JP3480204B2 - Optical recording medium - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an optical recording medium using a composition of a metal chelate compound of an azo compound and a metal and a metallocene compound.

[0002]

2. Description of the Related Art Optical recording using a laser has been particularly developed in recent years because it enables high-density information recording and storage and reproduction thereof. An optical disc can be given as an example of the optical recording medium. Generally, an optical disc has a thin recording layer provided on a circular substrate and has a thickness of 1 μm.
By irradiating a laser beam converged to a certain degree, high density information recording is performed. Among the optical discs, the one that has recently attracted attention is a writable compact disc (CD
There is a write-once disc. CD write once
A disk is usually constructed by sequentially stacking a recording layer containing a dye as a main component, a metal reflection film, and a protective film on a plastic substrate having a guide groove. Information is recorded by absorption of the energy of the irradiated laser light, and thermal decomposition such as decomposition, evaporation, and dissolution is generated in the recording layer, the reflective layer, or the substrate at that location. The information is reproduced by reading the difference in reflectance between the portion where the laser light is deformed and the portion where the deformation is not generated. Therefore, it is necessary to efficiently absorb the energy of laser light as an optical recording medium, and a laser absorbing dye is used.

A dye used in the recording layer of such a CD write-once disc is disclosed in JP-A-58-1127.
No. 90, No. 58-114989, No. 59-85791.
JP-A No. 60-83236 and JP-A No. 60-83236 disclose those using a cyanine dye. However, the cyanine dye has the advantages that it is highly soluble and can be coated by coating, but on the other hand, it has the problem of poor light resistance. In this regard, WO9 is used as a dye for the recording layer.
118057, JP-A-5-279580, 6-65
Japanese Patent Publication No. 514 and Japanese Patent Publication No. 7-51673 propose a method using a metal chelate compound of an azo compound and a metal. A metal chelate compound of an azo compound and a metal is generally excellent in light resistance and high in solubility in an organic solvent, which is preferable, but has a problem that the recording sensitivity is insufficient in high speed recording such as 4 × speed recording. Was there.

Further, Japanese Patent Laid-Open No. 3-215466 proposes a CD write-once medium using a phthalocyanine dye, but it still lacks recording sensitivity in high speed recording. As a means for solving these problems, JP-A-7-98887 proposes a method for improving recording characteristics by adding a metal compound as a pit / edge control agent to the recording layer. This method can improve the characteristics when a phthalocyanine dye is used as the dye for the recording layer, but a metal chelate compound of an azo compound and a metal having excellent light resistance was used as the dye for the recording layer. It has been found by the present inventors that in some cases the recording characteristics cannot be improved simply by adding a metal compound.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to further improve high speed recording characteristics by using a metal chelate compound of an azo compound and a metal having excellent light resistance in a recording layer.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve this object, the present inventors have found that a metal chelate compound of an azo compound and a metal represented by the following general formula [I] has the following general formula [II ] It was found that when a metallocene compound represented by the formula] is mixed, recording sensitivity is improved, high-speed recording characteristics are excellent, and recording storage stability is good. That is, the present invention comprises a substrate and a recording layer, the recording layer having the following general formula [I]

[0007]

[Chemical 3]

Where A represents a residue which, together with the carbon and nitrogen atoms to which it is attached, forms a heterocycle, B represents together with the two carbon atoms to which it is attached. Represents a residue that forms an aromatic group, and X represents a hydrogen atom or a cation, and a metal chelate compound of an azo compound and a metal, and the following general formula [II]

[0009]

[Chemical 4]

An optical recording medium characterized by containing a composition with a metallocene compound represented by the formula (wherein R represents a boric acid group or a benzoyl group and M represents Fe or Ni). And

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The azo compound in the present invention is not particularly limited as long as A in the general formula [I] is a residue which forms a heterocycle with the carbon atom and nitrogen atom to which it is bonded. . For example, in the general formula [I]

[0012]

[Chemical 5]

The following may be mentioned as examples:

[0014]

[Chemical 6]

[0015]

[Chemical 7]

[0016]

[Chemical 8]

