JP4373022B2 - Optical recording medium - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an optical recording medium, and in particular, by irradiating a light beam, optical changes such as transmittance and reflectance of a recording material are caused, information is recorded and reproduced, and additional recording is performed. The present invention relates to a possible optical information recording medium.
[0002]
[Prior art]
A recordable CD (CD-R) corresponding to the compact disc (CD) standard has been commercialized as an optical recording medium having a reflective layer on a substrate. This optical recording medium records and reproduces information by irradiating a recording layer with laser light having a wavelength of 770 to 830 nm, causing a physical or chemical change in the recording layer, and detecting reflected light. In addition, DVD-R is currently being developed as a next generation large capacity optical disk. Elemental technologies for improving the recording capacity require the development of recording materials for recording pit miniaturization, the adoption of image compression technology represented by MPEG2, and the shortening of the wavelength of a semiconductor laser for reading recording pits. is there.
[0003]
Recently, development of shorter-wavelength semiconductor lasers has progressed, and red semiconductor lasers with wavelengths of 630 to 660 nm have been put into practical use. However, until now, only 670 nm band AlGaInP laser diodes have been commercialized for bar code readers and measuring instruments, but red lasers are becoming more serious as the density of optical disks increases. Is being used in the optical storage market. According to this red laser, since the beam diameter can be further reduced by shortening the wavelength, the action of a high-density optical recording medium is possible. In the case of a DVD drive, the light source is standardized with two wavelengths of a laser diode of about 635 nm band and about 655 nm band. For high-density recording, it is desirable that the wavelength is shorter, and a wavelength of 635 nm is preferable as a write-once media drive. On the other hand, a read-only DVD-ROM drive is commercialized with a wavelength of about 655 nm.
[0004]
Under such circumstances, the most preferable DVD-R media is a medium (DVD-R) that can be recorded and reproduced at wavelengths of about 635 nm and about 650 nm, and a recording material excellent in light resistance and storage stability that can be applied thereto. It is desired. Recently, polymethine dyes and azo metal chelate dyes have been actively developed as recording materials (Japanese Patent Laid-Open Nos. 10-83577, 10-119434, 10-149583, and 10-188339). JP, 10-278426, JP 8-295811, JP 8-295812, JP 9-332772, JP 9-39394, JP 10-6650, JP 10-58828. JP-A-10-157293, JP-A-10-157300, JP-A-10-188340, JP-A-10-188341).
[0005]
Among polymethine dyes, particularly cyanine dyes are excellent in optical properties and satisfactory signal properties can be obtained, but their light resistance is extremely poor and they cannot be put into practical use by themselves. As an improvement, development of light stabilizers is underway (Japanese Patent Laid-Open Nos. 10-109475, 10-109476, 10-134413, 10-151861, and 10-166739). No.), a device that achieves both light stabilization and signal characteristics has not yet been found. In addition, azo metal chelate dyes can satisfy signal characteristics (JP-A-8-295079, JP-A-9-193546, JP-A-10-152623, JP-A-10-154350), but sufficient light resistance. Sex has not been obtained.
[0006]
On the other hand, formazan metal chelate dyes are known to have extremely high photostability, and have been tried to be applied as optical recording materials (JP-A-8-295079, JP-A-9-193546, JP-A-10-152623). No. 1, JP-A-10-154350) have long absorption wavelengths and are not suitable as recording materials for DVD-R. Also, application of cyanine dyes as light stabilizers has been attempted, but formazan dyes having an absorption characteristic close to the absorption wavelength of the main dyes are necessary in order to efficiently exhibit the light stabilization function. . In this sense, the conventional formazan metal chelate dye has an absorption wavelength that is too long, and has not been able to exhibit sufficient light stabilization ability.
[0007]
[Problems to be solved by the invention]
An optical recording medium having high solubility in organic solvents applicable to a high density optical disk system (DVD-R) using a semiconductor laser having an oscillation wavelength at a short wavelength in the conventional wavelength region, and excellent in light resistance and storage stability. Provide recording material.
