WO2010035484A1 - Method for producing azo metal complex dye - Google Patents

Abstract

A method for producing an azo metal complex dye wherein an azo dye having a partial structure represented by general formula (A) and a metal ion are reacted in the presence of a compound represented by general formula (1), thereby obtaining a complex of the azo dye and the metal ion.  In general formula (A), Q¹ represents an atomic group forming a nitrogen-containing heterocyclic ring together with an adjacent nitrogen atom and carbon atom; Y¹ represents a hydrogen atom which may be dissociated during formation of the azo metal complex dye; and * represents the bonding position with an -N=N- group.  In general formula (1), R¹¹-R¹⁴ independently represent a hydrogen atom or a substituent.

Description

Method for producing azo metal complex dye Cross-reference of related applications

This application claims the priority of Japanese Patent Application No. 2008-245926 filed on Sep. 25, 2008, the entire description of which is specifically incorporated herein by reference.

The present invention relates to a method for producing an azo metal complex dye, and more specifically, an azo metal complex excellent in light resistance, heat resistance, solubility, and film forming property and suitable as a dye for a recording layer of an optical information recording medium. The present invention relates to a method for producing a pigment.

BACKGROUND ART Azo metal complex dyes are used as photosensitive materials in various applications. In recent years, various azo metal complex dyes have been proposed as dyes for recording layers of optical information recording media. Such azo metal complex dyes are described in, for example, JP 2000-168237 A, JP 2008-105380 A, and English family members US2008 / 0081285A1 and US2008 / 0081286A1. The entire description of the above application is specifically incorporated herein by reference.

DISCLOSURE OF THE INVENTION The recording layer dye of an optical information recording medium has high solubility and excellent stability in a solution in order to enable formation of a recording layer by a film forming method such as a spin coating method. Is required.

Therefore, an object of the present invention is to provide an azo metal complex dye having excellent solubility and / or stability in a solution.

As a result of intensive studies to achieve the above object, the present inventors have obtained the following knowledge.
Conventionally, for azo metal complex dyes, wavelength control and solubility control have been performed mainly by changing metal ions and azo ligands (see, for example, the above publication).
On the other hand, the present inventors have newly investigated that the reaction conditions at the time of complex formation between an azo dye and a metal ion greatly affect the solubility of the obtained azo metal complex dye and the stability in solution. found.
Therefore, the present inventors have made further studies based on the above findings, and as a result, complex formation reaction between an azo dye having a specific partial structure and a metal ion can be performed by, for example, primary amine (such as n-butylamine) or tertiary. When the reaction was carried out in the presence of an amine (such as triethylamine), the resulting azo metal complex dye had poor solubility or poor stability in solution. Surprisingly, when it was carried out in the presence of, there were unique phenomena such as improved solubility and improved stability in solution.
The present invention has been completed based on the above findings.

In one embodiment of the present invention, an azo dye having a partial structure represented by the following general formula (A) is reacted with a metal ion in the presence of a compound represented by the following general formula (1). The present invention relates to a method for producing an azo metal complex dye that obtains a complex of a dye and a metal ion.

In the general formula (A), Q ¹ represents an atomic group that forms a nitrogen-containing heterocyclic ring together with adjacent nitrogen atoms and carbon atoms, Y ¹ represents a hydrogen atom that may be dissociated during formation of the azo metal complex dye, * Represents a bonding position to the —N═N— group.

In the general formula (1), R ¹¹ to R ¹⁴ each independently represents a hydrogen atom or a substituent.

The azo dye may be an azo dye represented by the following general formula (B).

In the general formula (B), Q ¹ represents an atomic group that forms a nitrogen-containing heterocyclic ring together with adjacent nitrogen atoms and carbon atoms, and Q ² represents an atomic group that forms a heterocyclic ring or carbocyclic ring with two adjacent carbon atoms. Y ¹ represents a hydrogen atom that may be dissociated when the azo metal complex dye is formed, and Y ² represents a group containing a hydrogen atom that may be dissociated when the azo metal complex dye is formed.

The partial structure represented by the general formula (A) can be a partial structure represented by the following general formula (C).

In general formula (C), R ¹ and R ² each independently represents a hydrogen atom or a substituent, Y ¹ has the same definition as in general formula (A), and * represents a —N═N— group. Represents the bonding position of.

R ¹ may represent an electron withdrawing group.

Q ² in the general formula (B) can be an atomic group forming a pyrazole ring.

The compound represented by the general formula (1) may be 1,8-diazabicyclo [5.4.0] -7-undecene or 1,5-diazabicyclo [4.3.0] -5-nonene. .

The amount of the compound represented by the general formula (1) can be 2.00 equivalents or more and 6.00 equivalents or less with respect to the azo dye.

In the above reaction, 1.00 equivalent or more and 1.25 equivalent or less of metal ions can be reacted with the azo dye.

By the above reaction, a multinuclear complex containing two or more metal ions can be obtained.

By the above reaction, a complex of an azo dye and a metal ion having the same number or more than the number of the azo dye can be obtained.

The metal ion may be a transition metal ion.

The transition metal ion may be a copper ion.

According to the present invention, an azo metal complex dye excellent in solubility and / or stability in a solution can be produced.
Furthermore, according to the present invention, an azo metal complex dye having excellent dye film stability, light resistance, and storage stability can be produced.
Since the azo metal complex dye obtained from the present invention can have the above-mentioned characteristics desirable as a dye for recording layers of optical information recording media, various light such as Blu-ray discs and other optical information recording media compatible with short wavelength lasers can be used. It is suitable as a dye for a recording layer of an information recording medium.