(Where R is¹~ R⁸Each independently water
Elementary atom; methyl group, ethyl group, n-propyl group, isop
Ropyl group, n-butyl group, tert-butyl group, sec
Carbon such as -butyl group, n-pentyl group, n-hexyl group
A straight-chain or branched alkyl group of the numbers 1 to 6; cyclopropyl
Group, cyclobutyl group, cyclopentyl group, cyclohexyl group
C3-C6 cyclic alkyl group such as sil group; methoxy
Group, ethoxy group, n-propoxy group, isopropoxy
Group, n-butoxy group, tert-butoxy group, sec-
Butoxy group, n-pentyloxy group, n-hexyloxy group
An alkoxy group having 1 to 6 carbon atoms such as a Si group; an acetyl group,
Ropionyl group, butyryl group, isobutyryl group, valeryl
Group, isovaleryl group, pivaloyl group, hexanoyl group,
Alkylcarbonyl having 2 to 7 carbon atoms such as heptanoyl group
Group; vinyl group, propenyl group, butenyl group, pentenyl group
Group, hexenyl group, etc., having a straight chain or branched chain having 2 to 6 carbon atoms
Alkenyl group; cyclopentenyl group, cyclohexenyl
A cyclic alkenyl group having 3 to 6 carbon atoms such as a group; fluorine atom
Child, halogen atom such as chlorine atom, bromine atom; formyl group;
Hydroxyl group; Carboxyl group; Hydroxymethyl
Group having 1 to 6 carbon atoms such as hydroxy group and hydroxyethyl group
Alkyl group; methoxycarbonyl group, ethoxycarbonyl
Group, n-propoxycarbonyl group, isopropoxyca
Rubonyl group, n-butoxycarbonyl group, tert-bu
Toxycarbonyl group, sec-butoxycarbonyl group,
n-pentyloxycarbonyl group, n-hexyloxy
C2-C7 alkoxycarbonyl such as carbonyl group
Group; nitro group; cyano group; amino group; methylamino group,
Ethylamino group, n-propylamino group, n-butyl group
Mino group, dimethylamino group, diethylamino group, di-n
-Carbon such as propylamino group and di-n-butylamino group
Number 1 to 10 alkylamino group; methoxycarbonyl group
Cyl group, methoxycarbonylethyl group, ethoxycarbo
Nylmethyl group, ethoxycarbonylethyl group, n-pro
Poxycarbonylethyl group, n-propoxycarbonyl
Propyl group, isopropoxycarbonylmethyl group, iso
C3-C7 alkenyl such as propoxycarbonylethyl group
Coxycarbonylalkyl group; methylthio group, ethylthio group
O group, n-propylthio group, isopropylthio group, n-
Butylthio group, tert-butylthio group, sec-butyl
Ruthio group, n-pentylthio group, n-hexylthio group, etc.
An alkylthio group having 1 to 6 carbon atoms; methylsulfonyl
Group, ethylsulfonyl group, n-propylsulfonyl group,
Isopropylsulfonyl group, n-butylsulfonyl group,
tert-butylsulfonyl group, sec-butylsulfo
Nyl group, n-pentylsulfonyl group, n-hexylsulfur
Alkylsulfonyl group having 1 to 6 carbon atoms such as phenyl group;
An aryl group having 6 to 16 carbon atoms which may have a substituent;
Aryl C7-C17 aryl which may have a substituent.
Rubonyl group; -CR ₉= C (CN) R_Ten(R₉Is hydrogen
Child, or R¹~ R⁸Synonymous with that defined in
Represents an alkyl group having 1 to 6 carbon atoms,_TenIs a cyano group
Or the above R ¹~ R⁸Charcoal as defined in
It represents an alkoxycarbonyl group having a prime number of 2 to 7. );

[0018]

[Chemical 9]

(R _{11 to} R ₁₃ each independently represent a hydrogen atom or a nitro group, and Z is SCH ₂ , SO ₂ or SO.
₂ represents CH ₃ . ); Trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group,
1 to 1 carbon atoms such as heptafluoroisopropyl group, perfluoro-n-butyl group, perfluoro-tert-butyl group, perfluoro-sec-butyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group 6 fluoroalkyl group; trifluoromethoxy group, pentafluoroethoxy group, heptafluoro-n-propoxy group, heptafluoroisopropoxy group, perfluoro- group
a fluoroalkoxy group having 1 to 6 carbon atoms such as an n-butoxy group, a perfluoro-tert-butoxy group, a perfluoro-sec-butoxy group, a perfluoro-n-pentyloxy group, a perfluoro-n-hexyloxy group; Fluoromethylthio group, pentafluoroethylthio group,
Heptafluoro-n-propylthio group, heptafluoroisopropylthio group, perfluoro-n-butylthio group, perfluoro-tert-butylthio group, perfluoro-sec-butylthio group, perfluoro-n-pentylthio group, perfluoro-n A hexylthio group and the like, and a fluoroalkylthio group having 1 to 6 carbon atoms and the like. )

In the above general formula [I], B is not particularly limited as long as it is a residue which forms an aromatic group with the two carbon atoms to which it is bound, and examples thereof include a benzene ring and Naphthalene ring,

[0021]

[Chemical 10]

(R _{14 to} R ₂₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms and having the same meaning as defined in R ^{1 to} R ⁸ above. R ₂₂ is defined below.) And a residue forming an aromatic ring containing a hetero atom such as a residue forming an aromatic ring.