[0008]
[Means for Solving the Problems]
As a result of investigations, the present inventors have found that a recording layer mainly composed of a formazan metal chelate dye having a specific structure has the above characteristics, and has developed a high-density optical disk system using a semiconductor laser having an oscillation wavelength of 630 to 660 nm or less. Applicable and highly light-resistant optical recording media have been produced. That is, the said subject of this invention is following (1)-( 15 ).
[0009]
(1) A recording layer is provided directly on the substrate or via an undercoat layer, and further thereon Against An optical recording medium comprising a projecting layer, a protective layer or an adhesive layer and a second substrate, wherein the recording layer contains at least one compound represented by the following general formula (I) recoding media.
Formula (I)
[Formula 4]
(In the formula, Z is a residue which forms a polyheterocycle which may have a substituent together with the carbon atom and the nitrogen atom to which Z is bonded. Any of the pyridazine ring, pyrimidine ring, pyrazine ring, and triazine ring R represents a substituted or unsubstituted alkyl group, an alkoxy group or an aryl group, A represents an aryl group which may have a substituent, M represents a divalent metal atom, n represents the number of formazan ligands coordinated to M. )
[0011]
( 2 In the general formula (I), M is iron, cobalt, nickel, copper, zinc or palladium. 1 ).
[0012]
( 3 The recording layer comprises a mixed layer of a light-absorbing dye having a maximum absorption wavelength at 550 to 630 nm in addition to the compound represented by the general formula (I). Or (2) The optical recording medium described.
[0013]
( 4 ) The light-absorbing dye is a polymethine dye or an azo metal chelate dye, and is represented by the general formula (I) having a maximum absorption wavelength longer than −50 nm of the maximum absorption wavelength of the polymethine dye or azo metal chelate dye. Characterized by comprising a mixed layer with 3 ).
[0014]
( 5 The polymethine dye is a cyanine dye. 4 ).
[0015]
( 6 ) A recording layer is provided directly on the substrate or via an undercoat layer, and further on Against An optical recording medium comprising a reflective layer, a protective layer or an adhesive layer, and a second substrate, wherein the recording layer contains at least one compound represented by the following general formula (II) recoding media.
Formula (II)
[Chemical formula 5]
(In the formula, Z is a residue which forms a polyheterocycle which may have a substituent together with the carbon atom and the nitrogen atom to which Z is bonded. Any of the pyridazine ring, pyrimidine ring, pyrazine ring, and triazine ring Represents R ₁ Represents a linear or branched alkyl group having 1 to 6 carbon atoms, A represents an aryl group which may have a substituent, M1 represents a divalent metal atom, and n represents M1. Represents the number of formazan ligands coordinated. )
[0017]
( 7 In the general formula (II), M is iron or copper. 6) An optical recording medium according to 1.
[0018]
( 8 The recording layer comprises a mixed layer of a light-absorbing dye having a maximum absorption wavelength at 550 to 630 nm in addition to the compound represented by the general formula (II). 6 ) Or (7) An optical recording medium according to 1.
[0019]
( 9 ) The light absorbing dye is a polymethine dye or an azo metal chelate dye, and is represented by the general formula (II) having a maximum absorption wavelength longer than −50 nm of the maximum absorption wavelength of the polymethine dye or azo metal chelate dye. Characterized by comprising a mixed layer with 8 ).
[0020]
( 10 The polymethine dye is a cyanine dye. 9 ).
[0021]
( 11 ) A recording layer is provided directly on the substrate or via an undercoat layer, and further on Against An optical recording medium comprising a reflective layer, a protective layer or an adhesive layer and a second substrate, wherein the optical recording medium comprises at least one compound represented by the following general formula (III).
