JPH09240149A - Optical recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recording material for an optical recording medium adaptable to a high density optical disk system using semiconductor laser having an oscillation wavelength within a short wavelength region and exbellent in light fastness and storage stability by adding a specific compd. to a recording layer. SOLUTION: At least one compd. represented by either one of formulae I, II, III is added to the recording layer of an optical recording medium. In the formulae I, II, III, R<1> -R<3> are respectively independently an amino group, a 1-6C dialkylamino group which may be substituted, a halogen atom, a nitro group, a hydroxyl group or a substituted or non-substituted alkyl group, R<4> -R<6> are respectively independently a halogen atom, a nitro group, a hydroxyl group or a substituted or non-substituted alkyl group, O<-> , COO<-> or SO3 <-> , (l), (m) and (n) are respectively independently an integer of 0-4, R<7> is a halogen atom, a nitro group, a hydroxyl group, a substituted or non-substituted alkyl group, a substituted or non-substituted alkoxy group, a substituted or non-substituted alkylthio group, O<-> , COO<-> or SO3 <-> , Z is a heterocyclic residue, X is an acid anion or a metal complex anion and Q is 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium, and more particularly, to irradiating a light beam to cause an optical change such as transmittance and reflectance of a recording material.
The present invention relates to an optical recording medium on which information can be recorded, reproduced, and additionally recorded.

[0002]

2. Description of the Related Art The current write-once optical disk system (WO
RM, CD-R), the oscillation wavelength of the laser used is 770.
nm to 790 nm, and the recording medium records at the above wavelength,
It is configured to be able to reproduce. In the future, it is indispensable to increase the capacity of the recording medium as the amount of information increases. Therefore, it is easily expected that the wavelength of the laser used for recording and reproduction will inevitably be shortened. As a write-once optical disc for data, a number of proposals have been made using a cyanine dye or a phthalocyanine dye as a recording material (for example, JP-A-57-82093 discloses a disc using a cyanine dye as a recording material. JP-A-58-56892, JP-A-58-112790,
JP-A-58-114989, JP-A-59-85791
JP-A-60-83236, JP-A-60-8984
No. 2, JP-A-61-25886, and those using a phthalocyanine dye as a recording material are described in JP-A-61-150243 and JP-A-61-177287.
JP-A-61-154888, JP-A-61-246
No. 091, JP-A-62-39286, JP-A-63-3
No. 7791, JP-A-63-39888, etc.), but a recording material which is excellent in light resistance and storage stability and which can be recorded and reproduced by an optical pickup using a laser of 700 nm or less is still being developed. It has not been done yet.

The current CD-R disk system is also configured so that recording and reproduction can be performed at a laser oscillation wavelength of 770 nm to 790 nm. This system is also required to have a large capacity and a short recording / reproducing wavelength, similarly to the above. In this regard, current CDs and CD-ROMs
Al is coated on the unevenness of the substrate itself.
Has a small wavelength dependence of the reflectance, so that it is possible to reproduce even if the laser wavelength is shortened in the future. However,
The CD-R uses a dye having a maximum absorption wavelength at 680 nm to 750 nm for the recording layer, and is set so as to obtain a high reflectance at 770 nm to 790 nm from the optical constant and the film thickness configuration. In this case, the reflectivity is extremely low, so that it is impossible to cope with the shortening of the laser wavelength, and information recorded and reproduced by the current CD-R system cannot be reproduced by a future system. Until now CD
Numerous proposals have been made for -R using a cyanine dye / metal reflection layer, a phthalocyanine dye / metal reflection layer, or an azo metal chelate dye / metal reflection layer as a recording material (for example, a cyanine dye / metal reflection layer is used. JP-A-1-159842, JP-A-2-42652, JP-A-2-13656 and JP-A-2-168446 each use a phthalocyanine dye as a recording material. Japanese Patent Laid-Open No. 1-1765
No. 85, JP-A-3-215466, JP-A-4-113
886, JP-A-4-226390, JP-A-5-12
72, JP-A-5-171052, and JP-A-5-116.
456, JP-A-5-69860, JP-A-5-139
Nos. 044-46186, and those using an azo metal chelate dye as a recording material are described in JP-A-4-46186.
JP-A-4-141489, JP-A-4-36088
And Japanese Unexamined Patent Application Publication No. 5-279580), however, no solution has been found to solve such a problem.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above situation, and has a high density optical disk using a semiconductor laser having an oscillation wavelength shorter than that of the conventional system. It provides a recording material for optical recording media with excellent light resistance and storage stability that can be applied to systems, and a CD-ROM that can be recorded and played back with the current system and can be played back even in the next-generation high-density optical disk system. It is an object to provide a recording material for an R medium.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by providing a recording layer containing a dye having a specific structure as a main component, a high-density semiconductor laser having an oscillation wavelength of 700 nm or less can be used. It is found that it can be applied to optical disc systems, and furthermore, it is possible to obtain a high reflectance even in the wavelength region of 700 nm or less by using this dye in combination with an organic dye currently used as a recording material for CD-R. Have been found possible, and the present invention has been completed.