B is -NR ₂₂ R ₂₃ (wherein R ₂₂ and R ₂₃ are each independently a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert- Butyl group, sec-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-octadecyl group and the like having 1 to 20 carbon atoms A linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms; a phenyl group, a tolyl group, a xylyl group, C6-C12 aryl group such as naphthyl group; vinyl group,
A straight-chain or branched alkenyl group having 2 to 10 carbon atoms such as propenyl group, butenyl group, pentenyl group, and hexenyl group; cyclic alkyl group having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group Represents a group. Such a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, and 3 carbon atoms
The cyclic alkyl group of 10 is a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, a sec-butoxy group, n.
An alkoxy group having 1 to 10 carbon atoms such as a pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-decyloxy group; a methoxymethoxy group, an ethoxymethoxy group, a propoxymethoxy group,
C2-C12 alkoxyalkoxy groups such as methoxyethoxy group, ethoxyethoxy group, propoxyethoxy group, methoxypropoxy group, ethoxypropoxy group, methoxybutoxy group, ethoxybutoxy group; methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxy Ethoxymethoxy group, methoxyethoxyethoxy group,
C3 to C15 alkoxyalkoxy groups such as ethoxymethoxymethoxy group, ethoxymethoxyethoxy group, ethoxyethoxymethoxy group and ethoxyethoxyethoxy group; allyloxy group; phenyl group, tolyl group, xylyl group, naphthyl group and the like having 6 carbon atoms To 12 aryl group; aryloxy group having 6 to 12 carbon atoms such as phenoxy group, tolyloxy group, xylyloxy group and naphthyloxy group; cyano group; nitro group; hydroxy group; tetrahydrofuryl group; methylsulfonylamino group, ethylsulfonyl Amino group, n-propylsulfonylamino group, isopropylsulfonylamino group, n-butylsulfonylamino group,
1 to 6 carbon atoms such as tert-butylsulfonylamino group, sec-butylsulfonylamino group, n-pentylsulfonyl group amino group, n-hexylsulfonylamino group
Alkylsulfonylamino group; halogen group such as fluorine atom, chlorine atom, bromine atom; methoxycarbonyl group
Ethoxycarbonyl group, n-propoxycarbonyl group,
Isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyloxycarbonyl group, n
-C2-C7 alkoxycarbonyl group such as hexyloxycarbonyl group; methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, tert-butylcarbonyl group C2-C7 alkylcarbonyloxy groups such as oxy group, sec-butylcarbonyloxy group, n-pentylcarbonyloxy group, n-hexylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyl An alkoxycarbonyloxy group having 2 to 7 carbon atoms such as an oxy group, an isopropoxycarbonyloxy group, an n-butoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and an n-hexyloxycarbonyloxy group. It may be substituted with group.
Further, the above-mentioned carbon number of 6 to 1 represented by R ₂₂ and R ₂₃
The aryl group of 2 and the cyclic alkyl group having 3 to 10 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, s.
It may be substituted with a linear or branched alkyl group having 1 to 6 carbon atoms such as an ec-butyl group, an n-pentyl group, an n-hexyl group or a vinyl group. ); Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
tert-butyl group, sec-butyl group, n-pentyl group, n-hexyl group and other linear or branched alkyl groups having 1 to 6 carbon atoms; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-
C1-C6 alkoxy groups such as butoxy group, sec-butoxy group, n-pentyloxy group, n-hexyloxy group; halogen groups such as fluorine atom, chlorine atom, bromine atom; cyano group; nitro group; methyl Sulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, tert-
Butylsulfonyl group, sec-butylsulfonyl group, n
An alkylsulfonyl group having 1 to 6 carbon atoms such as a pentylsulfonyl group and an n-hexylsulfonyl group; a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group and a tert-butoxy group. Carbonyl group, se
2 carbon atoms such as c-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group
~ 7 alkoxycarbonyl group; and may have one or more substituents selected from thiocyanate groups.

In the general formula [I], X is water.
Elementary atom or Na⁺, Li⁺, K ⁺Inorganic sun
On or

[0025]

[Chemical 11]

Represents a cation such as an organic cation. In the present invention, the metal forming the chelate compound with the azo compound is not particularly limited as long as it is a metal capable of forming the chelate compound with the azo compound, but Ni, Co, Fe, Zn, Cu, Pd is not particularly limited. , Pt, R
Transition metals such as u, Rh, and Os are preferable, and Ni and Co are particularly preferable in terms of light resistance and durability.

