JP2002254813A - Optical recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording material in an optical recording medium, which can be applied to a DVD-R disc system employing semiconductor laser having a wavelength shorter than that employed in the conventional system as an oscillating wavelength and is excellent in light resistance and storage stability, and, at the same time, the recording material for a CD-R medium, in which the information recorded with a CD-R disc system can be reproduced with the DVD-R disc system. SOLUTION: In the optical recording medium, a supplying layer is provided directly or through an undercoating layer onto a first substrate and, when necessary, a reflecting layer and a protective layer or a reflecting layer and a second substrate are provided onto the supplying layer under the state that the recording layer includes at least one kind of a compound among azo metal chelate compounds represented by general formula (1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a data write-once optical disc and a write-once compact disc in the technical field, and to an optical disc, an optical card and a CD-ROM in application fields.
R, CD-I, CD-V or DVD-R.

[0002]

2. Description of the Related Art Conventionally, a. As a write-once type recording medium (for information recording), (1) a medium using a cyanine dye as a recording material (JP-A-57-82093, JP-A-58-1983)
No. 56892, JP-A-58-114989,
JP-A-59-85791, JP-A-60-8323
No. 6, JP-A-60-89842 and JP-A-61-1986.
(2) Using a phthalocyanine dye as a recording material (JP-A-61-1502).
No. 43, JP-A-61-177287, JP-A-61-154888, JP-A-61-24609, JP-A-62-39286, JP-A-63-63-3
7991, JP-A-63-39888, etc.).

[0003] Also, b. As a write-once compact disc, a recording medium comprising a cyanine dye and a metal reflection layer (JP-A-1-159842, JP-A-2-4265)
No. 2, JP-A-2-13656, JP-A-2-1-1
(4) a recording material comprising a phthalocyanine dye and a metal reflection layer (see JP-A-1-1765).
No. 85, JP-A-3-215466, JP-A-4
JP-A-113886, JP-A-4-226390, JP-A-5-1272, JP-A-5-17105
No. 2, JP-A-5-116456, JP-A-5-116456
96860, JP-A-5-139044, JP-A-5-139044, etc.), and (5) a recording material comprising an azo metal chelate dye and a metal reflective layer (JP-A-4-46186, JP-A-4-141489, JP-A-4-36088, JP-A-5-279
No. 580).

Further, c. (6) Basic development of a dye disc for DVD-R (PIONEER R & D voL.6 No.2: DVD-Recorda)
ble), ISOM / ODS ('96: High densit
y of recording on Dye material Disk approach for
4.7G), (7) Recording materials comprising an imidazole-based azomethine dye and a metal reflective layer (JP-A-8-198872, JP-A-8-209012, JP-A-8-283)
No. 263) has been proposed, and further (8)
Other recording materials using a dye and a metal reflective layer as recording materials have also been proposed (JP-A-8-169182, JP-A-8-2090).
12, JP-A-8-283263, JP-A-9
No. -58130).

At present, DVD-R is being developed as a next-generation large-capacity optical disk. Elemental technologies for improving the recording capacity include the development of recording materials for miniaturizing recording pits, the adoption of image compression technology typified by MPEG2, and the development of shorter wavelength semiconductor lasers for reading recording pits. is there.

Heretofore, as a semiconductor laser in the red wavelength range, 670 nm Al has been used for bar code readers and measuring instruments.
Although only GaInP laser diodes have been commercialized, red lasers are being used in the optical storage market in earnest as the density of optical disks increases. DVD
In the case of a drive, the light source is 635 nm band and 650 nm
It is standardized at two wavelengths of the laser diode in the band. For high-density recording, the wavelength is desirably shorter, and as a drive for write-once media, a wavelength of 635 nm is used.
Is preferred. On the other hand, a read-only DVD-ROM drive is commercialized at a wavelength of up to 650 nm.

[0007] Under these circumstances, the most preferable DVD-
The R media is a medium that can record and reproduce at wavelengths up to 635 nm and can reproduce at wavelengths up to 650 nm. However, it has excellent light resistance and storage stability,
Recording materials that can be recorded and reproduced by an optical pickup using a laser of 0 nm or less have not yet been developed. The current CD-R disc system has an oscillation wavelength of a used laser of 770 to 790 nm, and is configured to perform recording and reproduction. CD-R has a recording layer of 680 to 750 nm.
Is set so that a high reflectance can be obtained in the range of 770 to 790 nm from the optical constant and the film thickness configuration using a dye having a maximum absorption wavelength. It is impossible to cope with the shortening of the wavelength, and information recorded and reproduced by the current CD-R system cannot be reproduced by the DVD-R disk system.

[0008]

