JP3409626B2 - 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 complex compound of an azo compound and a metal, an indolenine cyanine dye 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 absorbing the irradiated laser light energy and causing thermal deformation such as decomposition, evaporation, and dissolution in the recording layer, the reflective layer, or the substrate at that location. Further, the recorded information is reproduced by reading the difference in reflectance between the portion where the laser beam is deformed and the portion where the laser beam is not deformed. 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 the recording characteristics by adding a metal compound as a pit / edge control agent to the recording layer. By this method, when a phthalocyanine dye is used as the dye for the recording layer, the characteristics can be improved, but a metal complex 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]

DISCLOSURE OF THE INVENTION According to the present invention, a dye composition mainly containing a metal complex compound of an azo compound having excellent light resistance and a metal is used in a recording layer to further improve high-speed recording characteristics. To aim.

[0006]

Means for Solving the Problems As a result of intensive studies aimed at achieving this object, the present inventors have found that a metal chelate compound of an azo compound represented by the following general formula [I] and a metal, a general formula [II] ] When a metallocene compound represented by the following general formula [III] is mixed with a dye mixture comprising an indolenine cyanine dye represented by the formula, the recording sensitivity is improved, the high-speed recording characteristic is excellent, and the recording storage stability is good. I found a thing. That is, the present invention comprises a substrate and a recording layer, the recording layer having the following general formula [I]

[0007]

[Chemical 6]

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 forming an aromatic ring or a heterocycle,
X represents a group having active hydrogen. ) A complex compound of an azo compound and a metal represented by the following general formula [II]

[0009]

[Chemical 7]

Wherein P and P'each independently represent a residue which, together with the two carbon atoms to which it is attached, forms an aromatic ring, and Q may be substituted. Represents a pentamethine group, R ¹ , R ² , R ³ , R ⁴ , R
⁵ and R ⁶ each independently represent an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group or an optionally substituted cycloalkyl group, and Z ⁻ Represents an anion residue. ) An indolenine cyanine dye represented by the following general formula [III]

[0011]

[Chemical 8]

An optical recording medium characterized by being 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

[0013]

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]

[0014]

[Chemical 9]

The following may be mentioned as examples.

[0016]

[Chemical 10]

[0017]

[Chemical 11]

[0018]

[Chemical 12]

(Where R is⁹~ R¹⁶Each 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
Number 1 to 6 alkyl group; cyclopropyl group, cyclobutyl
Number of carbon atoms such as vinyl, cyclopentyl, and cyclohexyl groups
3 to 6 cyclic alkyl groups; methoxy group, ethoxy group,
n-propoxy group, isopropoxy group, n-butoxy
Group, tert-butoxy group, sec-butoxy group, n-
1 carbon atom such as pentyloxy group and n-hexyloxy group
~ 6 alkoxy group; acetyl group, propionyl group, bromo group
Tyryl group, isobutyryl group, valeryl group, isovaleryl
Group, pivaloyl group, hexanoyl group, heptanoyl group, etc.
An alkylcarbonyl group having 2 to 7 carbon atoms; a vinyl group, a
Lopenyl group, butenyl group, pentenyl group, hexenyl group
A straight-chain or branched alkenyl group having 2 to 6 carbon atoms;
C3-C3 such as clopentenyl and cyclohexenyl
6 cyclic alkenyl groups; fluorine atom, chlorine atom, bromine
Halogen groups such as atoms; formyl group; hydroxyl group;
Ruboxyl group; hydroxymethyl group, hydroxyethyl
A hydroxyalkyl group having 1 to 6 carbon atoms such as a group; methoxy
Carbonyl group, ethoxycarbonyl group, n-propoxy
Carbonyl group, isopropoxycarbonyl group, n-but
Xycarbonyl group, tert-butoxycarbonyl group,
sec-butoxycarbonyl group, n-pentyloxyca
Carbon such as rubonyl group and n-hexyloxycarbonyl group
Number 2 to 7 alkoxycarbonyl group; nitro group; cyano
Group; amino group; methylamino group, ethylamino group, n-
Propylamino group, n-butylamino group, dimethylamido
Group, diethylamino group, di-n-propylamino group,
Alkyl having 1 to 10 carbon atoms such as di-n-butylamino group
Amino group: methoxycarbonylmethyl group, methoxycar
Bonylethyl group, ethoxycarbonylmethyl group, Etoki
Cycarbonylethyl group, n-propoxycarbonylethyl
Group, n-propoxycarbonylpropyl group, isopro group
Poxycarbonylmethyl group, isopropoxycarbonyl
Alkoxycarbonylal having 3 to 7 carbon atoms such as ethyl group
Kill group; methylthio group, ethylthio group, n-propylthio group
O group, isopropylthio group, n-butylthio group, ter
t-butylthio group, sec-butylthio group, n-plier
Alkyl groups having 1 to 6 carbon atoms such as ruthio group and n-hexylthio group
Kirthio group; methylsulfonyl group, ethylsulfonyl group
Group, n-propylsulfonyl group, isopropylsulfoni
Group, n-butylsulfonyl group, tert-butylsulfur group
Fonyl group, sec-butylsulfonyl group, n-pentyl group
Carbon number 1 such as sulfonyl group, n-hexylsulfonyl group
~ 6 alkylsulfonyl group; may have a substituent
An aryl group having 6 to 16 carbon atoms; even if it has a substituent
A good arylcarbonyl group having 7 to 17 carbon atoms; -CR¹⁷
= C (CN) R ¹⁸(R¹⁷Is a hydrogen atom or the above R⁹~
R¹⁶C1-C6 al having the same meaning as defined in
Represents a kill group, R¹⁸Is a cyano group or the above R⁹~ R¹⁶
Alkoxy having 2 to 7 carbon atoms, which has the same meaning as defined in 1.
Represents a carbonyl group. );

