JPH04361088A - Optical record medium - Google Patents

Abstract

PURPOSE:To obtain optical record medium with high reflection coefficient of 65% or above having excellent light resistance by providing at recording layer containing 1 or 2 or more kinds of azo metal chelate compounds of azo compound and metal to be shown by a specific general formula. CONSTITUTION:An optical record medium is constituted of a recording layer, a metal reflecting layer and a protective layer laid in sequence on a substrate. The optical record medium has a reflection coefficient of 65% or above and the recording layer contains 1 or 2 or more kinds of azo metal chelate compounds of azo compound and metal to be shown by the formula I, where A represents residue forming heterocycle together with carbon atom and nitrogen atom to which it is combined, B represents residue forming aromatic nucleous or heterocycle together with two carbon atoms to which it is combined, and X denotes group having active hydrogen.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to an optical recording medium, and more particularly, a high reflectance optical recording medium having a reflectance of 65% or more and containing an azo metal chelate compound of an azo compound and a metal in the recording layer. Regarding.

0002

2. Description of the Related Art Optical recording using lasers has been particularly developed in recent years because it enables high-density information storage and reproduction. An example of optical recording is an optical disc. In general, optical discs record high-density information by irradiating a thin recording layer provided on a circular base with laser light focused to about 1 μm. The recording is performed by thermal deformation such as decomposition, evaporation, melting, etc. occurring in the recording layer at that location due to absorption of the irradiated laser light energy. Also,
Reproduction of recorded information is performed by reading the difference in reflectance between a portion where deformation has occurred and a portion where no deformation has occurred by laser light. Therefore, the recording layer needs to efficiently absorb the energy of laser light, and for this reason, laser-absorbing dyes are used.

Conventionally, as this type of optical recording medium,
Although various types of discs are known, compact discs (CDs) have become particularly popular in homes in recent years. The CD is
It has a reflective layer made of metal such as aluminum, and is a read-only type of medium. Recently, proposals have been made for recordable (write-once) type CD media, but in order to be compatible with commercially available CD players,
A recording medium with a high reflectance of 65% or more is required. Examples of such high reflectance media include JP-A-2-42652, JP-A-2-87339,
JP-A No. 2-87340 and others disclose recording layers in which a cyanine dye is provided as a recording layer.

0004

[Problems to be Solved by the Invention] However, the conventional medium mainly using cyanine dyes has high solubility;
Although it has the advantage of being able to be coated by application, it has the problem of poor light resistance.

An object of the present invention is to solve the above-mentioned conventional problems and provide a high reflectance optical recording medium with excellent light resistance.

[0006]

[Means for Solving the Problems] The optical recording medium of claim 1 is an optical recording medium comprising a recording layer, a metal reflective layer and a protective layer sequentially laminated on a substrate, and has a reflectance of 65% or more. In the optical recording medium having the following general formula [I], the recording layer has the following general formula [I]
It is characterized by containing one or more kinds of azo metal chelate compounds of an azo compound and a metal represented by:

[0007]

[C4]

(In the formula, A represents a residue that forms a heterocycle together with the carbon atom and nitrogen atom to which it is bonded, and B represents a residue that forms a heterocycle together with the two carbon atoms to which it is bonded. (X represents a group having active hydrogen.) The optical recording medium according to claim 2 is the optical recording medium according to claim 1, in which the azo compound has the following general formula It is characterized by being a compound represented by [II].

[0009]

[C5]

(In the formula, A represents a residue that forms a heterocycle together with the carbon atom and nitrogen atom to which it is bonded, and R1 and R2 are each independently a hydrogen atom or a substituted represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, or an optionally substituted cycloalkyl group, and X represents a group having active hydrogen. Ring D represents a substituent. ) The optical recording medium according to claim 3 is characterized in that, in the optical recording medium according to claim 2, the azo compound is a compound represented by the following general formula [III].

