , R ³⁸⁰ and R ³⁸⁵ represent a substituent. X ³⁴¹ represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom. n ₃₇₉ and n ₃₈₀ each independently represents an integer of 0 to 4, when n ₃₇₉ and n ₃₈₀ is 2 or more, plural R ³⁷⁹ and R ³⁸⁰ may be the same or different. n ₃₈₅ represents an integer of 0 to 6, and when n ₃₈₅ is 2 or more, a plurality of R ³⁸⁵ may be the same or different.
Here, groups adjacent to each other may be bonded to each other to form a ring.

Examples of the substituents represented by R ^{311 to} R ³¹⁴ , R ^{321 to} R ³⁶⁶ , R ^{371 to} R ³⁷⁸ , R ^{381 to} R ³⁸⁴ , R ^{386 to} R ³⁸⁹ , and R ^{391 to} R ⁴⁰⁰ include the above-mentioned substituted alkyl groups. Examples include a substituent, a substituent of a substituted alkenyl group, a substituent of a substituted alkynyl group, or a substituent of an alkyl moiety of a substituted aralkyl group.
R ^{311 to} R ³¹⁴ , R ^{321 to} R ³⁶⁶ , R ^{371 to} R ³⁷⁸ , R ^{381 to} R ³⁸⁴ , R ^{386 to} R ³⁸⁹ , and R ^{391 to} R ⁴⁰⁰ are more preferably a hydrogen atom, a halogen atom, an alkyl group, or an alkenyl. Group, alkynyl group, aryl group, cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group , Aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group , Al Le or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group.

R ^{311 to} R ³¹⁴ are more preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a cyano group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, an amino group, or an alkylthio group. , An arylthio group, an imide group and a silyl group, more preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a silyloxy group and an amino group, more preferably a hydrogen atom and a halogen atom. And an alkyl group, and most preferably a hydrogen atom and a halogen atom.

R ³¹⁵ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or 2 carbon atoms. -30 alkynyl groups and aryl groups having 6 to 30 carbon atoms, more preferably hydrogen atoms, alkyl groups having 1 to 25 carbon atoms, alkenyl groups having 2 to 25 carbon atoms and aryl groups having 6 to 25 carbon atoms. More preferably an alkyl group having 1 to 22 carbon atoms and an aryl group having 6 to 22 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and most preferably an orthohydroxy having 6 to 20 carbon atoms. It is a phenyl group.

R ^{321 to} R ³³⁰ are preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a cyano group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, an acyloxy group, an acylamino group, Aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, sulfamoyl group, sulfo group, alkyl or arylsulfonyl group, Acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, silyl group, more preferably hydrogen atom, halogen atom, alkyl group, aryl group, hydroxyl group, alkoxy Aryloxy group, acyloxy group, acylamino group, alkyl or arylsulfonylamino group, sulfamoyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, more preferably hydrogen atom, halogen atom, alkyl group, A hydroxyl group, an alkoxy group, an acyloxy group, an acylamino group, an acyl group, an alkoxycarbonyl group, and a carbamoyl group, and more preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an acylamino group, and an alkoxycarbonyl group. . Most preferably, R ³²¹ is a hydroxy group.

R ^{331 to} R ³⁴⁰ are preferably hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, acylamino group, Aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, sulfamoyl group, sulfo group, alkyl or arylsulfonyl group, Acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, silyl group, more preferably hydrogen atom, halogen atom, alkyl group, aryl group, hydroxyl group, alkoxy , Aryloxy group, acyloxy group, acylamino group, alkyl or arylsulfonylamino group, sulfamoyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, more preferably hydrogen atom, halogen atom, alkyl group, A hydroxyl group, an alkoxy group, an acyloxy group, an acylamino group, an acyl group, an alkoxycarbonyl group, and a carbamoyl group, and more preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an acylamino group, and an alkoxycarbonyl group. . Most preferably, R ³³¹ is a hydroxy group.

R ^{341 to} R ³⁵⁰ are preferably hydrogen atom, halogen atom, alkyl group, aryl group, hydroxyl group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyl Oxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, alkylthio group, arylthio group, sulfamoyl group, acyl group, Aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, silyl group, more preferably hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, amino , An acylamino group, an alkylthio group, an arylthio group, more preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group, an acylamino group, and most preferably a hydrogen atom, an alkoxy group, an amino group.

X ³⁴¹ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or 2 carbon atoms. -30 alkynyl groups and aryl groups having 6 to 30 carbon atoms, more preferably hydrogen atoms, alkyl groups having 1 to 25 carbon atoms, alkenyl groups having 2 to 25 carbon atoms and aryl groups having 6 to 25 carbon atoms. And more preferably an alkyl group having 1 to 22 carbon atoms and an aryl group having 6 to 22 carbon atoms, and most preferably an alkyl group having 1 to 18 carbon atoms.