[0006] That is, according to the present invention, firstly, a recording layer is provided on a substrate directly or via an undercoat layer, and if necessary, a reflection layer and a protective layer are provided on the recording layer. In a recording medium, provided is an optical recording medium characterized in that the recording layer contains at least one compound represented by the following general formula (I), (II) or (III).

Embedded image

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Embedded image ^{Wherein, R 1 ~R 7, 1,} m, n, Z, X, and Q represents the following, respectively. R ^{1 to} R ³ each independently represent an amino group, a dialkylamino group having 1 to 6 carbon atoms which may be substituted, a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group; group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted carboxylic acid ester group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted arylthio group, R ⁴ to R ⁶ : each independently a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted dialkylamino group,
O ⁻ , COO ⁻ , or SO ₃ ⁻ , 1, m, n: each independently an integer of 0 to 4; R ⁷ : halogen atom, nitro group, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted Alkoxy group, substituted or unsubstituted alkylthio group, amino group,
Dialkylamino group, O ⁻ , COO ⁻ , or SO ₃ ⁻ , Z: heterocyclic residue, X: acid anion or metal complex anion, Q: 0 or 1. Secondly, the recording layer has the general formula (I), (II) or (I
II) and at least one compound of 680 nm
There is provided an optical recording medium as described in the first item, which comprises an organic dye having a maximum absorption wavelength at 750 nm. Thirdly, there is provided the optical recording medium according to the second aspect, wherein the organic dye having the maximum absorption wavelength at 680 nm to 750 nm is at least one of a pentamethine cyanine dye, a phthalocyanine dye, and an azo metal chelate dye. Fourth, the recording layer has wavelengths of 630 to 72.
There is provided the optical recording medium according to any one of the above first to third, which is recorded by a laser beam of 0 nm. Fifthly, there is provided the optical recording medium according to any one of the first to fourth aspects, wherein the reflection layer is made of aluminum or gold. Sixth, there is provided the optical recording medium according to any one of the first to fifth, wherein the protective layer is made of an ultraviolet curable resin.

Since the optical recording medium of the present invention is provided with a recording layer containing at least one compound represented by the general formula (I), (II) or (III), it has a thickness of 700 nm.
It becomes possible to record and reproduce with a laser beam in the following wavelength range, and it has excellent light resistance and storage stability. In another aspect, it is represented by the general formula (I), (II) or (III). Since a recording layer made of a mixture of at least one compound described above and an organic dye having a maximum absorption wavelength in the range of 680 to 750 nm is provided, it can be used as a CD-R medium in the current system and has a high density in the next generation. Even if it becomes an optical disk system, it becomes possible to reproduce the described information.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The optical recording medium of the present invention has the following general formula (I) in the recording layer:
It is characterized by containing at least one compound represented by (II) or (III).

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Embedded image

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First, the compound represented by the above general formula (I), (II) or (III) used in the present invention will be described. In the above general formulas (I) to (III), R ¹ ,
R ² and R ³ are each independently an amino group, an optionally substituted dialkylamino group having 1 to 6 carbon atoms, a halogen atom,
Nitro group, hydroxyl group, substituted or unsubstituted alkyl group,
Substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted carboxylic acid ester group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, or substituted or unsubstituted arylthio group And R ⁴ , R ⁵ , and R ⁶ are each independently a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a substituted or Unsubstituted dialkylamino group, O ⁻ , COO ⁻ , or S
O ₃ ^- represents a. l, m, and n each independently represent an integer of 0 to 4. R ⁷ is a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, an amino group, a dialkylamino group, O ⁻ , COO ⁻ , or SO
₃ ^- represents, Z is a heterocyclic residue. X represents an acid anion or a metal complex anion, and Q represents 0 or 1.