SUMMARY OF THE INVENTION The present invention is directed to an optical recording system having excellent light resistance and storage stability applicable to a DVD-R disk system using a semiconductor laser having an oscillation wavelength shorter than the conventional system. An object of the present invention is to provide a recording material in a medium, and a recording material for a CD-R medium in which information recorded in a CD-R disk system can be reproduced in a DVD-R disk system.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a recording layer containing a dye having a specific structure as a main component is used as a recording layer, and a high-density disk using a semiconductor laser having an oscillation wavelength of 700 nm or less is obtained. We found that it is applicable to the system. In addition, the compounds of the present invention can be converted to the current CD-R
It has been found that by using a mixture with an organic dye used as a recording material for recording, recording and reproduction can be performed with the current system and reproduction is also possible with the high-density disk system. Therefore, the above-mentioned problem is solved by the present invention which provides “(1) a supply layer directly or via an undercoat layer on a first substrate, and further a reflective layer, a protective or reflective layer, and a second substrate And (2) an optical recording medium comprising: a recording layer comprising at least one azo metal chelate compound represented by the general formula (1) in a recording layer. M ₁ in the azo metal chelate compound represented by the general formula (1) described in the item (1)
Is a metal atom selected from chromium, iron, cobalt, nickel, and copper ", (3)
"Optical recording medium characterized in that the azo metal chelate compound represented by the general formula (1) is contained in the recording layer as the azo metal chelate compound represented by the general formula (1)", (4) " In the azo metal chelate compound represented by the general formula (2) described in the above item (3), M ₂ is chromium;
An optical recording medium characterized by being a metal atom selected from iron, cobalt, nickel, and copper "; (5) an azo metal chelate compound represented by the general formula (1) represented by the general formula (3): Wherein the azo metal chelate compound is contained in a recording layer, wherein the optical recording medium according to the above item (1) or (3) "; An optical recording medium wherein M ₃ in the azo metal chelate compound represented by the formula (3) is a metal atom selected from chromium, iron, cobalt, nickel and copper ”, (7)“ contained in the recording layer Wherein the metal atom of the azo metal chelate compound is selected from cobalt or nickel. (1) The optical recording medium according to any one of (1) to (6), Azo metal sharpening contained in Wherein the metal atom of the compound is copper, the optical recording medium according to any one of the above items (1) to (6), (9) "the general formula (1), (2) The above-mentioned (1) to (8), comprising a mixed layer with a dye having a maximum absorption wavelength at 680 to 750 nm, in addition to the azo metal chelate compound represented by the general formula (3). (10) wherein the dye having the maximum absorption wavelength at 680 to 750 nm is a cyanine dye, a phthalocyanine dye, or an azo metal chelate compound. Optical recording medium described in item (1)), (1)
1) The above-mentioned (1), wherein the reflective layer is a gold, silver, aluminum or gold-based alloy, a silver-based alloy, or an aluminum-based alloy when a reflective layer is required. )) To (10), the optical recording medium according to any one of the above (10) to (12), wherein the recording / reproducing wavelength is 630 to 690.
(1) to (1).
The optical recording medium according to any one of the above items 1) ", (13)
"The recording wavelength is 770-810 nm, and the reproduction wavelength is 770-810 nm.
(10) The optical recording medium according to any one of (9) to (11), wherein the recording wavelength is 780 to 690 nm.
nm, the reproduction wavelength is 770-810 nm and 630-69.
(1) to (1).
(1) Recording / reproducing method using the optical recording medium according to any one of (1)) and (15) “Recording wavelength is 770 to 810n.
m, reproduction wavelength 770-810 nm and 630-690
(9) to (1).
Recording / reproducing method using the optical recording medium according to any one of 1)),

[0010]

Embedded image In the general formula (1), X ₁ , X ₂ , X ₃ , and X ₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a carboxy group, a cyano group, a sulfone group, a substituted or unsubstituted alkyl group. Group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic residue, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted Sulfonamide group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group,
Represents a substituted or unsubstituted amino group, Y ₁ , Y ₂ , Y ₃ ,
Y ₄ , Y ₅ and Y ₆ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a carboxy group, a cyano group,
Sulfone group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic residue, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted Carbamoyl group, substituted or unsubstituted sulfonamide group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or Represents an unsubstituted amino group; M ₁ represents an atom selected from transition metals;
Represents a hydrogen ion, a monovalent metal ion, a divalent metal ion, an ammonium ion, a substituted or unsubstituted aliphatic ammonium ion, a substituted or unsubstituted alicyclic ammonium ion, and m represents 1 or 2 Represents an integer, n
Represents an integer of 0, 1 or 2.

[0011]

Embedded image In the general formula (2), X ₅ and X ₆ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a carboxy group, a cyano group, a sulfone group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Aryl group, substituted or unsubstituted heterocyclic residue, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfonamide group, substituted or Represents an unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted amino group, Y ₇ is a halogen atom, Nitro group, hydroxyl group, carboxy group, cyano group, sulfone group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted A substituted heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfonamide group, a substituted or unsubstituted alkoxycarbonyl group, A substituted or unsubstituted aryloxycarbonyl group,
It represents a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted amino group, and M ₂ represents an atom selected from transition metals.

[0012]

Embedded image In the general formula (3), X ₇ and X ₈ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a carboxy group, a cyano group, a sulfone group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Aryl group, substituted or unsubstituted heterocyclic residue, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfonamide group, substituted or Represents an unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted amino group, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are
Each independently a hydrogen atom, a halogen atom, a nitro group,
Hydroxyl group, carboxy group, cyano group, sulfone group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group,
Substituted or unsubstituted heterocyclic residue, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfonamide group, substituted or unsubstituted alkoxy group A carbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted amino group, and M ₃ represents an atom selected from a transition metal . Further, R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , and R ₄ and R ₅ may be independently linked to form a ring. ] Is solved.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the general formulas (1), (2) and (3) used in the present invention,
In the azo metal chelate compound, as described above,
X₁, X_Two, X_Three, X_Four, X_Five, X₆, X₇, X₈, Y₁, Y_Two,
Y_Three, Y_Four, Y_Five, Y₆, Y₇, R₁, R_Two, R _Three, R_Four, R
_FiveAre each independently a hydrogen atom, a halogen atom,
B, hydroxyl, carboxy, cyano, sulfone,
Substituted or unsubstituted alkyl group, substituted or unsubstituted aryl
Group, substituted or unsubstituted heterocyclic residue, substituted or unsubstituted
An alkoxy group, a substituted or unsubstituted aryloxy group,
Substituted or unsubstituted carbamoyl group, substituted or unsubstituted
Sulfonamide group, substituted or unsubstituted alkoxycarbo
Nyl group, substituted or unsubstituted aryloxycarbonyl
Group, substituted or unsubstituted acyl group, substituted or unsubstituted acyl group
Represents a substituted or unsubstituted amino group.

Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and n
-Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, primary alkyl group such as n-decyl group, isobutyl group, isoamyl group,
2-methylbutyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2-ethylbutyl group, 2-methylhexyl group, 3-methylhexyl group,
4-methylhexyl group, 5-methylhexyl group, 2-ethylpentyl group, 3-ethylpentyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 2- Ethylhexyl group, 3
-Ethylhexyl group, isopropyl group, sec-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1,
2-dimethylpropyl group, 1-methylheptyl group, 1-
Ethylbutyl group, 1,3-dimethylbutyl group, 1,2-
Dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1-methylhexyl group, 1-ethylheptyl group, 1
-Propylbutyl group, 1-isopropyl-2-methylpropyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-propyl-2-methylpropyl group, 1-methylheptyl group, 1 -Ethylhexyl group, 1-propylpentyl group, 1-isopropylpentyl group, 1-isopropyl-2-methylbutyl group, 1-isopropyl-3-methylbutyl group, 1-methyloctyl group, 1-ethylheptyl group, 1-propylhexyl Group,
Secondary alkyl groups such as 1-isobutyl-3-methylbutyl group, neopentyl group, tert-butyl group, tert-
Tertiary alkyl groups such as hexyl group, tert-amyl group and tert-octyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-
Cyclohexyl groups such as tert-butylcyclohexyl group, 4- (2-ethylhexyl) cyclohexyl group, bornyl group, isobornyl group (adamantane group) and the like. Further, these primary and secondary alkyl groups may be substituted with a hydroxyl group, a halogen atom, a nitro group, a carboxy group, a cyano group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic residue. , Also oxygen,
The alkyl group may be substituted via an atom such as sulfur or nitrogen. Examples of the alkyl group substituted via oxygen include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, a butoxyethyl group, an ethoxyethoxyethyl group, a phenoxyethyl group,
Methoxypropyl group, ethoxypropyl group, piperidino group, morpholino group, etc., as the alkyl group substituted via sulfur, methylthioethyl group, ethylthioethyl group, ethylthiopropyl group, phenylthioethyl group, etc. Examples of the alkyl group substituted via nitrogen include a dimethylaminoethyl group, a diethylaminoethyl group, and a diethylaminopropyl group.

Specific examples of the above aryl group include phenyl, pentalenyl, indenyl, naphthyl, azulenyl, heptalenyl, biphenylenyl, as
-Indacenyl group, s-indacenyl group, acenaphthalenyl group, fluorenyl group, phenalenyl group, phenanthranyl group, anthranyl group, fluoracenyl group, acephenanthrenyl group, aceanthrylene group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group And the like. Further, these aryl groups may be substituted with a hydroxyl group, a halogen atom, a nitro group, a carboxy group, a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic residue, It may be substituted with the above-mentioned alkyl group via an atom such as oxygen, sulfur, or nitrogen.

Specific examples of the above heterocyclic residue include furyl, thienyl, pyrrolyl, 2H-pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, prazolyl, furazanyl, and pranyl. Group, pridyl group, pyridazinyl group, pyrimidinyl group, prazinyl group, pyrrolinyl group, proridinyl group, imidazolinyl group, pyrazolinyl group, pyrazolidinyl group, piperidyl group, pyrrelidino group, piperazinyl group, morpholinyl group, morpholino group, indolyl group, isoindolyl group 1H-indazolyl group, 4H-chromenyl group, quinolyl group, isoquinolyl group, cinnolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, prenyl group, pteridinyl group, xanthenyl group, carbazolyl group, Ntorijiniru group, acridinyl group, phenazinyl group, Renantororiniru group, indolinyl group, isoindolinyl group, etc. chromanyl group. Further, these heterocyclic residues may be substituted with a hydroxyl group, a halogen atom, a nitro group, a carboxy group, a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic residue. And may be substituted with the above-mentioned alkyl group via an atom such as oxygen, sulfur, or nitrogen. Further, these substituents may be such that a plurality of the same or different substituents are substituted on the ring.

Specific examples of the above alkoxy group may be those in which a substituted or unsubstituted alkyl group is directly bonded to an oxygen atom, and specific examples of the alkyl group include the aforementioned specific examples. .

Specific examples of the above aryloxy group include:
What is necessary is just that the substituted or unsubstituted aryl group is directly bonded to the oxygen atom, and specific examples of the aryl include the specific examples described above.

Specific examples of the carbamoyl group include those in which a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group is directly and independently bonded to the nitrogen atom of the carbamoyl group. Of the above, specific examples of the alkyl group and the aryl group include the specific examples described above.

Specific examples of the above-mentioned sulfonamide group may be those in which a hydrogen atom or a substituted or unsubstituted alkyl group is directly and independently bonded to the nitrogen atom of the sulfonamide group. The above-mentioned specific examples can be given as examples.

Specific examples of the above alkoxycarbonyl group include:
It is sufficient that a substituted or unsubstituted alkyl group is directly bonded to the oxygen atom of the alkoxycarbonyl group, and specific examples of the alkyl group include the aforementioned specific examples.

Specific examples of the above aryloxycarbonyl group may be those in which a substituted or unsubstituted aryl group is directly bonded to the oxygen atom of the aryloxycarbonyl group. Specific examples of the aryl group are those described above. Examples can be given.

Specific examples of the acyl group include those having a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group bonded directly to the carbonyl carbon atom of the acyl group. The above-mentioned specific examples can be mentioned as specific examples.