R ^{351 to} R ³⁶⁰ are preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group, an acylamino group, a mercapto group, an alkylthio group, Arylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, silyl group, more preferably hydrogen atom, halogen atom, alkyl group, aryl group, Most preferred are a hydroxyl group, an alkoxy group, an acyloxy group, an amino group, an acylamino group, an arylthio group, an acyl group, an aryloxycarbonyl group, and an alkoxycarbonyl group, and R ³⁵¹ is a hydroxy group.

R ^{361 to} R ³⁶⁶ are preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, or an alkoxycarbonyl group. , Acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or aryl A sulfonylamino group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an imide group, more preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, A minocarbonylamino group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl and an arylsulfonylamino group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl Group, an acylamino group.

Here, R ³⁶² , R ³⁶³ , R ³⁶⁴ and R ³⁶⁶ are more preferably hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, alkoxy group, aryloxy group, silyl group. More preferably a hydrogen atom, a halogen atom or an alkyl group, and most preferably a hydrogen atom.
On the other hand, R ³⁶⁵ is more preferably a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group. , Carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group , Alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, aacyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, silyl group, more preferably a hydrogen atom, Alkyl group, aryl group, heterocyclic group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, more preferably A heterocyclic group, an amino group, and an acylamino group;

R ³⁷¹ , R ³⁷⁴ , R ³⁷⁵ and R ³⁷⁸ are more preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, a hydroxyl group, an alkoxy group, an amino group, and a mercapto group, and more preferably a hydrogen atom. , A halogen atom, an alkyl group, a hydroxyl group, an alkoxy group and an amino group, most preferably a hydrogen atom.

R ³⁷² , R ³⁷³ , R ³⁷⁶ and R ³⁷⁷ are more preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group, an acylamino group, a mercapto group, An alkylthio group and a sulfamoyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an amino group, a mercapto group, and an alkylthio group, and more preferably a hydrogen atom, an alkyl group, an aryl group, and an alkoxy group. .

R ³⁷⁹ and R ³⁸⁰ are more preferably a halogen atom, alkyl group, aryl group, cyano group, hydroxyl group, alkoxy group, aryloxy group, silyloxy group, amino group, acylamino group, mercapto group, alkylthio group, arylthio group, Heterocyclic thio group and silyl group, more preferably halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group and heterocyclic thio group, more preferably halogen atom and alkyl group An aryl group or an alkoxy group.
n ₃₇₉ and n ₃₈₀ are preferably 0 to 3, more preferably 0 to 2, still more preferably 0 or 1, and most preferably 0.

Preferred ranges of R ³⁸¹ , R ³⁸⁴ , R ³⁸⁶ and R ³⁸⁹ are the same as those for R ³⁷¹ described above. The preferred ranges of R ³⁸² , R ³⁸³ , R ³⁸⁷ and R ³⁸⁸ are the same as those for R ³⁷² described above.
R ³⁸⁵ is preferably a halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, amino group, acylamino group, mercapto group, alkylthio group , An arylthio group, a heterocyclic thio group, and a silyl group, more preferably a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an alkylthio group, and an arylthio group, still more preferably a halogen atom, An alkyl group, an alkoxy group, an amino group, and an alkylthio group are preferable, and a halogen atom and an alkyl group are more preferable.
n ₃₈₅ is preferably 0 to 4, more preferably 0 to 2, still more preferably 0 to 1, and most preferably 0.

Preferred ranges for R ³⁹¹ , R ³⁹⁴ , R ³⁹⁷ and R ⁴⁰⁰ are the same as those for R ³⁷¹ described above. The preferred ranges of R ³⁹² , R ³⁹³ , R ³⁹⁸ and R ³⁹⁹ are the same as R ³⁷² described above.
R ³⁹⁵ and R ³⁹⁶ are preferably hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, nitro group, hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, amino group , Acylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, silyl group, more preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an alkoxy group , Aryloxy group, silyloxy group, amino group, acylamino group, alkylthio group, arylthio group, more preferably a hydrogen atom, halogen atom, alkyl group, cyano group, alkoxy group, amino group, more preferably a hydrogen atom. , An alkyl group.

  Of the compounds represented by the general formulas (III-1) to (III-9), the general formulas (III-1), (III-2), (III-3), (III-4), ( III-6), (III-7) or (III-9), and more preferred are those represented by the general formulas (III-1), (III-2), (III-3), (III- 6) or a compound represented by (III-7), more preferably a compound represented by the general formula (III-1), (III-2), (III-3) or (III-6) More preferably a compound represented by the general formula (III-1), (III-2) or (III-6), most preferably a compound represented by the general formula (III-1).