General formula (III)
[Chemical 6]
(In the formula, Z is a residue which forms a polyheterocycle which may have a substituent together with the carbon atom and the nitrogen atom to which Z is bonded. Any of the pyridazine ring, pyrimidine ring, pyrazine ring, and triazine ring Represents R ₂ Represents a halogen, an alkyl group, an alkoxy group, a thioalkoxy group or a substituted amino group, A represents an aryl group which may have a substituent, M2 represents a divalent metal atom, and n represents , M2 represents the number of formazan ligands coordinated. )
[0023]
( 12 In the general formula (III), M is cobalt, nickel or copper. 11) An optical recording medium according to 1.
[0024]
( 13 The recording layer comprises a mixed layer of a light-absorbing dye having a maximum absorption wavelength at 550 to 630 nm in addition to the compound represented by the general formula (III). 10 ) ~ ( 12 The optical recording medium according to any one of the above.
[0025]
( 14 ) The light absorbing dye is a polymethine dye or an azo metal chelate dye, and is represented by the general formula (III) having a maximum absorption wavelength longer than −50 nm of the maximum absorption wavelength of the polymethine dye or azo metal chelate dye. Characterized by comprising a mixed layer of the above compounds ( 13 ).
[0026]
( 15 The polymethine dye is a cyanine dye. 14 ).
[0027]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
[0028]
The optical recording medium of the present invention may have a write-once optical disk structure (a so-called air sandwich structure in which two recording layers are provided on a substrate) and a CD-R structure (a recording layer on a substrate, a reflective layer). A structure in which a layer and a protective layer are stacked), or a structure in which a CD-R structure is bonded.
[0029]
(substrate)
The substrate to be used must be transparent to the laser used only when recording / reproduction is performed from the substrate side, and the substrate need not be transparent when recording / reproduction is performed from the recording layer side. As the substrate material, for example, plastic such as polyester, acrylic resin, polyamide, polycarbonate resin, polyolefin resin, phenol resin, epoxy resin, polyimide, glass, ceramic, or metal can be used. A tracking guide groove, a guide pit, and a preformat such as an address signal may be formed on the surface of the substrate.
[0030]
(Recording layer)
The recording layer causes some optical change upon irradiation with laser light, and records information by the change. The recording layer contains at least one compound represented by the above general formula (I). It is necessary to become. Further, more preferred specific structural examples include compounds represented by the general formula (II) or (III), and it is necessary to contain at least one of them.
[0031]
R in the general formula (I) represents a substituted or unsubstituted alkyl group, alkoxy group, or aryl group, and A represents substitution of an alkyl group, alkoxy group, halogen group, carboxyl group or ester thereof, nitrile group, nitro group, or the like. Represents an aryl group which may have a group, M represents a divalent metal atom, and n represents the number of formazan ligands coordinated to M.
[0032]
R in general formulas (II) and (III) ₁ Represents a linear or branched alkyl group having 1 to 6 carbon atoms, R ₂ Represents a halogen, an alkyl group, an alkoxy group, a thioalkoxy group, or a substituted amino group, and A has a substituent such as an alkyl group, an alkoxy group, a halogen group, a carboxyl group or an ester thereof, a nitrile group, or a nitro group. Represents an aryl group, M1 and M2 represent a divalent metal atom, and n represents the number of formazan ligands coordinated to M1 and M2.
[0033]
In common with the general formulas (I), (II), and (III), Z in the formula is a residue that forms a polyheterocycle together with the carbon atom and nitrogen atom to which it is bonded. The heterocyclic ring may have a substituent such as an alkyl group, an alkoxy group, a thioalkoxy group, a substituted amino group, an aryl group, an aryloxy group, an anilino group, and a keto group.
[0034]
Specific examples of Z include thiazole ring, benzothiazole ring, oxazole ring, benzoxazole ring, pyrazole ring, benzopyrazole ring, imidazole ring, benzimidazole ring, oxadiazole ring, triazole ring, thiadiazole ring, pyridazine ring, pyrimidine Examples include a ring, a pyrazine ring, and a triazine ring. From the viewpoint of optical properties, storage stability, and light resistance, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring are particularly preferable.