Specific examples of the above-mentioned alkyloxy group include those in which a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is directly bonded to the carbonyl carbon atom of an acyloxy group. Specific examples of the group include the specific examples described above.

Specific examples of the amino group include those having a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group bonded directly to a nitrogen atom.
Specific examples of the aryl group include the specific examples described above.

The above M ₁ , M ₂ and M ₃ represent atoms selected from transition metals. Specific examples of the transition metal atom include titanium,
Vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, technenium, ruthenium, rhodium, palladium and the like can be mentioned. Z represents a hydrogen ion, a monovalent metal ion, a divalent metal ion, an ammonium ion, a substituted or unsubstituted aliphatic ammonium ion, or a substituted or unsubstituted alicyclic ammonium ion. Further, m represents an integer of 1 or 2, and n represents an integer of 0, 1 or 2.

The azo metal chelate compound contained in the recording medium of the present invention will be described. FIG. 4 shows the absorption wavelength of the compound of the general formula (1). The compound of the general formula (1) is a compound having a maximum absorption wavelength in the range of 450 nm to 600 nm. By using the compound of the general formula (1) as the compound of the general formula (2), the compound having a maximum absorption wavelength in the range of 540 nm to 570 nm was obtained, and a highly reliable optical recording medium was obtained. FIG. 5 shows the absorption wavelength of the compound of the general formula (2). Further, by using the compound of the general formula (3), the solubility in various solvents is improved. The azochelate compounds of the general formulas (1), (2) and (3) greatly change the shape of the absorption spectrum due to the change in the metal. Good optical characteristics were obtained by using chromium, iron, cobalt, nickel and copper metals among the transition metals. In particular, an azo metal chelate compound using a cobalt or nickel metal has a steep peak in the first absorption band of the absorption spectrum, and has provided an optical recording medium having a high contrast in the recording / reproducing wavelength region of the system. FIG. 6 shows the absorption wavelength. Further, the azo metal chelate compound using copper metal was rapidly decomposed at a specific temperature, and became an optical recording medium with few errors. The azo chelate compounds represented by the general formulas (1), (2) and (3) can be produced by the following steps. A diazo component represented by the following general formula (4) (wherein X _{1 to} X ₈ are as defined above) is diazotized by an ordinary method,

[0028]

Embedded image The resulting diazo compound is represented by the following general formula (5) (wherein Y ₁
~ Y ₇ , R ₁ -R ₅ are as previously defined. ) By coupling with the coupling component represented by

[0029]

Embedded image The following general formula (6) (where X _{1 to} X ₈ , Y _{1 to} Y ₇ , R ₁ to
R ₅ is as previously defined. ) To synthesize a monoazo compound represented by

[0030]

Embedded image Next, the monoazo compound is reacted with the corresponding polyvalent metal salt in water or an organic solvent, and then, if necessary, with Z (Z is as defined above). Can be obtained in high yield.

1. Configuration of Recording Body The recording body of the present invention is a normal write-once optical disc shown in FIG.
(A so-called air sandwich in which two pieces of the structure shown in FIG. 1 are bonded together or a close bonding structure may be used) and a structure of a CD-R medium having the structure shown in FIG. DVD of the structure
-R.

2. Required Characteristics of Each Layer and Examples of Constituent Materials The basic structure of the recording medium of the present invention is a structure in which a first substrate and a second substrate are bonded with an adhesive via a recording layer. The recording layer may be a single layer of an organic dye layer, or may be a laminate of an organic dye layer and a metal reflection layer to increase the reflectance.
The recording layer and the substrate may be layered with an undercoat layer or a protective layer interposed therebetween, or may be formed by laminating them for improving the function. The most commonly used structure is the first substrate / organic dye layer / metal reflective layer / protective layer / adhesive layer / second substrate.

Substrate A required characteristic of the substrate is that it must be transparent to the laser beam used only when recording / reproducing from the substrate side.
When performing recording and reproduction from the recording layer, the substrate does not need to be transparent. Therefore, in the present invention, when only one substrate is used, the first substrate may be transparent or opaque as long as only the second substrate is transparent. As a substrate material, for example, plastics such as polyester, acrylic resin, polyamide, polycarbonate resin, polyolefin resin, phenol resin, epoxy resin, and polyimide, glass, ceramic, and metal can be used. When only one substrate is used, or when two substrates are used in a sandwich form, guide grooves and guide pits for tracking and a preformat such as an address signal are formed on the surface of the first substrate. Must have been.

Intermediate Layer Layers provided other than the substrate, the recording layer, the reflective layer, and the protective layer, including the undercoat layer and the like, are herein referred to as intermediate layers. This intermediate layer comprises (a) improved adhesion, (b) a barrier against water or gas, (c) improved storage stability of the recording layer, (d) improved reflectance, and (e) substrate from solvent. And protection of the recording layer,
(F) It is used for the purpose of forming guide grooves, guide pits / preformats, and the like. For the purpose of (a), polymer materials, for example, various polymer materials such as ionomer resins, polyamide resins, vinyl resins, natural resins, natural polymers, silicones, liquid rubbers, and silane coupling agents For the purposes of (b) and (c), inorganic compounds other than the above-mentioned polymer materials, for example, SiO ₂ , MgF ₂ , SiO, TiO ₂ , ZnO, Ti
Metals such as N, SiN, or semimetals, such as Zn, Cu, N
i, Cr, Ge, Se, Au, Ag, Al and the like can be used. For the purpose of (d), metals such as Al and Ag, and organic thin films having metallic luster such as methine dyes and xanthene dyes can be used.
For the purposes (e) and (f), an ultraviolet curable resin, a thermosetting resin, a thermoplastic resin, or the like can be used. The thickness of the undercoat layer is 0.01 to 30 μm, preferably 0.05 to 30 μm.
10 to 10 μm is appropriate.