[0011]

[C6]

(In the formula, A represents a residue that forms a heterocycle together with the carbon atom and nitrogen atom to which it is bonded, and R1 and R2 are each independently a hydrogen atom or a substituted represents an alkyl group that may be substituted, an aryl group that may be substituted, an alkenyl group that may be substituted, or a cycloalkyl group that may be substituted. Ring D may have a substituent.) Below: The present invention will be explained in detail below. In the azo compound represented by the general formula [I], A
represents a residue that forms a heterocycle together with the carbon and nitrogen atoms to which it is attached, preferably a plurality of atoms necessary to form at least one 5- to 7-membered heterocycle represents. The hydrogen atom on the heterocycle formed by A may be substituted with one or more substituents. In this case, the substituent includes an alkyl group, an alkoxy group, an aryloxy group, an aralkyl group, an aryl group, a halogen atom, a cyano group, a nitro group, an ester group, a carbamoyl group,
Examples include an acyl group, an acylamino group, a sulfamoyl group, a sulfonamide group, an amino group, an alkylamino group, an arylamino group, a hydroxyl group, a phenylazo group, a pyridinoazo group, and among the substituents, preferred are those having 1 to 1 carbon atoms. 25 optionally substituted alkyl groups,
an optionally substituted alkoxy group having 8 to 25 carbon atoms,
Halogen atom, cyano group, nitro group, optionally substituted alkylsulfamoyl group having 1 to 25 carbon atoms, optionally substituted phenylsulfamoyl group having 6 to 30 carbon atoms, phenylazo group, pyridinoschizo group , carbon number 1~
25 ester group, carbamoyl group having 1 to 25 carbon atoms,
Examples include an acyl group having 1 to 25 carbon atoms, an acylamino group having 1 to 25 carbon atoms, a sulfonamide group having 1 to 25 carbon atoms, an alkylamino group represented by the following general formula [IV], an arylamino group, a hydrogen group, etc. It will be done.

[0013]

[C7]

(In the formula, R3 and R4 represent a hydrogen atom, an optionally substituted alkyl group having 1 to 25 carbon atoms, or a phenyl group. R3 and R4 together form a 5- or 6-membered ring. ) Preferred examples of the heterocycle formed by A include a thiazole ring, a benzothiazole ring, a pyridobenzothiazole ring, a benzopyridothiazole ring, a pyridothiazole ring, a pyridine ring, and a quinoline ring. can be mentioned.

[0015] In the azo compound represented by the general formula [I], B represents a residue that forms an aromatic ring or a heterocycle together with the two carbon atoms to which it is bonded, and preferably , represents a plurality of atoms necessary to form at least one 5- to 7-membered aromatic ring or heterocycle. The hydrogen atom on the ring formed by B may be substituted with one or more substituents. In this case, the substituent is
Alkyl group, alkoxy group, aryloxy group, aralkyl group, aryl group, halogen atom, cyano group, nitro group, ester group, carbamoyl group, acyl group, acylamino group, sulfamoyl group, sulfonamide group, amino group, alkylamino group , an arylamino group, a hydroxyl group, etc., and preferred among the substituents are an optionally substituted alkyl group having 1 to 25 carbon atoms, an optionally substituted alkoxy group having 8 to 25 carbon atoms, Halogen atom, cyano group, nitro group, optionally substituted alkylsulfamoyl group having 1 to 25 carbon atoms, optionally substituted phenylsulfamoyl group having 6 to 30 carbon atoms, phenylazo group, pyridinoazo group , carbon number 1-2
5 ester group, a carbamoyl group having 1 to 25 carbon atoms, an acyl group having 1 to 25 carbon atoms, an acylamino group having 1 to 25 carbon atoms, a sulfonamide group having 1 to 25 carbon atoms, represented by the above general formula [IV] Examples include an alkylamino group, an arylamino group, a hydrogen group, etc.

Among the rings formed by B, preferred are a benzene ring, a naphthalene ring, a pyridine ring, a pyridone ring, and a pyrazole ring.

Furthermore, in the azo compound represented by the general formula [I], X may be any group having active hydrogen and is not particularly limited, but is preferably -O
H, -COOH, -SO3H, -B(OH)2, -HN
SO2R5 (R5 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 25 carbon atoms, or a phenyl group)
, -CONH2, -SO2NH2, -NH2, etc., and particularly preferred ones include -OH, -COOH,
-SO3H, -HNSO2R5 (R5 is the same as defined above). In addition, X is -COOH, -OH, -
When the group is capable of dissociating an anion, such as SO3H, it may be used as is when forming an azo metal chelate compound, or it may be used in the form of a salt with a cation. Cations include Na+, Li+, K
Inorganic cations such as + or P+ (Ph), N+ (C2
H4)4, N+(C4H9(n))4, Ph-N+(C
Examples include organic cations such as H3)3 (in the above, Ph indicates a benzene nucleus).