[0035]
A is an aryl group, and specific examples thereof include a phenyl group, a pentarenyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group, an as-indacenyl group, an s-indacenyl group, an acenaphthalenyl group, a fluorenyl group, Examples include a phenalenyl group, a phenanthrenyl group, an anthranyl group, a fluoracenyl group, an acephenanthrenyl group, an aceanthrylene group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, and a naphthacenyl group. These include an alkyl group, an alkoxy group, and a halogen group. May have a substituent such as a carboxyl group or an ester thereof, a nitrile group, or a nitro group.
[0036]
Specific examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.
[0037]
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n -Primary alkyl group such as decyl group, isobutyl group, isoamyl group, 2-methylbutyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2-ethylbutyl group, 2-methylhexyl group, 3 -Methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2-ethylpentyl group, 3-ethylpentyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methyl Heptyl, 2-ethylhexyl, 3-ethylhexyl, isopropyl, sec-butyl, 1-ethylpropyl, 1-methylbutyl, 1,2 Dimethylpropyl group, 1-methylheptyl group, 1-ethylbutyl group, 1,3-dimethylbutyl group, 1,2-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1-methylhexyl group, 1-ethyl Heptyl group, 1-propylbutyl group, 1-isopropyl-2-methylpropyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-propyl-2-methylpropyl group, 1-methyl Heptyl group, 1-ethylhexyl group, 1-propylpentyl group, 1-isopropylpentyl group, 1-isopropyl-2-methylbutyl group, 1-isopropyl-3-methylbutyl group, 1-methyloctyl group, 1-ethylheptyl group, Secondary alkyl groups such as 1-propylhexyl group, 1-isobutyl-3-methylbutyl group, neopentyl group, Tertiary alkyl groups such as tert-butyl group, tert-hexyl group, tert-amyl group, tert-octyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-tert-butylcyclohexyl group, 4 Examples thereof include cycloalkyl groups such as-(2-ethylhexyl) cyclohexyl group, bornyl group, and isobornyl group (adamantane group). Furthermore, these primary and secondary alkyl groups may be substituted with a hydroxyl group, a halogen atom, a nitro group, a carboxy group, a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic residue, and the like. In addition, the alkyl group may be substituted with an atom such as oxygen, sulfur or nitrogen. Examples of the alkyl group substituted through oxygen include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, a butoxyethyl group, an ethoxyethoxyethyl group, a phenoxyethyl group, a methoxypropyl group, an ethoxypropyl group, As an alkyl group in which a piperidino group, a morpholino group, or the like is substituted through sulfur, a methylthioethyl group, an ethylthioethyl group, an ethylthiopropyl group, a phenylthioethyl group, or the like is substituted through nitrogen Examples of the alkyl group include a dimethylaminoethyl group, a diethylaminoethyl group, and a diethylaminopropyl group.
[0038]
Specific examples of the aryl group include a phenyl group, a pentarenyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group, an as-indacenyl group, an s-indacenyl group, an acenaphthalenyl group, a fluorenyl group, a phenalenyl group, and a phenanthrenyl group. , Anthranyl group, fluoracenyl group, acephenanthrenyl group, aceanthrylene group, triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group and the like. Further, these aryl groups may be substituted with a hydroxyl group, a halogen atom, a nitro group, a carboxy group, a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic residue, and the like. The alkyl group may be substituted via an atom such as sulfur or nitrogen.
[0039]
Specific examples of the alkoxy group are not particularly limited as long as a directly substituted or unsubstituted alkyl group is bonded to an oxygen atom, and specific examples of the alkyl group include the above-described specific examples. Specific examples of the group may be those in which a substituted or unsubstituted aryl group is bonded directly to the oxygen atom, and specific examples of the aryl include the above-described specific examples.