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an azo metal complex dye of the present invention comprises reacting an azo dye with a metal ion in the presence of a compound represented by the general formula (1). An azo metal complex dye, which is a complex of benzene and a metal ion, is obtained. The azo metal complex dye may be a complex containing an azo dye and a metal ion as constituent components, such as an ion necessary for neutralizing the charge of the ligand or molecule together with the azo dye and the metal ion. Other components may be included.
Hereinafter, the metal ion, the compound represented by the general formula (1), and the azo dye will be described in order.

Metal ion In the present invention, the metal ion is not particularly limited, but a transition metal ion is preferable. The transition metal ion represents an ion of a transition metal atom. The transition metal atom is an element having an incomplete d electron shell, including elements of Group IIIa to Group VIII and Group Ib of the periodic table. Although it does not specifically limit as a transition metal atom, Mn, Fe, Co, Ni, Cu, and Zn are preferable, Co, Ni, Cu, and Zn are more preferable, Cu is still more preferable.

The transition metal ion is preferably a monovalent or divalent transition metal ion. Examples of monovalent or divalent transition metal ions include Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ⁺ , Cu ²⁺ , Zn ²⁺ , Ru ²⁺ , Pd ²⁺ , and Ag. ⁺ , Re ⁺ , Pt ²⁺ , Au ^{+ and the} like, preferably including transition metal ions such as Co ²⁺ , Ni ²⁺ , Cu ²⁺ and Zn ^2+, and more preferably Cu ²⁺ .

Compound Represented by General Formula (1) In the present invention, in forming a complex of an azo dye having a partial structure described later and a metal ion, the compound represented by the general formula (1) In the presence of

[In General Formula (1), R ¹¹ to R ¹⁴ each independently represents a hydrogen atom or a substituent. ]

Hereinafter, the general formula (1) will be described.

R ¹¹ to R ¹⁴ each independently represents a hydrogen atom or a substituent. Although it does not specifically limit as a substituent, For example, an alkyl group (a cycloalkyl group and a bicycloalkyl group are included), an alkenyl group (a cycloalkenyl group and a bicycloalkenyl group are included), an alkynyl group, an aryl group, a heterocyclic group, carboxyl Examples include groups, sulfamoyl groups, alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups.

More specifically, an 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 group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group), Bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, 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 a ring structure There tricyclo structure is intended to encompass such. 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 are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl group, allyl group, prenyl group, geranyl group, oleyl group), cycloalkenyl groups (preferably having 3 carbon atoms). A substituted or unsubstituted cycloalkenyl group having ˜30, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl, 2-cyclohexene- 1-yl), a bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, one hydrogen atom of a bicycloalkene having one double bond. Monovalent groups removed, such as bicyclo [2,2,1] hept-2-en-1-yl, bicycl [2,2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, a trimethylsilylethynyl group, an aryl group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms) An aryl group such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or A monovalent group obtained by removing one hydrogen atom from a non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), carboxyl group, sulfamoyl group (preferably carbon 0-30 substituted or unsubstituted sulfamoyl groups such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group Group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6 to 30 Substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, p-methylphenylsulfinyl group), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted groups having 1 to 30 carbon atoms) Substituted alkylsulfonyl groups, 6 30 substituted or unsubstituted arylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group), acyl groups (preferably formyl group, substituted or unsubstituted groups having 2 to 30 carbon atoms) A substituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a heterocyclic carbonyl group bonded to the carbonyl group by a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as acetyl Group, pivaloyl group, 2-chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, 2-pyridylcarbonyl group, 2-furylcarbonyl group), aryloxycarbonyl group (preferably carbon number) 7-30 substituted or unsubstituted aryloxycarls Bonyl groups such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt-butylphenoxycarbonyl group), alkoxycarbonyl groups (preferably substituted or unsubstituted having 2 to 30 carbon atoms) An alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, and an n-octadecyloxycarbonyl group), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms such as Carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group).

Among the above functional groups, those having a hydrogen atom may be further substituted by removing this. These substituents may be bonded to each other to form a ring.

R ¹¹ to R ¹⁴ are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and even more preferably an alkyl group. R ¹¹ to R ¹⁴ may combine with any of adjacent R ¹¹ to R ¹⁴ to form a ring, and in that case, it is also preferable.

Specific examples of the compound represented by the general formula (1) are given below, but the present invention is not limited thereto.

The compound represented by the general formula (1) is 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) [Compound Example (1-1)] or 1,5-diazabicyclo [4.3. 0.0] -5-nonene (DBN) [Compound Example (1-2)] is particularly preferable.

Azo Dye In the present invention, an azo dye represents a dye compound having an acyclic azo group (—N═N—) and capable of complexing with a metal ion, and serving as a ligand in the metal complex. Including. For example, when two azo ligands are coordinated to one metal ion in one molecule, the number of azo dyes in one molecule is two. A case where an azo dye is complexed with a metal ion is called an azo metal complex dye. In the present invention, the azo ligand refers to a case where an azo dye becomes a ligand.

In the present invention, an azo dye that is subjected to a reaction with a metal ion in the presence of a secondary amine is an azo dye having a partial structure represented by the following general formula (A).

[In General Formula (A), Q ¹ represents an atomic group that forms a nitrogen-containing heterocycle with adjacent nitrogen and carbon atoms, Y ¹ represents a hydrogen atom that may be dissociated during azo metal complex dye formation, * Represents a bonding position with the —N═N— group. ]

Hereinafter, the general formula (A) will be described.