Among the azo compounds represented by the general formula [I], preferred are the azo compounds represented by the general formula [II], and particularly preferred are the azo compounds represented by the general formula [II]. III]. In addition, as a substituent of ring D, an alkyl group, an alkoxy group, and a halogen atom are preferable.

[0019] The metal that forms an azo metal chelate compound with such an azo compound is generally any metal that has the ability to form a chelate compound with the azo compound, and there is no particular restriction, but nickel (Ni) may be used. , cobalt (Co), iron (Fe), ruthenium (Ru), rhodium (Rh), palladium (Pd), copper (Cu), osmium (Os), iridium (Ir), platinum (Pt), etc. Preferably, Ni and Co are particularly preferable. These are Ni(CH3COO)2, Ni
Cl2, CoCl2, Co(BF4)2, Co(CH3
COO)2 and other salts, Ni2+, Co2+
It is obtained as a chelate compound coordinated with , Co3+, etc.

[0020] The synthesis of the azo metal chelate compound used in the present invention is described, for example, in "Furukawa; Analytic
a Chimica Acta 140 (198
2) 281-289". Specifically, the metal chelate compound of the azo compound represented by the general formula [II] is first prepared by the following general formula [V
] is diazotized according to a conventional method, and coupled with a substituted aniline sulfonic acid derivative represented by the following general formula [VI] to obtain an azo compound represented by the general formula [II], and then It can be produced by reacting the obtained azo compound with a metal salt in water and/or an organic solvent such as dioxane, tetrahydrofuran, acetone, or ethanol.

[0021]

[Chemical formula 8]

(In the formula, A, and rings D, R1, R2 and X are the same as defined above.) The anion of the metal salt such as Ni2+ or Co2+ used in the production of the above azo metal chelate compound is preferably SCN-, SbF6-, Cl-
, Br-, F-, ClO4-, BF4-, PF6-, C
H3COO-, TiF62-, SiF62-, ZrF6
2-, Ph-SO3-, CH3-Ph-SO3-, B-
Monovalent or divalent anions such as (Ph)4 are preferred;
In particular, BF4-, PF6-, and CH3COO- are preferably used (Ph represents a benzene nucleus).

Next, the structure of the optical recording medium of the present invention will be explained.

The high reflectance optical recording medium of the present invention basically has a layer structure in which a recording layer containing at least one kind of the azo metal chelate compound, a metal reflective layer, and a protective layer are sequentially laminated on a substrate. Take.

The substrate in the present invention may be either transparent or opaque to the laser beam used. Examples of the material for the substrate include supports for general recording materials such as glass, plastic, paper, plate-like or foil-like metals, and plastics are preferably used from various points of view. Plastics include acrylic resin, methacrylic resin,
Vinyl acetate resin, vinyl chloride resin, nitrocellulose,
Examples include polyethylene resin, polypropylene resin, polycarbonate resin, polyimide resin, epoxy resin, polysulfone resin, etc., but injection molded polycarbonate resin substrates are particularly preferably used from the viewpoint of productivity, cost, and moisture absorption resistance.

[0026] In the optical recording medium of the present invention, the recording layer containing the azo metal chelate compound has a thickness of 100 mm.
It is preferably Å to 5 μm, more preferably 10 μm.
00 Å to 3 μm.

