OPTICAL INFORMATION RECORDING MEDIUM

Abstract: An optical information recording medium comprises at least one compound selected from the compounds of the general formulae (1-I) to (3-III) shown and pyrylium compounds, and a metal chelate compound in the recording medium.

Description: BACKGROUND OF THE INVENTION Field of the Invention This invention relates to an optical information recording medium suitable for optical writing recording by laser, etc., more particularly to an improved optical information recording medium which can be used for optical disc and optical card. Related Background Art Generally speaking, an optical disc or optical card can memory a high density information with an optically detectable small, for example, about 1 µ pit formed on a thin recording layer provided on a substrate being in the track form of a spiral, circular or linear shape. For writing information in such disc or card, converged laser is scanned on the surface of a laser sensitive layer, whereby only the surface irradiated with the laser beam forms pits, which pits are formed in the form of spiral, circular or linear tracks. The laser sensitive layer can form optically detectable pits through absorption of laser energy. For example, according to the heat mode recording system, the laser sensitive layer absorbs heat energy, and can form a small concavity (pit) at that site through vaporization or melting. Also, according to another heat mode recording system, through absorption of the laser energy irradiated, a pit having an optically detectable density difference can be formed at that site. The information recorded on such optical disc and optical card is detected by scanning laser beam along the track and reading the optical change at the portion where a pit is formed and the portion where no pit is formed. For example, in the case of an optical disc or optical card, laser beam is scanned along the track, and the energy reflected by the disc or the card is monitored by a photodetector. At the portion where a pit is formed, reflection of laser becomes lower and the output from the photodetector becomes smaller. On the other hand, at the portion where no pit is formed, reflection is sufficiently effected to make the output from the photodetector greater. As an optical information recording medium to be used for such optical disc and optical card, there have been hitherto proposed those using primarily inorganic materials, for example, a metal thin film such as aluminum, gold vapor deposited film, etc., bismuth thin film, tellurium oxide thin film, chalcogenide type amorphous glass film, etc. These thin films have drawbacks such that storability is poor, decomposition ability is low, recording density is low, the cost is high, etc. Also, it has been recently proposed to use an organic dye thin film which can undergo change in physical properties with a light of relatively longer wavelength for the recording layer. The organic dye thin film can remove the above drawbacks, but an organic dye having absorption characteristic on the longer wavelength side will generally involve a problem in that stability is low to heat and light. Including these points, the organic coloring matter to be used in recording material is required to have the following properties, namely: 1. to have no toxicity; 2. to have an absorption at around 800 nm, with a great coefficient of absorption; 3. to have good solubility in an organic solvent; 4. to have a great reflectance at around 800 nm in a thin film state; 5. to be crystallized with difficulty in a thin film state; 6. to be stable to UV-ray and visible light; 7. to be thermally stable; 8. to be stable to humidity; 9. to be synthesized with ease, etc. The advantages of organic dyes as compared with inorganic compounds which have been used in the prior art may include no toxicity (item 1.) and good solubility (item 3.), but there is the problem that although it can provide sufficient reflectance it readily crystallizes when in the state of a thin film. Reflectance is necessary for scanning of laser on the track wtih good precision when monitored with a photodetector, but the absorbance of the organic film will be greatly reduced if crystallization occurs, so that it becomes difficult to form in it the pits needed for recording. SUMMARY OF THE INVENTION According to the present invention, there is provided an optical information recording medium, comprising in the recording medium firstly at least one compound, selected from the compounds of the general fomulae (1-I) to (3-III) and pyrylium compounds, and secondly a metal chelate compound selected from the compounds of formulae (1) to (8) set out below. The above recording media exhibit high reflectance and good storage stability. DE-A-3537539 discloses a compound of the formula 3-I in an optical information recording medium together with a bis-dithionickel chelate compound. However, the recording media disclosed in that reference do not have a reflectance which is as stable to ageing as the recording media of this invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The organic coloring matter compound used in the optical information recording medium of this invention may include the following. R₁₋₁, R₁₋₂, R₁₋₃, R₁₋₄ and R₁₋₅ each represent hydrogen atom or an alkyl group (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-amyl, t-amyl, n-hexyl, n-octyl, t-octyl, etc.), and further include other alkyl groups such as substituted alkyl groups (e.g. 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-acetoxyethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfate propyl, 4-sulfate butyl, N-(methylsulfonyl)-carbamylmethyl, 3-(acetylsulfamyl)propyl, 4-(acetylsulfamyl)butyl, etc.), cyclic alkyl groups (e.g. cyclohexyl, etc.), alkenyl groups (e.g. vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, dodecynyl, prenyl, etc.), aralkyl groups (e.g. benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, etc.), substituted aralkyl groups (e.g. caboxybenzyl, sulfobenzyl, hydroxybenzyl, etc.). Further, R₁₋₁, R₁₋₂, R₁₋₃, R₁₋₄ and R₁₋₅ each represent a substituted or unsubstituted aryl group (e.g. phenyl, naphthyl, tolyl, xylyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, dimethylaminophenyl, diethylaminophenyl, dipropylaminophenyl, dibenzylaminophenyl, diphenylaminophenyl, etc.), a substituted or unsubstituted heterocyclic group (e.g. pyridyl, quinolyl, lepidyl, methylpyridyl, furyl, thienyl, an indolyl, pyrrole, carbazolyl, an N-ethylcarbazolyl, etc.) or a substituted or unsubstituted styryl group (e.g. styryl, methoxystyryl, dimethoxystyryl, trimethoxystyryl, ethoxystyryl, dimethylaminostyryl, diethylaminostyryl, dipropylaminostyryl, dibenzylaminostyryl, diphenylaminostyryl, 2,2-diphenylvinyl, 2-phenyl-2-methylvinyl, 2-(dimethylaminophenyl)-2-phenylvinyl, 2-(diethylaminophenyl)-2-phenylvinyl, 2-(dibenzylaminophenyl)-2-phenylvinyl, 2,2-di(diethylaminophenyl)vinyl, 2,2-di(methoxyphenyl)vinyl, 2,2-di(ethoxyphenyl)vinyl, 2-(dimethylaminophenyl)-2-methylvinyl, 2-(diethylaminophenyl)-2-ethylvinyl, etc.). m₁₋₁ is 0 or 1 and n 1-1 is 0, 1 or 2. X₁₋₁ ⊖ represents an anion such as chloride, bromide, iodide, perchlorate, benzenesulfonate, p-toluenesulfonate, methylsulfate, ethylsulfate, propylsulfate, tetrafluoroborate, tetraphenylborate, hexafluorophosphate, benzenesulfinate, acetate, trifluoroacetate, propionacetate, benzoate, oxalate, succinate, malonate, oleate, stearate, citrate, monohydrogen