JP3328169B2 - Optical recording media using metal complex dyes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an optical recording medium using a metal complex dye in a recording layer.

[0002]

2. Description of the Related Art The inventors of the present invention have proposed a C (Compact Disc) standard as a recordable optical recording medium conforming to the CD (Compact Disk) standard.
D-R (write-once compact disc) has been developed.
In recent years, further high-density optical recording media have been desired. One of them is to increase the recording wavelength of CD-R from the current 780 nm to 68
Next-generation optical recording media having a shorter wavelength from 0 to 635 nm have been proposed. However, as a result of the development proceeding up to 780 nm, almost no dyes satisfying various properties such as light fastness, solubility and recording sensitivity on the short wavelength side such as 680 nm to 635 nm are known. An additional requirement that cannot be ignored is compatibility with current standards. In other words, if the medium recorded by the current recording machine is at least short-wavelength and cannot be read at least, there is a problem that the accumulation of past information cannot be used simply and quickly. Therefore, the recording layer for short wavelengths to be developed in the future has to comply with the standard at the current wavelength of 780 nm, that is, satisfy the so-called Orange Book standard, and at the same time, have a wavelength of 680 nm to 635 nm.
It is important to have characteristics similar to those of the current standard.

In order to realize this most practically, a proper amount of a dye having good characteristics in the current standard and having no large absorption on the short wavelength side is mixed and the characteristics are satisfied at both wavelengths. There is a way to do it. In this case, it is necessary to sufficiently examine the recording characteristics in the mixed system.

Although the recording wavelength is also important, a particularly important and difficult characteristic is the light resistance of the dye for the recording layer. Until now, some metal complex dyes have been mainly disclosed as high lightfast dyes. For example, as disclosed in JP-A-59-55795, there is an example in which a light-fast cyanine dye is combined with a metal complex quencher to improve the light fastness. However, this system has the drawback that the solubility in a coating solvent used during spin coating is significantly reduced, and that the stabilizer itself is decomposed and deteriorated. In addition, examples of dyes having high light resistance include, for example, azo metal complex dyes (JP-B-7-51682, JP-B-7-51673, and JP-A-8-156408) and formazan nickel complex dyes (JP-A-8-156408). Showa 60-254038, 62-14
No. 4997). Certainly, these metal complex dyes are excellent in light resistance, but generally have low recording sensitivity, relatively low solubility, and have the disadvantage that they are dissolved only in a specific solvent. Considering recording and reproduction at a short wavelength of 680 nm to 635 nm, the absorption wavelength of the formazan nickel metal complex dye is too long, and it is considered that this skeleton can no longer cope with the short wavelength.

With respect to phthalocyanine dyes which have long been known as high lightfast dyes, it is still difficult to avoid the above-mentioned disadvantages, and it is considered impossible to develop them as dyes for short-wavelength dye recording layers. As described above, 680 nm to 63
Dye having desired recording / reproducing characteristics even when used in a mixed system with a dye having absorption at the longer wavelength side, especially when used in a mixed system with a dye having a short wavelength of 5 nm. There is a strong need for a skeleton.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is, first, to provide a high-sensitivity optical recording medium having excellent light resistance and good recording / reproducing characteristics at a wavelength of about 680 nm to 635 nm. . Second, it is an object of the present invention to provide a high-sensitivity optical recording medium capable of performing good recording and reproduction even at a wavelength of about 780 nm and having recording and reproduction characteristics conforming to the Orange Book standard.

[0007]

This and other objects are achieved by the present invention which is defined below as (1) to (3). (1) The following formulas (I), (II), (III) and (IV)
An optical recording medium using a metal complex-based dye having a recording layer containing a metal complex-based dye obtained by reacting a compound selected from a cyanine dye-type compound or a merocyanine dye-type compound with a metal compound.

[0008]

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[In the formula (I), Q ₁ represents an atomic group necessary for forming a benzo [cd] indole ring together with C and N, and Q ₂ represents an atomic group necessary for forming a heterocyclic ring. Represents The heterocyclic skeleton completed by Q ₁ or Q ₂ may be the same or different. R represents a hydrogen atom or a monovalent substituent, but R may form a part of a heterocyclic ring with Q ₂ . In the formula (II), Q ₁ and Q
₂ represents a group of atoms necessary for forming a heterocyclic ring together with C and N, and the heterocyclic skeleton completed by Q ₁ or Q ₂ may be the same or different. In the formula (III), Q ₁ and Q ₂ each represent an atom group necessary for forming a heterocyclic ring together with C and N, and Q ₁ or Q ₂
May be the same or different. R ₁ and R ₂ each represent a hydrogen atom or a monovalent substituent, but R ₁ and R ₂ may each form a part of a heterocyclic ring with Q ₁ or Q ₂ . In the formula (IV), Q
₁ represents a group of atoms necessary for forming a heterocyclic ring together with C and N, and Q ₃ represents a group of atoms necessary for forming a cyclic enol having active hydrogen. (2) The central metal of the metal complex dye is Co, Mn,
Ti, V, Ni, Cu, Zn, Mo, W, Ru, Fe,
An optical recording medium using the metal complex dye of the above (1), which is Pd, Pt or Al. (3) An optical recording medium using the metal complex dye of (1) or (2), wherein the recording layer further contains a light absorbing dye different from the metal complex dye.

[0010]

Embodiments of the present invention will be described below in detail. The optical recording medium of the present invention has a recording layer containing a metal complex dye, and the metal complex dye has the formula (I)
It is obtained by reacting a compound represented by (IV) with a metal compound.

Referring to the formula (I), Q ₁ and Q ₂ represent a group of atoms necessary to form a heterocyclic ring together with a carbon atom (C) and a nitrogen atom (N), and Q ₁ or Q ₂ The heterocyclic skeleton completed in may be different. The heterocycle completed by Q ₁ and Q ₂ may be monocyclic or polycyclic. In the case of a polycyclic ring, it may be a condensed polycyclic ring or a ring assembly.

Examples of such a heterocyclic ring include a pyrrole ring, a pyrazoline ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, an oxazole ring, and a benzooxazole ring. , Naphthoxazole ring, selenazole ring, benzoselenazole ring, naphthoselenazole ring, thiazoline ring, oxazoline ring, selenazoline ring, 2
-Quinoline-based ring, 1-isoquinoline-based ring, 3-isoquinoline-based ring, indolenine-based ring, benzo [cd]
Indole ring, pyridine ring, imidazole ring, benzimidazole ring, quinoxaline ring,
Isoindoline-based rings and the like.

Among them, a pyrrole-based ring, a 2-quinoline-based ring, an indolenine-based ring, a benzo [cd] indole-based ring, and a quinoxaline-based ring are preferred, and a pyrrole-based ring and a 2-quinoline-based ring are particularly preferred. And quinoxaline-based rings.

In particular, in the case of the formula (1), the heterocycle completed by Q ₁ and Q ₂ is such that one Q ₁ is a benzo [cd] indole ring and the other Q ₂ is an indolenine benzothiazole Preferred is a combination which is a ring selected from the group consisting of benzoxazole, benzoxazole, and quinoline.

Such a heterocyclic ring may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a nitro group, a cyano group, a halogen atom, an aryl group, an aryloxy group, an acyl group, and an alkoxycarbonyl group. Group, carbamoyl group, amino group and the like.

The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and may be linear or branched. And may have a cycloalkyl group. Further, it may have a substituent, and examples of such a substituent include a halogen atom (eg, a fluorine atom and a chlorine atom). Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a trifluoromethyl group.

The alkoxy group preferably has 1 to 6, more preferably 1 to 4 carbon atoms in the alkyl moiety, and may be substituted with a halogen atom (such as a fluorine atom). Specific examples of such an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentafluoropropoxy group.

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

The aryl group may further have a substituent, for example, a phenyl group, (o-, m
-, P-) tolyl group and the like.

The aryloxy group may further have a substituent, for example, a phenoxy group and the like are preferable.

Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.

Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The carbamoyl group may further have a substituent, for example, a carbamoyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group and the like.

The amino group preferably has a substituent, but may be unsubstituted. The substituted amino group is particularly preferably a dialkylamino group. In this case, the alkyl portion of the dialkylamino group may be linear or branched. Also, the two alkyl groups may be asymmetric. Specific examples of the amino group include an amino group and a methylamino group.

Two or more of these substituents may be present, and when they are two or more, they may be the same or different. Further, adjacent substituents are bonded to each other to form a condensed ring. May be.

R represents a hydrogen atom or a monovalent substituent.
Examples of the monovalent substituent represented by R include an alkyl group, a nitro group, a cyano group, a halogen atom, an aryl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a heterocyclic group, and an arylazo group.

The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and may be linear or branched. And may have a cycloalkyl group. Further, it may have a substituent, and examples of such a substituent include a halogen atom (eg, a fluorine atom and a chlorine atom). Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a trifluoromethyl group.

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

The aryl group may further have a substituent, for example, a phenyl group, (o-, m
-, P-) tolyl group and the like.

Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.

Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The carbamoyl group may further have a substituent, for example, a carbamoyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group and the like.

Examples of the heterocyclic group include a 2-benzothiazolyl group.

The arylazo group may further have a substituent, for example, a phenylazo group.

R may form a part of a heterocyclic ring together with Q ₁ or Q ₂ .

R is preferably a hydrogen atom, a cyano group or an alkoxycarbonyl group.