The film can be formed by commonly used thin film forming methods such as vacuum evaporation method, sputtering method, doctor blade method, casting method, spinner method, and dipping method. The spinner method is preferable from the viewpoint of surface, etc. In the case of film formation by spinner method, the rotation speed is 50
0~5000r. p. m. is preferable, and after spin coating, treatment such as heating or exposure to solvent vapor can be performed as necessary. Note that during film formation, a binder can also be used if necessary. As the binder, known binders such as polyvinyl alcohol, polyvinylpyrrolidone, ketone resin, nitrocellulose, cellulose acetate, polyvinyl butyral, and polycarbonate can be used. In order to improve the stability and light resistance of the recording layer, transition metal chelate compounds (e.g., acetylacetonate chelate, bisphenyldithiol, salicylaldehyde oxime, bisdithio-α-diketone, etc.) are used as singlet oxygen quenchers. May contain
Furthermore, dyes of the same type or other types of dyes such as triarylmethane dyes, azo dyes, cyanine dyes, squarylium dyes, and nickel-indoaniline dyes can also be used in combination. When forming a recording layer by a coating method such as a doctor blade method, a casting method, a spinner method, or a dipping method, especially a spinner method, examples of coating solvents include tetrafluoropropanol, octafluoropentanol, tetrachloroethane, bromoform, dibromoethane, Diacetone alcohol, ethyl cellosolve, xylene, 3-
Boiling points of hydroxy-3-methyl-2-butanone, chlorobenzene, cyclohexanone, methyl lactate, etc. 120-1
A temperature of 60° C. is preferably used.

Among these, diacetone alcohol and 3-hydroxy-3-methyl are particularly suitable as solvents that can be suitably used for injection molded polycarbonate resin substrates, which are excellent in productivity, cost, and moisture absorption resistance, without damaging the substrates. Ketone alcohol solvents such as -2-butanone; Cellosolve solvents such as methyl cellosolve and ethyl cellosolve; Perfluoroalkyl alcohol solvents such as tetrafluoropropanol and octafluoropentanol; Hydroxyester solvents such as methyl lactate and methyl isobutyrate Examples include solvents.

As the metal reflective layer, gold (Au), silver (A
g), metals such as copper (Cu), aluminum (Al), or alloys thereof.

For the protective layer, a compound having a hardness of H or higher in the pencil hardness test according to JIS K5400 is effective from the viewpoint of preventing scratches, and any compound can be used as long as it satisfies this condition, but from the viewpoint of simplicity of the manufacturing process, , those that can be applied by spin coating are preferred. Protective layer materials that can be formed by spin coating or other conventional coating methods include thermosetting resins such as silicone, acrylic, melamine, and epoxy, alkyltrialkoxysilane,
Examples include partial cohydrolysates such as tetraalkoxysilane, silicone hard coating agents blended with colloidal silica, photopolymerizable photopolymers such as acrylates, photocrosslinkable photopolymers, azide photopolymers, etc. . The thickness of the protective layer is 1 to 200μ
m, particularly preferably about 2 to 100 μm.

Recording on the optical recording medium of the present invention is carried out by irradiating the recording layer with laser light, preferably semiconductor laser light, focused to about 1 μm through the substrate. In the portion irradiated with the laser beam, thermal deformation of the recording layer such as decomposition, evaporation, and melting occurs due to absorption of laser energy. Therefore, recorded information can be reproduced by reading the difference in reflectance between a portion where thermal deformation has occurred due to laser light and a portion where no thermal deformation has occurred.

[0032] The laser beam used for recording and reproducing the optical recording medium of the present invention includes N2, He-Cd
, Ar, He-Ne, ruby, semiconductor, and dye lasers, among which semiconductor lasers are particularly preferably used because of their light weight, ease of handling, and compactness.

[0033]

[Action] The general formula [I], especially the general formula [II],
In particular, the azo metal chelate compound of the azo compound represented by the general formula [III] and a metal can be coated by coating, has excellent light resistance, and can be used to produce a highly durable and highly reflective optical recording medium at a low cost. can be provided.

[0034]

[Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

Example 1 (a) Manufacture of optical recording media

[0036]

[Chemical formula 9]

0.15 g of the Ni chelate compound of the azo compound represented by the above structural formula (1) was dissolved in 7.5 g of octafluoropentanol and filtered through a 0.22 μm filter to obtain a solution. Spread 5 ml of this solution to a depth of 700 Å.
, onto an injection molded polycarbonate resin substrate (5 inches) with a groove having a width of 0.7 μm, and was applied by a spinner method at a rotation speed of 500 rpm. After application, 6
It was dried at 0°C for 10 minutes. The maximum absorption wavelength of the coating film is 64
5 and 712 nm. Next, on this coating film,
A reflective layer was formed by depositing an Au film with a thickness of 2000 Å by sputtering. Further, an ultraviolet curable resin was spin-coated on this reflective layer and cured by irradiating ultraviolet rays to form a protective film with a thickness of 10 μm.