[0010] X represents a halogen ion, perhalogen acid ion, alkyl sulfate anion, PF ₆ anion, a BF ₄ anion, SbF ₆ anion anion, R ^1, R
^{2. When} the substituent in R ³ has 6 or more alkyl carbon atoms in the dialkylamino group, the stability (light resistance and storage stability) is extremely reduced.

Specific examples of the alkyl groups (including an alkoxy group, an alkylalkoxy group, and an alkyl moiety in a carboxylic acid ester group) represented by R ^{1 to} R ^{7 in} the general formulas (I) to (III) include a methyl group, Ethyl group, n-propyl group, n-
Butyl group, isobutyl group, n-pentyl group, neopentyl group, isoamyl group, 2-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group,
4-methylpentyl group, 2-ethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2
-Ethylpentyl group, 3-ethylpentyl group, n-octyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 2
-Primary alkyl groups such as ethylhexyl group, 3-ethylhexyl group, n-nonyl group, n-decyl group, n-dodecyl group; isopropyl group, sec-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1, 2-dimethylpropyl group, 1-methylheptyl group, 1-ethylbutyl group,
1,3-dimethylbutyl group, 1,2-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1-methylhexyl group, 1-ethylheptyl group, 1-propylbutyl group, 1-isopropyl-2- Methylpropyl group, 1-ethyl-2-methylbutyl group, 1-propyl-2-methylpropyl group, 1-methylheptyl group, 1-ethylhexyl group, 1-propylpentyl group, 1-isopropylpentyl group, 1-isopropyl -2-methylbutyl group, 1-
Secondary alkyl groups such as isopropyl-3-methylbutyl group, 1-methyloctyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-isobutyl-3-methylbutyl group; tert-butyl group, tert-hexyl group,
Tertiary alkyl groups such as tert-amyl group and tert-octyl group; cyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-tert-butylcyclohexyl group, 4- (2-ethylhexyl) cyclohexyl group, bornyl And cycloalkyl groups such as an isobornyl group and an adamantane group. These alkyl groups may be substituted with a substituent such as a halogen atom.

Specific examples of the substituted or unsubstituted aryl group (including the aryl portion of the substituted or unsubstituted aryloxy group) include phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group,
Examples include an ethylphenyl group, a tert-butylphenyl group, a butylphenyl group, a nonylphenyl group, a methoxyphenyl group, a dimethoxyphenyl group, a butoxyphenyl group, a naphthyl group, a pyridyl group, and a methylpyridyl group. Further, these aryl groups may be substituted with a substituent such as a halogen atom.

Z represents a heterocyclic residue, and specific examples thereof include a substituted or unsubstituted pyridine residue, pyridazine residue, pyrimidine residue, pyrazine residue, thiophene residue and the like.

Further, Q is 0 or 1, but R
⁴ or R ⁷ is _{^{O -, COO -, SO 3}} - is Q only when it becomes either are all 0, otherwise 1.

Further, specific examples of the metal complex anion for X include the following.

Embedded image In the formula, R ¹¹ and R ¹² represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic residue. M represents Ni, Pd, Pt, Cu or Co.

Embedded image In the formula, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group directly or indirectly bonded via a divalent linking group. Represents a residue. M is the same as above.

[Chemical 6] In the formula, X represents S or CR ¹¹ R ¹² . R ¹¹ and R ¹² are C
N, COR ¹³ , COOR ¹⁴ , CONR ¹⁵ R ¹⁶ or S
OR ^17, 5-membered ring, represents an atomic group necessary to form a 6-membered ring, R ¹³ to R ¹⁷ is a substituted or unsubstituted alkyl group,
Or an aryl group. M is the same as above.

[0016]

Embedded image In the formula, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group directly or indirectly bonded via a divalent linking group. Represents a residue. R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carboxyl group, or a sulfonyl group. M is the same as above.

Embedded image In the formula, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group directly or indirectly bonded via a divalent linking group. Represents a residue. R ¹⁵ and R ¹⁶ represent a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carboxyl group, or a sulfonyl group. M is the same as above.