In the general formula (A), Q ¹ represents an atomic group that forms a nitrogen-containing heterocyclic ring together with adjacent nitrogen atoms and carbon atoms. The atomic group represented by Q ¹ may have a substituent, and preferably has a substituent from the viewpoint of solubility in a coating solvent. Examples of the substituent include the above-described substituents.

Examples of the nitrogen-containing heterocycle formed by Q ¹ include pyrazole ring, pyrrole ring, imidazole ring, thiazole ring, isothiazole ring, oxazole ring, isoxazole ring, 1,2,4-thiadiazole ring, 1,3 , 4-thiadiazole ring, 1,2,4-triazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring and the like.
The nitrogen-containing heterocycle formed by Q ¹ is preferably a pyrazole ring or a triazole ring, more preferably a pyrazole ring, and a pyrazole ring in which one N atom on the ring is a hydrogen atom. Further preferred.

In general formula (A), Y ¹ represents a hydrogen atom that may be dissociated when forming an azo metal complex dye, and * represents a bonding position with the —N═N— group. The hydrogen atom is a hydrogen atom that is easily deprotonated and can be dissociated when complexed with a metal ion.

The azo dye containing the partial structure is preferably an azo dye represented by the following general formula (B) capable of forming a divalent azo dye anion. As the general formula (B), only the azoform in the azo-hydrazone tautomeric equilibrium is shown, but a corresponding hydrazone form may be used.

[In General Formula (B), Q ¹ represents an atomic group that forms a nitrogen-containing heterocycle with adjacent nitrogen atoms and carbon atoms, and Q ² is an atom that forms a heterocycle or carbocycle with two adjacent carbon atoms. Y ¹ represents a hydrogen atom that may be dissociated when forming an azo metal complex dye, and Y ² represents a group containing a hydrogen atom that may be dissociated when forming an azo metal complex dye. ]

Hereinafter, the general formula (B) will be described.

Definitions and details the general formula (B) Q ¹ and Y ¹ in the same as Q ¹ and Y ¹ in the general formula (A).

In the general formula (B), Q ² represents an atomic group that forms a heterocyclic ring or a carbocyclic ring with two adjacent carbon atoms.

The atomic group represented by Q ² may have a substituent, and preferably has a substituent from the viewpoint of solubility in a coating solvent. Examples of the substituent include the above-described substituents.

If Q ² form a heterocyclic ring, the ring formed by Q ² are carbon atoms and hetero atoms (oxygen atom, a sulfur atom, a nitrogen atom and the like) may be a heterocyclic ring formed together with, but are not limited to For example, pyrazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, thiazole ring, isothiazole ring, oxazole ring, isoxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, pyridone ring, β-diketone Mention may be made of rings having a structure. These rings may have a substituent and may be condensed.

When the ring formed by Q ² is a carbocycle, the carbocycle is preferably a benzene ring.

The ring formed by Q ² is preferably a heterocyclic ring, more preferably a pyrazole ring, a pyridone ring, or a ring having a β-diketone structure, and more preferably a pyrazole ring.

Y ² represents a group containing a hydrogen atom that may be dissociated during formation of the azo metal complex dye. Although it does not specifically limit as said group, For example, a hydroxyl group, a thiol group, an amino group, a carboxyl group, a sulfonic acid group etc. are mentioned.

Y ² represents a hydroxyl group, 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 an amino group, Methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, carbon A substituted or unsubstituted arylcarbonylamino group of formula 6-30, such as formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonyl Amino group), aminocarbonylamino group (preferably a group having 1 to 30 carbon atoms). Or an unsubstituted aminocarbonylamino group such as a carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group, or alkoxycarbonylamino group (preferably having 2 carbon atoms) To 30 substituted or unsubstituted alkoxycarbonylamino groups such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group), aryl Oxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group mn-octyloxyphenoxycarbonylamino group), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as a sulfamoylamino group, N, N— Dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms) An unsubstituted arylsulfonylamino group, for example, a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, or a p-methylphenylsulfonylamino group). . When Y ² is an amino group having a substituent, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 30 carbon atoms Substituted arylcarbonylamino group, substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, substituted or unsubstituted group having 7 to 30 carbon atoms Aryloxycarbonylamino group, substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms An arylsulfonylamino group is preferable, a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms, carbon number A substituted or unsubstituted arylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, and 0 to 30 carbon atoms More preferably a substituted or unsubstituted sulfamoylamino group, a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms, It is more preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted acylamino group having 2 to 30 carbon atoms, This is a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. It is particularly preferred.

Preferred examples of the partial structure represented by the general formula (A) include a partial structure represented by the following general formula (C). In addition, although the pyrazole ring described in the general formula (C) can have a tautomeric structure, it is also included in the general formula (C).

Hereinafter, the general formula (C) will be described.

In general formula (C), Y ¹ has the same definition as in general formula (A), and the details thereof are also the same. In the partial structure represented by the general formula (C), the hydrogen atom Y ¹ on the pyrazole ring is dissociated to form a transition metal ion with the transition metal ion via the other nitrogen atom on the pyrazole ring in the partial structure (C). Complex formation becomes possible, and as described later, even when the number of transition metal ions is larger than the number of azo dyes, high film stability can be exhibited.

In the general formula (C), * represents a bonding position with the —N═N— group.

R ¹ and R ² each independently represents a hydrogen atom or a substituent. R ¹ and R ² are preferably substituents from the viewpoint of improving solubility. Although it does not specifically limit as a substituent, A halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic 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, amino group (anilino group) ), Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, aryl O group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imido group Examples include phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, and silyl group.