The metallocene compound in the present invention is a ferrocene or nickelocene derivative in which M is Fe or Ni in the above-mentioned general formula [II], and has improved sensitivity, excellent high-speed recording property, and storage of records. In order to achieve good stability, it is necessary that one of the cyclopentadienyl groups is a boric acid group or a benzoyl group.

As will be seen from the examples and comparative examples described later, sufficient effects are exhibited when the compound is unsubstituted or substituted with another substituent, or when a substituent is introduced into both cyclopentadienyl groups. Not done. This phenomenon is unique when a metal chelate compound of an azo compound and a metal is used as a dye.

The composition of the metal chelate compound of an azo compound and a metal and the metallocene compound used in the present invention is in a weight ratio of 50:50 to 99.9: 0.1, preferably 70:30 to 99 :. It is mixed at a ratio of 1. This is because the mixing ratio of the metallocene compound is 50:50.
This is because if it is above the range, it is not preferable in terms of recording characteristics and durability, and if it is 99.9: 0.1 or less, the effect does not appear.

These metal chelate compounds of azo compounds and metals and metallocene compounds may be used alone or in combination of two or more.

The optical recording medium of the present invention basically comprises a substrate and a recording layer containing a composition of the above-mentioned azo compound, a metal chelate compound of metal and a metallocene compound, Further, an undercoat layer may be provided on the substrate if necessary. Further, as an example of a preferable layer structure, a metal reflective layer and a protective layer such as gold, silver and aluminum are provided on the recording layer to form a medium having a high reflectance,
An example is a write-once CD media.

The substrate is preferably transparent to the laser light used, and glass or various plastics are used. Examples of the plastic include acrylic resin, methacrylic resin, polycarbonate resin, vinyl chloride resin, vinyl acetate resin, nitrocellulose, polyester resin, polyethylene resin, polypropylene resin, polyimide resin, polystyrene resin, epoxy resin, etc., but high productivity In terms of cost and moisture absorption resistance, an injection molded polycarbonate resin substrate is particularly preferable.

The thickness of the recording layer containing the composition of the metal chelate compound of the azo compound and the metal and the metallocene compound in the optical recording medium of the present invention is 100Å to 5
μm, preferably 700 Å to 3 μm. The recording film can be formed by a commonly used thin film forming method such as a vacuum vapor deposition method, a sputtering method, a doctor blade method, a casting method, a spinner method, and a dipping method. From the viewpoint, the spinner method is preferable.

If desired, a binder may be used. Known binders such as polyvinyl alcohol, polyvinylpyrrolidone, ketone resins, nitrocellulose, cellulose acetate, polyvinyl butyral, and polycarbonate are used. In this case, a metal chelate compound of the monoazo compound of the present invention and a metal,
The composition with the metallocene compound is 10% by weight in the resin.
It is preferable that the above is contained.

In the case of film formation by the spinner method, the rotation speed is 5
0 to 5000 rpm is preferable, and after spin coating,
Depending on the case, treatment such as heating or exposure to solvent vapor may be performed. In order to improve the stability and light resistance of the recording layer, a transition metal chelate compound (for example, acetylacetonate chelate, as a singlet oxygen quencher,
Bisphenyldithiol, salicylaldehyde oxime, bisdithio-α-diketone, etc.) may be contained. Furthermore, other dyes can be used in combination, if necessary. Other dyes may be compounds of the same family of different types, or triarylmethane dyes, azo dyes, cyanine dyes, squarylium dyes, metal-containing indoaniline dyes, phthalocyanine dyes, and other dyes of other systems. But it's okay. Even when used in combination with other dyes, primary dye the
It is necessary to be a metal chelate compound of an azo compound represented by the general formula [I] and a metal.

The coating solvent for forming the recording layer by a coating method such as a doctor blade method, a casting method, a spinner method, a dipping method, or a spinner method is not particularly limited as long as it does not attack the substrate. For example, diacetone alcohol, ketone alcohol solvents such as 3-hydroxy-3-methyl-2-butanone, cellosolve solvents such as methyl cellosolve and ethyl cellosolve, hydrocarbon solvents such as n-hexane and n-octane, cyclohexane. , Hydrocarbon solvents such as methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, n-butylcyclohexane, t-butylcyclohexane and cyclooctane, ether solvents such as diisopropyl ether and dibutyl ether, tetrafluoropropanol, octafluoropentanol, hexa Examples thereof include perfluoroalkyl alcohol solvents such as fluorobutanol, and hydroxy ester solvents such as methyl lactate, ethyl lactate, and methyl isobutyrate.