Embedded image In the formula, R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group, or an aryl group. R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are a hydrogen atom,
Represents a halogen atom, an alkyl group, or an aryl group. M is the same as above.

[0017]

Embedded image In the formula, X ¹ represents O or S. R ¹¹ , R ¹² , and R ¹³ represent a substituted or unsubstituted alkyl group, aryl group, or cycloalkyl group directly bonded through an oxy group, a thio group, or an amino group. M is the same as above.

Embedded image In the formula, R ¹¹ , R ¹² and R ¹³ represent a substituted or unsubstituted alkyl group, aryl group or cycloalkyl group bonded directly or via an oxy group, a thio group or an amino group. X ¹ represents O or S. R ¹⁴ represents an alkyl group or an aryl group. M is the same as above.

Embedded image In the formula, R ¹¹ and R ¹² represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic residue. M is the same as above.

[0018]

Embedded image In the formula, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group directly or indirectly bonded via a divalent linking group. Represents a residue. M is the same as above.

Embedded image In the formula, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group directly or indirectly bonded via a divalent linking group. Represents a residue. R ¹⁵ and R ¹⁶ represent a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carboxyl group, or a sulfonyl group. M is the same as above.

Embedded image In the formula, R ¹¹ represents an alkyl group or an aryl group. R ¹² ,
R ¹³ , R ¹⁴ , and R ¹⁵ represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. M is the same as above.

Table 1 shows examples of metal complex anion compounds.

[0020]

[Table 1- (1)]

[0021]

[Table 1- (2)]

Specific examples of the compounds represented by the above general formulas (I) to (III) include, for example, Table 2- (1) to Table 2-.
Examples shown in (3) are given.

[0023]

[Table 2- (1)]

[0024]

[Table 2- (2)]

[0025]

[Table 2- (3)]

As described above, the recording layer mainly contains a mixture of at least one compound represented by the above general formula (I) and an organic dye having a maximum absorption wavelength at 680 to 750 nm. As a result, the CD-R recording medium can be recorded and reproduced by the current system and can be reproduced only by the next-generation system. In this case, as the dye having the maximum absorption wavelength at 680 to 750 nm, pentamethine cyanine dye, phthalocyanine dye and azo metal chelate dye are preferable.

Preferred examples of pentamethine cyanine dyes include those represented by the following general formula (IV).

Embedded image In the formula, R ²¹ and R ²² are an alkyl group having 1 to 3 carbon atoms, R ²³ ,
R ²⁴ represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms;
Represents an acid anion. Note that the aromatic ring may be condensed with another aromatic ring, or may be substituted with an alkyl group, a halogen atom, an alkoxy group, or an acyl group.

Preferred examples of the phthalocyanine dye include those represented by the following general formula (V-1) or (V-2).

Embedded image In the formula, M ¹ is Ni, Pd, Cu, Zn, Co, Mn, F
e, TiO or VO, X ^{5 to} X ⁸ each independently represent -OR or -SR at the substitution position α-position, and R represents an optionally substituted linear, branched or alicyclic group having 3 to 12 carbon atoms. Represents an alkyl group or an aryl group which may be substituted. Substituents on the benzene ring other than X ^{5 to} X ⁸ are a hydrogen atom or a halogen atom.

[0029]

Embedded image In the formula, M ² is Si, Ge, In, or Sn, and is X ⁹ to X.
¹² is each independently -OR or -SR at the substitution position α.
R is an optionally substituted straight chain having 3 to 12 carbon atoms,
A branched or alicyclic alkyl group or an aryl group which may be substituted, wherein Y ⁵ and Y ⁶ are each —OSiR ²⁵ R ²⁶ R
²⁷ , -OCOR ²⁵ R ²⁶ R ²⁷ , or -OPOR ²⁵ R ²⁶ R ²⁷
Wherein R ^{25 to} R ²⁷ each independently represent 1 to 10 carbon atoms.
Represents an alkyl group or an aryl group. Substituents on the benzene ring other than X ^{9 to} X ¹² are a hydrogen atom or a halogen atom.

Preferred examples of the azo metal chelate dye include one or more azo metal chelate compounds of an azo compound represented by the following general formula (VI) and a metal, and the metal is preferable. Examples include Ni, Pt,
Pd, Co, Cu, Zn etc. are mentioned.