Referring to the formula (II), Q ₁ and Q ₂ have the same meanings as those in the formula (I).

Examples of such a heterocyclic ring include a pyrrole ring, a pyrazoline ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, an oxazole ring, and a benzooxazole ring. , Naphthoxazole ring, selenazole ring, benzoselenazole ring, naphthoselenazole ring, thiazoline ring, oxazoline ring, selenazoline ring, 2
-Quinoline-based ring, 1-isoquinoline-based ring, 3-isoquinoline-based ring, indolenine-based ring, benzo [cd]
Indole ring, pyridine ring, imidazole ring, benzimidazole ring, quinoxaline ring,
Isoindoline-based rings and the like. Of these, a pyrrole ring, a benzothiazole ring, a naphthothiazole ring, and a benzo [cd] indole ring are preferable. In particular, in the formula (II), the heterocycle completed by Q ₁ and Q ₂ is a pyrrole-based ring, or one is a benzo [cd] indole-based ring and the other is a benzothiazole- or isoquinoline-based ring. Combinations that are selected rings are preferred.

Describing the equation (III), Q ₁ , Q ₂
Has the same meaning as in formula (I).

Of these, an indolenine ring and a pyridine ring are preferred.

R ₁ and R ₂ have the same meanings as R in the formula (I), and particularly preferably a hydrogen atom.

Referring to the formula (IV), Q ₁ represents a group of atoms necessary for forming a heterocyclic ring together with C and N, and the heterocyclic ring completed by Q ₁ may be a single ring; In the case of a polycyclic ring, it may be a condensed polycyclic ring or a ring assembly.

Examples of such a heterocyclic ring include those similar to those of the formula (I).

Of these, a benzo [cd] indole ring is preferred.

Q ₃ represents an atomic group necessary for forming a cyclic enol having active hydrogen. The ring completed by Q ₃ may be monocyclic or polycyclic. May be a condensed polycyclic ring or a ring assembly. Examples of such a cyclic enol include a 6-hydroxy-2-pyridone ring, a barbituric acid ring, an imidazopyridone ring, a 4-hydroxycoumarin ring, a 5-pyrazolinone ring, and a 3-hydroxy ring. Examples include a thionaphthene-based ring, an indoxyl-based ring, an o-phenol-based ring, a β-naphthol-based ring, and a rhodanine-based ring.

Among them, a 6-hydroxy-2-pyridone ring, a 4-hydroxycoumarin ring, a 5-pyrazolinone ring, a β-naphthol ring and the like are preferable.

In the formulas (I) to (IV), the active hydrogen is shown, but the active hydrogen is coordinated in a removed form. When the compound is represented as a ligand compound, it may be in the form of not only H but also a salt such as an alkali metal salt such as Na or an ammonium salt, and the formulas (I) to (IV) typically represent these. It's just that.

In obtaining the metal complex in the present invention, the metal compound to be reacted with the compound represented by the formula (I) may be selected according to the central metal of the metal complex.

The central metals of the metal complex dyes obtained by coordinating the compounds represented by the formulas (I) to (IV) are Co, M
n, Ti, V, Ni, Cu, Zn, Mo, W, Ru, F
e, Pd, Pt and Al are preferred. Among them, V, M
o and W are oxide ions, for example, VO ²⁺ , VO ³⁺ , MoO
_It may be in the form of ²⁺ , MoO3 ⁺ , WO3 ⁺ . As the central metal, Co, Cu, Ni, particularly Co, Ni is preferable.

Accordingly, such metal compounds include chlorides (eg, cobalt chloride, zinc chloride, chromium chloride, manganese chloride, iron chloride, vanadium oxytrichloride, etc.), acetates (eg, nickel acetate, copper acetate, etc.), and the like. Acetylacetone complex salt (acetylacetone cobalt salt (III
) Etc. are commonly used.

The compounds represented by formulas (I), (II) and (IV) are bidentate ligands, and according to these formulas, represented by formulas (I), (II) and (IV) -NH in the compound,
N -OH active hydrogen has been established ^- or O ^- coordinated to the metal in and the N, metal and 1: 1 complexes, 1: 2 complex or 1:
Form three complexes. In the case of the formula (III), the compound is a tridentate ligand and forms a 1: 1 complex or a 1: 2 complex with a metal.

When the coordination number of the central metal cannot be satisfied only by the ligands of the compounds represented by the formulas (I) to (IV), other ligands may be coordinated in addition to the above compounds. You may. Such other ligands include chlorine atoms, water molecules,
Hydroxo and the like are mentioned, and these other ligands are derived from raw materials, reaction solvents and the like.

When the metal complex dye has a positive charge, the counter ion includes chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodide ion (I ⁻ ), tetrafluoroborate ion ( BF ₄ ⁻ ), hexafluorophosphate ion (PF ₆ ⁻ ), tetraphenylborate ion (B
^{_{(C 6 H 5) 4 -}} ), perchlorate ion (ClO ₄ ^-), tungstate ions (WO ₄ ^2-), acetylacetone anion _{(CH 3 COCH = C (CH} 3) O -) and the like, Preferably, chloride ion (Cl ⁻ ), tetrafluoroborate ion (BF ₄ ⁻ ), hexafluorophosphate ion (PF ₆ ⁻ ),
Examples include perchlorate ion (ClO ₄ ⁻ ) and acetylacetone anion (CH ₃ COCH (C (CH ₃ ) O ⁻ ), and particularly, tetrafluoroborate ion (BF ₄ ⁻ ) and hexafluorophosphate ion (PF ₆ ^-), perchlorate ion (ClO ₄ ^-), acetylacetone anion _{(CH 3 COCH = C (CH} 3) O -) is preferred.

Counter ions when the metal complex dye has a negative charge include sodium ion (Na ⁺ ), potassium ion (K ⁺ ), tetraethylammonium ion ((C ₂ H ₅ ) ₄ N ⁺ ), tetra-t - butylammonium ion _{((t-C 4 H 9} ) 4 N +) , and the like.

A metal complex dye obtained from a compound represented by the formula (I) and a metal compound is schematically shown, for example, when R is a hydrogen atom. Become.

[0056]

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In the formula (V), Q ₁ and Q ₂ have the same meanings as those in the formula (I), M ₁ represents a central metal, and m ₁ is 1-3. L represents another ligand. m
₂ is usually 0 or an integer of 1 to 4. Y represents a counter ion, and y is a number for maintaining charge balance.

Hereinafter, specific examples of the metal complex dyes used in the present invention are shown by combinations of the compounds represented by formulas (I) to (IV), a central metal and a counter ion. Note that the formulas (I) to (I
The compound of V) is shown in a form in which active hydrogens of -NH and -OH are removed.

[0059]

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[0063]

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[0065]

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Formula (I) used as a ligand in the present invention
Compounds represented by the formulas (IV) to (IV) were obtained from AHCook, JRMAjer, JC
hem.Soc., 482 (1944), AHCook, RFNaylor, J.Chem.So
c., 397 (1943), AIKiprianov, TMVerbovskaya, Zh.Obs
ch.Khim., 33,479 (1963), UK Patent No. 554,101
, US Pat. No. 2,469,830 and the references cited therein.

The compound was identified by mass spectrum, ¹ H-
It can be performed by a nuclear magnetic resonance spectrum, an infrared absorption spectrum, or the like.

The metal complex dyes are represented by formulas (I) to (I)
It can be obtained by reacting the compound of V) with the above-mentioned metal compound such as acetate in a suitable solvent such as alcohol (methanol, ethanol, etc.), ketone (acetone, etc.) or tetrahydrofuran (THF).
In this case, the complex formation reaction proceeds instantaneously at a temperature of about room temperature (15 ° C. to 30 ° C.), but usually, the complex formation reaction is usually performed at room temperature to 1 ° C.
The reaction may be performed at a temperature of about 00 ° C. for about 3 minutes to 1.5 hours. The formation of such a complex can be confirmed by the coloration of the solution. It can be obtained as a solid by crystallization, and this can be identified by a visible ultraviolet absorption spectrum, an infrared absorption spectrum, a mass spectrum, or the like.

When the metal complex dye obtained as described above has a counter ion, it has a counter ion (eg, Cl ⁻ , CH ₃ COO ^−, etc.) derived from the metal salt of the raw material for synthesis. ClO ₄ carried out exchange ^-, BF ₄ ^-, PF
It is preferable to convert to ₆ ^- etc. For salt exchange, perchlorate (sodium perchlorate, ammonium perchlorate, magnesium perchlorate, etc.), tetrafluoroborate (sodium tetrafluoroborate, ammonium tetrafluoroborate, etc.), hexafluorophosphoric acid Using a salt (potassium hexafluorophosphate, ammonium hexafluorophosphate, etc.), the above metal complex-based dye is dissolved in a solution (0.5 to 4 wt%) of these salts dissolved in a solvent such as methanol or ethanol. It can be carried out by adding and stirring such that the amount ratio of the dye to the salt (molar ratio of dye / salt) is 1 / 0.5 to 1/2. Then, crystallization may be performed thereafter.

The product can be identified by a visible ultraviolet absorption spectrum, mass spectrum, X-ray fluorescence measurement, or the like.

The following shows a synthesis example.