More specifically, R ¹ and R ² represent a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [a linear, branched, cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group), Bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, 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 a ring structure There tricyclo structure is intended to encompass such. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl group, allyl group, prenyl group, geranyl group, oleyl group), cycloalkenyl groups (preferably having 3 carbon atoms). A substituted or unsubstituted cycloalkenyl group having ˜30, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl, 2-cyclohexene- 1-yl), a bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, one hydrogen atom of a bicycloalkene having one double bond. Monovalent groups removed, such as bicyclo [2,2,1] hept-2-en-1-yl, bicycl [2,2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, a trimethylsilylethynyl group, an aryl group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms) An aryl group such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or A monovalent group obtained by removing one hydrogen atom from a non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano, hydroxyl, nitro, carboxyl An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, 2-methoxyethoxy group) An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms such as phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 2- Tetradecanoylaminophenoxy group), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as a trimethylsilyloxy group or a t-butyldimethylsilyloxy group), a heterocyclic oxy group (preferably having a carbon number of 2 to 30 substituted or unsubstituted heterocyclic oxy groups, 1-phenyltetrazol-5-oxy Group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms) Group, for example, formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Carbamoyloxy groups such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy Group), alkoxy A carbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-octylcarbonyloxy group), an aryloxy Carbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group ), 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 an amino group, a methylamino group, dimethyl group, Amino group, a Lino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms) Substituted arylcarbonylamino groups such as formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group), aminocarbonylamino group (Preferably, a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group) , Alkoxycarbonyl Mino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl Rumethoxycarbonylamino group), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, m- n-octyloxyphenoxycarbonylamino group), sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino group, N, N-dimethylamino group) Sulfo Nylamino group, Nn-octylaminosulfonylamino group), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted groups having 6 to 30 carbon atoms) Arylsulfonylamino group, for example, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group), mercapto group, alkylthio group (preferably Is a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group or an n-hexadecylthio group, an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, Phenylti Group, p-chlorophenylthio group, m-methoxyphenylthio group), heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio group, 1 -Phenyltetrazol-5-ylthio group), sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably Is a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6 to 30 carbon atoms Or an unsubstituted arylsulfinyl group, for example, a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group), an alkyl and an arylsulfonyl group (preferably a substituted or unsubstituted group having 1 to 30 carbon atoms) Alkylsulfonyl group, 6-30 substituted or unsubstituted arylsulfonyl group, for example, methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group), acyl group (preferably formyl group, carbon number 2 A substituted or unsubstituted alkylcarbonyl group having 30 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, and a heterocycle bonded to the carbonyl group via a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms Carbonyl group, for example acetyl , Pivaloyl group, 2-chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, 2-pyridylcarbonyl group, 2-furylcarbonyl group), aryloxycarbonyl group (preferably having 7 carbon atoms) To 30 substituted or unsubstituted aryloxycarbonyl groups such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt-butylphenoxycarbonyl group), alkoxycarbonyl group (preferably A substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, n-octadecyloxycarbonyl group), carbamoyl group (preferably having 1 to 30 carbon atoms) Replace Or an unsubstituted carbamoyl group, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-di-n-octylcarbamoyl group, an N- (methylsulfonyl) carbamoyl group), an aryl and A 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 a phenylazo group, a p-chlorophenylazo group, 5- Ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably substituted or unsubstituted phosphino group having 2 to 30 carbon atoms) For example, dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphine Group), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl group, dioctyloxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy group ( Preferably, it is a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group, or a phosphinylamino group (preferably having a carbon number of 2-30 substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino group, dimethylaminophosphinylamino group, silyl groups (preferably substituted or unsubstituted groups having 3 to 30 carbon atoms) Silyl groups such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl) It is possible.

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.

When R ¹ is an electron-attracting group, an azo metal complex having extremely excellent light resistance can be easily obtained, which is preferable from the viewpoint of solubility. In the present invention, the electron withdrawing group means a group having a positive Hammett's substituent constant σp value (that is, 0 <σp).
The electron withdrawing group preferable as R ^{1 includes} an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. R ¹ is preferably an electron withdrawing group having a σp value of 0.30 or more and 1.0 or less. Specific examples of the electron withdrawing group having a σp value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diaryl Phosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated Alkoxy groups, halogenated aryloxy groups, halogenated alkylamino groups, halogenated alkylthio groups, aryl groups substituted with other electron withdrawing groups with a σp value of 0.20 or more, heterocyclic groups, halogen atoms, azo Group and selenocyanate group Can be mentioned.

Hammett's substituent constant σp value used in the present invention will be described. Hammett's rule is an empirical rule proposed by L. P. Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. Yes. 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. A. Dean, “Lange's Handbook of Chemistry "12th edition, 1979 (Mc-Graw-Hill) and" Chemical domain "extra edition, 122, 96-103, 1979 (Nankodo), all of which are hereby specifically incorporated by reference. Be familiar with In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it can be found in the above-mentioned book and is limited only to a substituent having a known value in the literature. However, it goes without saying that even if the value is unknown, it includes substituents that would be included in the range when measured based on Hammett's rule.

R ¹ is a substituted or unsubstituted alkyloxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 10 carbon atoms, or a substituted or unsubstituted alkylaminocarbonyl group having 2 to 10 carbon atoms. From a substituted or unsubstituted arylaminocarbonyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, and a cyano group And a group selected from a substituted or unsubstituted alkyloxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, and a cyano group. More preferably, it is a substituted or unsubstituted alkyloxycarbonyl group or cyano group having 2 to 10 carbon atoms. More preferably a group selected, and particularly preferably a cyano group.