[0040]
Specific examples of the divalent metal atom include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium and the like, optical characteristics, From the viewpoints of storage stability and light stability, iron, cobalt, nickel, copper, zinc, and palladium are particularly preferable, and cobalt, nickel, and copper are more preferable. Among these, in general formula (II), iron and copper are particularly preferable, and in general formula (III), cobalt, nickel and copper are particularly preferable.
[0041]
In forming the recording layer, the dye compound (formazan metal chelate dye) represented by the general formulas (I), (II) and (III) of the present invention may be used alone or in combination of two or more. Further, the dye compound of the present invention may be used by mixing or laminating with other organic dyes, metals and metal compounds for the purpose of improving optical characteristics, recording sensitivity, signal characteristics and the like. Examples of the other organic dyes include polymethine dye, naphthalocyanine dye, phthalocyanine dye, squarylium dye, croconium dye, pyrylium dye, naphthoquinone dye, anthraquinone dye (indanthrene dye), xanthene dye, triphenylmethane dye, azulene And dyes, tetrahydrocholine dyes, phenanthrene dyes, triphenothiazine dyes and metal complex compounds thereof. Here, examples of metals and metal compounds include In, Te, Bi, Se, Sb, Ge, Sn, Al, Be, and TeO. ₂ , SnO, As, Cd, etc., each of which can be used in the form of dispersion mixing or lamination.
[0042]
Moreover, when using said other organic pigment | dye as a light stabilizer, the pigment | dye which has an absorption maximum wavelength in 550 nm-630 nm is selected, and this and the formazan metal chelate pigment | dye of this invention are mixed and used. In this case, it is preferable in terms of efficiency that the formazan metal chelate dye of the present invention has absorption at a wavelength longer than the maximum absorption wavelength −50 nm of the other organic dye (light stabilizer).
[0043]
Preferred examples of the dye having the maximum absorption wavelength at 550 nm to 630 nm include polymethine dye, squarylium dye, croconium dye, pyrylium dye, naphthoquinone dye, anthraquinone dye (indanthrene), xanthene dye, triphenylmethane dye, tetrahydrocholine There are a dye, a phenanthrene dye, a triphenothiazine dye, an azo metal chelate dye, and the like, and a polymethine dye and an azo metal chelate dye are particularly preferable in terms of optical characteristics.
[0044]
In addition, polymer materials such as ionomer resins, polyamide resins, vinyl resins, natural polymers, silicones, liquid rubbers, or silane coupling agents may be dispersed and mixed in the dyes to improve characteristics. For this purpose, they may be dispersed and mixed with a stabilizer (for example, a transition metal complex), a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer and the like.
[0045]
The recording layer can be formed by ordinary means such as vapor deposition, sputtering, CVD or solvent coating. In the case of using the coating method, the above dye, resin and the like can be dissolved in an organic solvent, and can be performed by a conventional coating method such as spraying, roller coating, dipping and spin coating.
[0046]
As the organic solvent used here, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, dimethyl sulfoxide Sulfoxides such as, tetrahydrofuran, dioxane, diethyl ether, ethers such as ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, aliphatic halogenated carbonization such as chloroform, methylene chloride, dichloroethane, carbon tetrachloride and trichloroethane Hydrogen, aromatics such as benzene, xylene, monochlorobenzene and dichlorobenzene, cellosolves such as methoxyethanol and ethoxyethanol, hexa , Pentane, cyclohexane, and hydrocarbons such as methylcyclohexane.
[0047]
The film thickness of the recording layer is 100 to 10 μm, preferably 200 to 2000 μm.