Synthesis Example 1 Synthesis of Dye No. 1 (1-1) 2-[(3 ′, 3′-dimethyl-2 ′ (1 ′)
Synthesis of H) -Indolinylidene) methyl] benzo [cd] indole (Ligand 1) Benzo [cd] indole-2 (1H) -one 10.1
5 g and 9.55 g of 1,3,3-trimethylindolenine
Was taken up in 90 ml of dry chlorobenzene and heated. 8
At 0 ° C., 9.66 g of phosphorus oxychloride was added dropwise, and 100 to 1
The mixture was heated and stirred at 05 ° C for 3 hours. After the completion of the reaction, when cooled, an oily dye was obtained. This was taken out and neutralized to obtain 12.50 g of Ligand 1.

(1-2) Synthesis of Dye No. 1 3.10 g of the above ligand compound 1 and 1.26 g of cobalt acetate tetrahydrate were added to a mixed solvent of 30 ml of THF and 10 ml of ethanol and refluxed for 4 hours. The reaction solution was poured into water, and the precipitated solid was taken out to obtain 3.28 g of Dye No. 1.

Synthesis Example 2 Synthesis of Dye No. 2 Synthesis Example 1 except that nickel acetate was used as the metal compound
Was synthesized in the same manner as described above.

Synthesis Example 3 Synthesis of Dye No. 3 According to the synthesis of ligand 1 of Synthesis Example 1, 2-[(1 ′,
1′-Dimethyl-2 ′ (1′H) -benzo (e) indolinylidene) methyl] benzo [cd] indole (ligand 2) was synthesized and synthesized in the same manner as in Synthesis Example 1 using this. did.

Synthesis Example 4 Synthesis of Dye No. 4 Synthesis was performed in the same manner as in Synthesis Example 2 except that the ligand 2 of Synthesis Example 3 was used.

Synthesis Example 5 Synthesis of Dye No. 5 (5-1) 2,2′-methylenebis (3,3 ′, 5,5)
Synthesis of 5′-tetraphenylpyrrole (ligand 3) 2.2 g of 2,4-diphenylpyrrole and 1.65 g of ethyl orthoformate were dissolved in 20 ml of acetic acid, and 0.8 ml of a 50% hydrobromic acid acetic acid solution was added. And stirred at 100 ° C. for 1 hour.
The resulting precipitate is collected by filtration, and 2.0 g of crimson ligand 3 is obtained.
Obtained.

(5-2) Synthesis of Dye No. 5 Synthesis was performed in the same manner as in Synthesis Example 1 except that the above-mentioned ligand 3 was used.

Synthesis Example 6 Synthesis of Dye No. 6 Synthesis was performed in the same manner as in Synthesis Example 2 except that the ligand 3 of Synthesis Example 5 was used.

Synthesis Example 7 Synthesis of Dye No. 13 (7-1) 2,2 ′, 4,4′-tetramethyl-3,
Synthesis of 3'-diethylazapyrromethene (ligand 7) 3.06 g of 2,4-dimethyl-3-ethyl-5-nitrosopyrrole and 2.56 g of 2,4-dimethyl-3-ethylpyrrole were added to 30 ml of acetic acid. Dissolved and refluxed. The resulting precipitate was collected by filtration and washed with a small amount of acetone to obtain Ligand 7.

(7-2) Synthesis of Dye No. 13 Synthesis was performed in the same manner as in Synthesis Example 1 except that the above-mentioned ligand 7 was used.

Synthesis Example 8 Synthesis of Dye No. 14 Synthesis was performed in the same manner as in Synthesis Example 2 except that the ligand 7 of Synthesis Example 7 was used.

Synthesis Example 9 Synthesis of Dye No. 22 (9-1) Synthesis of (Ligand 11) 2-Aminomethyl-3,3-dimethylindolenine
48 g and 2.14 g of pyridine-2-aldehyde were dissolved in 40 ml of ethanol and refluxed for 1 hour. The resulting precipitate was collected by filtration and washed with a small amount of ethanol to obtain Ligand 11.

(9-2) Synthesis of Dye No. 22 Synthesis was performed in the same manner as in Synthesis Example 1 except that the above-mentioned ligand 11 was used.

Synthesis Example 10 Synthesis of Dye No. 23 Synthesis was performed in the same manner as in Synthesis Example 2 except that the ligand 11 of Synthesis Example 9 was used.

Synthesis Example 11 Synthesis of Dye No. 26 (11-1) Synthesis of (ligand 13) 3.38 g of naphtholactam and 4.46 g of benzimidazopyridone having the following structure were taken in 200 ml of chlorobenzene, and 8
When heated to 0 ° C., 3.37 g of phosphorus oxychloride was added. After stirring at about 100 ° C. for 3 hours, ligand 15 was obtained.

(11-2) Synthesis of Dye No. 26 Synthesis was performed in the same manner as in Synthesis Example 1 except that the above-mentioned ligand 13 was used.

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Synthesis Example 12 Synthesis of Dye No. 27 Synthesis was performed in the same manner as in Synthesis Example 2 except that the ligand 13 of Synthesis Example 11 was used.

Other exemplified dyes can be synthesized in the same manner with reference to the above-mentioned literatures and the like.

The melting point (mp) of the metal complex dye of the present invention is from 200 to 350 ° C., and λmax (in methanol)
Is in the range of 500-650 nm.

These dyes have a wavelength of 635 nm or 6 nm.
The real part n of the complex refractive index at 50 nm is 2.00 to 2.50, and the imaginary part k is 0.01 to 0.20.

The dyes n and k are determined by forming a dye film on a predetermined transparent substrate to a thickness of about the recording layer of the optical recording medium, for example, about 40 to 100 nm under the same conditions as the recording layer. Then, a measurement sample was prepared, and then the reflectance and transmittance at 635 nm or 650 nm of the measurement sample were measured. From these measured values, for example, according to Kyoritsu Zensho “Optics” Kozo Ishiguro P168-178, It is calculated. The reflectance is the reflectance of the measurement sample through the substrate or the reflectance from the dye film side, and is measured by specular reflection (about 5 °).

When these metal complex dyes are used in the recording layer of an optical recording medium, they may be used alone or in combination of two or more. In the synthesis process, when two or more compounds having different ligand coordination numbers or different ligands are obtained, they may be used as they are without separation.

Such a metal complex dye has sufficient solubility in an organic solvent, and has a high solubility in a coating solvent which does not corrode a polycarbonate resin (PC) generally used as a substrate material of an optical recording medium. .

A recording layer using such a metal complex dye is particularly suitable for a write-once optical recording disk (CD-R or DVD-R).
R, etc.). Such a recording layer is
It is preferable to form a layer using a dye-containing coating solution. In particular, it is preferable to use a spin coating method in which a coating solution is spread and applied on a rotating substrate. In addition, gravure coating,
Spray coating, dipping or the like may be used. The application solvent will be described later.

After the spin coating as described above, the coating film is dried if necessary. The thickness of the recording layer formed in this way is appropriately set according to the target reflectance and the like, but is usually about 400 to 3000 A.

The content of the dye in the coating solution is preferably 0.05 to 10% by weight. Since the metal complex dye of the present invention has good solubility, a coating solution having such a content can be easily prepared. Specifically, the metal complex dye of the present invention is an alcohol or cellosolve, a keto alcohol such as diacetone alcohol,
0.5 to ketones such as cyclohexanone, fatty acid carbohydrates such as ethylcyclohexane, and fluorinated alcohols such as 2,2,3,3-tetrafluoropropanol.
Dissolves up to 10 wt%. Particularly, it is possible to dissolve 4 wt% or more in ethyl cellosolve or ethylcyclohexane, which is a preferable coating solvent when applying to a polycarbonate disk, and to form a high-quality spin-coated film in a short time.

The coating solution may appropriately contain a binder, a dispersant, a stabilizer and the like.

The recording layer of the optical recording medium of the present invention may contain another type of light absorbing dye in addition to the metal complex dye of the present invention. Examples of such a dye include a phthalocyanine dye, a cyanine dye, a metal complex dye, a styryl dye, a porphyrin dye, an azo dye, and a formazan metal complex.

Therefore, in such a case, the recording layer may be coated by including such a dye in the coating solution.

In particular, according to the present invention, recording and reproduction can be performed at two wavelengths of a short wavelength of about 680 to 635 nm and a conventional wavelength of about 780 nm, and recording and reproduction can be performed separately for these two wavelengths. . In this case, the present invention is suitable for a recording and reproducing method of CD-RII in which recording is performed with a conventional wavelength light of about 780 nm and reproduction is performed with two wavelengths of a short wavelength and a conventional wavelength light of about 780 nm. In such a configuration, it is preferable to use a dye having different optical characteristics such as absorption characteristics in addition to the metal complex dye of the present invention in the recording layer. As such a combination, the metal complex dye of the present invention is used for short wavelength, and other types of light absorbing dyes are used for long wavelength, and conversely, the metal complex dye is used for long wavelength, Other types of light-absorbing dyes may be used for short wavelengths, but usually the former combination is preferably used. In such a case, in addition to the metal complex dye of the present invention, the absorption maximum (λ _max ) is 68.
It is preferable to contain a dye of about 0 to 750 nm,
A dye having such an absorption maximum (λ _max ) may be selected from the above dyes and used. Among them, phthalocyanine dyes and pentamethine cyanine dyes are usually used.