The substrate used must be transparent to the laser used only when recording and reproduction are performed from the substrate side. When recording and reproduction are performed from the recording layer side, the substrate does not need to be transparent. As the substrate material, for example, polyester resin, acrylic resin, polyamide resin, polycarbonate resin, polyolefin resin, phenol resin,
Plastic such as epoxy resin, polyimide resin or
Glass, ceramic, metal, or the like can be used. A guide groove for tracking, a guide pit, and a preformat such as an address signal may be formed on the surface of the substrate.

Recording Layer The recording layer causes some optical change by laser beam irradiation, and can record information by the change. The recording layer contains the dye of the present invention. If necessary, the dye of the present invention may be used alone or in combination of two or more in forming the recording layer. Further, the dye of the present invention may be mixed or laminated with other organic dyes, metals, and metal compounds for the purpose of improving optical characteristics, recording sensitivity, signal characteristics, and the like. Examples of organic dyes include polymethine dyes, naphthalocyanine-based, phthalocyanine-based, squarylium-based, croconium-based, pyrylium-based, naphthoquinone-based, anthrequinone (indanthrene) -based, xanthene-based, triphenylmethane-based, azulene-based, and tetrahydrogen-based. Examples thereof include choline-based, phenanthrene-based, triphenothiazine-based dyes, and metal chelate compounds. These dyes may be used alone or in combination of two or more.

In addition, metals and metal compounds such as In, Te, Bi, Se, Sb, Ge, Sn, A
1, Be, TeO ₂ , SnO, As, Cd and the like can be used in the form of dispersion mixing or lamination. Further, various materials such as an ionomer resin, a polyamide resin, a vinyl resin, a natural polymer, a silicone, a liquid rubber, or a silane coupling agent may be dispersed and mixed in the above-mentioned dye. Alternatively, it can be used together with a stabilizer (eg, a transition metal complex), a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer, and the like for the purpose of improving properties.

The recording layer is formed by vapor deposition, sputtering, C
It can be carried out by ordinary means such as VD or solution application. When the coating method is used, the above-mentioned dye or the like is dissolved in an organic solvent or the like, and the coating is performed by a conventional coating method such as spraying, roller coating, dipping, and spin coating.

As the organic solvent used, generally, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, N, N-dimethylformamide, N, N
Amides such as dimethylacetamide, sulfoxides such as dimethylsulfoxide, ethers such as tetrahydrofuran, dioxane, diethyl ether, ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, chloroform, methylene chloride, dichloroethane and tetrachloride Carbon, aliphatic halogenated hydrocarbons such as trichloroethane, or aromatics such as benzene, xylene, monochlorobenzene, and dichlorobenzene; cellosolves such as methoxyethanol and ethoxyethanol; hexane, pentane, cyclohexane, and methylcyclohexane. Hydrocarbons and the like can be used. The thickness of the recording layer is 100 to 10 μm, preferably 200 to
Å2000Å is appropriate.

Metal Reflective Layer The reflective layer is made of a metal, a semi-metal, or the like, which can provide a high reflectance by itself and is hardly corroded. Examples of the material include Au, Ag, and the like.
Examples thereof include Cr, Ni, Al, Fe, and Sn. Au, Ag, and Al are most preferable from the viewpoint of reflectivity and productivity. These metals and metalloids may be used alone.
It may be a kind of alloy. Examples of the film forming method include vapor deposition and sputtering, and the film thickness is 50 to 5000.
{, Preferably 100-3000}.

Protective Layer, Substrate Surface Barcode Layer The protective layer or substrate surface barcode layer (a) protects the recording layer (reflection / absorption layer) from scratches, dust, dirt, etc., (b) recording layer (reflection / absorption layer) ) Is used for the purpose of improving the storage stability, and (c) improving the reflectance. For these purposes, the materials shown for the intermediate layer can be used. Also, SiO, SiO _{2 and the} like can be used as the inorganic material, and polymethyl acrylate,
Thermal softening of polycarbonate, epoxy resin, polystyrene, polyester resin, vinyl resin, cellulose, aliphatic hydrocarbon resin, aromatic hydrocarbon resin, natural rubber, styrene butadiene resin, chloroprene rubber, wax, alkyd resin, drying oil, rosin, etc. And a heat-meltable resin can also be used.

Among the above materials, the most preferable example of the protective layer or the hard coat layer on the substrate surface is an ultraviolet curable resin having excellent productivity. The thickness of the protective layer or the hard coat layer on the substrate surface is 0.01 to 30 μm, preferably 0.0 to 30 μm.
5 to 10 μm is appropriate. In the present invention, a stabilizer, a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer, and the like are used in the lower intermediate layer, the protective layer, and the substrate-side hard coat layer, as in the case of the recording layer. It can be contained.

Further, the dyes having the maximum absorption wavelength at 680 nm to 750 nm and the dyes of the present invention are mixed with each other, and the known dyes mentioned in the prior art for forming a short wavelength CD-R medium can be used as they are.

Preferred examples of the dye having an absorption maximum wavelength at 680 nm to 750 nm include a cyanine dye.

[0045]

Embedded image Phthalocyanine dye

[0046]

Embedded image

[0047]

Embedded image Azo metal chelate compound

[0048]

Embedded image One or more azo metal chelate compounds of an azo compound represented by the above general formula and a metal, and preferable examples of the metal include Ni, Pt, Pd, Co, Cu, Zn and the like. A represents a residue that forms a heterocyclic ring together with the carbon atom and the nitrogen atom to which it is bonded, and B represents an aromatic ring or a group that is bonded together with the two carbon atoms to which it is bonded. X represents a residue forming a heterocyclic ring, and X represents a group having a lubricating hydrogen.