The recording layer of the optical recording medium of the present invention may be provided on both sides or one side of the substrate. Recording on the optical recording medium obtained as described above is performed by irradiating a recording layer provided on both sides or one side of the substrate with a laser beam focused to about 1 μm, preferably a semiconductor laser beam. In the portion irradiated with laser light, thermal deformation of the recording layer such as decomposition, heat generation, and melting occurs due to absorption of laser light energy.

Reproduction of the recorded information is performed by reading the difference in reflectance between the portion where thermal deformation has occurred and the portion where thermal deformation has not occurred, using laser light. The laser light used for the optical recording medium of the present invention is N ₂ , He-C.
Examples thereof include d, Ar, He-Ne, ruby, semiconductor, dye laser, and the like, and the semiconductor laser is particularly preferable from the viewpoints of lightness, easy handling, compactness, and the like.

[0039]

EXAMPLES The present invention will be described in detail with reference to the following examples, but the examples are not intended to limit the present invention as long as the gist thereof is not exceeded.

Example 1 (a) Recording medium example A metal chelate compound of an azo compound represented by the following general formula [III] and nickel and a ferrocene derivative represented by the following structural formula [IV] (weight ratio 10: 1). 2.4 wt% solution of tetrafluoropropanol of was prepared and filtered to obtain a solution.

[0041]

[Chemical 12]

This solution has a diameter of 120 mm and a thickness of 1.2 m.
m was dropped onto an injection-molded polycarbonate resin substrate and applied by a spinner method. After coating, it was dried at 100 ° C. for 30 minutes. Next, a silver film having a film thickness of 600 Å was formed on the coating film by a sputtering method to form a reflective layer. Further, an ultraviolet curable resin is spin-coated on this reflective layer, and this is irradiated with ultraviolet rays to be cured to have a thickness of 5 μm.
m protective layer was formed.

[0043]

[Chemical 13]

(B) Optical recording method When the recording medium was rotated at 5.6 m / s and recorded at 4 × speed with a semiconductor laser beam having a central wavelength of 780 nm,
Optimal recording power for recording EFM signals 10.2 m
W was required, and the sensitivity was improved by adding the metallocene compound. Next, when this recording portion was reproduced with a CD player having a semiconductor laser with a central wavelength of 780 nm, a good reproduced signal was obtained. The storage stability of the recording portion under high temperature and high humidity was good as shown in Table 1.

Example 2 (a) Recording medium example A metal chelate compound of an azo compound represented by the following general formula [III] and nickel and a ferrocene derivative represented by the following structural formula [V] (weight ratio 10: 1). A 4.0 wt% solution of octafluoropentanol was prepared and filtered to obtain a solution.

[0046]

[Chemical 14]

This solution has a diameter of 120 mm and a thickness of 1.2 m.
m was dropped onto an injection-molded polycarbonate resin substrate and applied by a spinner method. After coating, it was dried at 105 ° C. for 20 minutes. Next, a silver film having a film thickness of 700 Å was formed on the coating film by a sputtering method to form a reflective layer. Further, an ultraviolet curable resin is spin-coated on this reflective layer, and this is irradiated with ultraviolet rays to be cured to have a thickness of 5 μm.
m protective layer was formed.

(B) Optical recording method When the recording medium was rotated at 5.6 m / s and recorded at 4 × speed with a semiconductor laser beam having a central wavelength of 780 nm,
Optimal recording power for recording EFM signals 10.2 m
Since W was required, the sensitivity was improved by adding the metallocene compound. Next, when this recording portion was reproduced with a CD player having a semiconductor laser with a central wavelength of 780 nm, a good reproduced signal was obtained. Further, the storage stability of the recording portion under high temperature and high humidity was evaluated, and it was good as shown in Table 1.

Example 3 (a) Recording medium example A metal chelate compound of an azo compound represented by the following general formula [VI] and nickel and a ferrocene derivative represented by the following structural formula [IV] (weight ratio 10: 1). Of tetrafluoropropanol of 2.4 wt% solution was prepared, filtered,
A solution was obtained.

[0050]

[Chemical 15]

The solution is 120 mm in diameter and 1.2 m in thickness.
m was dropped onto an injection-molded polycarbonate resin substrate and applied by a spinner method. After coating, it was dried at 100 ° C. for 30 minutes. Next, a silver film having a film thickness of 600 Å was formed on the coating film by a sputtering method to form a reflective layer. Further, an ultraviolet curable resin is spin-coated on this reflective layer, and this is irradiated with ultraviolet rays to be cured to have a thickness of 5 μm.
m protective layer was formed.

[0052]

[Chemical 16]

(B) Optical recording method When the recording medium was rotated at 5.6 m / s and recorded at 4 × speed with a semiconductor laser beam having a central wavelength of 780 nm,
Optimum recording power for recording EFM signals 10.3m
W was required, and the sensitivity was improved by adding the metallocene compound. Next, when this recording portion was reproduced with a CD player having a semiconductor laser with a central wavelength of 780 nm, a good reproduced signal was obtained. The storage stability of the recording portion under high temperature and high humidity was good as shown in Table 1.