diphosphate, dihydrogen monophosphate, pentachlorostannate, chlorosulfonate, fluorosulfonate, trifluoromethanesulfonate, hexafluoroantimonate, molybdate, tungstate, titanate, zirconate and so on. wherein A₂₋₁, B₂₋₁, D₂₋₁ and E₂₋₁ each represent hydrogen atom, an alkyl, an alkenyl, a substituted or unsubstituted aralkyl and a substituted or unsubstituted aryl group; Y₂₋₁ represents a divalent residue having a group of atoms necessary for the completion of a 5-membered or 6-membered ring; R₂₋₁, R₂₋₂, R₂₋₃, R₂₋₄ and R₂₋₅ represent hydrogen atom, a halogen atom or an alkyl; X₂₋₁ ⊖ represents an anion; and m₂₋₁ and n₂₋₁ represent 0, 1 or 2.) (wherein A₂₋₁, B₂₋₁, D₂₋₁ and E₂₋₁ each represent hydrogen atom, an alkyl, an alkenyl, a substituted or unsubstituted aralkyl and a substituted or unsubstituted aryl group; Y₂₋₁ represents a divalent residue having a group of atoms necessary for the completion of a 5-membered or 6-membered ring; R₂₋₁, R₂₋₂ and R₂₋₃ each represent hydrogen atom, a halogen atom or an alkyl; and X₂₋₁⊖ represents an anion.) (wherein Z₂₋₁ ⊖ represents or A₂₋₁, B₂₋₁, D₂₋₁ and E₂₋₁ each represent hydrogen atom, an alkyl, an alkenyl, a substituted or unsubstituted aralkyl and substituted or unsubstituted aryl; R₂₋₁, R₂₋₂, R₂₋₃ and R₂₋₄ represent hydrogen atom, halogen atom or an alkyl; and m₂₋₁ and n₂₋₁ represent 0, 1 or 2. ) In the above Formulae (2-I), (2-II) and (2-III), A₂₋₁, B₂₋₁, D₂₋₁ and E₂₋₁ each represent hydrogen atom, a substituted or unsubstituted alkyl, an alkenyl, a substituted or unsubstituted aralkyl and substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl, methoxyphenyl, ethoxyphenyl, dimethylaminophenyl, diethylaminophenyl, dipropylaminophenyl, dibenzylaminophenyl, pyrrolidinophenyl, diphenylaminophenyl, etc.). R₂₋₁, R₂₋₂, R₂₋₃, R₂₋₄ and R₂₋₅ each represent hydrogen atom, a halogen atom or an alkyl group. The alkyl group may include unsubstituted alkyls (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, secbutyl, isobutyl, t-butyl, n-amyl, t-amyl, n-hexyl, n-octyl, t-octyl, etc.), and substituted alkyls (e.g. 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-acetoxyethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, etc.). Y₂₋₁ represents a divalent hydrocarbon capable of forming a substituted or unsubstituted 5- or 6-membered ring (e.g. -CH₂-CH₂-, ( CH₂ )₃, -CH₂-CHCl-CH₂-, etc.), and the 5-membered or 6-membered ring may be fused with benzene ring, naphthalene ring, etc. In the formula, Z₂₋₁ ⊖ represents or X₂₋₁ ⊖ represents an anion such as chloride, bromide, iodide, perchlorate, benzenesulfonate, p-toluenesulfonate, methylsulfate, ethylsulfate, propylsulfate, tetrafluoroborate, tetraphenylborate, hexafluorophosphate, benzenesulfinate, acetate, trifluoroacetate, propionacetate, benzoate, oxalate, succinate, malonate, oleate, stearate, citrate, monohydrogen diphosphate, dihydrogen monophosphate , pentachlorostannate, chlorosulfonate, fluorosulfonate, trifluoromethanesulfonate, hexafluoroantimonate, molybdate, tungstate, titanate, zirconate and so on. m₂₋₁ and n₂₋₁ represent an integer of 0, 1 or 2. Typical examples of the compound represented by the above formulae are mentioned below. Among the typical examples, with respect to Z₂₋₁ ⊖ , is represented by Z₁₀ and is represented by Z₂₀. The arrow (←) indicates the same substituents as the left (wherein, in general formulae (3-I), (3-II) and (3-III), R₃₋₁, R₃₋₂, R₃₋₃, R₃₋₄, R₃₋₅, R₃₋₆ and R₃₋₇ each represent hydrogen atom, a halogen atom or a monovalent organic residue, or a substituted or unsubstituted fused ring may be formed by at least one of the combinations of R₃₋₁ and R₃₋₂, R₃₋₂ and R₃₋₃, R₃₋₃ and R₃₋₄, R₃₋₄ and R₃₋₅, R₃₋₅ and R₃₋₆, and R₃₋₆ and R₃₋₇; A₃₋₁ represents a divalent organic residue; and Z₃₋₁ ⊖ represents an anion residue.) In the general formulae, R₃₋₁ to R₃₋₇ represent hydrogen atom, halogen atom (chlorine atom, bromine atom, iodine atom) or monovalent organic residue. The monovalent organic residue, which can be widely selected, may particularly include alkyl groups (methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-amyl, n-hexyl, n-octyl, 2-ethylhexyl, t-octyl, etc.), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, chlorophenyl, nitrophenyl, dimethylaminophenyl, α-naphthyl, β-naphthyl, etc.), substituted or unsubstituted aralkyl groups (benzyl, 2-phenylethyl, 2-phenyl-1-methylethyl, bromobenzyl, 2-bromophenylethyl, methylbenzyl, methoxybenzyl, nitrobenzyl), acyl groups (acetyl, propionyl, butyryl, valeryl, benzoyl, toluoyl, naphthoyl, phthaloyl, furoyl, etc.), substituted or unsubstituted amino groups (amino, dimethylamino, diethylamino, dipropylamino, acetylamino, benzoylamino, etc.), substituted or unsubstituted styryl groups (styryl, dimethylaminostyryl, diethylaminostyryl, dipropylaminostyryl, methoxystyryl, ethoxystyryl, methylstyryl, etc.), nitro, hydroxy, caboxyl, cyano or substituted or unsubstituted arylazo groups (phenylazo, α-naphthylazo, β-naphthylazo, dimethylaminophenylazo, chlorophenylazo, nitrophenylazo, methoxyphenylazo, tolylazo, etc.). Further, a substituted or unsubstituted fused ring may be formed at least one of the combinations of R₃₋₁ and R₃₋₂, R₃₋₂ and R₃₋₃, R₃₋₃ and R₃₋₄, R₃₋₄ and R₃₋₅, R₃₋₅ and R₃₋₆, and R₃₋₆ and R₃₋₇. The fusedring is a 5-, 6- or 7-membered, including aromatic rings (benzene, naphthalene, chlorobenzene, bromobenzene, methylbenzene, ethylbenzene, methoxybenzene, ethoxybenzene, etc.), hetero rings (furan ring, benzofuran ring, pyrrole ring, thiophene ring, pyridine ring, quinoline ring, thiazole ring, etc.), aliphatic rings (dimethylene, trimethylene, tetramethylene, etc.). Z₃₋₁ ⊖ represents an anion residue. A₃₋₁ represents a divalent organic residue bonded through double bond. Specific examples of the dye containing A₃₋₁ to be used in this invention may include those represented by the general formulae (3-1) to (3-11) shown below. However, in the formulae, Q ⊕ represents the following azulenium salt nucleus, and A₃₋₁ is represented by the right portions, i.e. the formulae from which Q ⊕ 's are removed. In the formula, R₃₋₁ to R₃₋₇ have the same meanings as defined above. In the formula, R₃₋₁ to R₃₋₇ have the same meanings as defined above. In the formula, R′₃₋₁ to R′₃₋₇ each represent hydrogen atom, a halogen atom (chlorine, bromine, iodine atom) or a monovalent organic residue. The monovalent organic residue, which can be widely selected, may particularly include alkyl groups (methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-amyl, n-hexyl, n-octyl, 2-ethylhexyl, t-octyl, etc.), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, chlorophenyl, nitrophenyl, dimethylaminophenyl, α-naphthyl, β-naphthyl, etc.), substituted or unsubstituted aralkyl groups (benzyl, 2-phenylethyl, 2-phenyl-1-methylethyl, bromobenzyl, 2-bromophenylethyl, methylbenzyl, methoxybenzyl, nitrobenzyl), acyl groups (acetyl, propionyl, butyryl, valeryl, benzoyl, toluoyl, naphthoyl, phthaloyl, furoyl, etc.), substituted or unsubstituted amino groups (amino, dimethylamino, diethylamino, dipropylamino, acetylamino, benzoylamino, etc.), substituted or unsubstituted styryl groups (styryl, dimethylaminostyryl, diethylaminostyryl, dipropylaminostyrylmethoxystyryl, ethoxystyryl, methylstyryl, etc), nitro, hyroxy, carboxyl, cyano or substituted or unsubstituted arylazo groups (phenylazo, α-naphthylazo, β-naphthylazo, dimethylaminophenylazo, chlorophenylazo, nitrophenylazo, methoxyphenylazo, tolylazo, etc.). Further, a