[0048]
(Underlayer)
The undercoat layer is (i) improved adhesion, (ii) a barrier such as water or gas, (iii) improved storage stability of the recording layer, (iv) improved reflectivity, (v) the substrate from the solvent. Used for the purpose of protection, (vi) formation of guide grooves, guide pits, preformats, etc. For the purpose of (i), various polymeric compounds such as ionomer resin, polyamide resin, vinyl resin, natural resin, natural polymer, silicone, liquid rubber, and silane coupling agent are used for the purpose of (i). In addition to the above polymer materials, inorganic compounds such as SiO, MgF, SiO can be used for the purposes of (ii) and (iii) ₂ , TiO, ZnO, TiN, SiN and the like, and metal or semimetal such as Zn, Cu, Ni, Cr, Ge, Se, Au, Ag, Al, etc. can be used. For the purpose of (iv), metals such as Al, Au and Ag, and organic thin films having metallic luster such as methine dyes and xanthene dyes can be mentioned. For the purpose of vi), an ultraviolet curable resin, a thermosetting resin, a thermoplastic resin, or the like can be used.
[0049]
The thickness of the undercoat layer is 0.01 to 30 μm, preferably 0.05 to 10 μm.
[0050]
(Metal reflective layer)
Examples of the metal reflective layer include a metal, a semi-metal, and the like that are not easily corroded to obtain high reflectivity, and examples of materials include Au, Ag, Cr, Ni, Al, Fe, Sn, etc. Au, Ag, and Al are most preferable from the viewpoint of productivity, and these metals and metalloids may be used alone or as two kinds of alloys. Examples of the film forming method include vapor deposition and sputtering, and the film thickness is 50 to 5000 mm, preferably 100 to 3000 mm.
[0051]
(Protective layer or substrate surface hard coat layer)
The protective layer and the substrate hard coat layer (i) protect the recording layer (reflection / absorption layer) from scratches, dust, dirt, etc. (ii) improve the storage stability of the recording layer (reflection / absorption layer), (iii) Used for the purpose of improving reflectivity. For these purposes, the materials shown in the undercoat layer can be used. In addition, as inorganic materials, SiO, SiO ₂ , Etc. can also be used, such as polymethyl acrylate, polycarbonate, epoxy resin, polystyrene, polyester resin, vinyl resin, cellulose, aliphatic hydrocarbon resin, natural rubber, styrene butadiene resin, chloroprene rubber, wax, alkyd resin Also, heat softening and heat melting resins such as drying oil and rosin can be used. The most preferable example among the above materials is an ultraviolet curable resin excellent in productivity.
[0052]
The film thickness of the protective layer or the substrate surface hard coat layer is 0.01 to 30 μm, preferably 0.05 to 10 μm.
[0053]
In the present invention, the undercoat layer, the protective layer, and the substrate-side hard coat layer are the same as in the recording layer, such as a stabilizer, a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, and a plasticizer. Etc. can be contained.
[0054]
The typical formazan metal chelate used in the present invention is exemplified below.
[0055]
[Table 1]
[0056]
[Table 2]
[0057]
[Table 3]
[0058]
[Table 4]
[0059]
[Table 5]
[0060]
[Table 6]
[0061]
【Example】
Next, the present invention will be specifically described with reference to examples.
[0062]
Example 1
On an injection molded polycarbonate substrate having a depth of 1600 mm, a half width of 0.30 μm, and a guide groove having a track pitch of 0.8 μm and a thickness of 0.6 mm, Compound Example No. A solution prepared by dissolving 2 in tetrafluoropropanol was applied with a spinner to form an organic dye layer having a thickness of 700 mm, and then a reflective layer of 2000 mm gold was formed by a sputtering method, and an acrylic photopolymer of 5 μm was further formed thereon. After providing the protective layer, it was bonded to an injection molded polycarbonate flat substrate having a thickness of 0.6 mm to obtain an optical recording medium.
[0063]
(Example 2)
Compound Example No. 1 of Example 1 Instead of 2, Compound Example No. 14 was used to obtain an optical recording medium exactly as in Example 1.
[0064]
(Examples 3 and 4)
Compound Example No. 1 of Example 1 In place of Compound No. 2, Compound Example No. Using a mixed dye (weight ratio 5/5) of 2 and 19 and a compound represented by the following (ratio-1), an optical recording medium was obtained in exactly the same manner as in Example 1.