Embedded image In the formula, A represents a residue which forms a heterocyclic ring together with the carbon atom and nitrogen atom to which it is bonded, and B represents an aromatic ring together with the two carbon atoms to which it is bonded. Or, it represents a residue forming a heterocycle, and X ² represents a group having active hydrogen.

At least one dye represented by the general formulas (I) to (III) of the present invention and the general formulas (IV) to (VI)
The weight composition ratio in the case of using together with at least one kind of dye is represented by the following formula: dye of the present invention / [dye of (IV) to (VI)] =
10/100 to 90/100, preferably 40/100
~ 20/100. When both dyes are used in combination, the recording layer has a film thickness of 500Å to 5 μm, preferably 1000.
It is from Å to 5000Å.

Next, the configuration of the recording medium of the present invention will be described. FIG. 1 is a diagram showing an example of a layer configuration applicable to the recording medium of the present invention, which is an example of a write-once optical disc. The recording layer 2 is provided on the substrate 1 via an undercoat layer 3 if necessary.
And, if necessary, a protective layer 4. Further, a hard coat layer can be provided under the substrate 1 as needed. FIG. 2 is a diagram showing another example of a layer structure applicable to the recording medium of the present invention, which is an example of a CD-R medium. A reflective layer 6 is formed on the recording layer 2 having the structure shown in FIG.
Is provided. The recording medium of the present invention may have an air sandwich structure in which the recording layer (organic thin film layer) having the structure shown in FIGS. A bonding structure in which the layers are bonded via a protective layer may be used.

Next, the required characteristics of the constituent layers and the constituent materials thereof will be described. 1) Substrate As a necessary characteristic of the substrate, when recording / reproducing is performed from the substrate side, it must be transparent to the laser beam to be used. However, when recording / reproducing is performed from the recording layer side, it is not necessary to be transparent. As the substrate material, for example, polyester, acrylic resin, polyamide, polycarbonate resin, polyolefin resin, phenol resin, epoxy resin, plastic such as polyimide, glass, ceramic, metal or the like can be used. Note that a guide groove or guide pit for tracking, and a preformat such as an address signal may be formed on the surface of the substrate.

2) Recording Layer The recording layer is capable of recording some information by causing some kind of optical change by irradiation with laser light, and
The recording layer contains at least one of the compounds represented by formulas (I) to (III), and optionally, at least one of the dyes represented by formulas (IV) to (VI). Need to be. Further, these dyes can be used by mixing or laminating them with other organic dyes, metals, and metal compounds in order to improve optical characteristics, recording sensitivity, and signal characteristics. Other organic dyes in this case include polymethine dyes, naphthalocyanine-based, phthalocyanine-based, squarylium-based, croconium-based, pyrylium-based, naphthoquinone-based, anthraquinone (indanthrene) -based, xanthene-based, triphenylmethane-based, and azulene-based , A tetrahydrocholine-based, a phenanthrene-based, a triphenothiazine-based dye, and a metal complex compound. Examples of metals and metal compounds include In and T
e, Bi, Se, Sb, Ge, Sn, Al, Be, Te
O ₂ , SnO, As, Cd and the like can be mentioned, and each can be used in the form of dispersion mixing or lamination. Further, various materials such as a polymer material, for example, an ionomer resin, a polyamide resin, a vinyl resin, a natural polymer, silicone, a liquid rubber, or a silane coupling agent may be dispersed and mixed in the dye, For improvement purposes, they can be used together with stabilizers (e.g. transition metal complexes), dispersants, flame retardants, lubricants, antistatic agents, surfactants, plasticizers and the like.

The recording layer is formed by vapor deposition, sputtering,
It can be carried out by ordinary means such as CVD or solvent application. In the case of using a coating method, the above dye or the like can be dissolved in an organic solvent, and the coating can be performed by a conventional coating method such as spraying, roller coating, dipping or spin coating. Examples of the organic solvent used include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; amides such as N, N-dimethylacetamide and N, N-dimethylformamide; and sulfoxides such as dimethyl sulfoxide. , Tetrahydrofuran, dioxane, diethyl ether, ethers such as ethylene glycol monomethyl ether, methyl acetate, esters such as ethyl acetate,
Aliphatic halogenated carbons such as chloroform, methylene chloride, dichloroethane, carbon tetrachloride, and trichloroethane; aromatics such as benzene, xylene, monochlorobenzene, and dichlorobenzene; and cellsolves such as methoxyethanol and ethoxyethanol; hexane and pentane And hydrocarbons such as cyclohexane and methylcyclohexane. The thickness of the recording layer is
100 ° to 10 μm, preferably 200 ° to 2000 °
Is appropriate.