substituted or unsubstituted fused ring may be formed by at least one of the combinations of R′₃₋₁ and R′₃₋₂, R′₃₋₂ and R′₃₋₃, R′₃₋₃ and R′₃₋₄, R′₃₋₄ and R′₃₋₅, R′₃₋₅ and R′₃₋₆, and R′₃₋₆ and R′₃₋₇. The fused ring is a 5-, 6- or 7-membered, including aromatic rings (benzene, naphthalene, chlorobenzene, bromobenzene, methylbenzene, ethylbenzene, methoxybenzene, ethoxybenzene, etc.), hetero rings (furan ring, benzofuran ring, pyrrole ring, thiophene ring, pyridine ring, quinoline ring, thiazole ring, etc.), aliphatic rings (dimethylene, trimethylene, tetramethylene, etc.). Further, the azulenium salt nucleus represented by Q ⊕ and the azulenium salt nucleus of the right portion in the above Formula (3-3) may be symmetric or asymmetric. Z ⊖ has the same meanings as defined above. R₃₋₈ represents hydrogen atom, nitro, cyano, an alkyl group (methyl, ethyl, propyl, butyl, etc.) or an aryl group (phenyl, tolyl, xylyl, etc.). n₃₋₁ represents an integer of 0, 1 or 2. In the formula, R₃₋₁ to R₃₋₇ and Z₃₋₁ ⊖ have the same meanings as defined above. In the formula, R₃₋₁ to R₃₋₇, R′₃₋₁ to R′₃₋₇ and Z₃₋₁ ⊖ have the same meanings as defined above. In the formula X₃₋₁ represents a group of nonmetallic atoms necessary for the completion of a nitrogen-containing hetero ring such as pyridine, thiazole, benzothiazole, naphthothiazole, oxazole,benzoxazole, naphthoxazole, imidazole, benzoimidazole, naphthoimidazole, 2-quinoline, 4-quinoline, isoquinoline or indole ring. Such hetero ring may be substituted by a halogen atom (chlorine, bromine, iodine atom), an alkyl group (methyl, ethyl, propyl, butyl, etc.), an aryl group (phenyl, tolyl, xylyl, etc.) and so on. R₃₋₉ represents an alkyl group (methyl, ethyl, propyl, butyl, etc.), a substituted alkyl group (2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-hydroxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3-chloropropyl, 3-bromopropyl, 3-carboxypropyl, etc.), a cyclic alkyl group (cyclohexyl, cyclopropyl), an allyl group, an aralkyl group (benzyl, 2-phenylethyl, 3-phenylpropyl,4-phenylbutyl, α-naphthylmethyl, β-naphthylmethyl), a substituted aralkyl (methylbenzyl, ethylbenzyl, dimethylbenzyl, trimethylbenzyl, chlorobenzyl, bromobenzyl, etc.), an aryl group (phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl) or a substituted aryl group (chlorophenyl, dichlorophenyl, trichlorophenyl, ethylphenyl, methoxyphenyl, dimethoxyphenyl, aminophenyl, nitrophenyl, hydroxyphenyl, etc.). m₃₋₁ represents an integer of 0 or 1. Z₃₋₁ ⊖ has the same meaning as defined above. In the formula, R₃₋₁₀ represents a substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, biphenyl, α-naphthyl, β-naphthyl, anthralyl, pyrenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, dibromophenyl, tribromophenyl, ethylphenyl, diethylphenyl, nitrophenyl, aminophenyl, dimethylaminophenyl, diethylaminophenyl, dibenzylaminophenyl, dipropylaminophenyl, morpholinophenyl, piperidinylphenyl, piperazinophenyl, diphenylaminophenyl, acetylaminophenyl, benzoylaminophenyl, acetylphenyl, benzoylphenyl, cyanophenyl, etc.). Z₃₋₁ ⊖ has the same meaning as defined above. In the formula, R₃₋₁₁ represents a monovalent heterocyclic group derived from a hetero ring such as furan, thiophene, benzofuran, thionaphthene, dibenzofuran, carbazole, phenothiazine, phenoxazine and pyridine. Z₃₋₁ ⊖ has the same meaning as defined above. In the formula, R₃₋₁₂ represents hydrogen atom, an alkyl group (methyl, ethyl, propyl, butyl, etc.) or a substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, biphenyl, ethylphenyl, chlorophenyl, methoxyphenyl, ethoxyphenyl, nitrophenyl, aminophenyl, dimethylaminophenyl, diethylaminphenyl, acetylaminophenyl, α-naphthyl, β-naphthyl, anthralyl, pyrenyl, etc.). R₃₋₁₀ and Z₃₋₁ ⊖ have the same meanings as defined above. In the formula, R₃₋₁₀ and Z₃₋₁ ⊖ have the same meanings as defined above. In the formula, X₃₋₂ represents a group of atoms necessary for the completion of pyran, thiapyran, selenapyran, benzopyran, benzothiapyran, benzoselenapyran, naphthopyran, naphthothiapyran ornathoselenapyran, each of which may be substituted. ℓ₃₋₁ is an integer of 0 or 1. Y₃₋₁ represents sulfur, oxygen or selenium atom. R₃₋₁₃ and R₃₋₁₄ each represent hydrogen atom, an alkyl group (methyl, ethyl, propyl, butyl, etc.), an alkoxy group (methoxy, ethoxy, propoxy, butoxy, etc.), a substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, chlorophenyl, biphenyl, methoxyphenyl, etc.), a substituted or unsubstituted styryl group (styryl p-methylstyryl, o-chlorostyryl, p-methoxystyryl, etc.), a substituted or unsubstituted 4-phenyl or 3-butadienyl group (4-phenyl-1,3-butadienyl, 4-(p-methylphenyl)-1,3-butadienyl, etc.) or a substituted or unsubstituted heterocyclic group (quinolyl, pyridyl, carbazolyl, furyl, etc.). Z₃₋₁ ⊖ is an anion residue. Further, in the formula, the anion residue Z₃₋₁ ⊖ represents an anion such as chloride, bromide, iodide, perchlorate, benzenesulfonate, p-toluenesulfonate, methylsulfate, ethylsulfate, propylsulfate, tetrafluoroborate, tetraphenylborate, hexafluorophosphate, benzenesulfinate, acetate, trifluoroacetate, propione acetate, benzoate, oxalate, succinate, malonate, oleate, stearate, citrate, monohydrogen diphosphate, dihydrogen monophosphate, pentachlorostannate, chlorosulfonate, fluorosulfonateion, trifluoromethanesulfonate, hexafluoroantimonate, molybdate, tungstate, titanate, zirconate and so on. Typical examples of the pyrylium compound are represented by the following Formula (4-I), (4-II), (4-III) or (4-IV). In the formula, X₄₋₁ and X₄₋₂ each represent sulfur, oxygen, selenium or tellurium atom. Z₄₋₁ represents a hydrocarbon group comprising a group of atoms necessary for the completion of pyrylium, thiopyrylium, selenapyrylium, telluropyrylium, benzopyrylium, benzothiopyrylium, benzoselenapyrylium, benzotelluropyrylium, naphthopyrylium, naphthothiopyrylium, naphthoselenapyrylium or naphthotelluropyrylium, each of which may be substituted. Z₄₋₂ represents a hydrocarbon group comprising a group of atoms necessary for the completion of pyran, thiopyran, selenapyran, telluropyran, benzopyran, benzothiopyran, benzoselenapyran, benzotelluropyran, naphthopyran, naphthothiopyran, naphthoselenapyran or naphthotelluropyran, each of which may be substituted. The substituent may include halogen atoms such as chlorine, bromine and fluorine atoms; alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl, isoamyl, hexyl, octyl, nonyl and dodecyl; alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, amyloxy, hexoxy and octoxy; aryl groups such as phenyl, α-naphthyl and β-naphthyl; substituted aryl groups such as tolyl, xylyl, biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, amyloxyphenyl, dimethoxyphenyl, diethoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl, diethylaminophenyl, dimethylaminophenyl and dibenzylaminophenyl. R₄₋₁, R₄₋₂, R₄₋₃ and R₄₋₄ each represent: (a) hydrogen atom; (b) a substituted or unsubstituted alkyl group, particularly an alkyl group having 1 to 15 carbon atoms: for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl, isoamyl, hexyl, octyl, nonyl, dodecyl; (c) an aryl group: phenyl, α-naphthyl, β-naphthyl; (d) a substituted aryl group: tolyl, xylyl, biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, amyloxyphenyl, dimethoxyphenyl, diethoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl, diethylaminophenyl, dimethylaminophenyl, dibenzylaminophenyl. R₄₋₅, R₄₋₆ and R₄₋₇ each represent hydrogen atom, a halogen atom (chlorine, bromine, fluorine atom), a substituted or unsubstituted alkyl group (methyl, ethyl, propyl, butyl, amyl, hydroxyethyl, methoxyethyl, carboxypropyl), a substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, hydroxyphenyl, carboxyphenyl, α-naphthyl, β-naphthyl) or a substituted or unsubstituted aralkyl group (benzyl, phenethyl, 3-phenylpropyl, methoxybenzyl, methylbenzyl). A₄₋₁ ⊖ represents an anion such as perchlorate, fluoroborate, iodide, chloride, bromide, sulfate, periodide and p-toluenesulfonate ions. m₄₋₁ and ℓ₄₋₁ represent 1 or 2. n₄₋₁ represents 0, 1, 2 or 3. However, when n₄₋₁ is 2 or 3, R₄₋₅ may be the same or different, and R₄₋₆ may be also the same or different. Z₄₋₃ represents a group of nonmetallic atoms necessary for the completion of substituted or unsubstituted nitrogen-containing hetero ring including, for example, thiazole type nucleus (e.g. thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)-thiazole, etc.), benzothiazole type nucleus (e.g. benzothiazole, 5-chlorobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5,6-dimethyl-benzothiazole, 5-bromobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5,6-dimethoxy-benzothiazole, 5,6-dioxymethylenebenzothiazole, 5-hydroxybenzo-thiazole, 6-hydroxybenzothiazole, 4,5,6,7-tetrahydrobenzothia-zole, etc.), naphthothiazole type nucleus (e.g. naphtho-[2,1-d]thiazole, naphtho[1,2-d]thiazole, 5-methoxynaphtho-[1,2-d]thiazole, 5-ethoxynaphtho[1,2-d]-thiazole, 8-methoxy-naphtho[2,1-d]thiazole, 7-methoxynaphtho[2,1-d]thiazole, etc.), thionaphthene-[7,6-d]thiazole type nucleus (e.g. 7-methoxy-thionaphthene[7,6-d]thiazole), an oxazole type nucleus (e.g. 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole, 5-phenyloxazole), benzoxazole type nucleus (e.g. benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methyl-benzoxazole, 5,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 6-methoxybenzoxazole, 5-hyroxybenzoxazole, 6-hydroxybenzoxa-zole, etc.), naphthoxazole type nucleus (e.g. naphtho-[2,1-d]oxazole, naphtho[1,2-d]oxazole, etc.), selenazole type nucleus (e.g. 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazole type nucleus (e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-methylbenzoselenazole, 5,6-dimethyl-benzoselenazole, 5-methoxybenzoselenazole, 5-methyl-6-methoxybenzoselenazole, 5,6-dioxymethylenebenzoselenazole, 5-hydroxybenzoselenazole, 4,5,6,7-tetrahydrobenzoselenazole, etc.), naphthoselenazole type nucleus (e.g. naphtho[2,1-d]-selenazole, naphtho[1,2-d]selenazole), thiazoline type nucleus (e.g. thiazoline, 4-methylthiazoline, 4-hydroxymethyl-4-methyl-thiazoline, 4,4-bis-hydroxymethylthiazoline, etc.), oxazoline type nucleus (e.g. oxazoline), selenazoline type nucleus (e.g. selenazoline), 2-quinoline type nucleus (e.g. quinoline, 6-methylquinoline, 6-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline), 4-quinoline type nucleus (e.g. quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline), 1-isoquinoline type nucleus (e.g. isoquinoline, 3,4-dihydroisoquinoline), 3-isoquinoline type nucleus (e.g. isoquinoline), 3,3-dialkylindolenine type nucleus (e.g. 3,3-dimethylindolenine, 3,3-dimethyl-5-chloroindolenine, 3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine), pyridine type nucleus (e.g. pyridine, 5-methyl-pyridine), benzimidazole type nucleus (e.g. 1-ethyl-5,6-dichlorobenzimidazole, 1-hydroxyethyl, 5,6-dichlorobenzimidazole, 1-ethyl-5-dichlorobenzimidazole, 1-ethyl-5,6-dibromobenzimidazole, 1-ethyl-5-phenylbenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-ethyl-5-dianobenzimidazole, 1-(β-acetoxyethyl)-5-diano-benzimidazole, 1-ethyl-5-chloro-6-cyanobenzimidazole, 1-ethyl-5-fluoro-6-cyanobenzimidazole, 1-ethyl-5-acetylbenzimidazole, 1-ethyl-5-carboxybenzimidazole, 1-ethyl-5-ethoxycarbonylbenzimidazole, 1-ethyl-5-sulfamylbenzimidazole, 1-ethyl-5-N-ethylsulfamylbenzimidazole, 1-ethyl-5,6-difluorobenzimidazole, 1-ethyl-5,6-dicyanobenzimidazole, 1-ethyl-5-ethylsulfonylbenzimidazole, 1-ethyl-5-methylsulfonylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylsulfonylbenzimidazole, 1-ethyl-5-trifluoromethylsulfinylbenzimidazole, etc.). Z₄₋₂ represents a group of atoms necessary for the completion of pyran, thiopyran, selenapyran, telluropyran, benzopyran, benzothiopyran, benzoselenapyran, benzotelluropyran, naphthopyran, naphthothiopyran, naphthoselenapyran or naphthotelluropyran, each of which may be substituted. X₄₋₁ represents sulfur, oxygen, selenium or tellurium atom. As the substituent, there may specifically be mentioned those shown for R₄₋₂ and R₄₋₂ described below except for hydrogen atom. Z₄₋₄ represents a divalent hydrocarbon capable of forming a substituted or unsubstituted 5- or 6-membered ring (-CH₂-CH₂-, -CH₂-CH₂-CH₂-, The 5-membered or 6-membered ring may be fused with benzene ring or naphthalene ring. R₄₋₁ represents hydrogen atom or an alkyl group (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-amyl, t-amyl, n-hexyl, n-octyl, t-octyl, etc.), and further includes other alkyls such as substituted alkyls (e.g. 2-hydroxyethyl, 3-hydroxypropyl, 2-acetoxyethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-sulfobutyl, 3-sulfate propyl, 4-sulfate butyl, N-(methylsulfonyl)-carbamylmethyl, 3-(acetylsulfamyl)propyl, 4-(acetylsul-famyl)butyl, etc.), cyclic alkyls (e.g. cyclohexyl, etc.), an allyl (CH₂=CH-CH₂-), aralkyls (e.g. benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, etc.), substituted aralkyls (e.g. carboxybenzyl, sulfobenzyl, hydroxybenzyl, etc.). R₄₋₂ and R₄₋₃ each form: (a) hydrogen atom; (b) a halogen atom: chlorine, bromine, iodine atom or a monovalent organic residue, for example, (c) an alkyl group, particularly an alkyl group having 1 to 15 carbon atoms: for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl, isoamyl, hexyl, octyl, nonyl, dodecyl (d) an alkoxy group: for example, methoxy, ethoxy, propoxy, butoxy, amyloxy, hexoxy, octoxy; (e) an aryl group: phenyl, α-naphthyl, β-naphthyl (f) a substituted aryl group: tolyl, xylyl, biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, amyloxyphenyl, dimethoxyphenyl diethoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl, diethylaminophenyl, dimethylaminophenyl, dibenzylaminophenyl; (g) styryl; (h) a substituted styryl group: methoxystyryl, dimethoxystyryl, ethoxystyryl, diethoxystyryl, dimethylaminostyryl, diethylaminostyryl; (i) a substituted or unsubstituted heterocyclic group: for example, 3-carbazolyl, 9-methyl-3-carbazolyl, 9-ethyl-3-carbazolyl, 9-carbazolyl rings R₄₋₄ represents hydrogen atom or a halogen atom (e.g. chlorine, bromine, iodine atom). A₄₋₁ ⊖ represents an anion such as chloride, bromide, iodide, perchlorate, benzenesulfonate, p-toluenesulfonate, methylsulfate, ethylsulfate, propylsulfate, etc. No A₄₋₁ ⊖ exists when R₄₋₁ contains an anion such as -SO₃ ⊖ , OSO₃ ⊖ , -COO ⊖ , SO₂ ⊖ NHS-, -SO₂-N ⊖ -CO- or -SO₂-N ⊖ -SO₂-. m₄₋₁ and n₄₋₁ represent 0 or 1, and ℓ₄₋₁ represents 0, 1 or 2. The compound represented by the above Formula (4-II) may form a resonance product together with the compound represented by the following Formula (4-1), and such resonance product is included in this invention. (wherein Z₄₋₁, Z₄₋₃, Z₄₋₄, R₄₋₁ to R₄₋₄, X₄₋₁ A₄₋₁ ⊖ , ℓ₄₋₁, m₄₋₁ and n₄₋₁ have the same meanings as defined above. However, Z₄₋₁ represents a pyrylium salt type compound such as