[0020]

[Chemical 13]

(R¹⁹~ R^{twenty one}Are each independently a hydrogen atom
Or represents a nitro group, Z is SCH ₂, SO₂, SO
₂CH₃Represents ); Trifluoromethyl group, penta
Fluoroethyl group, heptafluoro-n-propyl group,
Heptafluoroisopropyl group, perfluoro-n-bu
Cyl group, perfluoro-tert-butyl group, perflu
Oro-sec-butyl group, perfluoro-n-pentyl
Group, a perfluoro-n-hexyl group or the like having 1 to 6 carbon atoms
Fluoroalkyl group; trifluoromethoxy group, penta
Fluoroethoxy group, heptafluoro-n-propoxy
Group, heptafluoroisopropoxy group, perfluoro-
n-butoxy group, perfluoro-tert-butoxy
Group, perfluoro-sec-butoxy group, perfluoro
-N-pentyloxy group, perfluoro-n-hexyl
Fluoroalkoxy group having 1 to 6 carbon atoms such as oxy group; tri
Fluoromethylthio group, pentafluoroethylthio group,
Heptafluoro-n-propylthio group, heptafluoro
Isopropylthio group, perfluoro-n-butylthio
Group, perfluoro-tert-butylthio group, perflu
Oro-sec-butylthio group, perfluoro-n-pen
Carbon such as tylthio group and perfluoro-n-hexylthio group
It represents a fluoroalkylthio group of the formulas 1 to 6 and the like. ) The above
In the general formula [I], B is bonded to it.
A residue that, together with two carbon atoms, forms an aromatic
There is no particular limitation as long as it is, for example, a benzene ring,
Naphthalene ring,

[0022]

[Chemical 14]