(Ratio-1)
[Chemical 7]
[0065]
(Examples 5 and 6)
In Example 1, Compound Example No. In place of Compound No. 2, Compound Example No. An optical recording medium was obtained in exactly the same manner as in Example 1 using a mixed dye (weight ratio 5/5) of 14 and 26 and a compound represented by the following (ratio-2).
(Ratio-2)
[Chemical 8]
[0066]
(Comparative Examples 1 and 2)
As an organic thin film in Example 1, Compound Example No. Instead of 1, an optical recording medium was prepared using the compounds represented by the above ratios -1,2.
[0067]
A semiconductor laser beam having an oscillation wavelength of 635 nm is recorded on these optical recording media, an EFM signal (linear speed: 3.0 m / sec, minimum mark length: 0.4 μm) is recorded while tracking, and a continuous laser beam with an oscillation wavelength of 650 nm is recorded. (Reproduction was performed at a reproduction power of 0.7 mW, and the reflectance and C / N were measured. The results are shown in Table 7.
Light resistance test: Tungsten lamp, 50,000 lux, 20 hours irradiation
[0068]
[Table 7]
[0069]
(Examples 7 and 8)
On the injection molded polycarbonate flat plate having a thickness of 1.2 mm, the compound (ratio-1) and the compound example No. 2 was dissolved in tetrafluoropropanol in a weight ratio (10/2) and weight ratio (10/4) mixture and spinner coated to form an organic dye layer having a thickness of 1000 mm. This dye thin film was placed under a tungsten lamp at 50,000 lux, and the change in absorbance of the dye was measured. The results are shown in Table 8.
[0070]
(Examples 9 and 10)
In Examples 5 and 6, a dye thin film was obtained in the same manner using the compound (ratio-2) instead of the compound (ratio-1). This dye thin film was placed under a tungsten lamp at 50,000 lux, and the change in absorbance of the dye was measured. The results are shown in Table 8.
[0071]
(Comparative Example 3)
In Example 7, Compound Example No. Without using 2, a dye thin film of only the compound (ratio-1) was obtained. This dye thin film was placed under a tungsten lamp at 50,000 lux, and the change in absorbance of the dye was measured. The results are shown in Table 8.
[0072]
(Comparative Example 4)
In Example 9, a dye thin film containing only the compound (ratio-2) was obtained. This dye thin film was placed under a tungsten lamp at 50,000 lux, and the change in absorbance of the dye was measured. The results are shown in Table 8.
[0073]
[Table 8]
[0074]
Compound No. Similarly, 5, 11, 16, 22, and 35 obtained a remarkable light stabilization effect.
[0075]
【The invention's effect】
As described above, the formazan metal chelate of the present invention can be coated by coating, can provide a medium having a high refractive index, a high reflectance, and a high degree of modulation with excellent light resistance and storage stability. By mixing with a dye, a medium excellent in light resistance can be provided as compared with the case of using them alone.
[0076]
The invention according to claim 1 can provide an optical information recording medium capable of high-density recording and reproduction with a laser beam having a wavelength region of 660 nm or less, and excellent in light resistance and storage stability. An excellent optical information recording medium can be provided by a preferable chemical structure.
According to the invention of claim 4, an optical information recording medium used as a light stabilizer can be provided. The invention of claim 5 is a basic structure that works more efficiently as a light stabilizer, and the invention of claim 6 is a preferred material thereof. The structure is shown, and an excellent optical information recording medium can be provided.
According to the invention of claims 7 to 18, a more preferable optical recording medium can be provided.