Here, the dye of the present invention and the above specific examples 6
The mixing ratio with the dye having an absorption maximum wavelength at 80 nm to 750 nm is as follows: dye of the present invention / dye having absorption at 680 nm to 750 nm = 10/100 to 900/100, preferably 40/100 to 20/100; The thickness of the recording layer is 500 to 5 μm, preferably 1000 to
5000 $.

[0050]

The present invention will be more specifically described below with reference to examples. Example 1 Example of Method for Synthesizing Compound (8) In 100 ml of water, 5.8 g of 4-nitro-2-aminophenol is charged, and 7.4 g of 35% hydrochloric acid is poured with stirring. While cooling to 10 ° C. or lower, an aqueous solution of 5 ml of water and 2.1 g of sodium nitrite is added. After stirring at the same temperature for another 2 hours, excess nitrous acid is decomposed with sulfamic acid to prepare a diazonium liquid. Next, water 50
Then, 4.4 g of 2-naphthol was added to the mixture, and while stirring, 5.8 g of 24% sodium hydroxide and 6.3 g of sodium carbonate were added.
Add and dissolve. Crushed ice is added thereto, and a diazo solution is poured while keeping the temperature at 10 ° C. or lower to perform a coupling reaction. After completion of the reaction, the mixture was filtered and dried to obtain a monoazo dye.
The monoazo dye is dispersed in 50 ml of ethylene glycol, and a solution of 4 g of chromium sulfate dissolved in 20 ml of water is added thereto. Adjust the pH to 10-11 with caustic soda,
The mixture was stirred at 0 to 100 ° C. for about 10 minutes to obtain a chromium complex dye. The obtained chromium complex dye was dispersed in a mixed solvent of 70 ml of water and 30 ml of ethylene glycol, 5 g of dodecyldiethanolamine was added, the pH was adjusted to 6 to 7, and the mixture was stirred at 60 to 70 ° C for about 4 hours. After cooling, water was further added for dilution and filtration. Since the obtained dye contains an excess of inorganic salts and impurities such as amines, it is preferable to use it by washing with various solvents, recrystallization, or by column chromatography or the like.

Example 2 Example of a method for synthesizing the compound (15) 5.8 g of 5-nitro-2-aminophenol was charged in 100 ml of water, and 7.4 g of 35% hydrochloric acid was poured with stirring. While cooling to 10 ° C. or lower, an aqueous solution of 5 ml of water and 2.1 g of sodium nitrite is added. After stirring at the same temperature for another 2 hours, excess nitrous acid is decomposed with sulfamic acid to prepare a diazonium liquid. Next, water 50
ml and 20 ml of n-butanol with 2-hydroxy-
7.9 g of 3-naphthoanilide is charged, and while stirring, 5.8 g of 24% sodium hydroxide and 4.5 g of sodium carbonate are added and dissolved. Crushed ice is added thereto, and a diazo solution is poured while keeping the temperature at 10 ° C. or lower to perform a coupling reaction. After completion of the reaction, the mixture was filtered and dried to obtain a monoazo dye.
The monoazo dye is dispersed in 50 ml of ethylene glycol, and a solution prepared by dissolving 8 g of nickel sulfate in 20 ml of water is added. Adjust the pH to 10-11 with caustic soda,
The mixture was stirred at 90 to 100 ° C. for about 10 hours to obtain a nickel complex dye. Since the obtained dye contains an excess of impurities such as inorganic salts, it is preferable to use the dye by washing it with various solvents, recrystallizing it, or producing it by column chromatography or the like.

Example 3 On a 0.6 mm thick injection molded polycarbonate substrate, a depth of 1200 ° and a half width of 0.35 μm were formed using a photopolymer.
m, a compound groove having a compound pitch of 1.0 μm was formed on a substrate having a guide groove having a track pitch of 1.0 μm. A methylcellosolve solution of No. 1 was applied by spinner to form a recording layer having a thickness of 700 °, thereby obtaining a recording medium. Examples 4 to 11 Examples of Compound Nos. Compound Example No. Using 2 to 9, a recording medium was formed in exactly the same manner as in Example 3. Comparative Example 1 In Example 3, Compound Example No. A recording medium was formed in the same manner as in Example 3 except that the following compound (ratio -1) was used instead of 1.

[0053]

Embedded image

Evaluation of Samples The samples obtained in Examples 3 to 11 and Comparative Example 1 were evaluated under the following conditions. Table 1 shows the results. Recording conditions Laser oscillation wavelength: 635 nm Recording frequency: 3.75 MHz Recording linear velocity: 3.0 m / sec. Reproduction conditions Laser oscillation wavelength: 635 nm Reproduction power: Continuous light of 0.5 to 0.7 mW Scanning band: 30 KHz Weather resistance test conditions Light resistance test: 40000 Lux, Xe light, continuous irradiation for 20 hours Storage test: 85 ° C., 85% 720 hours Neglect

[0055]

[Table 1]

Example 12 Compound Example No. 1 was placed on a 0.6 mm thick injection-molded polycarbonate substrate having a guide groove with a depth of 1400 °, a half width of 0.35 μm and a track pitch of 1.0 μm. A solution prepared by dissolving 10 in a mixed solution of methylcyclohexane, 2-methoxyethanol, methyl ethyl ketone and tetrahydrofuran was applied by spinner to form an organic dye layer having a thickness of 800 mm, and then a reflective layer of 2000 mm of gold was provided by a sputtering method. Acrylic photopolymer on top 5
The recording medium was provided with a protective layer of μm.