  Hereinafter, exemplary compounds (III-1) to (III-165) are shown as specific examples of the compound defined in 3) above, but the present invention is not limited thereto.

  These compounds are disclosed in JP-B-50-25337, U.S. Pat. No. 3,785,827, JP-A-5-4449, JP-B48-30492, JP-A-2-188573, EP0684278A1. Can be easily synthesized by the method described in No. Specification, Journal of Organic Chemistry, Vol. 23, p. 1344 (issued in 1958) or the like. Also, it is sold by Ciba Specialty Chemicals Co., Ltd. under the trade name such as “Chinubin 109”, the product group of Whitsufuluor manufactured by Sumitomo Chemical Co., Ltd., and the product group of Hakkol manufactured by Showa Chemical Co., Ltd. It is possible to select from the product group of Hostalx manufactured by Hoechst Co., Ltd. and the product group of Kayalight manufactured by Nippon Kayaku Co., Ltd.

<Content ratio of compounds contained in the near-infrared absorbing material of the present invention>
In the present invention, the compound defined in 1) is preferably in a total mole of 0.1 mol or more, more preferably 0.1 to 2.0, relative to 1 mol of the compound defined in 2). It is preferable to use 1 mol, more preferably 0.1 to 1.0 mol, and most preferably 0.1 to 0.5 mol.
In the present invention, the compound defined in 3) is preferably 0.1 mol or more, more preferably 0.1 to 1 mol relative to 1 mol of the compound defined in 2). It is preferable to use 2.0 mol, more preferably 0.1 to 1.0 mol, and most preferably 0.1 to 0.5 mol.

<Usage method of near infrared ray absorbing material of the present invention>
The near-infrared absorbing material according to the present invention comprises the compound defined in 1) above, the compound defined in 2) above, and further the compound defined in 3) as is or in solution, or Used in combination with binders and other compounds for various applications as near-infrared absorbing materials by polymerizing a mixture of paper, resin sheet, resin, film, glass, metal plate, etc., kneading, hard coat or monomer. Can be used for That is, it can be used for optical recording media for long wavelength lasers, recording materials for invisible printing, optical filters, architectural and agricultural filters, coating materials, and the like. Of these, optical filters, architectural and agricultural filters, coating materials, and the like are preferable, and optical filters are more preferable.

<The manufacturing method of the near-infrared absorption material of this invention>
The near-infrared absorbing material in the present invention comprises, for example, a compound (for example, chloroform) containing the compound defined in 1) above, the compound defined in 2) above, and further the compound defined in 3) above. , Methylene chloride, toluene, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, dibutyl ether, tetrahydrofuran, dimethylformamide) or a resin (for example, ABS resin, polyethylene resin, polypropylene resin, polyvinyl chloride) Resin, polycarbonate resin, polystyrene resin, polyacrylonitrile resin, methacrylonitrile resin, polymethacrylic acid ester resin, polyester resin), and kneading or, for example, to the place where the above solvent is dissolved or dispersed Heating dissolved the thinned by the addition of fat, obtained by coating as it solidifies, or a material obtained by dissolving or dispersing, for example, in the resin film in a solvent.

  Since the near-infrared absorbing material of the present invention can achieve both light resistance and other physical properties, it can be used for new applications.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
For convenience of explanation, the compound defined in 1) above is referred to as Compound (I), the compound defined in 2) above is referred to as Compound (II), and the compound defined in 3) above is referred to as Compound (III).

Example 1
(Manufacture of near infrared absorption filter)
In 10 g of polystyrene, the compound (I) having the structure and amount shown in the following Tables 1-2, the compound (III) having the structure and amount shown in the following Tables 1-2, and 0.1 g of the exemplary compound (II-1) A solution prepared by adding 100 ml of chloroform and stirring and dissolving at 40 ° C. for 15 minutes was applied to a glass plate and blown and dried at room temperature to prepare a sample.
(Light resistance test)
The sample obtained above was irradiated with a xenon lamp at 95,000 lux for 3 days, and the residual ratio was obtained by measuring the concentration of the spectral absorption maximum wavelength of the exemplified compound (II-1) with respect to that before irradiation. The property (light fastness) was evaluated.

  As shown in Tables 1 and 2 above, the samples of the present invention all show good light resistance, and the effect is very large.