R ² is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and from the viewpoint of solubility, a hydrogen atom, carbon More preferably, it is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and from the viewpoint of solubility, carbon A substituted or unsubstituted alkyl group having a number of 1 to 4 is particularly preferred.

As a preferred embodiment of the azo dye, the partial structure represented by the general formula (A) in the general formula (B) is a partial structure represented by the general formula (C), which is represented by the following general formula (D): Mention may be made of the azo dyes represented.

The definition and details of R ¹ , R ² , Y ¹ , Y ² , and Q ^{2 in} the general formula (D) are the same as described above.

Specific examples of the azo dye are given below, but the present invention is not limited thereto.

As general methods for synthesizing the azo dye, JP-A-61-36362 and English family member US Pat. No. 4,685,934, JP-A 2006-57076 and English family member US2008 / 0199615A1, and their The full description includes the methods described in, which is specifically incorporated herein by reference. However, the reaction is not limited to this, and other reaction solvents and acids may be used, and the coupling reaction may be performed in the presence of a base (for example, sodium acetate, pyridine, sodium hydroxide, etc.). Specific examples of the synthesis method of the azo dye are shown below.

Complex Formation Next, a complex formation reaction between the azo dye and a metal ion will be described.
As a general method for obtaining a metal azo chelate dye by reacting an azo dye with a metal ion, an azo dye or a metal salt (including a metal complex or a metal oxide salt) is used in an organic solvent, water, or a mixture thereof. And a method of stirring. Here, in the present invention, the reaction is carried out in the presence of the compound represented by the general formula (1).

Although the equivalent of the compound represented by the general formula (1) is not particularly limited, it should be 2.00 equivalents or more with respect to the azo dye in order to stably produce a high purity azo metal complex with high yield. Preferably 2.00 equivalents or more and 6.00 equivalents or less, more preferably 2.05 equivalents or more and 4.50 equivalents or less, and 2.10 equivalents or more and 3.00 equivalents or less. Is particularly preferred.

The equivalent of the metal ion is not particularly limited, but is preferably 1.00 equivalent or more, preferably 1.00 equivalent or more with respect to the azo dye, in order to stably produce a high purity azo metal complex with high yield. The amount is more preferably 1.25 equivalents or less, further preferably 1.10 equivalents or more and 1.23 equivalents or less, and particularly preferably 1.12 equivalents or more and 1.20 equivalents or less.

In the complex formation reaction, the equivalent of the compound represented by the general formula (1) is 2.00 equivalents or more with respect to the azo dye, and the equivalent of the metal ion is 1 quantity or more with respect to the azo dye. The equivalent of the compound represented by the general formula (1) is more preferably 2.00 equivalents to 6.00 equivalents, and the equivalent of the metal ions is more preferably 1.00 equivalents to 1.25 equivalents. More preferably, the equivalent of the compound represented by the general formula (1) is 2.05 equivalents or more and 4.50 equivalents or less, and the equivalent of the metal ion is 1.10 equivalents or more and 1.23 equivalents or less. It is particularly preferable that the equivalent of the compound represented by formula (1) is 2.10 equivalents or more and 3.00 equivalents or less, and the equivalent of the metal ions is 1.12 equivalents or more and 1.20 equivalents or less.

The reaction solvent is not particularly limited, and examples thereof include alcohol solvents, ketone solvents, nitrile solvents, ester solvents, amide solvents, aqueous solvents, and mixed solvents thereof. The reaction solvent is preferably an alcohol solvent, more preferably methanol, ethanol or isopropanol, and even more preferably methanol. It is also preferable to mix an alcohol solvent and an aqueous solvent.

The amount of the reaction solvent is not particularly limited, but is preferably 1 to 100 times the mass ratio of the azo dye, more preferably 2 to 50 times the mass ratio of the azo dye, Is more preferably 2.5 times or more and 20 times or less, and particularly preferably 3 to 10 times that of the azo dye.

The reaction temperature is not particularly limited, but is preferably in the range of 0 ° C to 250 ° C, more preferably in the range of 20 ° C to 200 ° C, still more preferably in the range of 40 ° C to 150 ° C, A range of 50 ° C. to 120 ° C. is particularly preferable. The reaction time can be appropriately set.

As an azo metal complex dye obtained by reacting an azo dye having a partial structure represented by the general formula (A) with a metal ion in the presence of a compound represented by the general formula (1), five metal ions and azo 5-nuclear complex formed from 4 dyes, 7-nuclear complex formed from 7 metal ions and 6 azo dyes, binuclear complex formed from 2 metal ions and 2 azo dyes, or 1 metal ion and azo dye 2 And mononuclear complexes formed from the two. Moreover, the case where it exists as a mixture of these is also considered. The azo metal complex dye obtained by the above reaction can be identified by a known method such as ESI-TOF-MS, MALDI-TOF-MS, X-ray structural analysis, ICP or the like.

According to the study by the present inventors, a recording layer dye for an optical information recording medium, particularly a recording layer preferable as a recording layer dye for an optical information recording medium compatible with a short wavelength laser (for example, a wavelength of 440 nm or less) such as a Blu-ray disc. In order to obtain reproduction characteristics, it is effective to deactivate the excited state of the dye for the recording layer efficiently. From this point,
(1) A polynuclear complex containing two or more metal ions in one molecule (2) A complex containing two or more metal ions equal to or more than the number of azo dyes. According to the present invention, the above-mentioned complexes (1) and (2) can be obtained by the reaction in the presence of the secondary amine, as shown in Examples described later. Complexes corresponding to the above (1) and (2) include pentanuclear complexes formed from five metal ions and four azo dyes, seven-nuclear complexes formed from seven metal ions and six azo dyes, or metal A binuclear complex formed from two ions and two azo dyes is preferred, and a pentanuclear complex formed from five metal ions and four azo dyes or a seven-nuclear complex formed from seven metal ions and six azo dyes is more preferable. A 7-nuclear complex formed from 7 metal ions and 6 azo dyes is more preferable.