Example 4 (a) Recording medium example A metal chelate compound of an azo compound represented by the above general formula [VI] and nickel and a ferrocene derivative represented by the following structural formula [V] (weight ratio 10: 1). Octafluoropentanol 4.0 wt% solution of
A solution was obtained.

[0055]

[Chemical 17]

This solution has a diameter of 120 mm and a thickness of 1.2 m.
m was dropped onto an injection-molded polycarbonate resin substrate and applied by a spinner method. After coating, it was dried at 105 ° C. for 20 minutes. Next, a silver film having a film thickness of 700 Å was formed on the coating film by a sputtering method to form a reflective layer. Further, an ultraviolet curable resin is spin-coated on this reflective layer, and this is irradiated with ultraviolet rays to be cured to have a thickness of 5 μm.
m protective layer was formed.

(B) Optical recording method When the recording medium was rotated at 5.6 m / s and recorded at 4 × speed with a semiconductor laser beam having a central wavelength of 780 nm,
Optimum recording power for recording EFM signal 10.6m
Since W was required, the sensitivity was improved by adding the metallocene compound. Next, when this recording portion was reproduced with a CD player having a semiconductor laser with a central wavelength of 780 nm, a good reproduced signal was obtained. Further, the storage stability of the recording portion under high temperature and high humidity was evaluated, and it was good as shown in Table 1.

Example 5 (a) Recording medium example A metal chelate compound of an azo compound represented by the following general formula [VII] and nickel and a ferrocene derivative represented by the following structural formula [IV] (weight ratio 10: 1). 2.4 wt% solution of tetrafluoropropanol of was prepared and filtered to obtain a solution.

[0059]

[Chemical 18]

This solution was prepared as follows: diameter 120 mm, thickness 1.2 m
m was dropped onto an injection-molded polycarbonate resin substrate and applied by a spinner method. After coating, it was dried at 100 ° C. for 30 minutes. Next, a silver film having a film thickness of 600 Å was formed on the coating film by a sputtering method to form a reflective layer. Further, an ultraviolet curable resin is spin-coated on this reflective layer, and this is irradiated with ultraviolet rays to be cured to have a thickness of 5 μm.
m protective layer was formed.

[0061]

[Chemical 19]

(B) Optical recording method When the recording medium was rotated at 5.6 m / s and recorded at 4 × speed with a semiconductor laser beam having a central wavelength of 780 nm,
Optimal recording power for recording EFM signals 10.8m
W was required, and the sensitivity was improved by adding the metallocene compound. Next, when this recording portion was reproduced with a CD player having a semiconductor laser with a central wavelength of 780 nm, a good reproduced signal was obtained. The storage stability of the recording portion under high temperature and high humidity was good as shown in Table 1.

Example 6 (a) Recording medium example A metal chelate compound of an azo compound represented by the general formula [VII] and nickel and a ferrocene derivative represented by the following structural formula [V] (weight ratio 10: 1). A 4.0 wt% solution of octafluoropentanol was prepared and filtered to obtain a solution.

[0064]

[Chemical 20]

This solution has a diameter of 120 mm and a thickness of 1.2 m.
m was dropped onto an injection-molded polycarbonate resin substrate and applied by a spinner method. After coating, it was dried at 105 ° C. for 20 minutes. Next, a silver film having a film thickness of 700 Å was formed on the coating film by a sputtering method to form a reflective layer. Further, an ultraviolet curable resin is spin-coated on this reflective layer, and this is irradiated with ultraviolet rays to be cured to have a thickness of 5 μm.
m protective layer was formed.

(B) Optical recording method When the recording medium was rotated at 5.6 m / s and recorded at 4 × speed with a semiconductor laser beam having a central wavelength of 780 nm,
Optimal recording power for recording EFM signals 10.8m
Since W was required, the sensitivity was improved by adding the metallocene compound. Next, when this recording portion was reproduced with a CD player having a semiconductor laser with a central wavelength of 780 nm, a good reproduced signal was obtained. Further, the storage stability of the recording portion under high temperature and high humidity was evaluated, and it was good as shown in Table 1.

Example 7 (a) Recording medium example A metal chelate compound of an azo compound represented by the general formula [III] and nickel and a nickelocene derivative represented by the following structural formula [VIII] (weight ratio 10: 1). A 4.0 wt% solution of octafluoropentanol was prepared and filtered to obtain a solution.