(R ^{22 to} R ³⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which has the same meaning as defined in R ^{9 to} R ¹⁶ above). Residues that form aromatic rings containing heteroatoms such as groups are mentioned. In addition, B is -NR ³¹ R ³² (where R ³¹
And R ³² 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, C1-C20 alkyl group such as n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, and n-octadecyl group, preferably C1-10 alkyl group, more preferably carbon. Number 1-6
Alkyl group; aryl group having 6 to 12 carbon atoms such as phenyl group, tolyl group, xylyl group and naphthyl group; vinyl group,
It represents an alkenyl group having 2 to 10 carbon atoms such as propenyl group, butenyl group, pentenyl group and hexenyl group; and a cyclic alkyl group having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.
Such an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and a carbon number 3
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,
Alkoxyalkoxyalkoxy groups having 3 to 15 carbon atoms such as ethoxymethoxymethoxy group, ethoxymethoxyethoxy group, ethoxyethoxymethoxy group, ethoxyethoxyethoxy group; allyloxy group; carbon number of phenyl group, tolyl group, xylyl group, naphthyl group, etc. 6-12 aryl group; C6-12 aryloxy group such as phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group; cyano group; nitro group; hydroxy group; tetrahydrofuryl group; methylsulfonylamino group, ethyl Sulfonylamino group, n-propylsulfonylamino group,
Isopropylsulfonylamino group, n-butylsulfonylamino group, tert-butylsulfonylamino group, s
an ec-butylsulfonylamino group, an n-pentylsulfonylamino group, an n-hexylsulfonylamino group, or another alkylsulfonylamino group having 1 to 6 carbon atoms; a halogen group such as a fluorine atom, a chlorine atom, or a bromine atom; a methoxycarbonyl group. Ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, se
2 carbon atoms such as c-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group
~ 7 alkoxycarbonyl group; methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-
Butylcarbonyloxy group, tert-butylcarbonyloxy group, sec-butylcarbonyloxy group, n-
C2-C7 alkylcarbonyloxy groups such as pentylcarbonyloxy group, n-hexylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, isopropoxycarbonyloxy group, n-butoxy Carbonyloxy group, tert-butoxycarbonyloxy group, n
2 to 7 carbon atoms such as hexyloxycarbonyloxy group
It may be substituted with an alkoxycarbonyloxy group or the like. Further, the aryl group having 6 to 12 carbon atoms and the cyclic alkyl group having 3 to 10 carbon atoms represented by R ³¹ and R ³² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n- It may be substituted with an alkyl group having 1 to 6 carbon atoms such as a butyl group, a tert-butyl group, a sec-butyl group, an n-pentyl group, an n-hexyl group or a vinyl group. ); An alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, an n-pentyl group and an n-hexyl group. Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-
An alkoxy group having 1 to 6 carbon atoms such as butoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, n-hexyloxy group; fluorine atom, chlorine atom,
Halogen group such as bromine atom; cyano group; nitro group; methylsulfonyl 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, sec-butoxycarbonyl group, n
It may have one or more substituents selected from a C2-C7 alkoxycarbonyl group such as a -pentyloxycarbonyl group and an n-hexyloxycarbonyl group; and a thiocyanate group.

The azo compound represented by the general formula [I]
And X is not particularly limited as long as it is a group having active hydrogen.
However, preferred are -OH, -COO.
H, -SO₃H-, -B (OH)₂-, -HNSO₂R
³³(R³³Is a hydrogen atom, the number of carbon atoms that may have a substituent
1 to 25 alkyl groups or optionally substituted groups
Represents a phenyl group. ) -CONH₂, -SO₂NH₂,
-NH₂And the like, and particularly preferred one is -O.
H, -COOH, -SO₃H, -NHSO₂R ³³(R³³
Is as defined above. ) Is mentioned. In addition, X is -CO
OH, -OH, -SO₃Dissociates into anions like H
If it is a volatile group, it forms an azo metal chelate compound.
At this time, it may be used as it is, but with cations
It may be used in the form of salt. Such cations include N
a⁺, Li⁺, K⁺Inorganic cations such as [P (C
₆H_Five)_Four]⁺, [N (C₂H_Five)_Four]⁺, [N (C_Four
H ₉(N))_Four]⁺, [C₆H_FiveN (CH₃)₃]⁺etc
The organic cations of In the present invention,
As a preferable metal complex compound, the following general formula [IV]

[0025]

[Chemical 15]

Wherein 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 forming an aromatic group) and a complex compound of an azo compound and a metal. In the general formula [IV], the hydrogen atom of the —SO ₃ H group is Na
^+, Li ^+, cations or of inorganic K ^+, etc., [P
(C ₆ H ₅ ) ₄ ] ⁺ , [N (C ₂ H ₅ ) ₄ ] ⁺ , [N
(C ₄ H ₉ (n)) ₄ ] ⁺ , [C ₆ H ₅ N (C
It may be substituted with a cation such as an organic cation such as H ₃ ) ₃ ] ⁺ .