In the azo metal complex dye obtained by the present invention, the valence of the metal ion may change depending on the difference of the metal ion or the environment (solution, solid) of the azo metal complex dye. If the valence of the metal ion changes, the charge and number of the salt can change, so the counter salt of the metal chelate dye of the azo dye and the metal ion is not particularly limited, in order to neutralize the charge It is only necessary to form a counter salt with necessary ions. When an anionic azo metal complex dye is obtained, it is generally an ammonium cation derived from a secondary amine. When a cationic azo metal complex dye is obtained, it is used as a raw material for the metal ion used. In general, the contained salt or hydroxide ion is contained as an anion.

Specific examples of azo metal complex dyes that can be produced according to the present invention are shown below. However, the present invention is not limited to the following specific examples. For the reasons described above, the compounds shown in the following specific examples can have a plurality of structures having different valences of metal ions.

The azo metal complex dye obtained by the present invention can be used for various applications such as pigments, photographic materials, UV absorbing materials, dyes for color filters, and color conversion filters. In particular, since the azo metal complex dye obtained by the present invention can have desirable physical properties as a dye for recording layers in an optical information recording medium as described above, an optical information recording medium compatible with a short wavelength laser beam such as a Blu-ray disc can be used. It is suitable as a dye for recording layers of various optical information recording media including the above.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.

Specific examples of the synthesis method of the azo dye represented by the general formula (D) are shown below, but the present invention is not limited to these methods.

Synthesis Example of Azo Dye [ Synthesis of Compound (L-1)]

To a 100 ml three-necked flask, 1.1 g of compound (1), 1.3 ml of acetic acid and 2 ml of propionic acid were poured, and 1.9 ml of hydrochloric acid (35 to 37% by mass) was slowly added dropwise under ice cooling. After cooling to 0-5 ° C in an ice bath, 1 ml of an aqueous solution having 0.46 g of NaNO ₂ dissolved therein (cooled to 5 ° C or lower) was slowly added dropwise, followed by stirring at 0-5 ° C for 1 hour. did. This acidic solution was gradually added to 20 ml of a methanol solution containing 0.94 g of compound (2) kept at 0 to 5 ° C. under ice cooling, and stirred for 1 hour. After returning to room temperature and stirring for 2 hours, the precipitate was filtered and washed with a minimum amount of methanol. The obtained solid was dried to obtain 0.8 g of compound (L-1). The compound was identified by 300 MHz ¹ H-NMR.
¹ H-NMR (DMSO-d6) [ppm]; δ13.70 (1H, br), 13.31 (1H, s), 3.331 (3H, s), 1.413 (9H, s), 1.331 (9H, s)

[Synthesis of Compound (L-11)]

100 g of compound (1), 120 ml of acetic acid and 180 ml of propionic acid were poured into a 3 L three-necked flask, and 185 ml of hydrochloric acid (35-37%) was slowly added dropwise under ice cooling. The mixture was cooled to −5 to 5 ° C. in an ice bath, and 80 ml of an aqueous solution in which 42 g of NaNO ₂ was dissolved was slowly added dropwise thereto, followed by stirring at 0 to 5 ° C. for 30 minutes. This acidic solution was gradually added to 500 ml of a methanol solution containing 106.1 g of compound (2) kept at 0 to 5 ° C. under ice cooling, and stirred at 0 to 10 ° C. for 1 hour. After returning to room temperature, the precipitate was filtered, washed with 250 ml of methanol, and then washed with 600 ml of distilled water. The obtained solid was dispersed in ethanol and stirred at 60 ° C. for 1 hour, and then the crystals were filtered, washed with methanol and dried to obtain 140 g of Compound (L-11). The compound was identified by 300 MHz ¹ H-NMR.
¹ H-NMR (DMSO-d6) [ppm]; δ 13.33 (1H, br), 7.88 (2H, d), 7.47 (2H, t), 7.25 (1H, t), 2.26 (3H, s), 1.42 (9H, s)

(L-3) to (L-18), (L-20) to (L-31), and (L-33) were synthesized by the same method as the synthesis of compound (L-1) described above. Various azo dyes that can be used in the present invention can be synthesized in the same manner. The compound was identified by 300 MHz ¹ H-NMR.

[Example 1]
Next, as a synthesis example of the azo metal complex dye, a synthesis method of the exemplary compound (M-10) will be shown, but the present invention is not limited to the following method.

Into a 3 L three-necked flask, 0.5 g of the compound (L-11) and 7 ml of methanol were added, and 0.43 ml of DBU was added dropwise with stirring. After complete dissolution, 0.33 g of copper acetate monohydrate was further added with stirring, and the mixture was refluxed at 60 to 65 ° C. for 3.5 hours. After returning to room temperature, the precipitate was filtered, washed with methanol, and dried to obtain 0.53 g of compound (M-10). The compound was identified by ESI-TOF-MS and X-ray structural analysis.
ESI-TOF-MS: m / z = 2556 (nega), 1279 (nega)
From the results of ESI-TOF-MS and X-ray structural analysis, it was confirmed that the product was a polynuclear copper complex composed of 6 azo dyes and 7 copper ions.

[Examples 2 to 32]
Using the same production method as (M-10) (however, the reaction scales were different), the azo metal complex dyes shown in Table 2 were synthesized by changing the raw materials and the equivalent ratio. The compound can be identified by ESI-TOF-MS, MALDI-TOF-MS, X-ray structural analysis, and the like.