(b) Optical recording While rotating the optical recording medium obtained above at 1.2 m/s, it was irradiated with a semiconductor laser beam with a center wavelength of 780 nm at a recording power of 7.0 mW to record an EFM signal. . Next, when this recorded portion was reproduced by a CD player having a semiconductor laser with a center wavelength of 780 nm, a good reproduced signal was obtained. This optical recording medium has light resistance (xenon fade meter accelerated test; 60 hours) and storage stability (70 hours).
0°C, 85% RH; 500 hours) As a result of the test,
Compared to the initial stage, no deterioration in sensitivity or reproduced signals was observed, making it an extremely excellent optical recording medium.

Example 2

[0040]

[Chemical formula 10]

(a) Production of optical recording medium Example 1 (
Coating and drying were performed in the same manner as in a). The maximum absorption wavelengths of the coating films were 644 and 714 nm. Next, on top of this coating film, a film thickness of 2000 mm was applied by sputtering.
A reflective layer was formed by depositing an Ag film with a thickness of .ANG. Further, an ultraviolet curable resin was spin-coated on this reflective layer, and then cured by irradiation with ultraviolet rays to form a protective layer with a thickness of 10 μm.

(b) Optical recording Regarding the optical recording medium obtained above, (b) of Example 1
Recording and reproduction were performed in the same manner as above, and a good reproduction signal was obtained. Further, as a result of similar light resistance and storage stability tests, no deterioration in sensitivity or reproduced signal was observed compared to the initial stage, and it was found to be extremely excellent as an optical recording medium.

Example 3 (a) Manufacture of optical recording media

[0044]

[Chemical formula 11]

A blended composition of 0.10 g of the Ni chelate compound of the azo compound represented by the above structural formula (3) and 0.05 g of the Ni chelate compound of the azo compound shown by the above structural formula (4) was mixed with 7.5 g of tetrafluoropropanol. 5 g and filtered through a 0.22 μm filter to obtain a solution, which was coated and dried in the same manner as in Example 1 (a). The maximum absorption wavelengths of the coating films were 644 and 712 nm. Next, on this coating film, by sputtering method,
A Cu film with a thickness of 2000 Å was formed to form a reflective layer. Further, an ultraviolet curable resin was spin-coated on this reflective layer, and then cured by irradiation with ultraviolet rays to form a protective layer with a thickness of 10 μm.

(b) Optical recording Regarding the optical recording medium obtained above, (b) of Example 1
Recording and reproduction were performed in the same manner as above, and a good reproduction signal was obtained. Further, as a result of similar light resistance and storage stability tests, no deterioration in sensitivity or reproduced signal was observed compared to the initial stage, and it was found to be extremely excellent as an optical recording medium.

Example 4 (a) Manufacture of optical recording media

[0048]

[Chemical formula 12]

0.15 g of the Ni chelate compound of the azo compound represented by the above structural formula (5) was dissolved in 7.5 g of methyl lactate and filtered through a 0.22 μm filter to obtain a solution. Coating and drying were performed in the same manner as in a). The maximum absorption wavelengths of the coating films were 646 and 717 nm. Next, an Au film with a thickness of 2000 Å was formed on this coating film by sputtering to form a reflective layer. Furthermore, a silicone-based hard coat agent was spin-coated on this reflective layer to form a protective layer with a thickness of 10 μm.

(b) Optical recording Regarding the optical recording medium obtained above, (b) of Example 1
Recording and reproduction were performed in the same manner as above, and a good reproduction signal was obtained. Further, as a result of similar light resistance and storage stability tests, no deterioration in sensitivity or reproduced signal was observed compared to the initial stage, and it was found to be extremely excellent as an optical recording medium.

Example 5 (a) Manufacture of optical recording media

[0052]

[Chemical formula 13]

Coating and drying were carried out in the same manner as in Example 1 (a) except that the Ni chelate compound of the azo compound represented by the above structural formula (6) was used as the complex. The maximum absorption wavelengths of the coating films were 652 and 723 nm. Next, an Al film with a thickness of 2000 Å was formed on this coating film by sputtering to form a reflective layer. Further, an ultraviolet curable resin was spin-coated on this reflective layer, and then cured by irradiation with ultraviolet rays to form a protective layer with a thickness of 10 μm.