In the present invention, the metal forming a complex with the azo compound is not particularly limited as long as it is a metal capable of forming a chelate compound with the azo compound, but Ni, Co, Fe, Zn, Cu. , Pd, 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 indolenine-based cyanine dye in the present invention has the following general formula [II]

[0028]

[Chemical 16]

(Wherein P and P'each independently represent a residue which, together with the two carbon atoms to which it is attached, form an aromatic ring, and Q is optionally substituted. Represents a pentamethine group, R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ and R ⁸ each independently represent an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group or an optionally substituted cycloalkyl group, and Z ^- represents an anion residue. ) Indolenin type cyanine dye represented by.

In the metallocene compound of the present invention, in the general formula [III], M is Fe or Ni.
A ferrocene or nickelocene derivative represented by, in order to improve sensitivity, excellent high-speed recording property, and good storage stability of recording, one of the cyclopentadienyl groups is a boric acid group or a benzoyl group. It is a substituted compound. The composition of the complex compound, the indolenine cyanine dye and the metallocene compound used in the present invention is preferably in the range of 3: 7 to 7: 3 by weight ratio of the complex compound: indolenine cyanine dye. Among them, the range of 3: 7 to 6: 4 is particularly preferable when the sensitivity is important as the optical recording medium, and the range of 4: 6 to 7: 3 is particularly preferable when the light resistance is important.

The metallocene compound is contained in an amount of 5 to 20% by weight, preferably 10 to 20 w, based on the total weight of the complex compound, the indolenine cyanine dye and the metallocene compound.
It is recommended to use t%. This is because an increase in the mixing ratio of the metallocene compound may result in undesirable recording characteristics and durability. These complex compounds, indolenine-based cyanine dyes, and metallocene-based 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 an azo compound and a metal complex compound, an indolenine cyanine dye and a metallocene compound, and an undercoat layer is further provided on the substrate, if necessary. be able to. In addition, as an example of a preferable layer structure, a recording medium is provided with a metal reflection layer such as gold, silver, and aluminum and a protective layer to provide a medium having a high reflectance and a write-once CD medium.

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.

In the optical recording medium of the present invention, the recording layer containing the composition of the complex compound of an azo compound and a metal, the indolenine cyanine dye and the metallocene compound has a thickness of 100Å to 5 µm, Preferably from 700Å to 3
μm. As a method for forming the recording film, a vacuum vapor deposition method,
Sputtering method, doctor blade method, casting method,
The film can be formed by a commonly used thin film forming method such as a spinner method or an immersion method, but the spinner method is preferable from the viewpoint of mass productivity and cost.

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 complex compound of the azo compound of the present invention and a metal, indolenine
The composition of the cyanine dye and the metallocene compound is preferably contained in the resin in an amount of 10% by weight or more.

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, another transition metal chelate compound (for example, acetylacetonate chelate, bisphenyldithiol, salicylaldehyde oxime, bisdithio-α-diketone, etc.) is used as a singlet oxygen quencher. It 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, and triarylmethane dyes, azo dyes, cyanine dyes, aquarylium dyes, metal-containing indoaniline dyes, phthalocyanine dyes, and other types of dyes. It may be a dye. Even when other dyes are used in combination, the main dyes must be a complex compound of an azo compound represented by the general formula [I] and a metal and an indolenine cyanine dye represented by the general formula [II]. Is.

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.

The recorded information is reproduced by reading the difference in reflectance between the portion where thermal deformation has occurred and the portion where thermal deformation has not occurred, by means of 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.

[0040]

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 structural formula [A-1] and nickel, an indolenine cyanine dye represented by the following structural formula [B-1] and the following structure Ferrocene derivative represented by the formula [C-1] (weight ratio: 3
3:50:17) octafluoropentanol 1.6
A wt% solution was prepared and filtered to obtain a solution.

[0041]

[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 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.

(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,
The optimum recording power for recording the EFM signal is 9.8 m.
W, and the sensitivity improvement was achieved 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 good.