In particular, when used in a recording layer of a CD-RII of the type which performs recording and reproduction at two wavelengths as described above, the metal complex dye has a real part n of a complex refractive index at 650 nm of 1.8 to 1.8.
2.6, the imaginary part is preferably 0.02 to 0.20. On the other hand, the dye used in combination with this is 780 nm
The real part n of the complex refractive index is 1.8 to 2.6, the imaginary part k is 0.02 to 0.30, and particularly 0.02 to 0.15 when used for a laminated recording layer. The half-width of the absorption spectrum of the thin film, that is, the half-width of the spectrum line near λmax is 170 nm or less, preferably 150 nm or less. The lower limit of the half width is not particularly limited, but is usually 50 nm. The use of such a half-value width does not affect the absorption characteristics of the metal complex dye used in combination, and the reflectance and modulation in a short wavelength region are sufficient. On the other hand, if the half-value width exceeds 170 nm, the absorption edge extends to the wavelength region of the short-wavelength laser, which causes a decrease in the reflectance in the short-wavelength region. In addition, the half value width is such that the transmittance T at the absorption maximum λmax is 25%.
This was determined by preparing a sample in which a dye film was formed on a transparent substrate as described below, and measuring the absorption spectrum of this sample. For example, explaining according to the absorption spectrum of FIG. 1, the transmittance T _{1 at} λmax
When, further when the wavelength is shifted to the long wavelength side without depending on the transition wavelengths, obtains the transmittance T ₂ which is substantially constant, T ₂
Is set as the base line (base), and the width Δλ of half the depth of the bottom up to T ₁ is defined as the half-value width. The thickness of the dye film of the sample is
Usually, it is about 500 to 1500 A (50 to 150 nm).

Note that the above n and k were determined in the same manner as above, with the measurement wavelengths being 650 nm and 780 nm, respectively.

Such a dye is particularly preferably a phthalocyanine dye represented by the formula (VI).

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In the formula (VI), M represents a central atom.
X ₁ , X ₂ , X ₃ and X ₄ each represent a halogen atom, which may be the same or different. p
1, p2, p3 and p4 are each 0 or an integer of 1 to 4, and p1 + p2 + p3 + p4 is 0 to 15. Y
₁ , Y ₂ , Y ₃ and Y ₄ each represent an oxygen atom or a sulfur atom, which may be the same or different. Z ₁ , Z ₂ , Z ₃ and Z ₄ each represent an alkyl group having 4 or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group, which may be the same or different, Is also good. q1, q2, q3, and q4 are each 0 or an integer of 1 to 4; they do not become 0 at the same time; q1 + q2 + q3 + q4 is 1 to 8;

The formula (VI) will be described in more detail. In the formula (VI), M represents a central atom. The central atom represented by M includes a hydrogen atom (2H) or a metal atom. At this time, as the metal atom, the periodic tables 1-1
It may be a metal atom or the like belonging to Group 4 (1A to 7A, 8 or 1B to 4B), specifically, Li, Na, K, M
g, Ca, Ba, Ti, Zr, V, Nb, Ta, Cr,
Mo, W, Mn, Tc, Fe, Co, Ni, Ru, R
h, Pd, Os, Ir, Pt, Cu, Ag, Au, Z
n, Cd, Hg, Al, In, Tl, Si, Ge, S
n, Pb, etc., especially Li, Na, K, Mg, Ca, Ba,
Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn,
Tc, Fe, Co, Ni, Ru, Rh, Pd, Os, I
r, Pt, Cu, Ag, Au, Cd, Hg, Al, I
n, Tl, Si, Ge, Sn, and Pb. Among them, Al, Si, Ge, Zn, Cu, Pd, Ni,
Fe, Co, etc. are preferred, and in particular, Cu, Pd, Ni, F
e, Co, VO, etc. are preferred in terms of stability over time.

Incidentally, these metal atoms may be in the form of VO or the like, such as V, etc.
Like Ge, Co, Fe, and the like, ligands such as an ether group, an ester group, pyridine, and derivatives thereof may be further coordinated above and below or on one of the metal atoms.
A preferred example of Si will be described later.

X _{1 to} X ₄ each represent a halogen atom;
Halogen atoms include F, Cl, Br, I and the like. Particularly, Br and F are preferable.

P1, p2, p3 and p4 are each 0 or an integer of 1 to 4, and p1 + p2 + p3 + p4 is 0 to
15 and preferably 0-10.

X _{1 to} X ₄ may be the same or different. When p 1, p 2, p 3, and p 4 are each an integer of 2 or more, X ₁ , X ₂ , X ₃ , X ₄
They may be the same or different.

Y _{1 to} Y ₄ each represent an oxygen atom or a sulfur atom, and particularly preferably an oxygen atom. Y _{1 to} Y
₄ are usually the same, but may be different. Z
_{1 to} Z ₄ each represent an alkyl group having 4 or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group,
These may be the same or different.

Each of q1, q2, q3 and q4 is 0 or an integer of 1 to 4, and they are not simultaneously 0, and q1 + q2 + q3 + q4 is 1 to 8, preferably 2 to 6.

The bonding position of Y _{1 to} Y _{4 to} the phthalocyanine ring is preferably at the 3-position and / or 6-position (see the following structural formula) of the phthalocyanine ring, and it is preferable that at least one such bond is contained. preferable.

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The alkyl group represented by Z _{1 to} Z ₄ is preferably an alkyl group having 4 to 16 carbon atoms, and may be linear or branched. preferable. It may have a substituent, and examples of the substituent include a halogen atom (F, Cl, Br, I, etc., particularly preferably F, Br, etc.). Specific examples of such an alkyl group include nC ₄ H ₉ and iC ₄ H
_{9 -, s-C 4 H} 9 -, t-C 4 H 9 -, n-C 5 H 11
—, (CH ₃ ) ₂ CHCH ₂ CH ₂ —, (CH ₃ ) ₃ C
CH ₂ —, (C ₂ H ₅ ) ₂ CH—, C ₂ H ₅ C (CH
_{3) 2 -, n-C} 3 H 7 CH (CH 3) -, n-C 6 H
_{13 -, (CH 3) 2} CHCH 2 CH 2 CH 2 -, (CH
₃ ) ₃ C—CH ₂ —CH ₂ —, n—C ₃ H ₇ CH (CH
_{3) CH 2 -, n-} C 4 H 9 CH (CH 3) -, n-C 7
_{H 15 -, [(CH 3} ) 2 CH] 2 -CH-, n-C 4
_{H 9 CH (CH 3) CH} 2 -, (CH 3) 2 CHCH 2
_{CH (CH 3) CH 2 -} , n-C 8 H 17 -, (CH 3)
₃ CCH ₂ CH (CH ₃ ) CH ₂ —, (CH ₃ ) ₂ CH
_{CH (i-C 4 H 9} ) -, n-C 4 H 9 CH (C 2 H
_{5) CH 2 -, n-} C 9 H 19 -, CH 3 CH 2 CH (C
_{H 3) CH 2 CH (CH} 3) CH 2 CH 2 -, (CH
₃ ) ₂ CHCH ₂ CH ₂ CH ₂ CH (CH ₃ ) CH _{2
-, n-C 3 H 7} CH (CH 3) CH 2 CH (CH 3)
CH ₂ —, nC ₁₀ H ₂₁ —, (CH ₃ ) ₃ CCH ₂ CH
_{2 C (CH 3) 2 CH} 2 -, n-C 11 H 23 -, n-C 12
_{H 25 -, n-C 13} H 27 -, n-C 14 H 29 -, n-C 15 H
_{31 -, n-C 16 H} 33 -, CHF 2 CF 2 CH 2 -, CF
_{3 CH 2 -, CF 3 CF} 2 CH 2 CH 2 -, (CF 3)
_{2 (CH 3) C-CH} 2 -, n-C 4 F 9 -, i-C 4
_{F 9 -, s-C 4} F 9 -, t-C 4 F 9 - , and the like.

Examples of the alicyclic hydrocarbon group represented by Z _{1 to} Z ₄ include a cyclohexyl group and a cyclopentyl group, and a cyclohexyl group is preferred. These may further have a substituent, and examples of such a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, a halogen atom, a nitro group, a carboxyl group, an ester group, and an acyl group. Group, amino group, amide group, carbamoyl group, sulfonyl group, sulfamoyl group, sulfo group, sulfino group, arylazo group, alkylthio group, arylthio group and the like. Among them, an alkyl group having 1 to 5 carbon atoms (for example, methyl Group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-
Butyl group, n-pentyl group, iso-pentyl group, ne
o-pentyl group, tert-pentyl group, 1-methylbutyl group), alkoxy group (for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group), An aryl group (eg, phenyl, tolyl, biphenyl, naphthyl), a halogen atom (eg, F,
Cl, Br, I, preferably F, Br) and the like are preferred.
The substitution position of these substituents is preferably one or both of the adjacent positions of the bonding position of Y _{1 to} Y ₄ , and preferably contains at least one such substitution.

The aromatic hydrocarbon group represented by Z _{1 to} Z ₄ may be a single ring, a group having a condensed ring, or a group having a substituent. Further, the total number of carbon atoms is preferably 6 to 20. Specific examples include a phenyl group and a naphthyl group, and a phenyl group is preferable. These may further have a substituent, and examples of such a substituent include the same as those exemplified for the alicyclic hydrocarbon group, and preferable ones are also the same. The same applies to the preferred substitution position, which is preferably the ortho position of the bonding position of Y _{1 to} Y ₄ , and preferably contains at least one ortho substitution.