[Comparative Examples 1 to 8]
Comparative compounds (A) to (H) using the same production method as exemplary compound (M-10) except that the types of azo dyes, metal ions, bases and equivalent ratios were changed as shown in Table 3. Was synthesized.

[Comparative Example 9]
Comparative compound (I) was prepared using the same production method as Exemplified Compound (M-10), except that the azo dye used, the type of metal ion and the equivalent ratio were changed as shown in Table 3 (no base used). Synthesized.

Evaluation Method (1) Confirmation of Dye Film Formability and Light Resistance Evaluation of Dye Film 10 mg of each of the azo metal complex dyes synthesized in the examples and comparative examples shown in Table 4 are added to 1 ml of 2,2,3,3-tetrafluoropropanol. The dye-containing coating solution was prepared by adding and dissolving therein. The prepared dye-containing coating solution was coated on a glass plate having a thickness of 1.1 mm in a nitrogen atmosphere at room temperature while changing the rotational speed from 500 to 1000 rpm by a spin coating method. After coating, whether or not a dye film was formed was visually confirmed.
Thereafter, the formed dye film was stored at room temperature for 24 hours, and then subjected to a light resistance test using a merry-go-round type light resistance tester (manufactured by Eagle Engineering Co., Ltd., Cell Tester Type III, with Schott WG320 filter). With respect to the dye film immediately before the light resistance test and the dye film after 48 hours from the light resistance test, the absorption spectrum of the dye film was measured using UV-1600PC (manufactured by SHIMADZU), and the change in absorbance at the maximum absorption wavelength was read.

(2) Solubility Evaluation The dye-containing coating solution prepared by the same method as in (1) above was visually observed to evaluate the solubility of the dye in the solvent.

(3) Solution storage stability Each of the azo metal complex dyes synthesized in the examples and comparative examples shown in Table 4 is in the range of abs. = 0.9 to 1.1 in 2,2,3,3-tetrafluoropropanol. A dye solution was prepared. At this time, the absorption spectrum of the dye solution was measured using UV-1600PC (manufactured by SHIMADZU). These dye solutions were stored in a thermostat set at 60 ° C., and the absorption spectrum of the dye solution after 48 hours was measured. Absorption wavelength shift was observed for unstable dyes, and the shift value was read and used as a criterion for stability. In Table 4, with respect to the compounds whose storage stability was indicated as “◯”, the abs. Value of the absorption maximum after 48 hours was 90% or more with respect to the initial abs. Value.

(Note 1) When completely dissolved in the coating solution ○, when partially dissolved but partially insoluble component Δ, when hardly dissolved ×
(Note 2) Wavelength shift value of λmax is less than 3nm ○ 3nm or more ×
(Note 3) When an amorphous film that is not crystallized can be formed ○, when the crystallization or film thickness is as thin as 10 nm or less and its existence cannot be confirmed ×
(Note 4) ◯ when the dye residual ratio at absorption λmax 48 hours after Xe light irradiation is 80% or more, Δ when it is 70% or more and less than 80%, and × when it is less than 70%.

As shown in Table 4, compared with the azo metal complex synthesized without using the compound represented by the general formula (1), the azo metal complex dyes synthesized in Examples all have solubility, solution storage stability, It has been found that the light resistance is compatible and suitable for various applications. In addition, since it was possible to form a film only with a dye, it was confirmed that it was suitable as an optical information recording medium.

Further, it was found that the azo metal complex dyes synthesized in the examples have good film stability and excellent storage stability under high temperature and high humidity.

[Reference Example 1]
Next, an example in which the compound (M-10) is applied as a recording layer dye of an optical information recording medium is shown.

1. Production of optical information recording media (fabrication of substrates)
Thickness 1.1 mm, outer diameter 120 mm, inner diameter 15 mm and spiral pre-groove (track pitch: 320 nm, groove width: groove (recess) width 170 nm, groove depth: 37 nm, groove inclination angle: 52 °, wobble amplitude: An injection molded substrate made of polycarbonate resin having a thickness of 20 nm) was produced. Mastering of the stamper used at the time of injection molding was performed using laser cutting (351 nm).

(Formation of light reflection layer)
An ANC light reflecting layer (Ag: 98.1 at%, Nd: 0.7 at%, as a vacuum film-forming layer having a film thickness of 60 nm was formed on the substrate by DC sputtering in an Ar atmosphere using Cube manufactured by Unaxis. Cu: 0.9 at%) was formed. The film thickness of the light reflecting layer was adjusted by the sputtering time.

(Formation of write-once recording layer)
As Reference Example 1, 1 g of compound (M-10) was added and dissolved in 100 ml of 2,2,3,3-tetrafluoropropanol to prepare a dye-containing coating solution. Then, the prepared dye-containing coating solution was coated on the light reflecting layer under the conditions of 23 ° C. and 50% RH while changing the rotational speed from 500 to 2200 rpm by a spin coating method to form a write-once recording layer.

After forming the write-once recording layer, it was annealed in a clean oven. The annealing treatment was performed by supporting the substrate on a vertical stack pole while leaving a gap with a spacer, and holding at 80 ° C. for 1 hour.

(Formation of barrier layer)
Thereafter, a barrier layer having a thickness of 10 nm made of Nb ₂ O ₅ was formed by DC sputtering in an Ar atmosphere on the write-once recording layer using Cube manufactured by Unaxis.