(b) Optical recording Regarding the optical recording medium obtained above, (b) of Example 1
Recording and reproduction were performed in the same manner as above, and a good reproduction signal was obtained. Further, as a result of similar light resistance and storage stability tests, no deterioration in sensitivity or reproduced signal was observed compared to the initial stage, and it was found to be extremely excellent as an optical recording medium.

Example 6 (a) Manufacture of optical recording media

[0056]

[Chemical formula 14]

Coating and drying were carried out in the same manner as in Example 1 (a) except that the Ni chelate compound of the azo compound represented by the above structural formula (7) was used as the complex. The maximum absorption wavelengths of the coating films were 642 and 711 nm. Next, a 2000 Å thick Ag film was formed on this coating film by sputtering to form a reflective layer. Further, an ultraviolet curable resin was spin-coated on this reflective layer, and then cured by irradiation with ultraviolet rays to form a protective layer with a thickness of 10 μm.

(b) Optical recording Regarding the optical recording medium obtained above, (b) of Example 1
Recording and reproduction were performed in the same manner as above, and a good reproduction signal was obtained. Further, as a result of similar light resistance and storage stability tests, no deterioration in sensitivity or reproduced signal was observed compared to the initial stage, and it was found to be extremely excellent as an optical recording medium.

Example 7 (a) Manufacture of optical recording media

[0060]

[Chemical formula 15]

A mixed dye consisting of 0.12 g of the Ni chelate compound of the azo compound shown by the above structural formula (8) and 0.03 g of the cyanine dye shown by the above structural formula (9) was dissolved in 7.5 g of octafluoropentanol. and 0.22μm
A solution was obtained by filtration with a filter of Example 1 (a).
Coating and drying were carried out in the same manner as above. The maximum absorption wavelengths of the coating films were 634, 702 and 716 nm. Next, on top of this coating film, a film with a thickness of 200 mm was applied by sputtering.
A 0 Å thick Ag film was deposited to form a reflective layer. Furthermore, after spin-coating an ultraviolet curable resin on this reflective layer,
It was cured by irradiation with ultraviolet rays to form a protective layer with a thickness of 10 μm.

(b) Optical recording Regarding the optical recording medium obtained above, (b) of Example 1
Recording and reproduction were performed in the same manner as above, and a good reproduction signal was obtained. Further, as a result of similar light resistance and storage stability tests, no deterioration in sensitivity or reproduced signal was observed compared to the initial stage, and it was found to be extremely excellent as an optical recording medium.

Example 8 (a) Manufacture of optical recording media

[0064]

[Chemical formula 16]

0.15 g of the Ni chelate compound of the azo compound represented by the above structural formula (10) was dissolved in 5 g of tetrafluoropropanol and filtered through a 0.22 μm filter to obtain a solution. ) Coating and drying were performed in the same manner. The maximum absorption wavelength of the coating film is 637 and 6
It was 97 nm. Next, an Au film with a thickness of 2000 Å was formed on this coating film by sputtering to form a reflective layer. Further, an ultraviolet curable resin was spin-coated on this reflective layer, and was cured by irradiating ultraviolet rays to form a protective layer with a thickness of 10 μm.

(b) Optical recording Regarding the optical recording medium obtained above, (b) of Example 1
Recording and reproduction were performed in the same manner as above, and a good reproduction signal was obtained. Further, as a result of similar light resistance and storage stability tests, no deterioration in sensitivity or reproduced signal was observed compared to the initial stage, and it was found to be extremely excellent as an optical recording medium.

Example 9 (a) Manufacture of optical recording media

[0068]

[Chemical formula 17]

0.14 g of the Ni chelate compound of the azo compound represented by the above structural formula (11) and the above structural formula (12)
) was dissolved in 5 g of diacetone alcohol, and 0.22
A solution was obtained by filtration through a μm filter. This solution 5
ml was dropped onto an injection molded polycarbonate resin substrate similar to that used in Example 1 (a), and 7 ml was added using a spinner method.
Coating was performed at a rotation speed of 00 rpm. After coating, 10 at 60℃
Dry for a minute. The maximum absorption wavelength of the coating film is 642, 711
and 805 nm. Next, an Au film with a thickness of 2000 Å was formed on this coating film by sputtering to form a reflective layer. Further, an ultraviolet curable resin was spin-coated on this reflective layer, and was cured by irradiating ultraviolet rays to form a protective layer with a thickness of 10 μm.