The heterocyclic groups represented by Z _{1 to} Z ₄ include:
It may be a single ring or one having a condensed ring, and a compound having a hetero atom of oxygen, nitrogen, sulfur or the like, particularly oxygen or nitrogen, is preferred. Specific examples include a pyridyl group, a furanone-yl group, a pyrazyl group, a pyrazolidyl group, a piperidinone-yl group, a quinoxalyl group, a pyranone-yl group, a thiophenetrion-yl group, and the like.
Furanone-yl groups and the like are preferred. These heterocyclic groups are
The compound may further have a substituent, and examples of the substituent include those exemplified for the alicyclic hydrocarbon group and the aromatic hydrocarbon group, and preferable examples are also the same. In particular, when a carbon atom is present adjacent to the bonding position of Y _{1 to} Y ₄ , it is preferable to have a substituent at such an adjacent position.

Z _{1 to} Z ₄ are particularly preferably an alicyclic hydrocarbon group or an aromatic hydrocarbon group, more preferably a cyclohexyl group or a phenyl group, and particularly preferably at least one of the bonding positions of Y ₁ to Y _4. Are preferably those having a substituent (particularly the above-mentioned preferred substituent) at the adjacent position.

Specific examples of such phthalocyanine dyes are shown below, but the present invention is not limited to these. Specific examples include X _{11 to} X ₁₄ and X _{15 to} X in the following formula (VIa).
₁₈ , X _{19 to} X ₂₂ , X _{23 to} X ₂₆ and M, and when all of H in X _{11 to} X _{14 and the} like are H,
When it is a substituent, only the substituent itself is shown and H is omitted. In addition, the 3-position, the 6-position, and the 4-position and 5-position in the phthalocyanine ring are respectively the same, and when any one of these has a substituent, only a representative example is shown.

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[0138]

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Further, the following formula (VI) in which the central atom is Si
The phthalocyanine dyes represented by I) are also preferred.

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In the formula (VII), A ₁ , A ₂ , A ₃ and A ₄ each represent a hydrogen atom or an alkyl group, which may be the same or different. A _f1 and A
_f2 represents a fluorinated alkyl group, which may be the same or different. R _f1 , R _f2 , R _f3 and R _f4
Represents a fluorinated alkyl group, which may be the same or different. r1, r2, r3 and r4 are each 0 or an integer of 1 to 4, and they are not 0 at the same time, and r1 + r2 + r3 + r4 = 1 to 16.

The alkyl group represented by A _{1 to} A ₄ is preferably one having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.
A _{1 to} A ₄ are usually preferably the same.

The fluorinated alkyl group represented by A _f1 or A _f2 is preferably one having 1 to 6 carbon atoms, and may be linear or branched. Further, it is more preferable not to be a perfluoro group. Examples of such a fluorinated alkyl group include CHF ₂ CF ₂ CH ₂ —, (CF ₃ )
₂ (CH ₃ ) C—CH ₂ —, CF ₃ —CH ₂ —, CF ₃
—CF ₂ —CH ₂ —CH ₂ — and the like. A _f1 , A
Preferably, _f2 is usually the same.

The fluorinated alkyl group represented by R _{f1 to} R _f4 is preferably one having 1 to 6 carbon atoms, and may be linear or branched. Further, it is preferable that it is not a perfluoro group. Examples of such a fluorinated alkyl group include CHF ₂ CF ₂ CH ₂ —, (CF ₃ ) ₂
(CH ₃ ) C—CH ₂ —, CF ₃ CH ₂ —, CF ₃ CF
₂ CH ₂ CH ₂ — and the like. Preferably, R _{f1 to} R _f4 are usually the same. r1 to r4 are 0 or 1 to 4
Which are not simultaneously 0 but 1
~ 16. r1 to r4 are each preferably 1 or 2, and particularly preferably r1 = r2 = r3 = r4 = 1.
It is. When r1 to r4 are 2 or more, each R _f1
, Each R _f2 , each R _f3 , and each R _f4 may be the same or different.

As described above, the bonding position of the oxygen atom to the phthalocyanine ring is preferably at the 3-position and / or 6-position of the phthalocyanine ring, and preferably contains at least one such bond.

Specific examples of such phthalocyanine dyes are shown below, but the present invention is not limited to these. Specific examples include A _{1 to} A ₄ , A _f1 , and A _{1 in the following} formula (VIIa).
_{f2, X 31 ~X 34, X} 35 ~X 38, X 39 ~X 42, X 43 ~X 46
Is used when X _{31 to} X _{34 and the} like are all H, and when it is a substituent, only H itself is shown and H is omitted. In addition, the 3-position, the 6-position, the 4-position and the 5-position of the phthalocyanine ring are equivalent to each other, and when any of these has a substituent, only a typical example is shown.

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[0148]

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The phthalocyanine dyes described above are disclosed in
3-313760, JP-A-63-301261, E
The compound can be synthesized with reference to the method described in P675489 or the like.

The melting points (mp) of these dyes are 60 to 40.
0 ° C.

For these phthalocyanine dyes,
Tables 1 and 2 show n and k at 80 nm. These n and k are obtained when the thickness of the dye film is 80 nm. Further, the half width of the absorption spectrum of the dye thin film was determined as described above.
(Thin film) is also shown.

[0152]

[Table 1]

[0153]

[Table 2]

These phthalocyanine compounds may be used alone or in combination of two or more.

Specific examples of the coating solvent used in the present invention include alcohols (including alkoxy alcohols such as keto alcohols and ethylene glycol monoalkyl ethers), aliphatic hydrocarbons, ketones, and esters. System, ether system, aromatic system, alkyl halide system and the like.

Of these, alcohols and aliphatic hydrocarbons are preferred. Among alcohols, alkoxy alcohols and keto alcohols are preferred.
In the alkoxy alcohol system, the alkoxy moiety preferably has 1 to 4 carbon atoms, and the alcohol moiety has 1 to 5 carbon atoms, more preferably 2 to 5 carbon atoms, and the total carbon atom is 3 To 7 is preferable.
Specifically, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (also referred to as ethyl cellosolve, ethoxyethanol), butyl cellosolve, 2-isopropoxy-1-
Ethylene glycol monoalkyl ether (cellosolve) such as ethanol, 1-methoxy-2-propanol, 1-methoxy-2-butanol, 3-methoxy-1
-Butanol, 4-methoxy-1-butanol, 1-ethoxy-2-propanol and the like. Examples of keto alcohols include diacetone alcohol.
Furthermore, a fluorinated alcohol such as 2,2,3,3-tetrafluoropropanol can also be used.

Examples of the aliphatic hydrocarbon system include n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, cyclooctane, dimethylcyclohexane, n-octane, iso-propylcyclohexane,
T-butylcyclohexane and the like are preferable, and among them, ethylcyclohexane and dimethylcyclohexane are preferable.

The ketones include, for example, cyclohexanone.

In the present invention, alkoxy alcohols such as ethylene glycol monoalkyl ether are particularly preferable. Among them, ethylene glycol monoethyl ether, 1-methoxy-2-propanol and 1-methoxy-
2-butanol and the like are preferable, and a mixed solvent thereof is also preferable. Examples thereof include a combination of ethylene glycol monoethyl ether and 1-methoxy-2-butanol.

The metal complex dyes and the phthalocyanine dyes of the present invention may be used in combination of two or more of the above-mentioned n,
k may be satisfied.

The ratio of the metal complex dye of the present invention to another dye such as a phthalocyanine dye in the recording layer of an optical recording medium for recording and reproducing at two wavelengths is determined by the ratio of the metal complex dye of the present invention / other dye. The molar ratio of the dye is 90/10 to 10/90
It is preferable that

Therefore, such a mixed type recording layer may be applied using a coating solution containing such a dye at a predetermined ratio.

When recording and reproduction at two wavelengths are intended, a recording layer in which a layer of the metal complex dye of the present invention and a layer of another dye are laminated may be used. The order of lamination may be appropriately selected, and the thickness per layer is usually 400 to 250.
It may be about 0A (40 to 250 nm). Such a laminated recording layer may be applied using a coating solution containing each dye.

In the case of such a laminated type recording layer having a two-layer structure, a recording layer lower layer (first recording layer) corresponding to a short wavelength containing a metal complex dye is provided on the substrate side, and the above-mentioned layer is formed thereon. 78 containing other dyes such as phthalocyanine dyes
It is preferable to provide a recording layer upper layer (second recording layer) corresponding to 0 nm. In this case, the lower layer of the recording layer is preferably thinner than the upper layer of the recording layer, and the ratio of the thickness of the lower layer to the upper layer of the recording layer is preferably such that the lower layer / upper layer is 1/10 to 1/1.

As an optical recording disk having such a recording layer corresponding to two wavelengths or a short wavelength, on a substrate,
2 and 3 show examples of the configuration. 2 and 3 are partial sectional views.

Referring to FIG. 2, the optical recording disk 1 shown in FIG. 2 is a contact type optical recording disk having a reflective layer adhered on a recording layer and capable of reproducing data in compliance with the CD standard. As shown, the optical recording disk 1 is
Recording layer 3 containing azo metal complex dye of the present invention on its surface
And a reflective layer (reflective film) 4 and a protective film (protective layer) 5 in close contact with the recording layer 3.