[0068]

[Chemical 21]

This solution was prepared to have a diameter of 120 mm and a thickness of 1.2 m.
m was dropped onto an injection-molded polycarbonate resin substrate and applied by a spinner method. After coating, it was dried at 105 ° C. for 20 minutes. Next, a silver film having a film thickness of 700 Å was formed on the coating film by a sputtering method to form a reflective layer. Further, an ultraviolet curable resin is spin-coated on this reflective layer, and this is irradiated with ultraviolet rays to be cured to have a thickness of 5 μm.
m protective layer was formed.

(B) Optical recording method When the recording medium was rotated at 5.6 m / s and recorded at 4 × speed with a semiconductor laser beam having a central wavelength of 780 nm,
Optimal recording power for recording EFM signals 10.2 m
Since W was required, the sensitivity was improved by adding the metallocene compound. Next, when this recording portion was reproduced with a CD player having a semiconductor laser with a central wavelength of 780 nm, a good reproduced signal was obtained. Further, the storage stability of the recording portion under high temperature and high humidity was evaluated, and it was good as shown in Table 1.

Comparative Example 1 (a) Recording Medium Example A recording medium was prepared in the same manner as in Example 1 except that the metallocene compound was not added. (B) Optical recording method When recording was performed with a semiconductor laser beam having a central wavelength of 780 nm while rotating the recording medium at 5.6 m / s, E
Optimum recording power 12.0mW for recording FM signals
Was required, and the recording sensitivity was inferior to the optical recording medium of the present invention shown in Example 1.

Comparative Example 2 (a) Recording Medium Example A recording medium was prepared in the same manner except that a metallocene compound represented by the following structural formula [IX] was used instead of the metallocene compound used in Example 1 above.

[0073]

[Chemical formula 22]

(B) Optical recording method When the above recording medium was recorded with a semiconductor laser beam having a central wavelength of 780 nm while rotating at 5.6 m / s, E
Optimum recording power 12.0mW for recording FM signals
Was required, and the recording sensitivity was inferior to the optical recording medium of the present invention shown in Example 1. Further, the storage stability of the recording portion under high temperature and high humidity was inferior as shown in Table 1.

Comparative Example 3 (a) Recording Medium Example A recording medium was prepared in the same manner except that a metallocene compound represented by the following structural formula [X] was used instead of the metallocene compound used in Example 1 above.

[0076]

[Chemical formula 23]

(B) Optical recording method When the above recording medium was recorded with a semiconductor laser beam having a central wavelength of 780 nm while rotating at 5.6 m / s, E
Optimum recording power 12.5mW for recording FM signals
Was required, and the recording sensitivity was inferior to the optical recording medium of the present invention shown in Example 1. Further, the storage stability of the recording portion under high temperature and high humidity was inferior as shown in Table 1.

Comparative Example 4 (a) Recording Medium Example A recording medium was prepared in the same manner except that a metallocene compound represented by the following structural formula [XI] was used instead of the metallocene compound used in Example 1 above.

[0079]

[Chemical formula 24]

(B) Optical recording method Recording was performed with a semiconductor laser beam having a central wavelength of 780 nm while rotating the recording medium at 5.6 m / s.
Optimal recording power for recording FM signals 11.6mW
Was required, and the recording sensitivity was inferior to the optical recording medium of the present invention shown in Example 1. Further, the storage stability of the recording portion under high temperature and high humidity was inferior as shown in Table 1.

Comparative Example 5 (a) Recording Medium Example A recording medium was prepared in the same manner except that a metallocene compound represented by the following structural formula [XII] was used instead of the metallocene compound used in Example 1 above.

[0082]

[Chemical 25]

(B) Optical recording method When the recording medium was recorded with a semiconductor laser beam having a central wavelength of 780 nm while rotating at 5.6 m / s, E
Optimum recording power 12.5mW for recording FM signals
Was required, and the recording sensitivity was inferior to the optical recording medium of the present invention shown in Example 1. Further, the storage stability of the recording portion under high temperature and high humidity was inferior as shown in Table 1.

Comparative Example 6 (a) Recording Medium Example A recording medium was prepared in the same manner except that an unsubstituted ferrocene was used in place of the metallocene compound used in Example 1 above. (B) Optical recording method When recording was performed with a semiconductor laser beam having a central wavelength of 780 nm while rotating the recording medium at 5.6 m / s, E
Optimum recording power 12.5mW for recording FM signals
Was required, and the recording sensitivity was inferior to the optical recording medium of the present invention shown in Example 1. Further, the storage stability of the recording portion under high temperature and high humidity was inferior as shown in Table 1.

Comparative Example 7 (a) Recording Medium Example A recording medium was prepared in the same manner except that a metallocene compound represented by the following structural formula [XIV] was used in place of the metallocene compound used in Example 1 above.