pyrylium, thiopyrylium, selenapyrylium, telluropyrylium, benzopyrylium, benzothiopyrylium, benzoselenapyrylium, benzotelluropyrylium, naphthopyrylium, naphthothiopyrrylium, naphthoselenapyrylium or naphthotelluropyrylium.) In the formula A₄₋₁ ⊖ represents or X₄₋₁ and X₄₋₂ each represent sulfur atom, oxygen atom, selenium atom or tellurium atom. Z₄₋₁ represents a group of atoms necessary for the completion of pyrylium, thiopyrylium, selenapyrylium, telluropyrylium, benzopyrilium, benzothiopyrylium, benzoselenapyrylium, benzotelluropyrylium, naphthopyrylium, naphthothiopyrylium, naphthoselenapyrylium or naphthotelluropyrylium. Z₄₋₂ represents a group of atoms necessary for the completion of pyran, thiopyran, selenapyran, telluropyran, benzopyran, benzothiopyran, benzoselenapyran, benzotelluropyran, naphthopyran, naphthothiopyran, naphthosele-napyran or naphthotelluropyran. These rings may be substituted by an alkyl group (methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-acyl, t-acyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, etc.), an alkoxy group (methoxy, ethoxy, propoxy, butoxy, etc.), a substituted or unsubstituted aryl group (phenyl,tolyl, xylyl, biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, diethoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl, diethylaminophenyl, dimethylaminophenyl, dibenzylaminophenyl, etc.), a styryl group such as styryl, 4-phenyl-1,3-butadienyl, methoxystyryl, dimethoxystyryl, ethoxystyryl, diethoxystyryl, dimethylaminostyryl, 4-(p-dimethylaminophenyl)-1,3-butadienyl, 4-(p-diethylaminophenyl)-1,3-butadienyl, or 4-phenyl-1,3-butadienyl or substituted product thereof, or a heterocyclic group such as 3-carbazolyl, 9-methyl-3-carbazolyl, 9-ethyl-3-carbazolyl, 9-carbazolyl and the like. R₄₋₁, R₄₋₂, R₄₋₃, and R₄₋₄ represent: (a) hydrogen atom; (b) an alkyl group, particularly an alkyl group having 1 to 15 carbon atoms: for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl, isoamyl, hexyl, octyl, nonyl and dodecyl; (c) an alkoxy group, for example, methoxy, ethoxy, propoxy, butoxy, amyloxy, hexoxy and octoxy; (d) an aryl: phenyl, α-naphthyl and β-naphthyl; (e) a substituted aryl group: tolyl, xylyl, biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, amyloxyphenyl, dimethoxyphenyl, diethoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl, diethylaminophenyl, dimethylaminophenyl, and benzylaminophenyl; (f) a styryl or 4-phenyl-1,3-butadienyl group: styryl and 4-phenyl-1,3-butadienyl; (g) a substituted styryl or 4-phenyl-1,3-butadienyl: methoxystyryl, dimethoxystyryl, ethoxystyryl, diethoxystyryl, dimethylaminostyryl, diethylaminostyryl, 4-(p-dimethyl-aminophenyl)-1,3-butadienyl and 4-(p-diethylaminophenyl)-1,3-butadienyl; (h) R₄₋₁ and R₄₋₂, and R₄₋₃ and R₄₋₄ may be bonded to form a benzene ring. (i) a substituted or unsubstituted heterocyclic group: for example, 3-carbazolyl, 9-methyl-3-carbazolyl, 9-ethyl-3-carbazolyl and 9-carbazolyl. In the formula, X₄₋₁ represents sulfur, oxygen, selenium or tellurium atom. Z₄₋₁ represents a hydrocarbon group comprising a group of atoms necessary for the completion of pyrylium, thiopyrylium, selenapyrylium, telluropyrylium, benzopyrylium, benzothiopyrylium, benzoselenapyrylium, benzotelluropyrylium, naphthopyrylium, naphthothiopyrylium, naphthoselenapyrylium or naphthotelluropyrylium, each of which may be substituted. The substituent may include a halogen atom such as chlorine, bromine and fluorine atom, an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl, isoamyl, hexyl, octyl, nonyl and dodecyl; an aryl group such as phenyl, α-naphthyl and β-naphthyl, a substituted aryl such as tolyl, xylyl, biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, amyloxyphenyl, dimethoxyphenyl, diethoxydiphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl,diethylaminophenyl, dimethylaminophenyl and dibenzylaminophenyl, a substituted or unsubstituted styryl group such as styryl, chlorostyryl, dimethylaminostyryl, diethylaminostyryl, dipropylaminostyryl, dibutylaminostyryl, dibenzylamino-styryl, diphenylaminostyryl, methoxystyryl and ethoxystyryl. R₄₋₁ and R₄₋₂ each represent: (a) hydrogen atom; (b) a substituted or unsubstituted alkyl group, particularly an alkyl having 1 to 15 carbon atoms: for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl, isoamyl, hexyl, octyl, nonyl and dodecyl; (c) an aryl group: phenyl, α-naphthyl and β-naphthyl; (d) a substituted aryl group: tolyl, xylyl, biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, amyloxyphenyl, dimethoxyphenyl, diethoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl, diethylaminophenyl, dimethylaminophenyl and benzylaminophenyl (e) a styryl group: styryl; (f) a substituted styryl group: chlorostyryl, dichlorostyryl, methylstyryl, dimethylstyryl, methoxystyryl, ethoxystyryl, dimethylaminostyryl, diethylaminostyryl, dipropylaminostyryl, dibutylaminostyryl, dibenzylaminostyryl and phenylaminostyryl; R₄₋₃ represents a substituted or unsubstituted aryl group (phenyl, -naphthyl, β-naphthyl, tolyl, xylyl, biphenyl, ethylphenyl, diethylphenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, amyloxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, dibromophenyl, tribromophenyl, dibromophenyl, tribromophenyl, nitrophenyl, dimethylaminophenyl, diethylaminophenyl, dibenzylaminophenyl, diphenylaminophenyl) or a substituted or unsubstituted heterocyclic group (3-carbazolyl, 9-methyl-3-carbazolyl, 9-ethyl-3-carbazolyl, 7-nitro-9-ethyl-3-carbazolyl, 2-pyridyl, 4-pyridyl-4-pyridyl, 2-quinolyl, 4-quinolyl-3-indolyl, 2-phenyl-3-indolyl, 1-methyl-2-phenyl-3-indolyl). R₄₋₄ and R₄₋₅ each represent hydrogen atom or an alkyl group (methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, nonyl). m₄₋₁ represents 1 or 2, and n₄₋₁ represents 0, 1, 2 or 3. However, when n₄₋₁ is 2 or 3, R₄₋₄ may be the same or different, and further, R₄₋₅ may be the same or different. A₄₋₁ ⊖ represents an anion such as perchlorate, fluoroborate, iodide, chloride, bromide, sulfate, periodide and p-toluenesulfonate. The coloring matter as described above has generally an absorption peak with great coefficient of absorption at around 800 nm, and also good solubility in an organic solvent as well as light resistance, thus being excellent as an optical information recording medium. Besides, while having sufficient reflectance, it tends to be crystallized with lapse of time. The present invention provides a medium with enhanced reflectance and also excellent storage stability by incorporating a metal chelate compound in such coloring matter. Although the behaviour of these metal chelate compounds in the recording layer has not been clarified, it may be considered that they affect the stacking mutual action between the coloring matters to change the packing state and increase the refractive index in the recording layer, whereby the reflectance in the thin film state is improved. Also, it seems likely that such associated state of the coloring matter and the chelate compound inhibits crystallization to increase the storage stability. The chelate compound to be used in the present invention should preferably have a center metal selected from transition metals such as Zn, Cu, Ni, Co, Mn, Pd, Zr, etc. Specific examples of the chelate compounds which can be used as the stabilizer as described above are mentioned below: (1) thiosalicylaldoxime type compound represented by the following formula: wherein each R₁₅ represents