The recording layer 3 is of a two-wavelength compatible type of the above-mentioned mixed type or laminated type using a metal complex dye and another dye, and of a short wavelength compatible type containing a metal complex dye as a main component. .

The substrate 2 is in the form of a disk. To enable recording and reproduction from the back side of the substrate 2,
Recording light and reproduction light (wavelength of about 500 to 900 nm, especially about 500 to 700 nm,
About 690 nm, especially about 635-680 nm laser light and about 680-900 nm laser light, especially about 680-780 nm laser light and about 770-900 nm, especially about 770-830 nm.
Substantially transparent (preferably at a transmittance of 8) for semiconductor laser light of a certain degree, in particular 635-650 nm and 780 nm.
(8% or more) using a resin or glass. The size is about 64 to 200 mm in diameter and about 1.2 mm in thickness.

As shown in FIG. 2, a tracking groove 23 is formed on the surface of the substrate 2 on which the recording layer 3 is formed.
The groove 23 is preferably a spiral continuous groove having a depth of 0.1 to 0.25 μm, a width of 0.35 to 0.60 μm for a mixed type and a short wavelength type,
In the case of a laminated type, it is preferable that the groove pitch is 0.35 to 0.80 μm and the groove pitch is 1.5 to 1.7 μm. With such a configuration of the groove, a good tracking signal can be obtained without lowering the reflection level of the groove. Particularly, the groove width is 0.35 to 0.80.
It is important to regulate the groove width to 0.35 μm or 0.35 to 0.60 μm. If the groove width is less than 0.35 μm, it is difficult to obtain a tracking signal of a sufficient magnitude,
Due to the slight offset of tracking when recording,
Jitter tends to be large. Also, as the groove width increases, waveform distortion tends to occur.

The substrate 2 is preferably made of a resin, and is preferably made of various thermoplastic resins such as a polycarbonate resin, an acrylic resin, an amorphous polyolefin, TPX, and a polystyrene resin. And it can manufacture according to well-known methods, such as injection molding, using such a resin. The groove 23 is preferably formed when the substrate 2 is formed. After the manufacture of the substrate 2, a resin layer having the groove 23 may be formed by a 2P method or the like. In some cases, a glass substrate may be used.

As shown in FIG. 2, the recording layer 3 provided on the substrate 2 is formed by using the above-mentioned dye-containing coating solution and preferably by the spin coating method as described above. The spin coating may be performed under normal conditions, for example, by adjusting the number of revolutions from 500 to 5000 rpm from the inner circumference to the outer circumference.

The thickness of the recording layer 3 formed in this way is 50% in dry film thickness in the mixed type and the short wavelength type.
It is preferably from 0 to 3000 A (50 to 300 nm). Outside of this range, the reflectivity decreases, making it difficult to perform reproduction conforming to the CD standard. At this time, groove 2
The thickness of the recording layer 3 in the recording track 3 is 1000A.
(100 nm) or more, especially 1300-3000 A (130
３００300 nm), the degree of modulation becomes extremely large.

In the case of the laminated type, as described above,
400 to 2500 A (40 to 250 n
m) is preferable. Thereby, good reproduction can be performed. The thickness of the recording layer 3 in the recording track in the groove 23 is 500 A (50 nm) or more, especially 50 A.
It is preferably from 0 to 800 A (50 to 80 nm).
Further, as described above, when the azo metal complex-based dye of the present invention is contained in the lower layer as a two-layer structure, the upper and lower layers are formed as described above to obtain a CD-RII. Recording and reproduction can be performed satisfactorily.

The recording layer 3 thus formed is
If the recording layer is of a wavelength-compatible dye-mixing type, then 6
At 35 to 650 nm, n = 1.8 to 2.3, k = 0.
N = 1.8-2 at 780 nm.
5, it is preferable that k = 0.03 to 0.15. Further, when the recording layer is of a laminated type corresponding to two wavelengths, 6
From 35 to 650 nm, n = 1.8 to 2.3, k =
0.02 to 0.20, n = 1.8 at 780 nm
2.6, and k is preferably 0.02 to 0.15. By controlling n and k in this manner, good recording and reproduction can be performed at two wavelengths. In particular, at a conventional wavelength of about 780 nm, recording and reproduction in accordance with the Orange Book standard can be performed. In the case of a short wavelength type of about 635 to 650 nm, the extinction coefficient (imaginary part of the complex refractive index) k of the recording light and the reproduction light wavelength is preferably 0 to 0.20. If k exceeds 0.20, a sufficient reflectance cannot be obtained. Further, the refractive index (real part of the complex refractive index) n of the recording layer 3 is preferably 1.8 or more. If n is less than 1.8, the modulation degree of the signal is too small. Although the upper limit of n is not particularly limited, it is usually about 2.6 for convenience in the synthesis of the dye compound.

The recording layers n and k can be determined by preparing a recording sample on a predetermined transparent substrate to a thickness of, for example, about 40 to 100 nm under actual conditions, and preparing a measurement sample. The reflectance is determined by measuring the reflectance of the measurement sample through the substrate or the reflectance from the recording layer side. In this case, the reflectance is measured by specular reflection (about 5 °) using the recording / reproducing light wavelength. Also, the transmittance of the sample is measured. And from these measurements, for example,
According to Kyoritsu Zensho "Optics" Kozo Ishiguro P168-178,
What is necessary is just to calculate n and k.

Incidentally, n and k of such a recording layer are as follows.
Depending on the dye used, the values correspond to the aforementioned n and k of each dye.

As shown in FIG. 2, on the recording layer 3,
The reflection layer 4 is provided in close contact with the substrate. The reflective layer 4 is preferably made of a high-reflectance metal or alloy such as Au, Cu, Al, Ag, and AgCu. The thickness of the reflection layer 4 is 50
It is preferably 0 A or more, and the layer may be formed by vapor deposition, sputtering or the like. The upper limit of the thickness is not particularly limited.
It is preferable that it is not more than about. Thereby, the reflection layer 4
The reflectance alone is 90% or more, and the reflectance through the substrate in the unrecorded portion of the medium is sufficient. The conventional wavelength of about 780 nm of the two-wavelength compatible type has 60% or more, particularly 70%
The above is obtained.

As shown in FIG. 2, on the reflection layer 4,
A protective film 5 is provided. The protective film 5 is made of, for example, various resin materials such as an ultraviolet curable resin, and is usually 0.5 to 100 μm.
It may be formed to a thickness of about m. The protective film 5 may be in the form of a layer or a sheet. The protective film 5 may be formed by an ordinary method such as spin coating, gravure coating, spray coating, dipping, or the like.

For recording or additional recording on the optical recording disk 1 having such a configuration, for example, 650 nm or 780 nm
The recording light of nm is irradiated in a pulse shape through the substrate 2 to change the light reflectance of the irradiated portion. When the recording light is irradiated, the recording layer 3 absorbs the light and generates heat, and at the same time, the substrate 2 is also heated. As a result, in the vicinity of the interface between the substrate 2 and the recording layer 3, the material of the recording layer such as a dye is melted or decomposed, and pressure is applied to the interface between the recording layer 3 and the substrate 2 to deform the bottom and side walls of the groove. Sometimes.

Referring to FIG. 3, the optical recording disk 6 shown in FIG. 3 has a reflection layer provided in close contact with a recording layer, and a protective film provided thereon. This is a contact type optical recording disk which has a structure in which a layer is adhered to the inside with an adhesive and can be reproduced by a commercially available DVD player. As shown, the optical recording disk 6
Has a recording layer 8 containing the metal complex-based dye of the present invention on the surface of a substrate 7 and is in close contact with the recording layer 8 to form a reflection layer (reflection film).
9, a protective film (protective layer) 10, and an adhesive layer 11 inside the protective films 10 of the two disks.

The substrate 7 has a disk shape. In order to enable recording and reproduction from the back side of the substrate 7,
Recording light and reproduction light (wavelength of about 500 to 900 nm, especially about 500 to 680 nm, especially 635 to
It is preferable to use a resin or glass which is substantially transparent (preferably at least 88% in transmittance) to a laser beam of about 680 nm, particularly 635 to 650 nm. Also,
The size is about 64-200 mm in diameter and about 0.6 mm in thickness.

As shown in FIG. 3, a tracking groove 78 is formed on the surface of the substrate 7 where the recording layer 8 is formed.
The groove 78 is preferably a spiral continuous groove, having a depth of 0.04 to 0.15 μm, a width of 0.20 to 0.45 μm, and a groove pitch of 0.74 to
It is preferably 0.80 μm. With such a configuration of the groove, a good tracking signal can be obtained without lowering the reflection level of the groove portion. In particular, it is important to restrict the groove width to 0.20 to 0.45 μm. If the groove width is less than 0.20 μm, it is difficult to obtain a tracking signal of a sufficient magnitude, and a slight offset in tracking during recording. As a result, jitter tends to increase. 0.45μ
If m is exceeded, waveform distortion of the reproduced signal is likely to occur, causing an increase in cross stroke.

For the material of the substrate 7, it is preferable to use resin, and various thermoplastic resins such as polycarbonate resin, acrylic resin, amorphous polyolefin, TPX, and polystyrene resin are suitable. And it can manufacture according to well-known methods, such as injection molding, using such a resin. The groove 78 is preferably formed when the substrate 7 is formed. After the manufacture of the substrate 7, a resin layer having the groove 23 may be formed by a 2P method or the like. In some cases, a glass substrate may be used.