Example 2 (a) Recording medium example A metal complex compound of an azo compound represented by the following structural formula [A-2] and nickel, and an indolenine cyanine dye represented by the following structural formula [B-2]. And the following structural formula [C-
2] ferrocene derivative (weight ratio 42: 4
2:16) octafluoropentanol 1.7 wt%
A solution was prepared and filtered to obtain a coating solution.

[0045]

[Chemical 18]

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 is 9.9m
It was W, 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. Further, the storage stability of the recording portion under high temperature and high humidity was evaluated, and it was good.

Example 3 (a) Recording medium example A metal complex compound of an azo compound represented by the following structural formula [A-3] and nickel, an indolenine cyanine dye represented by the following structural formula [B-1] And the following structural formula [C-
1] ferrocene derivative (weight ratio 36: 5
A 1.6 wt% solution of tetrafluoropropanol of 5: 9) was prepared and filtered to obtain a coating solution.

[0049]

[Chemical 19]

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,
The optimum recording power for recording the EFM signal is 9.8 m.
It was W, 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. Further, the storage stability of the recording portion under high temperature and high humidity was evaluated, and it was good.

Examples 4 to 10 Recording media were prepared in the same manner except that the compounds shown in Table 1 were used instead of the metal complex compound, indolenine type cyanine dye and metallocene compound used in Example 1. . Then, as in Example 1, recording was performed with a semiconductor laser beam having a center wavelength of 780 nm while rotating at 5.6 m / s. The optimum recording power required for recording the EFM signal is as shown in Table-1. Met. 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.

[0054]

[Table 1]

[0055]

The optical recording medium using the composition of the present invention, which is a metal complex compound of an azo compound and a metal, an indolenine cyanine dye and a metallocene compound, is excellent in light resistance and heat resistance, and is capable of high-speed recording. The sensitivity is good at the time, and the storage stability of recording is excellent, and it is extremely useful industrially.

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-9-54980 (JP, A) JP-A-10-116443 (JP, A) JP-A-7-98887 (JP, A) JP-A-10- 147062 (JP, A) JP-A-4-361088 (JP, A) JP-A-7-251567 (JP, A) International Publication 91/018950 (WO, A1) (58) Fields investigated (Int.Cl. ⁷⁾ , DB name) B41M 5/26 G11B 7/24 516 CAPLUS (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. An optical recording medium in which a recording layer capable of writing and / or reading information by a laser is provided on a substrate, wherein the recording layer is represented by the following general formula [I]: (Wherein A represents a residue which, together with the carbon and nitrogen atoms to which it is attached, forms a heterocycle, B is an aromatic group together with the two carbon atoms to which it is attached. Represents a residue forming a ring or a heterocycle, and X represents a group having active hydrogen), and a complex compound of an azo compound and a metal represented by the following general formula [II] (In the formula, P and P ′ each independently represent a residue that forms an aromatic ring together with the two carbon atoms to which it is bonded, and Q represents an optionally substituted pentamethine group. Represents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R
⁶ independently represents an alkyl group which may be substituted, an aryl group which may be substituted, an alkenyl group which may be substituted or a cycloalkyl group which may be substituted, and Z ⁻ is an anion Represents a residue. )
And an indolenine cyanine dye represented by the following general formula [III] (In the formula, R represents a boric acid group or a benzoyl group, and
Represents Fe or Ni. And a metallocene compound represented by the formula (1). 2. The azo compound is represented by the following general formula [IV]: (Wherein A represents a residue which, together with the carbon and nitrogen atoms to which it is attached, forms a heterocycle, B is an aromatic group together with the two carbon atoms to which it is attached. The optical recording medium according to claim 1, which is an azo compound represented by a group-forming residue). 3. The azo compound is represented by the following general formula [V]: (In the formula, A represents a residue which forms a heterocyclic ring together with the carbon atom and the nitrogen atom to which it is bonded, and R ⁷ and R ⁸ each independently have a hydrogen atom or a substituent. Represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group or an optionally substituted cycloalkyl group, and ring D is substituted. The optical recording medium according to claim 1, which is an azo compound represented by the formula (1) or (2). 4. The optical recording medium according to claim 1, wherein a metal reflection layer and a protective layer are provided on the recording layer.