hydrogen atom, hydroxyl, alkyl or aryl, and may be also bonded to another R₁₅; each R₁₆ represents alkyl, halogen atom, hydrogen atom, nitro or benzo-fused type group; and the center metal M represents Cu, Ni, Co or Pd. Compound No. R₁₅ R₁₆ M M-1-1 OH H Cu M-1-2 OH H Ni M-1-3 H 4-C₂H₅ Ni M-1-4 C₂H₅ 5-Cℓ Ni M-1-5 i-C₃H₇ H Co M-1-6 n-C₆H₁₃ 4-CH₃ Ni M-1-7 n-C₆H₁₃ 4-CH₃ Pd M-1-8 C₆H₅ H Ni M-1-9 H 5,6-C₆H₄ Ni M-1-10 -CH₂- 4-NO₂ Ni (2) oxyxanthione type compound: wherein each R₂₃ represents hydrogen atom, halogen atom or alkyl; and M represents Cu or Ni. Compound No. R₂₃ M M-5-1 H Cu M-5-2 H Ni M-5-3 4-CH₃ Ni (3) pyromeconic acid type compound: wherein R₂₄ represents hydrogen atom or alkyl; and M represents Cu, Ni, Co or Mn. Compound No. R₂₄ M M-6-1 H Mn M-6-2 H Ni M-6-3 2-C₂H₅ Ni (4) mercaptobenzothiazole type compound: wherein each R₂₇ represent sulfur atom, substituted or unsubstituted amino group, oxygen atom or thioketone group; each R₂₈ represents hydrogen atom, alkyl, halogen atom or amino group; and M represents Zn, Cu or Ni. Compound No. R₂₇ R₂₈ M M-8-1 O H Zn M-8-2 O 5-CH₃ Zn M-8-3 S H Ni M-8-4 S 5-Cℓ Ni M-8-5 S 5-CH₃ Ni M-8-6 S 4-CH₃ Ni M-8-7 S 5-(CH₃)₂N Ni M-8-8 NH H Ni M-8-9 NH 5-CH₃ Ni M-8-10 NCH₃ H Ni M-8-11 NH 6-C₂H₅ Ni M-8-12 C=S H Ni (5) hydroxamic acid type compound: wherein each R₂₉ represents alkyl, aryl or styryl; and M represents Cu, Ni or Co. No. R₂₉ M M-9-1 C₃H₇ Cu M-9-2 C₆H₅ Ni M-9-3 C₆H₅CH=CH- Ni M-9-4 Cℓ-C₆H₄CH=CH- Ni (6) nitrosohydroxylamine type compound; wherein each R₃₁ represents alkyl or aryl; and M represents Cu, Ni or Co. No. R₃₁ M M-11-1 C₃H₇ Cu M-11-2 C₃H₇ Ni M-11-3 p-(CH₃)₂N-C₆H₄- Cu M-11-4 p-(CH₃)₂N-C₆H₄- Ni (7) dioxime type compound: wherein R₃₂ and R₃₃ each represent alkyl or aryl; and M represents Ni. No. R₃₂ R₃₃ M M-12-1 CH₃ CH₃ Ni M-12-2 C₂H₅ C₂H₅ Ni M-12-3 C₆H₅ C₆H₅ Ni (8) anthranylic acid type compound: wherein each R₄₁ represents hydrogen atom, halogen atom, alkyl, acyl, nitro or alkoxy; and M represents Zn, Cu, Ni or Co. No. R₄₁ M M-17-1 H Cu M-17-2 4-Cℓ Ni M-17-3 4-NO₂ Ni M-17-4 5-CH₃ Ni By combining such metal chelate compound with a coloring matter, reflectance can be enhanced, storage stability can be improved and also a high C/N value can be obtained. Such chelate compound should be preferably contained in an amount of about 1 to 60 wt.% based on the total weight of the recording material for forming the recording layer, preferably 5 to 60 wt.%, more preferably 5 to 40 wt.%. Mentioned below are the typical examples of polymethine compounds represented by the foregoing general formula (1 - I). These polymethine compounds can be obtained easily by synthesis according to the synthetic methods as disclosed in Bernard S. Wildi et al., Journal of American Chemical Society, 80 , 3772 - 3777 (1958); H. Schmidt et al. Ann. (Liebig Annalen der Chemie) 623 , 204 - 216; or R. Wlzinger et al., Helvetica Chimica Acta, 24 , 369. Mentioned below are the concrete examples of coloring matters represented by the foregoing general formulae (3 - 1) - (3 - 11). The examples of compounds represented by the foregoing general formula (3 - 1). The examples of compounds represented by the foregoing general formula (3 - 2). The examples of compounds represented by the foregoing general formula (3 - 3). The examples of compounds represented by the foregoing general formula (3 - 4). The examples of compounds represented by the foregoing general formula (3 - 5). The examples of compounds represented by the foregoing general formula (3 - 6). The examples of compounds represented by the foregoing formula (3 - 7). The examples of compounds represented by the foregoing general formula (3 - 8). The examples of compounds represented by the foregoing general formula (3 - 9). The examples of compounds represented by the foregoing general formula (3 - 10). The examples of compounds represented by the foregoing general formula (3 - 11). The compounds represented by the formulae (3-1) and (3-2) can be easily obtained by allowing an azulene compound to react with a squaric acid or croconic acid in an appropriate solvent as described in Angewandte Chemie Vol. 78, No. 20, P.937 (1966). As for the compounds represented by the formula (3-3), the compound with n=0 can be obtained by heating a 1-formyl-azulene compound with an azulene compound as described in Journal of the Chemical Society, p.501, 1960 in an appropriate solvent in the presence of a strong acid, or by mixing an 1-ethoxymethylene-azulenium salt compound and an azulene compound in an appropriate solvent as described in Journal of the Chemical Society, P1724 - P.1730, 1961, or by heating a 2-hydroxymethylenecyclohexanone and an azulene compound in an appropriate solvent in the presence of a strong acid as described in Journal of the Chemical Society, P.359, 1961. In the formula (3-3), the compound with n₃₋₁=1 or n₃₋₁=2 can be obtained by mixing an azulene compound and a malondialdehyde or a glutacondialdehyde in an appropriate solvent in the presence of a strong acid as described in Journal of the Chemical Society, P.3591 - P.3592, 1961. The compound represented by the formula (3-4) can be obtained easily by heating an azulene compound and glyoxal in an appropriate solvent in the presence of a strong acid as described in Journal of the Chemical Society, P. 3588, 1961. The compound represented by the formula (3-5) can be obtained by heating a 1,3-diformylazulene compound and an azulene compound in an appropriate solvent in the presence of a strong acid as described in Journal of the Chemical Society, P. 501, 1960. The compounds represented by the formula (3-6) can be obtained by heating a 1-formylazulene compound and a heterocyclic quaternary ammonium salt compound having an active methyl group in an appropriate solvent as described in Journal of the Chemical Society, P. 163 - P. 167, 1961. The compounds represented by the formulae (3-7), (3-8), (3-9) and (3-10) can be obtained by mixing an azulene compound and a corresponding aldehyde compound in an appropriate solvent in the presence of a strong acid, as described in Journal of the Chemical Society, P.1100 - P.1117, 1958; Journal of the Chemical Society, P.494-P.501, 1960; and Journal of the Chemical Society, P.3579 - P.3593, 1961. The compound represented by the formula (3-11) can be obtained by allowing a 1-formyl-azulene compound to react with a compound represented by the formula (3-12) in a solvent. wherein X₃₋₂, Y₃₋₁, R₃₋₁₃, R₃₋₁₄ Z₃₋₁ ⊖ and ℓ₃₋₁ have the same meanings as defined above. Mentioned below are the examples of compounds represented by the foregoing general formula (4 - I) The examples of compounds represented by the foregoing general formula (4 - II) The examples of compounds represented by the foregoing general formula (4 - III) The examples of compounds represented by the foregoing general formula (4 - IV) Also, for formation of a recording layer, in addition to the coloring matter and the chelate compound, a binder may be mixed therein. Suitable binder may be selected from a wide scope of resins. Specific examples may include cellulose esters such as nitrocellulose, cellulose phosphate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose myristate, cellulose palmitate, cellulose acetate propionate, cellulose acetate butyrate, etc.; cellulose ethers such as methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, etc.; vinyl resins such as polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyvinyl pyrrolidone, etc.; copolymer resins such as styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, etc.; acrylic resins such as polymethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyacrylonitrile, etc.; polyesters such as polyethylene terephthalate, polyarylate resins such as poly(4,4′-isopropylidene, diphenylene-co-1,4-cyclohexylene-dimethylenecarbonate), poly(ethylenedioxy-3,3′-phenylenethiocarbonate), poly(4,4′-isopropylidenediphenylenecarbonate-coterephthalate), poly(4,4′-isopropylidenediphenylenecarbonate), poly(4,4′-secbutylidenediphenylenecarbonate), poly(4,4′-isopropylidenediphenylenecarbonate-block-oxyethylene), etc.; or polyamides; polyimides; epoxy resins; phenol resins; polyolefins such as polyethylene, polypropylene, chlorinated polyethylene, etc. The organic solvent which can be used during coating may depend on whether the coating is made under dispersed state or amorphous state, but there can be generally employed alcohols such as methanol, ethanol, isopropanol and the like; ketones such as acetone, methyl ethyl ketone, cyclohexanone and the like; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and the like; sulfoxides such as dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether; esters such as methyl acetate, ethyl acetate, butyl acetate and the like; aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, trichloroethylene, etc.; or aromatics such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, anisole, and so on. Coating can be practiced by use of dip coating, spray coating, spinner coating, bead coating, Meyer bar coating, blade coating, roller coating, curtain coating and other methods. As the substrate, glass, polyamide, polyester, polyolefin, polycarbonate, epoxy, polyimide, polymethyl methacrylate, etc. may be used. The substrate has usually grooves for tracking thereon, and may further have a subbing layer for improvement of adhesion to the recording layer or improvement of solvent resistance thereon. According to the present invention, it is possible to obtain an optical information recording medium with enhanced reflectance, application of stable tracking, which can obtain a high C/N ratio and good storage stability. The invention will now be further described in the following Examples and Comparative Examples in which the following are examples of the invention: 1-3 1-4 1-9 1-10 2-1 2-6 2-8 2-11 3-4 3-5 3-11 4-1 and the following are reference examples: 1-1 1-2 1-5 1-6 1-7 1-8 1-11 1-12 2-2 2-3 2-4 2-5 2-7 2-9 2-10 2-11 3-1 3-2 3-3 3-6 3-7 3-8 3-9 3-10 4-2 4-3 4-4 4-5 4-6 4-7 4-8 4-9 4-10 Examples 1-1 to 1-12 On an acrylic disc substrate with a diameter of 130 mm and an inner diameter of 15 mm, a subbing layer (100 - 200 Å) comprising SiO₂ was formed, and then a material comprising a combination of a coloring matter and a metal chelate compound as shown in Table 1-1 (infra) was formed into a recording layer with a film thickness of 800 to 1000 Å by use of a predetermined solvent. From the substrate side of the recording medium thus obtained, writing and reading were performed by use of a semiconductor laser beam of 830 nm at a recording frequency of 2MHz, a rotational number of 1800 rpm, a recording power of 8 mW and a reading power of 0.6 mW, and the reading waveform was analyzed by spectrum analysis to measure a C/N value. Next, the same recording medium was left to stand under the conditions of 60 °C and 90% RH for 1000 hours to perform the storage acceleration test, and the reflectance and C/N value were measured. The results are shown in Table 1-2(infra). Examples 2-1 to 2-11 On an acrylic disc substrate with a diameter of 130 mm and an inner diameter of 15 mm, a subbing layer (10 nm) comprising SiO₂ was formed, and then a material comprising a combination of a coloring matter and a metal chelate compound as shown in Table 2-1(infra) was formed into a recording layer with a film thickness of 80 to 100 nm by use of a predetermined solvent. From the substrate side of the recording medium thus obtained, writing and reading were performed by use of a semiconductor laser beam of 830 nm at a recording frequency of 2MHz, a rotational number of 1800 rpm, a recording power of 8 mW and a reading power of 0.6 mW, and the reading waveform was analyzed by spectrum analysis to measure a C/N value. Next, the same recording medium was left to stand under the conditions of 60 °C and 90% RH for 1000 hours to perform the storage acceleration test, and the reflectance and C/N value were measured. The results are shown in Table 2-2(infra). Comparative Example 2-1 to 2-3 By use of the same coloring matters as Examples 2-2, 2-4 and 2-10, and without use of any metal chelate compound, recording layers were formed according to the same methd as in Example 2-1, and the tests were conducted similarly as in Example 2-1. The results obtained are also shown in Table 2-1 and Table 2-2(infra). Examples 3-1 to 3-11 On an acrylic disc substrate with a diameter of 130 mm and an inner diameter of 15 mm, a material comprising a combination of a coloring matter and a metal chelate compound as shown in Table 3-1(infra) was formed into a recording layer with a film thickness of 800 to 1000 nm by use of a predetermined solvent. From the substrate side of the recording medium thus obtained, writing and reading were performed by use of a semiconductor laser beam of 830 nm at a recording frequency of 2MHz, a rotational number of 1800 rpm, a recording power of 7 mW and a reading power of 0.7 mW, and the reading waveform was analyzed by spectrum analysis to measure a C/N value. Next, the same recording medium was left to stand under the conditions of 60 °C and 90% RH for 1000 hours to perform the storage acceleration test, and the reflectance and C/N value were measured. The results are shown in Table 3-2(infra). Comparative examples 3-1 to 3-3 By use of the same coloring matters as Examples 3-1, 3-3 and 3-9, and without use of any metal chelate compound, recording layers were formed according to the same method as in Example 3-1, and the tests were conducted similarly as in Example 3-1. The results obtained are also shown in Table 3-1 and Table 3-2(infra). Examples 4-1 to 4-10 On an acrylic disc substrate with a diameter of 130 mm and an inner diameter of 15 mm, a material comprising a combination of a pyrylium compound and a metal chelate compound as shown in Table 4-1 (infra) was formed into a recording layer with a film thickness of 800 to 1000 nm by use of a predetermined solvent. From the substrate side of the recording medium thus obtained, writing and reading were performed by use of a semiconductor laser beam of 830 nm at a recording frequency of 2MHz, a rotational number of 1800 rpm, a recording power of 8 mW and a reading power of 0.6 mW, and the reading waveform was analyzed by spectrum analysis to measure a C/N value. Next, the same recording medium was left to stand under the conditions of 60 °C and 90% RH for 1000 hours to perform the storage acceleration test, and the reflectance and C/N value were measured. The results are shown in Table 4-2(infra). Comparative Examples 4-1 to 4-3 By use of the same pyrylium compound as Examples 4-3, 4-6 and 4-8, and without use of any metal chelate compound, recording layers were formed according to the same method as in Example 4-1, and the tests were conducted similarly as in Example 4-1. The results obtained are also shown in Table 4-1 and Table 4-2(infra).