As shown in FIG. 3, the recording layer 8 provided on the substrate 7 is formed by using the above-mentioned dye-containing coating solution and preferably by the spin coating method as described above. The spin coating may be performed under normal conditions, for example, by adjusting the number of revolutions from 500 to 5000 rpm from the inner circumference to the outer circumference.

The thickness of the recording layer 8 formed in this manner is 400 to 2000 A (40 to 200 nm) in dry film thickness.
It is preferable that Outside this range, the reflectivity decreases, and it becomes difficult to perform reproduction with a commercially available DVD player. At this time, the thickness of the recording layer 8 in the recording track in the groove 78 is set to 400 A (40 nm) or more, especially 600
When it is set to A2000 A (60 to 200 nm), the degree of modulation becomes extremely large.

The recording layer 8 thus formed is
When it is a short wavelength type of about 35 to 650 nm,
When recording a signal, the extinction coefficient (imaginary part of the complex refractive index) k at the wavelength of the recording light and the reproduction light is 0.02 to 0.02.
It is preferably 0.20. When k is less than 0.02, the absorptivity of the recording layer decreases, and it is difficult to perform recording with normal recording power. On the other hand, if k exceeds 0.20, the reflectance becomes low, and it is difficult to perform reproduction by a commercially available DVD player. The recording layer 3
Has a refractive index (real part of complex refractive index) n of 2.0 to 2.6. When n <2.0, the reflectance is reduced, and the reproduction signal is small, so that reproduction by a commercially available DVD player tends to be difficult. When n> 2.6, it is difficult to synthesize a dye.

As shown in FIG. 3, on the recording layer 8,
The reflection layer 9 is provided in direct contact. The reflective layer 9 is preferably made of a metal or alloy having high reflectivity such as Au, Cu, Al, Ag, and AgCu. The thickness of the reflective layer 9 is 400A
It is preferable that the thickness be as described above. Also, there is no particular upper limit on the thickness,
Considering cost, production work time, etc., the thickness is 1200
It is preferably about A or less. Thus, the reflectivity of the reflective layer 9 alone is 90% or more, and the reflectivity of the medium through the unrecorded portion of the substrate is sufficient.

[0188] As shown in FIG.
A protective film 10 is provided. The protective film 10 is made of various resin materials such as an ultraviolet curable resin, for example, usually 0.5 to 10
The layer may be formed to a thickness of about 0 μm. The protective film 10 may be in the form of a layer or a sheet. The protective film 10
It may be formed by a usual method such as spin coating, gravure coating, spray coating, and dipping.

As shown in FIG. 3, with the protective films 10 of the two disks inside, the adhesive layer 11 is placed between the protective films 10.
Layer. The adhesive layer 11 may be made of various adhesive resin materials such as a thermoplastic resin, an ultraviolet-curable resin, a thermosetting resin, and an anaerobic-curable resin. Good. The adhesive 11 may be in the form of a layer or a sheet. The adhesive layer 11 may be formed by a usual method such as spin coating, gravure coating, spray coating, or the like. After providing the adhesive layer 11, the adhesive layers 11 of the two disks may be bonded together.

For recording or additional recording on the optical recording disk 6 having such a configuration, recording light of, for example, 635 nm is irradiated in a pulse form through the substrate 7 to change the light reflectance of the irradiated portion. When the recording light is irradiated, the recording layer 8 absorbs the light and generates heat, and at the same time, the substrate 7 is also heated. As a result, in the vicinity of the interface between the substrate 7 and the recording layer 8, the material of the recording layer such as a dye is melted or decomposed, and pressure is applied to the interface between the recording layer 8 and the substrate 7 to deform the bottom and side walls of the groove. Sometimes.

[0191]

EXAMPLES Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention. Example 1 Of the metal complex dyes exemplified above, 2 of 1 wt% of 2
-Using an ethoxyethanol solution, a dye film was formed on a polycarbonate substrate (diameter 120 mm, thickness 1.2 mm) by a spin coating method, and the transmission spectrum and reflection spectrum of this thin film sample were measured. The thickness (dry film thickness) of the dye film was 500 A (50 nm). The result is shown in FIG.

As shown in FIG. 4, this compound was 700 to 500 nm
It can be seen that a high reflectivity is exhibited in a wide wavelength range. This shows that the pigment is compatible with a commercially available CD player or a commercially available DVD player in this wavelength region.

Example 2 Light resistance was examined using the thin film sample of Example 1. The light resistance was measured by measuring the initial transmittance T ₀ , further irradiating a xenon lamp (xenon fade meter manufactured by Shimadzu Corporation) with an 80,000 lux, measuring the transmittance T after irradiation, and (100−T) ×
The dye remaining rate (%) was calculated and determined at 100 / (100-T ₀ ). The dye remaining rate after irradiation for 100 hours was about 96%.

From this, it was found that Dye No. 1 had sufficient light fastness.

Example 3 An optical recording disk was prepared using the same dye No. 1 as in Example 1 as a dye for a recording layer. First, a pre-groove (depth 0.
10μm, width 0.42μm, groove pitch 0.80μ
A recording layer containing a dye was formed to a thickness of 900 A (90 nm) on a polycarbonate resin substrate having a diameter of 120 mm and a thickness of 0.6 mm having a thickness of m) by spin coating. In this case, a 2-wt% 2-ethoxyethanol solution was used as a coating solution. Next, an Au reflection film is formed on this recording layer by 85.
A transparent protective layer (thickness: 5 μm) of an ultraviolet curable acrylic resin was formed by sputtering to a thickness of 0A. The two protective layers formed in the same manner were adhered to the inner side with an adhesive to form a disk. This is designated as disk sample No. 1.

In addition, instead of Dye No. 1, Dye No. 13,
Disk samples Nos. 2, 3, and 4 were prepared in the same manner except that No. 22 and No. 26 were used, respectively.

Further, in disk sample No. 1, a 2.0 wt% 2-ethoxyethanol solution was prepared using an azocobalt complex dye having the following structure disclosed in Japanese Patent Publication No. 7-51682 and recorded using this solution. A disk sample No. 5 was prepared in the same manner except that a layer was formed.

[0198]

Embedded image

For the optical recording disk samples No. 1 to No. 5 thus manufactured, signals were subjected to 8/16 modulation at a linear velocity of 1.2 m / sec using a laser (oscillation wavelength: 635 nm). The signal is recorded, and the optimum recording power (P ₀ )
Jitter was measured. The optimum recording power means a range where the asymmetry is 0% with an evaluation machine (manufactured by Pulstec) used for recording evaluation. Table 3 shows the results. With respect to jitter, deterioration of jitter when light was irradiated under the same conditions as in Example 2 was also evaluated.

[0200]

[Table 3]

As is clear from Table 3, 7-51
Compared to the azocobalt complex dye disclosed in JP-A-682, the metal complex dye of the present invention has lower optimum recording power, that is, higher recording sensitivity. Also, it is understood that the jitter characteristics of the reproduced signal are excellent.

Example 4 An optical recording disk was manufactured using the same dye No. 1 as in Example 1 as a dye for a recording layer. First, a pre-groove (depth 0.
16 μm, width 0.48 μm, groove pitch 1.6 μm
) Was formed on a polycarbonate resin substrate having a diameter of 120 mm and a thickness of 1.2 mm by spin coating to form a recording layer containing a dye to a thickness of 2000 A (200 nm). In this case, a 2-wt% 2-ethoxyethanol solution was used as a coating solution. Next, an Au reflection film is formed on this recording layer to a thickness of 850 A by a sputtering method, and a transparent protective layer (5 μm thick) of an ultraviolet curable acrylic resin is formed.
) Formed. This is designated as disk sample No. 11.

Also, instead of Dye No. 1, Dye No. 13,
Disc samples Nos. 12, 13, and 14 were produced in the same manner except that No. 22 and No. 26 were used, respectively.

Further, in disk sample No. 11, an azo cobalt complex dye disclosed in Japanese Patent Publication No. 7-51682 (comparative dye used in disk sample No. 5 of Example 3) was used. -An ethoxyethanol solution was prepared, and a disc sample No. 15 was prepared in the same manner except that a recording layer was formed using the ethoxyethanol solution.

A signal was recorded at a linear velocity of 1.2 m / sec using a laser (oscillation wavelength: 650 nm) with respect to the disk sample Nos. 11 to 15 of the optical recording disk thus manufactured, and the optimum recording power was obtained. (P ₀ ), jitter (Jitt
er) was measured. The asymmetry of the optimum recording power was -2 with the evaluator (Pulstec) used for recording evaluation.
% Means the range. Table 4 shows the results. With respect to jitter, deterioration of jitter when light was irradiated under the same conditions as in Example 2 was also evaluated.

[0206]

[Table 4]

As is clear from Table 4, 7-51
Compared to the azocobalt complex dye disclosed in JP-A-682, the metal complex dye of the present invention has lower optimum recording power, that is, higher recording sensitivity. Also, it is understood that the jitter characteristics of the reproduced signal are excellent.