Examples 13 to 24 In Example 12, Compound Example Nos. Compound No. 16 in place of Compound No. Using 11 to 22, a recording medium was obtained in exactly the same manner as in Example 12.

Comparative Example 2 In Example 12, Compound No. 1 was used as an organic thin film. A recording medium was obtained by using (ratio-1) of Comparative Example 1 described above instead of 10.

Evaluation of Samples The samples obtained in Examples 12 to 24 and Comparative Example 2 were evaluated under the following conditions. Table 2 shows the results. Recording conditions This recording medium has an oscillation wavelength of 635 nm and a beam diameter of 1.0 μm.
EFM while tracking using semiconductor laser light
Signal (linear velocity 3.0m / sec., Shortest mark length 0.4μ)
m) was recorded and continuous light of the same laser (reproduction power 0.
7 mW), and the reproduced waveform was observed.

[0060]

[Table 2]

Example 25 A compound having the above-mentioned compound (ratio by weight) was formed on a 1.2 mm-thick injection-molded polycarbonate substrate having a guide groove with a depth of 1000 °, a half width of 0.40 μm and a track pitch of 1.1 μm.
1) and Compound Example No. 23 and a weight ratio (1/1) of a mixed solvent of methylcyclohexane, 2-methoxyethanol, methylethylketone, and tetrahydrofuran, and spin-coating to form an organic dye layer having a thickness of 1700 °, and then sputtering using gold to 2000 °. Of a reflective layer, and an acrylic photopolymer
A protective layer of μm was provided to obtain a recording medium.

Examples 26 to 28 In Example 25, the recording layer was prepared using the compound No. Compound No. 23 in place of Compound No. Using 24, 25, and 26, a recording medium was obtained in exactly the same manner as in Example 25.

Examples 29 to 32 In Example 25, the recording layer was prepared by using Compound Example No. Compound No. 23 instead of Compound No. 23, respectively. Using 27, 28, 29, 30
A recording medium was obtained in exactly the same manner as in Example 25 except that (ratio-2) was used instead of (ratio-1).

Comparative Examples 3 and 4 In Example 25, only the organic recording layer (comparative -1) was used.
A recording medium was obtained in the same manner as in Example 25 except for (ratio-2).

Evaluation of Samples The samples obtained in Examples 25 to 32 and Comparative Examples 3 and 4 were evaluated under the following conditions. Table 3 shows the results. Recording conditions This recording medium has an oscillation wavelength of 780 nm and a beam diameter of 1.6 μm.
EFM while tracking using semiconductor laser light
A signal (linear velocity: 1.4 m / sec.) Was recorded and reproduced with continuous light of the same laser and a semiconductor laser having an oscillation wavelength of 635 nm and a beam diameter of 1.0 μm, and a reproduced waveform was observed.

[0066]

Embedded image

[0067]

[Table 3] Table 4 shows compounds used in Examples and Comparative Examples.

[0068]

[Table 4-1]

[0069]

[Table 4-2]

[0070]

[Table 4-3]

[0071]

[Table 4-4]

[0072]

[Table 4-5]

[0073]

[Table 4-6]

[0074]

[Table 4-7]

[0075]

[Table 4-8]

[0076]

As described above, according to the present invention, recording and reproduction can be performed by using a laser beam having a wavelength of 7000 nm or less, light resistance, storage stability, and low temperature (according to the present invention). (About 250 ° C.) It is possible to provide an excellent information recording medium which can be decomposed and can be recorded with high sensitivity, and the M ₁ in the azo metal chelate compound represented by the general formula (1)
Is a metal atom selected from chromium, iron, cobalt, nickel and copper, whereby a recording medium having good optical characteristics can be provided, and the azo metal chelate compound represented by the general formula (1) is The azo metal chelate compound represented by the formula (2) provides a highly reliable optical recording medium. In this case, the M ₂ is a metal atom selected from chromium, iron, cobalt, nickel, and copper, and the optical properties are improved. And a azo metal chelate compound represented by the general formula (1)
By using the azo metal chelate compound represented by the general formula (2), it is possible to provide a recording medium that can be dissolved in an organic solvent at a high concentration, wherein M ₃ is chromium, iron, cobalt, or nickel. And a metal medium selected from copper can provide a recording medium having good optical characteristics, and the metal atom of the azo metal chelate compound represented by the general formulas (1), (2) and (3) can be provided. By being selected from cobalt or nickel, a high-contrast recording medium can be provided, and since the metal atom is copper, an optical recording medium with few errors can be provided. 1) In addition to the azo metal chelate compounds represented by the general formulas (2) and (3), 68
It can be used as a CD-R in the current system by being composed of a mixed layer with a dye having the maximum absorption wavelength at 0 to 750 nm, and the recorded information can be reproduced even in the next-generation high-density optical disk system. A high-quality signal characteristic can be recorded by limiting the mixed dyes, and when a reflective layer is required, the reflective layer is made of gold, silver, aluminum, or gold. , An alloy mainly composed of silver, and an alloy mainly composed of aluminum, a highly reflective medium having high productivity can be obtained, and the recording / reproducing wavelength is 630 to 690 nm and the recording wavelength is 770 to 810 nm and reproduction wavelengths of 770 to 810 nm and 630 to 690 nm limit the recording and reproduction wavelength to provide a new recording method and recording medium. It became.

[Brief description of the drawings]

FIG. 1 is a schematic view of a layer unit for forming a normal write-once optical recording medium of the present invention.

FIG. 2 is a schematic view of a unit for forming a medium for a CD-R of the present invention.

FIG. 3 is a schematic view of a unit for forming a DVD-R medium of the present invention.