3) Undercoating layer The undercoating layer is used to improve adhesiveness, a barrier against water or gas, improve storage stability of the recording layer, improve reflectivity, protect the substrate from a solvent, guide grooves and guides. It is used for forming pits and preformats. For the purpose of the polymer material, for example, ionomer resin, polyamide, vinyl resin, natural resin, natural polymer, silicone, various polymer compounds such as liquid rubber and silane coupling agent and the like can be used,
In addition to the above-mentioned polymer materials, inorganic compounds such as SiO ₂ , MgF ₂ , SiO, TiO ₂ , Z
nO, TiN, SiN, etc., and further, a metal or semimetal such as Zn, Cu, Ni, Cr, Ge, Se, A
u, Ag, Al and the like can be used. For the purpose, a metal such as Al, Au, Ag or the like, or an organic thin film having a metallic luster such as a methine dye or a xanthene-based dye can be used. Cured resin, thermosetting resin, thermoplastic resin, or the like can be used. The thickness of the undercoat layer is 0.
The thickness is suitably from 01 to 30 μm, preferably from 0.05 to 10 μm.

4) Reflective Layer The reflective layer may be made of a metal or semi-metal which has a high reflectance and is resistant to corrosion. Examples of materials include Au,
Ag, Al, Cr, Ni, Fe, Sn and the like.
Au and Al are most preferred in terms of reflectivity and productivity. These metals and metalloids may be used alone or as two or more alloys. Examples of the film forming method include vapor deposition and sputtering, and the film thickness is 50 to 5000.
Å, preferably 100 to 3000 Å.

5) Protective Layer, Substrate-side Hard Coat Layer The protective layer or substrate-side hard coat layer protects the recording layer (reflective / absorptive layer) from scratches, dust, dirt, etc. It is used for the purpose of improving stability and reflectance. For these purposes, the materials shown in the undercoat layer can be used. Also,
As an inorganic material, SiO, SiO _{2 and the} like can also be used, and as an organic material, polymethyl acrylate, polycarbonate, epoxy resin, polystyrene, polyester resin, vinyl resin, cellulose, aliphatic hydrocarbon resin,
Thermosoftening and heat melting resins such as natural rubber, styrene-butadiene resin, chloroprene rubber, wax, alkyd resin, drying oil, and rosin can also be used. The most preferable of the above materials is an ultraviolet curable resin having excellent productivity. The thickness of the protective layer or the hard coat layer on the substrate surface is 0.01 to 30 μm, preferably 0.05 to 10 μm.
Is appropriate.

In the present invention, the undercoat layer, the protective layer, and the hard coat layer on the substrate surface are formed in the same manner as in the case of the recording layer.
A stabilizer, a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer and the like can be contained.

[0040]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Example 1 A photopolymer was formed on a polymethylmethacrylate substrate having a thickness of 1.2 μm, and the depth was 1200Å and the half value width was 0.35 μm.
m, the compound specific example No. 2 was formed on the substrate on which the guide groove having the track pitch of 1.0 μm was formed. The 1,2-dichloroethane solution of No. 1 was applied by spinner, and a recording layer having a thickness of 900Å was provided to obtain a recording medium.

Examples 2 to 8 In Example 1, compound Nos. Instead of 1.
Compound specific example No. 2, No. 6, no. 11, No.
30, no. 41, no. 42, No. Recording media of Examples 2 to 8 were obtained in the same manner as in Example 1 except that 45 was used.

Comparative Example 1 In Example 1, the specific compound No. A recording medium of Comparative Example 1 was obtained in the same manner as in Example 1 except that the compound represented by the following formula (VII) was used in place of 1.