Claims (15)

The recording layer directly or via an undercoat layer on a substrate provided further anti picolinimidate thereon, the protective layer or adhesive layer and the second optical recording medium formed by providing a substrate, the recording layer is represented by the following general formula ( An optical recording medium comprising at least one compound represented by I). Formula (I)
(In the formula, Z is a pyridazine ring, pyrimidine ring, pyrazine ring which is a residue which forms a polyheterocycle which may have a substituent together with a carbon atom and a nitrogen atom to which Z is bonded. And R represents a substituted or unsubstituted alkyl group, alkoxy group or aryl group, A represents an aryl group which may have a substituent, and M represents 2 Represents a valent metal atom, and n represents the number of formazan ligands coordinated to M.) 2. The optical recording medium according to claim 1, wherein M in the general formula (I) is iron, cobalt, nickel, copper, zinc or palladium. 3. The optical recording according to claim 1, wherein the recording layer comprises a mixed layer of a light absorbing dye having a maximum absorption wavelength at 550 to 630 nm in addition to the compound represented by the general formula (I). Medium. The light absorbing dye is a polymethine dye or an azo metal chelate dye, and is represented by the general formula (I) having a maximum absorption wavelength longer than −50 nm of the maximum absorption wavelength of the polymethine dye or azo metal chelate dye. 4. The optical recording medium according to claim 3, comprising a mixed layer with a compound. 5. The optical recording medium according to claim 4, wherein the polymethine dye is a cyanine dye. In an optical recording medium in which a recording layer is provided directly on a substrate or via an undercoat layer, and further a reflective layer, a protective layer or an adhesive layer and a second substrate are provided thereon, the recording layer has the following general formula (II An optical recording medium comprising at least one compound represented by the formula: Formula (II)
(In the formula, Z is a pyridazine ring, pyrimidine ring, pyrazine ring which is a residue which forms a polyheterocycle which may have a substituent together with a carbon atom and a nitrogen atom to which Z is bonded. , And any of the triazine rings, R ₁ Represents a linear or branched alkyl group having 1 to 6 carbon atoms, A represents an aryl group which may have a substituent, M1 represents a divalent metal atom, and n represents M1. Represents the number of formazan ligands coordinated. ) 7. The optical recording medium according to claim 6, wherein M in the general formula (II) is iron or copper. 8. The optical recording according to claim 6, wherein the recording layer comprises a mixed layer with a light-absorbing dye having a maximum absorption wavelength at 550 to 630 nm in addition to the compound represented by the general formula (II). Medium. The light absorbing dye is a polymethine dye or an azo metal chelate dye, and is represented by the general formula (II) having a maximum absorption wavelength longer than −50 nm of the maximum absorption wavelength of the polymethine dye or azo metal chelate dye. 9. The optical recording medium according to claim 8, comprising a mixed layer with a compound. The optical recording medium according to claim 9, wherein the polymethine dye is a cyanine dye. An optical recording medium in which a recording layer is provided directly on a substrate or via a subbing layer, and further a reflective layer, a protective layer or an adhesive layer and a second substrate are provided thereon is represented by the following general formula (III) An optical recording medium comprising at least one compound. General formula (III)
(In the formula, Z is a pyridazine ring, pyrimidine ring, pyrazine ring which is a residue which forms a polyheterocycle which may have a substituent together with a carbon atom and a nitrogen atom to which Z is bonded. , And any of the triazine rings, R ₂ Represents a halogen, an alkyl group, an alkoxy group, a thioalkoxy group or a substituted amino group, A represents an aryl group which may have a substituent, M2 represents a divalent metal atom, and n represents , M2 represents the number of formazan ligands coordinated. ) 12. The optical recording medium according to claim 11, wherein M is cobalt, nickel or copper in the general formula (III). The optical recording according to claim 11 or 12, wherein the recording layer comprises a mixed layer with a light-absorbing dye having a maximum absorption wavelength at 550 to 630 nm in addition to the compound represented by the general formula (III). Medium. The light absorbing dye is a polymethine dye or an azo metal chelate dye, and is represented by the general formula (III) having a maximum absorption wavelength longer than −50 nm of the maximum absorption wavelength of the polymethine dye or azo metal chelate dye. 14. The optical recording medium according to claim 13, comprising a mixed layer of compounds. The optical recording medium according to claim 14, wherein the polymethine dye is a cyanine dye.