FIG. 4 is an absorption wavelength range diagram of a thin film of the compound of the general formula (1) used in the present invention.

FIG. 5 is an absorption wavelength range diagram of a thin film of the compound of the general formula (2) used in the present invention.

FIG. 6 is an absorption wavelength range diagram of an azo metal chelate compound thin film using cobalt or nickel metal used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Recording layer 3 Undercoat layer 4 Protective layer 5 Hard coat layer 6 Metal reflective layer 7 Protective substrate 8 Adhesive layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C09B 45/16 C09B 45/18 45/18 45/20 45/20 45/22 45/22 B41M 5/26 Y (72) Inventor Tsutomu Sato 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Hiroyoshi Yamaga 66-2 Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Prefecture 11th floor Kowa Kawasaki Nishiguchi Building Hodogaya Chemical Industry Co., Ltd. In-house (72) Inventor Mitsutoshi Anzai 66-2, Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Kowa Kawasaki West Exit Building 11F Hodogaya Chemical Co., Ltd.In-house F-term (reference) 2H111 FA01 FA11 FA12 FA14 FB42 5D029 JA04 JB47 MA13

Claims (13)

[Claims] 1. An optical recording medium comprising a supply layer provided directly or through an undercoat layer on a first substrate, and a reflective layer, a protective or reflective layer, and a second substrate provided thereon as required. An optical recording medium characterized in that the recording layer contains at least one azo metal chelate compound represented by the general formula (1). 2. The azo metal chelate compound represented by the general formula (1) according to claim 1, wherein M ₁ is chromium, iron,
An optical recording medium comprising metal atoms selected from cobalt, nickel, and copper. 3. An optical recording medium comprising an azo metal chelate compound represented by the general formula (2) in a recording layer as the azo metal chelate compound represented by the general formula (1). 4. The azo metal chelate compound represented by the general formula (2) according to claim 3, wherein M ₂ is chromium, iron,
An optical recording medium comprising metal atoms selected from cobalt, nickel, and copper. 5. The recording layer according to claim 1, wherein the azo metal chelate compound represented by the general formula (1) is contained in the recording layer. An optical recording medium according to claim 1. 6. The azo metal chelate compound represented by the general formula (3) according to claim 5, wherein M ₃ is chromium, iron,
An optical recording medium comprising metal atoms selected from cobalt, nickel, and copper. 7. The optical recording medium according to claim 1, wherein the metal atom of the azo metal chelate compound contained in the recording layer is selected from cobalt or nickel. 8. The optical recording medium according to claim 1, wherein the metal atom of the azo metal chelate compound contained in the recording layer is copper. 9. In addition to the azo metal chelate compounds represented by the general formulas (1), (2) and (3), 68
9. The optical recording medium according to claim 1, comprising a mixed layer with a dye having a maximum absorption wavelength at 0 to 750 nm. 10. The optical recording medium according to claim 9, wherein the dye having the maximum absorption wavelength at 680 to 750 nm is a cyanine dye, a phthalocyanine dye, or an azo metal chelate compound. 11. When the reflective layer is required, the reflective layer is made of gold,
The optical recording medium according to any one of claims 1 to 10, wherein the optical recording medium is silver, aluminum, an alloy mainly containing gold, an alloy mainly containing silver, or an alloy mainly containing aluminum. 12. The optical recording medium according to claim 1, wherein a recording / reproducing wavelength is from 630 to 690 nm. 13. The optical recording medium according to claim 9, wherein a recording wavelength is 770 to 810 nm, and a reproduction wavelength is 770 to 810 nm and 630 to 690 nm. Embedded image In the general formula (1), X ₁ , X ₂ , X ₃ and X ₄ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a carboxy group, a cyano group, a sulfone group, a substituted or unsubstituted alkyl group. Group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic residue, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted Sulfonamide group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group,
Represents a substituted or unsubstituted amino group, Y ₁ , Y ₂ , Y ₃ ,
Y ₄ , Y ₅ and Y ₆ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a carboxy group, a cyano group,
Sulfone group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic residue, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted Carbamoyl group, substituted or unsubstituted sulfonamide group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or Represents an unsubstituted amino group; M ₁ represents an atom selected from transition metals;
Represents a hydrogen ion, a monovalent metal ion, a divalent metal ion, an ammonium ion, a substituted or unsubstituted aliphatic ammonium ion, a substituted or unsubstituted alicyclic ammonium ion, and m represents 1 or 2 Represents an integer, n
Represents an integer of 0, 1 or 2. Embedded image In the general formula (2), X ₅ and X ₆ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a carboxy group, a cyano group, a sulfone group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Aryl group, substituted or unsubstituted heterocyclic residue, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfonamide group, substituted or Represents an unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted amino group, Y ₇ is a halogen atom, Nitro group, hydroxyl group, carboxy group, cyano group, sulfone group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted Substituted heterocyclic residue, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfonamide group, substituted or unsubstituted alkoxycarbonyl group, A substituted or unsubstituted aryloxycarbonyl group,
It represents a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted amino group, and M ₂ represents an atom selected from transition metals. Embedded image In the general formula (3), X ₇ and X ₈ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a carboxy group, a cyano group, a sulfone group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Aryl group, substituted or unsubstituted heterocyclic residue, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfonamide group, substituted or Represents an unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted amino group, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are
Each independently a hydrogen atom, a halogen atom, a nitro group,
Hydroxyl group, carboxy group, cyano group, sulfone group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group,
Substituted or unsubstituted heterocyclic residue, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfonamide group, substituted or unsubstituted alkoxy group A carbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted amino group, and M ₃ represents an atom selected from a transition metal . Also, R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , and R ₄ and R ₅ may be independently linked to form a ring.