Example 2
(Manufacture of near infrared absorption filter)
10 g of polystyrene, compound (I) having the structure and amount shown in Tables 3 to 5 below, compound (III) having the structure and amount shown in Tables 3 to 5 below, and compound (II) having the structure shown in Tables 3 to 5 below A sample prepared by adding 100 ml of chloroform to 0.1 g and stirring and dissolving at 40 ° C. for 15 minutes was applied to a glass plate and blown and dried at room temperature.

(Light resistance test)
The sample obtained above was irradiated with a xenon lamp at 95,000 lux for 3 days, and the residual ratio was determined by measuring the concentration of the spectral absorption maximum wavelength of compound (II) with respect to the pre-irradiation. Fastness) was evaluated.

上記表３〜５に示すように、化合物（ＩＩ）を種々変更して調べた結果も、本発明の試料は、いずれも良好な耐光性を示し、その効果は非常に大きい。

As shown in Tables 3 to 5, as a result of various changes in the compound (II), the samples of the present invention all show good light resistance, and the effect is very large.

  The physical property values of the compounds used in the examples of the present invention are shown below.

Claims (9)

  1) Contains at least one of a singlet oxygen scavenger, a radical trap agent and an antioxidant, and 2) at least one compound having a spectral absorption maximum wavelength in the range of 400 to 1600 nm in the solution of 700 nm or more. A near-infrared absorbing material characterized by: 2. The near-infrared absorbing material according to claim 1, wherein at least one of the compounds in 1) is a compound represented by the following general formula (I-1) or (I-2).

[In General Formula (I-1), R ¹¹ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group bonded by a carbon atom or a hydrolyzable protecting group, and R ^{12 to} R ¹⁶ are each independently selected. Represents a hydrogen atom or a substituent, and R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ^16, and R ¹⁶ and R ¹¹ are bonded to each other to form a ring. May be formed. R ²¹ represents a hydrogen atom, an aliphatic group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy radical group or a hydroxyl group, and Q is a nonmetallic atom group necessary for forming a 5-membered, 6-membered or 7-membered ring R ^{22 to} R ²⁵ each independently represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom, and R ²¹ and R ²² , R ²² and R ²³ , R ²⁴ and R ²⁵ and R ²¹ and R ²⁴ may be bonded to each other to form a ring. ]   The near-infrared absorbing material according to claim 1 or 2, comprising two or more kinds of the compounds in 1).   Furthermore, 3) At least 1 sort (s) of a ultraviolet absorber and a fluorescent whitening agent is contained, The near-infrared absorption material of any one of Claims 1-3 characterized by the above-mentioned.   5. The near-infrared absorbing material according to claim 4, wherein the compound in 3) has a spectral absorption maximum wavelength in the range of 270 nm to 1600 nm in the solution of 410 nm or less. 6. The near-infrared absorbing material according to claim 4, wherein the compound in 3) is a compound represented by any one of the following general formulas (III-1) to (III-9).

[Wherein R ^{311 to} R ³¹⁴ , R ^{321 to} R ³⁶⁶ , R ^{371 to} R ³⁷⁸ , R ^{381 to} R ³⁸⁴ , R ^{386 to} R ³⁸⁹ , and R ^{391 to} R ⁴⁰⁰ each independently represents a hydrogen atom or a substituent. . ^R315 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom. R ³⁷⁹ , R ³⁸⁰ and R ³⁸⁵ represent a substituent. X ³⁴¹ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom. n ₃₇₉ and n ₃₈₀ each independently represents an integer of 0 to 4, when n ₃₇₉ and n ₃₈₀ is 2 or more, plural R ³⁷⁹ and R ³⁸⁰ may be the same or different. n ₃₈₅ represents an integer of 0 to 6, and when n ₃₈₅ is 2 or more, the plurality of R ³⁸⁵ may be the same or different. Here, groups adjacent to each other may be bonded to each other to form a ring. ]   The near-infrared absorbing material according to any one of claims 4 to 6, comprising two or more kinds of the compound in 3).   The near-infrared absorbing material according to claim 1, wherein the spectral absorption maximum wavelength in 2) is 780 nm or more. The near-infrared absorbing material according to any one of claims 1 to 8, wherein the compound in 2) is a compound represented by the following general formula (II-1).

[In General Formula (II-1), R ^{211 to} R ²¹⁴ , R ^{221 to} R ²²⁴ , R ^{231 to} R ²³⁴ , and R ^{241 to} R ²⁴⁴ each independently represent a hydrogen atom or a substituent, Of these, adjacent groups may be bonded to each other to form a ring. M ²¹¹ represents two atoms selected from the group consisting of a hydrogen atom and a monovalent metal atom, a divalent metal atom, or a divalent substituted metal atom including a trivalent or tetravalent metal atom. ]