(b) Optical recording Regarding the optical recording medium obtained above, (b) of Example 1
Recording and reproduction were performed in the same manner as above, and a good reproduction signal was obtained. Further, as a result of similar light resistance and storage stability tests, no deterioration in sensitivity or reproduced signal was observed compared to the initial stage, and it was found to be extremely excellent as an optical recording medium.

Example 10 (a) Manufacture of optical recording media

[0072]

[Chemical formula 18]

0.15 g of the Ni chelate compound of the azo compound represented by the above structural formula (13) was dissolved in 5 g of tetrafluoropropanol and filtered through a 0.22 μm filter to obtain a solution. ) and dried in the same manner. The maximum absorption wavelength of the coating film is 643 nm and 7
It was 14 nm. Next, an Au film with a thickness of 2000 Å was formed on this coating film by sputtering to form a reflective layer. Furthermore, an epoxy thermosetting resin was spin-coated on this reflective layer and cured with heat to form a protective layer with a thickness of 10 μm.

(b) Optical recording Regarding the optical recording medium obtained above, (b) of Example 1
Recording and reproduction were performed in the same manner as above, and a good reproduction signal was obtained. Further, as a result of similar light resistance and storage stability tests, no deterioration in sensitivity or reproduced signal was observed compared to the initial stage, and it was found to be extremely excellent as an optical recording medium.

Example 11 Instead of the compounds used in Examples 1 to 10, Table 1
An optical recording medium was obtained in the same manner except that a solution obtained by using the azo metal chelate compound of an azo compound and a metal shown in 1 to 13 alone or in a mixed system was applied onto a substrate. In addition, the maximum absorption wavelength of the coating film was as shown in Tables 1 to 13. Regarding the obtained optical recording medium, (b
) Recording and reproduction were performed in the same manner as in the previous example, and the sensitivity was good in both cases, and good reproduced signals were obtained. Further, as a result of similar light resistance and storage stability tests, no deterioration in sensitivity or reproduced signal was observed compared to the initial stage, and it was found to be extremely excellent as an optical recording medium.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

[0080]

[Table 5]

[0081]

[Table 6]

[0082]

[Table 7]

[0083]

[Table 8]

[0084]

[Table 9]

[0085]

[Table 11]

[0086]

[Table 11]

[0087]

[Table 12]

[0088]

[Table 13]

[0089]

Effects of the Invention As described in detail above, the optical recording medium of the present invention has high sensitivity, excellent light resistance, and storage stability, particularly excellent light resistance, and is useful as, for example, a recordable CD medium. A high reflectance optical recording medium is provided.

Claims (2)

[Claims] Claim 1. An optical recording medium comprising a recording layer, a metal reflective layer, and a protective layer sequentially laminated on a substrate, the optical recording medium having a reflectance of 65% or more, in which the recording layer has the following general An optical recording medium containing one or more azo metal chelate compounds of an azo compound represented by formula [I] and a metal. [Formula 1] (wherein A represents a residue that forms a heterocycle together with the carbon atom and nitrogen atom to which it is bonded, and B represents a residue that forms a heterocycle together with the two carbon atoms to which it is bonded. represents a residue that forms an aromatic ring or a heterocycle, and X represents a group having active hydrogen.) 2. The optical recording medium according to claim 1, wherein the azo compound is a compound represented by the following general formula [II]. [Chemical formula 2] (In the formula, A represents a residue that forms a heterocycle together with the carbon atom and nitrogen atom to which it is bonded, and R1 and R2 are each independently a hydrogen atom or a substituted represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, or an optionally substituted cycloalkyl group, and X represents a group having active hydrogen. Ring D represents a substituted 3. The optical recording medium according to claim 2, wherein the azo compound is a compound represented by the following general formula [III]. [Chemical formula 3] (In the formula, A represents a residue that forms a heterocycle together with the carbon atom and nitrogen atom to which it is bonded, and R1 and R2 are each independently a hydrogen atom or a substituted (Ring D may have a substituent.)