Example 5 In the disk sample No. 1 of Example 3, the dye No. 1 and the phthalocyanine dye A-5 were used as dyes for the recording layer.
2 (lambda max 710 nm in a thin film state having a thickness of about the recording layer) was used to prepare a 2 wt% 2-ethoxyethanol solution of these mixed dyes (dye No. 1 / phthalocyanine dye molar ratio = 30/70). An optical recording disk was manufactured in the same manner except that a recording layer was formed. This is designated as Disk Sample No. 21.

In addition, except that the molar ratio of Dye No. 1 / phthalocyanine dye was 50/50, disc sample N
Disc sample No. 22 was prepared in the same manner as o.

In each of disk samples Nos. 21 and 22, Dye No. 13 and No. 13 were used instead of Dye No. 1.
Disc samples Nos. 23 to 28 were prepared in the same manner except that No. 22 and No. 26 were used (Table 5).

In this disk sample No. 22, instead of dye No. 1, an azocobalt complex dye disclosed in Japanese Patent Publication No. 7-51682 (a comparative dye used in disk sample No. 5 of Example 3) was used. A disk sample No. 29 was prepared in the same manner except that the sample was used.

On these disk samples, recording was performed in accordance with the Orange Book standard using a 780 nm laser beam in the same manner as in Example 3, and then the disk was placed on a 65
The degree of modulation (I ₁₁
Mod) and jitter (Jitter) were measured. Table 5 shows the results.

[0213]

[Table 5]

As is clear from Table 5, the metal complex dye of the present invention absorbs not only when the dye alone is used in the optical recording layer but also on the longer wavelength side for the purpose of achieving compatibility with 780 nm of the Orange Book standard. When used in a mixed system with a dye, for example, a phthalocyanine dye, and reproduction was performed on the short wavelength side near 650 nm, excellent characteristics were exhibited without deterioration in modulation and jitter. On the other hand, it was found that the azocobalt complex dyes of the type disclosed in Japanese Patent Publication No. 7-51682 had a large jitter of the reproduced signal and also had a small modulation degree as compared with the dye of the present invention. Further, it was found that the dye of the present invention can obtain desired characteristics with a smaller mixing amount than that of such an azocobalt complex dye.

Further, the degree of modulation and the jitter of each disk sample recorded at 780 nm as described above when the disk sample was reproduced by using a 780 nm laser beam were measured. In No. 21, the modulation was 68% and the jitter was 19 ns, and in Disk Sample No. 22, the modulation was 70% and the jitter was 20 ns, and the other disk samples of the present invention were also similar. On the other hand, Sample No. 29 using the comparative dye
The sample had a modulation degree of 62% and a jitter of 42 ns, and it was found that the dye of the present invention had better characteristics.

Further, recording (linear speed: 1.2 m / sec) was performed on each disk sample using a 650 nm laser beam, and reproduction was performed using a 650 nm laser beam. Reproduction could be performed, and the modulation degree and jitter were good. On the other hand, the characteristics of the comparative disk sample No. 29 were inferior to those of the disk sample of the present invention.

Further, when each disk sample recorded using a 650 nm laser beam was reproduced with a 780 nm laser beam, the disk sample of the present invention was able to perform good reproduction, and the modulation degree and the jitter were improved. The points were also good. On the other hand, the comparison disk sample N
In o. 29, the characteristics were inferior to those of the present invention.

Thus, the disk sample of the present invention has 2
It can be seen that the optical recording disk can be favorably used as a wavelength-compatible optical recording disk.

As described above, Dye No. 1, No. 13, No.
22, the metal complex-based dye of the present invention represented by No. 26 is superior in the recording sensitivity and the jitter characteristic to the known azo cobalt complex-based dye for an optical recording layer represented by the comparative dye. . It was also found that even when used in combination with other light-absorbing dyes, it had unexpected characteristics such as the jitter of the reproduced signal did not deteriorate.

In the disk Nos. 1 to 3 of Example 3, the disk Nos. 11 to 13 of Example 4, and the disk samples No. 21 to 28 of Example 5, dye Nos.
Dye No. 2 exemplified in place of No. 3, No. 22 and No. 26
~ 12, 14 ~ 21, 23 ~ 25, 27 ~ 35, or two or more of these dyes including dye Nos. 1, 13, 22, 26 in combination, When disk samples were prepared and their characteristics were examined in the same manner as in Examples 3 to 5, disk samples Nos. 1 to 3, Nos. 11 to 13, and Nos. 21 to 28 were obtained according to the configuration.
The same characteristics were obtained. Further, when the light resistance of the above-mentioned dyes of the present invention other than Dye No. 1 was examined in the same manner as in Example 2, it was found that they exhibited the same good light resistance as Dye No. 1. Among these dyes of the present invention, 50
When a dye film having a thickness of nm was used, λmax and n and k at 650 nm were λmax = 587 nm and n = 2.1 in Dye No. 1.
0, k = 0.03, and λmax = 577 n in Dye No. 2.
m, n = 2.20 and k = 0.04.

Example 6 On the same polycarbonate resin substrate as in Example 5, a lower layer of a recording layer having a thickness of 50 nm was formed in the same manner using a 2 wt% 2-ethoxyethanol solution of Dye No. 7, and the dye A-
10 using a 1.5 wt% ethylcyclohexane solution of 3
An upper layer of a recording layer having a thickness of 0 nm was formed. Thereafter, a disk sample was prepared in the same manner as in Example 5.

The disk sample thus produced
When the characteristics of No. 31 were examined in the same manner as in Example 5, good results similar to those of the sample of the present invention of Example 5 were shown. Among them, the modulation (I ₁₁ Mod) and the jitter (Jitte) when recording at 780 nm and reproducing at 650 nm were performed.
r) was as follows.

I ₁₁ Mod = 67% Jitter = 23 ns

[0224]

According to the present invention, an optical recording medium using the metal complex dye of the present invention having excellent solubility and light resistance as a light absorbing dye and having excellent characteristics such as high recording sensitivity and low jitter can be obtained. can get. Further, when mixed with a dye having absorption on the long wavelength side and used as a dye for an optical recording layer corresponding to two wavelengths, unlike a known azocobalt complex dye, there is a disadvantage that the mixing greatly deteriorates jitter. Unexpected characteristics, such as absence, can be realized, and a characteristic optical recording medium of two wavelength compatible type can be realized with excellent characteristics.

[Brief description of the drawings]

FIG. 1 is a graph illustrating a method for obtaining a half width of an absorption spectrum of a thin film of a phthalocyanine dye in the present invention.

FIG. 2 is a partial sectional view showing an example of the optical recording disk of the present invention.

FIG. 3 is a partial sectional view showing another example of the optical disk of the present invention.

FIG. 4 is a graph showing a transmission spectrum and a reflection spectrum of a metal complex dye used in the present invention.

[Explanation of symbols]

 1,6 Optical recording disk 2,7 Substrate 23,78 Groove 3,8 Recording layer 4,9 Reflective layer 5,10 Protective film 11 Adhesive layer

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shiro Yamamiya 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (72) Inventor Seishichi Sasaki 1-7 Nihonbashi Bakurocho, Chuo-ku, Tokyo No. 6 Inside Dainichi Seika Kogyo Co., Ltd. (72) Inventor Yoshio Abe 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (56) References JP-A-10-226172 (JP, A) JP-A-2-29385 (JP, A) JP-A-7-324170 (JP, A) JP-A-9-95520 (JP, A) WO 98/34988 (WO, A1) (58) Field (Int.Cl. ⁷ , DB name) B41M 5/26 C09B 23/00 C09B 55/00 C09B 57/00 G11B 7/24

Claims (3)

(57) [Claims] 1. A compound obtained by reacting a metal compound with a compound selected from cyanine dye-type compounds or merocyanine dye-type compounds represented by the following formulas (I), (II), (III) and (IV): An optical recording medium using a metal complex dye having a recording layer containing the metal complex dye. Embedded image [In the formula (I), Q ₁ represents an atomic group necessary for forming a benzo [cd] indole ring together with C and N, and Q ₂ represents an atomic group necessary for forming a heterocyclic ring. The heterocyclic skeleton completed by Q ₁ or Q ₂ may be the same or different. R represents a hydrogen atom or a monovalent substituent, but R may form a part of a heterocyclic ring with Q ₂ . In the formula (II), Q ₁ and Q ₂ each represent C
And N represent the group of atoms necessary to form a heterocyclic ring, and the heterocyclic skeleton completed by Q ₁ or Q ₂ may be the same or different. In the formula (III), Q ₁
And Q ₂ each represent an atom group necessary for forming a heterocyclic ring together with C and N, and the heterocyclic skeleton completed by Q ₁ or Q ₂ may be the same or different. R
₁ and R ₂ each represent a hydrogen atom or a monovalent substituent, but R ₁ and R ₂ may each form a part of a heterocyclic ring with Q ₁ or Q ₂ . In the formula (IV), Q ₁ represents a group of atoms necessary to form a heterocyclic ring together with C and N, and Q ₃ represents a group of atoms necessary to form a cyclic enol having active hydrogen. ] 2. The central metal of the metal complex dye is Co,
Mn, Ti, V, Ni, Cu, Zn, Mo, W, Ru,
2. An optical recording medium using the metal complex dye of claim 1, which is Fe, Pd, Pt or Al. 3. The optical recording medium using the metal complex dye according to claim 1, wherein the recording layer further contains a light absorbing dye different from the metal complex dye.