(Covering the cover layer)
As the cover layer, a polycarbonate film (Teijin Pure Ace, thickness: 80 μm) having an inner diameter of 15 mm and an outer diameter of 120 mm and having an adhesive layer (glass transition temperature of −52 ° C.) on one side, the adhesive layer and the polycarbonate film are used. The total thickness was set to 100 μm.
Then, after the cover layer was placed on the barrier layer through the adhesive layer, the cover layer was pressed and pressed with a pressing member.
Through the above steps, an optical information recording medium of Reference Example 1 having a light reflecting layer, a write-once recording layer, a barrier layer, an adhesive layer and a cover layer in this order on a substrate was produced. Recording / reproduction characteristics of this optical information recording medium were evaluated.

2. Evaluation of optical information recording media (jitter evaluation)
The produced optical information recording medium was irradiated with light from the cover layer side using a recording / reproduction evaluation machine (Pulstec Industrial Co., Ltd .: DDU1000) having a 405 nm laser and NA 0.85 pick-up, with a clock frequency of 66 MHz and a linear velocity of 4 A mark length modulation signal (17PP) subjected to (1.7) RLL-NRZI modulation was recorded at .92 m / s. Jitter measurement was performed using a time interval analyzer (Yokogawa Electric Corporation: TA520) by passing the recording signal through a limit equalizer.

The optical information recording medium of Reference Example 1 showed a jitter value of 7% or less, indicating good recording / reproduction characteristics.
Further, the optical information recording medium of Reference Example 1 was able to record and reproduce the optical information recording medium after being irradiated with Xe light for 55 hours, and had good light resistance even under the optical information recording medium. Further, after recording, the film was stored under high temperature and high humidity for 168 hours, but it was found that there was almost no change in jitter and the storage stability under high temperature and high humidity was extremely excellent.
From the above results, the production method of the present invention makes the azo metal complex excellent in recording / reproduction characteristics, light resistance and storage stability, and suitable as a recording layer dye in an optical information recording medium compatible with short wavelength laser light such as Blu-ray disc. A dye was shown to be obtained.

Since the azo metal complex dye produced by the present invention is excellent in light resistance and stability under high temperature and high humidity, it is a dye for recording layers of optical information recording media, photographic materials, dyes for color filters, color conversion filters. It has been found that it has desirable properties in various applications such as thermal transfer recording materials and inks. Note that the present invention is not limited to the above-described embodiment, and it is needless to say that various configurations can be adopted without departing from the gist of the present invention.

By using the production method of the present invention, a dye having excellent solubility and / or stability in a solution can be produced.
Furthermore, it is excellent in film forming property, light resistance, heat resistance, and moisture resistance, and it is possible to produce a dye suitable as a recording layer dye for an optical information recording medium or the like that performs recording and reproduction by irradiation with a short wavelength laser beam.
The azo metal complex dyes obtained by the present invention can also be applied to photographic materials, color filter dyes, color conversion filters, thermal transfer recording materials, inks, and the like.

Claims (12)

1. A complex of an azo dye and a metal ion by reacting an azo dye having a partial structure represented by the following general formula (A) with a metal ion in the presence of a compound represented by the following general formula (1) A process for producing an azo metal complex dye.
   

   

   [In General Formula (A), Q ¹ represents an atomic group that forms a nitrogen-containing heterocycle with adjacent nitrogen and carbon atoms, Y ¹ represents a hydrogen atom that may be dissociated during azo metal complex dye formation, * Represents a bonding position with the —N═N— group. ]
   

   

   [In General Formula (1), R ¹¹ to R ¹⁴ each independently represents a hydrogen atom or a substituent. ]
2. The method according to claim 1, wherein the azo dye is an azo dye represented by the following general formula (B).
   

   

   [In General Formula (B), Q ¹ represents an atomic group that forms a nitrogen-containing heterocycle with adjacent nitrogen atoms and carbon atoms, and Q ² is an atom that forms a heterocycle or carbocycle with two adjacent carbon atoms. Y ¹ represents a hydrogen atom that may be dissociated when forming an azo metal complex dye, and Y ² represents a group containing a hydrogen atom that may be dissociated when forming an azo metal complex dye. ]
3. The partial structure represented by general formula (A) is the manufacturing method of Claim 1 or 2 represented by the following general formula (C).
   

   

   [In General Formula (C), R ¹ and R ² each independently represent a hydrogen atom or a substituent, Y ¹ has the same definition as in General Formula (A), and * represents a —N═N— group. Represents the bonding position. ]
4. The production method according to claim 3, wherein R ¹ represents an electron-withdrawing group.
5. The production method according to any one of claims 2 to 4, wherein Q ² in the general formula (B) is an atomic group forming a pyrazole ring.
6. The compound represented by the general formula (1) is 1,8-diazabicyclo [5.4.0] -7-undecene or 1,5-diazabicyclo [4.3.0] -5-nonene. 6. The production method according to any one of 1 to 5.
7. The production method according to any one of claims 1 to 6, wherein the amount of the compound represented by the general formula (1) is 2.00 equivalents or more and 6.00 equivalents or less based on the azo dye.
8. The production method according to any one of claims 1 to 7, wherein a metal ion of 1.00 equivalent or more and 1.25 equivalent or less is reacted with the azo dye.
9. The production method according to any one of claims 1 to 8, wherein a polynuclear complex containing two or more metal ions is obtained by the reaction.
10. The production method according to any one of claims 1 to 9, wherein a complex of an azo dye and a number of metal ions equal to or more than the number of the azo dye is obtained by the reaction.
11. The production method according to any one of claims 1 to 10, wherein the metal ion is a transition metal ion.
12. The manufacturing method according to claim 11, wherein the transition metal ion is a copper ion.