[0086]

[Chemical formula 26]

(B) Optical recording method When the recording medium was recorded with a semiconductor laser beam having a central wavelength of 780 nm while rotating at 5.6 m / s, E
Optimal recording power of 12.2mW for recording FM signals
Was required, and the recording sensitivity was inferior to the optical recording medium of the present invention shown in Example 1. Further, the storage stability of the recording portion under high temperature and high humidity was inferior as shown in Table 1.

Comparative Example 8 (a) Recording Medium Example A recording medium was prepared in the same manner except that a metallocene compound represented by the following structural formula [XV] was used instead of the metallocene compound used in Example 1 above.

[0089]

[Chemical 27]

(B) Optical recording method When the above recording medium was recorded with a semiconductor laser beam having a central wavelength of 780 nm while rotating at 5.6 m / s, E
Optimum recording power of 12.3 mW for recording FM signals
Was required, and the recording sensitivity was inferior to the optical recording medium of the present invention shown in Example 1. Further, the storage stability of the recording portion under high temperature and high humidity was inferior as shown in Table 1.

Comparative Example 9 (a) Recording Medium Example A recording medium was prepared in the same manner except that a metallocene compound represented by the following structural formula [XVI] was used instead of the metallocene compound used in Example 1 above.

[0092]

[Chemical 28]

(B) Optical recording method When recording was performed with a semiconductor laser beam having a central wavelength of 780 nm while rotating the recording medium at 5.6 m / s, E
Optimal recording power for recording FM signals 12.4 mW
Was required, and the recording sensitivity was inferior to the optical recording medium of the present invention shown in Example 1. Further, the storage stability of the recording portion under high temperature and high humidity was inferior as shown in Table 1.

Comparative Example 10 (a) Recording Medium Example A recording medium was prepared in the same manner except that a metallocene compound represented by the following structural formula [XVII] was used instead of the metallocene compound used in Example 1 above.

[0095]

[Chemical 29]

(B) Optical recording method When the above recording medium was recorded with a semiconductor laser beam having a central wavelength of 780 nm while rotating at 5.6 m / s, E
Optimum recording power 12.5mW for recording FM signals
Was required, and the recording sensitivity was inferior to the optical recording medium of the present invention shown in Example 1. Further, the storage stability of the recording portion under high temperature and high humidity was inferior as shown in Table 1.

Comparative Example 11 (a) Recording Medium Example A recording medium was prepared in the same manner except that a metallocene compound represented by the following structural formula [XVIII] was used instead of the metallocene compound used in Example 1 above.

[0098]

[Chemical 30]

(B) Optical recording method When recording was performed with a semiconductor laser beam having a central wavelength of 780 nm while rotating the recording medium at 5.6 m / s, E
Optimum recording power 12.0mW for recording FM signals
Was required, and the recording sensitivity was inferior to the optical recording medium of the present invention shown in Example 1. Further, the storage stability of the recording portion under high temperature and high humidity was inferior as shown in Table 1.

[0100]

[Table 1]

[0101]

EFFECT OF THE INVENTION An optical recording medium using a composition of a metal chelate compound of an azo compound and a metal of the present invention and a metallocene compound is excellent in light resistance and heat resistance and has good sensitivity at high speed recording. In addition, it is excellent in storage stability of records and is extremely useful industrially.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoru Imamura 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Corporation Yokohama Research Institute (72) Inventor Souko Oshikawa 1000, Kamoshida-cho, Aoba-ku, Yokohama Chemicals Co., Ltd., Yokohama Research Institute (56) Reference JP 10-116443 (JP, A) JP 7-98887 (JP, A) JP 10-11799 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) B41M 5/26 G11B 7/24 516 CAPLUS (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. An optical recording medium in which only one recording layer capable of writing and / or reading information by a laser is provided on at least one side of a substrate , and the recording layer has the following general formula [I]: (In the formula, A represents a residue which forms a heterocycle together with the carbon atom and the nitrogen atom to which it is bonded, and B represents an aromatic group together with the two carbon atoms to which it is bonded. Represents a group-forming residue, and X represents a hydrogen atom or a cation), and a metal chelate compound of an azo compound and a metal, and a compound represented by the following general formula [II]: (In the formula, R represents a boric acid group or a benzoyl group, and
Represents Fe or Ni. ) An optical recording medium comprising a composition with a metallocene compound represented by the formula (1). 2. The optical recording medium according to claim 1, wherein a metal reflective layer and a protective layer are provided on the recording layer. 3. The weight ratio of the metal chelate compound of the azo compound and the metal and the metallocene compound is 5
It is blended in a ratio of 0:50 to 99.9: 0.1,
The optical recording medium according to claim 1.