Claims: An optical information recording medium, comprising in the recording medium firstly at least one compound selected from the compounds of the general formulae (1-I) to (3-III) shown below and pyrylium compounds, and secondly at least one metal chelate compound, characterised in that the metal chelate compound is selected from compounds of general formulae (1) to (8) shown below wherein R₁₋₁, R₁₋₂, R₁₋₃, R₁₋₄ and R₁₋₅ each mean hydrogen, alkyl, substituted alkyl, cyclic alkyl, alkenyl, aralkyl, substituted aralkyl, aryl, cyclic alkyl, alkenyl, aralkyl, substituted aralkyl, aryl, substituted aryl, styryl, substituted styryl, heterocyclic ring or substituted heterocyclic ring; m₁₋₁ means 0 or 1, n₁₋₁ 0, 1 or 2; and X₁₋₁ ⊖ an anion, wherein A₂₋₁, B₂₋₁, D₂₋₁ and E₂₋₁ each represent hydrogen atom, alkyl, alkenyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl; Y₂₋₁ represents a divalent residue having a group of atoms necessary for the completion of a 5- or or 6-membered ring; R₂₋₁, R₂₋₂, R₂₋₃, R₂₋₄ and R₂₋₅ each represent hydrogen atom, halogen atom or alkyl; represents an anion; m₂₋₁ and n₂₋₁ each represent 0, 1 or 2, wherein A₂₋₁, B₂₋₁, D₂₋₁ and E₂₋₁ each represent hydrogen atom, alkyl, alkenyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl; Y₂₋₁ represents a divalent residue having a group of atoms necessary for the completion of a 5- or 6-membered ring; R₂₋₁, R₂₋₂ and R₂₋₃ each represent hydrogen atom, halogen atom or alkyl; represents an anion, wherein Z₂₋₁ ⊖ represents or A₂₋₁, B₂₋₁, D₂₋₁ and E₂₋₁ each represent hydrogen atom, alkyl, alkenyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl; R₂₋₁, R₂₋₂, R₂₋₃ and R₂₋₄ each represent hydrogen atom, halogen atom or alkyl; m₂₋₁ and n₂₋₁ each represent 0, 1 or 2, (in the general formulae [3-I], [3-II] and [3-III], R₃₋₁, R₃₋₂, R₃₋₃, R₃₋₄, R₃₋₅, R₃₋₆ and R₃₋₇ each represent hydrogen atom, halogen atom or monovalent organic residue; or a substituted or unsubstituted fused ring may be formed by at least one combination of R₃₋₁ and R₃₋₂, R₃₋₂ and R₃₋₃, R₃₋₃ and R₃₋₄, R₃₋₄ and R₃₋₅, R₃₋₅ and R₃₋₆, R₃₋₆ and R₃₋₇; A₃₋₁ represents divalent organic residue; and Z₃₋₁ ⊖ represents anion residue). (1) thiosalicylaldoxime type compound represented by the following formula: wherein each R₁₅ represents hydrogen atom, hydroxyl, alkyl or aryl, and may be also bonded to another R₁₅; each R₁₆ represents alkyl, halogen atom, hydrogen atom, nitro or benzo-fused type group; and the center metal M represents Cu, Ni, Co or Pd, (2) oxyxanthione type compound: wherein each R₂₃ represents hydrogen atom, halogen atom or alkyl; and M represents Cu or Ni, (3) pyromeconic acid type compound: wherein R₂₄ represents hydrogen atom or alkyl; and M represents Cu, Ni, Co or Mn, (4) mercaptobenzoazole type compound: wherein each R₂₇ represent sulfur atom, substituted or unsubstituted amino group, oxygen atom or thioketone group; each R₂₈ represents hydrogen atom, alkyl, halogen atom or amino group; and M represents Zn, Cu or Ni, (5) hydroxamic acid type compound: wherein each R₂₉ represents alkyl, aryl or styryl; and M represents Cu, Ni or Co, (6) nitrosohydroxylamine type compound: wherein each R₃₁ represents alkyl or aryl; and M represents Cu, Ni or Co, (7) dioxime type compound: wherein R₃₂ and R₃₃ each represent alkyl or aryl; and M represents Ni, (8) anthranylic acid type compound: wherein each R₄₁ represents hydrogen atom, halogen atom, alkyl, acyl, nitro or alkoxyℓ; and M represents Zn, Cu, Ni or Co. An optical information recording medium according to Claim 1, wherein the pyrylium compound is at least one selected from the compounds of the general formulae (4-I) to (4-IV) shown below: wherein X₄₋₁ and X₄₋₂ each represent sulfur, oxygen, selenium or tellurium atom; Z₄₋₁ represents a hydrocarbon group comprising a group of atoms necessary for the completion of pyrylium, thiopyrylium, selenapyrylium, tellulopyrylium, benzopyrylium, benzothiopyrylium, benzoselenapyrylium, benzotellulopyrylium, naphthopyrylium, naphthothiopyrylium, naphthoselenapyrylium or naphthotellulopyrylium which may be substituted; Z₄₋₂ represents a hydrocarbon group comprising a group of atoms necessary for the completion of pyran, thiopyran, selenapyran, tellulopyran, benzopyran, benzothiopyran, benzoselenapyran, benzotellulopyran, naphthopyran, naphthothiopyran, naphthoselenapyran or naphthotellulopyran which may be substuteed; R₄₋₁, R₄₋₂, R₄₋₃ and R₄₋₄ each represent hydrogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted aryl; R₄₋₅, R₄₋₆ and R₄₋₇ each represent hydrogen atom, halogen atom, substituted or unsubstituted alkyl, substitued or unsubstituted aryl or substituted or unsubstituted aralkyl; m₄₋₁ and ℓ₄₋₁ each represent 1 or 2; n₄₋₁represents 0, 1, 2 or 3, with proviso that when n₄₋₁ is 2 or 3, R₄₋₅ may be all the same or different; and R₄₋₆ may be all the same or different; A₄₋₁ ⊖ represents an anion. wherein Z₄₋₃ represents a group of atoms necessary for the completion of substituted of unsubstituted nitrogen containing heterocyclic group; Z₄₋₂ represents a group of atoms necessary for the completion of pyran, thiopyran, selenapyran, tellulopyran, benzopyran, benzothiopyran, benzoselenapyran, benzotellulopyran, naphthopyran, naphtothiopyran, naphthoselenapyran or naphthotellulopyran which may be substituted; X₄₋₁ represents sulfur, oxygen, selenium or tellurium atom; Z₄₋₄ represents divalent hydrocarbon group for forming substituted or unsubstituted 5- or 6-membered ring; R₄₋₁ represents hydrogen atom or substituted or unsubstituted alkyl; R₄₋₂ and R₄₋₃ each represent hydrogen atom, halogen atom or monovalent organic residue; R₄₋₄ represents hydrogen atom or halogen atom; A ⊖ represents an anion; m₄₋₁ and n₄₋₁ each represent 0 or 1; and ℓ₄₋₁ represent 0, 1 or 2, wherein A₄₋₁⊖ represents or X₄₋₁ and X₄₋₂ each represent sulfur, oxygen, selenium or tellurium atom; Z₄₋₁ represents a group of atoms necessary for the completion of pyrylium, thiopyrylium, selenapyrylium, tellulopyrylium, benzopyrylium, benzothiopyrylium, benzoselenapyrylium, benzotellulopyrylium, naphthopyrylium, naphthothiopyrylium, naphthoselenapyrylium or naphthotellulopyrylium which may be each substituted. Z₄₋₂ represents a group of atoms necessary for the completion of pyran, thiopyran, selenapyran, tellulopyran, benzopyran, benzothiopyran, benzoselenapyran, benzotellulopyran, naphthopyran, naphthothiopyran, naphthoselenapyran or naphthotellulopyran which may be each substituted; R₄₋₁, R₄₋₂, R₄₋₃ and R₄₋₄ each represent hydrogen atom, alkyl, alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted styryl, substituted or unsubstituted 4-phenyl-1,3-butadienyl or substituted or unsubstituted heterocyclic group; also R₄₋₁ and R₄₋₂ may form substituted or unsubstituted benzene ring, or R₄₋₃ and R₄₋₄ may form substituted or unsubstituted benzene ring; m₄₋₁ and n₄₋₁ each represent 1 or 2, wherein X₄₋₁ represents sulfur, oxygen, selenium or tellurium atom; Z₄₋₁ represents a hydrocarbon group comprising a group of atoms necessary for the completion of pyrylium, thiopyrylium, selenapyrylium, tellulopyrylium, benzopyrylium, benzothiopyrylium, benzoselenapyrylium, benzotellulopyrylium, naphthopyrylium, naphthothiopyrylium, naphthoselenapyrylium or ntphthotellulopyrylium which may be each substituted; R₄₋₁ and R₄₋₂ each represent hydrogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted aryl or substituted or unsubstituted styryl; R₄₋₃ represents substituted or unsubstituted aryl or substituted or unsubstituted heterocyclic group; R₄₋₄ and R₄₋₅ each represent hydrogen atom or alkyl; A₄₋₁ ⊖ represents an anion; m₄₋₁ represents 1 or 2; n₄₋₁ represents 0, 1, 2 or 3, with proviso that when n₄₋₁ is 2 or 3, R₄₋₄ may be all the same or different, and R₄₋₅ may be all the same or different. An optical information recording medium according to Claim 1 or 2, wherein the metal-chelate compound is present in an amount of 1 to 60 wt.% based on the total weight of the recording material for forming the recording layer. An optical information recording medium according to Claim 1, 2 or 3 wherein the metal chelate compound is present in an amount of 5 to 60 wt.% based on the total weight of the recording material for forming the recording layer. An optical information recording medium according to any of Claims 1 to 4, wherein the optical information recording medium is an optical card. An optical information recording medium according to any of Claims 1 to 4, wherein the optical information recording medium is an optical disc.

Inventors: FUKUI, TETSURO, MIURA, KYO, OGUCHI, YOSHIHIRO, TAKASU, YOSHIO
Applicants: CANON KABUSHIKI KAISHA
Application year: 1987
Main classification: G11B7
IPC codes: G11B7, C09B57