Embedded image

Using the recording media of Examples 1 to 8 and Comparative Example 1, recording was performed by irradiating light from a substrate under the following recording conditions, and then the recording position was measured for C / N and reflectivity by reproduction light. did. Table 3 shows the results. Recording conditions: Laser oscillation wavelength 650 nm Recording frequency 1.25 MHz Recording linear velocity 1.2 m / sec Reproduction conditions: Laser oscillation wavelength 650 nm Reproduction power 0.25 to 0.3 mW continuous light scanning bandwidth 30 KHz Light resistance test conditions: Light resistance test 4 10,000 Lux, Xe light, 20 hours continuous irradiation storage test 85 ℃, 85%, leave for 720 hours

[0045]

[Table 3]

Example 9 On a 1.2 mm thick injection-molded polycarbonate substrate having guide grooves with a depth of 1000 Å, a half width of 0.35 μm and a track pitch of 1.0 μm, the compound No. 16 was dissolved in a mixed solution of methylcyclohexane, 2-methoxyethanol, methyl ethyl ketone, and tetrahydrofuran, and spin-coated to form a recording layer having a thickness of 1800１.
The reflective layer was provided, and a protective layer of 5 μm was further provided on the reflective layer with an acrylic photopolymer to obtain a recording medium.

Examples 10 to 16 In Example 9, the specific compound Nos. In place of Compound No. 16, each of Compound Specific Example Nos. 5, no. 10, No. 1
5, no. 17, No. 25, no. 34, no. 48
Example 10 was carried out in the same manner as in Example 9 except that
To 16 recording media were obtained.

Comparative Example 2 In Example 9, Compound No. A recording medium of Comparative Example 2 was obtained in the same manner as in Example 9 except that the compound represented by the formula (VII) used in Comparative Example 1 was used in place of 16.

EFM signals were recorded on the recording media of Examples 9 to 16 and Comparative Example 2 while tracking them using a semiconductor laser beam having an oscillation wavelength of 635 nm and a beam diameter of 1.0 μm (linear velocity 1.4 m / sec). The reproduced waveform was observed by reproducing with the continuous light of the same laser. The results are shown in Table 4.

[0050]

[Table 4]

Example 17 A compound represented by the following formula (VIII) was formed on a 1.2 mm thick injection-molded polycarbonate substrate having a guide groove with a depth of 1000 Å, a half width of 0.40 μm and a track pitch of 1.1 μm. Specific compound No. 3 and the weight ratio (1 /
It is dissolved in a mixed solvent of 1) methylcyclohexane, 2-methoxyethanol, methyl ethyl ketone, and tetrahydrofuran, and spin-coated to form a recording layer having a thickness of 1700 °, and then a reflective layer of 2000 ° gold is formed by a sputtering method. A 5 μm protective layer of an acrylic photopolymer was provided thereon to obtain a recording medium.

[0052]

[Chemical 21]

Examples 18 and 19 In Example 17, specific compound No. Instead of the compound specific example No. 3, 10, No. Examples 18 and 1 were carried out in the same manner as in Example 17 except that 16 was used.
9 recording media were obtained.

Examples 20 and 21 In Example 17, compound specific examples No. Instead of the compound specific example No. 3, 33, no. 38,
Example 1 was repeated except that the compound represented by the following formula (IX) was used in place of the compound represented by the above formula (VIII).
Recording media of Examples 20 and 21 were obtained in the same manner as in Example 7.

[0055]

Embedded image

Examples 22 and 23 In Example 17, compound specific examples No. Instead of the compound specific example No. 3, 20, no. 35,
Example 1 was repeated except that the compound represented by the following formula (X) was used instead of the compound represented by the formula (VIII).
In the same manner as in Example 7, recording media of Examples 22 and 23 were obtained.

[0057]

Embedded image

Comparative Examples 3 to 5 In Example 17, the recording layers were each formed by the above general formula (VI).
Comparative Examples 3 to 3 in the same manner as in Example 17 except that only the compound represented by II), only the compound represented by the general formula (IX), and only the compound represented by the general formula (X) were used.
5 recording media were obtained.

EFM signals were recorded on the recording media of Examples 17 to 23 and Comparative Examples 3 to 5 with a semiconductor laser beam having an oscillation wavelength of 780 nm and a beam diameter of 1.6 μm (linear velocity 1.4 m / sec). ), Reproduction was performed with continuous light of the laser and a semiconductor laser having an oscillation wavelength of 635 nm and a beam diameter of 1.1 μm, and the reproduction waveform was observed. The results are shown in Table 5.
Shown in

[0060]

[Table 5]

[0061]

The optical recording medium according to claim 1 comprises at least one compound represented by the general formula (I), (II) or (II) in the recording layer. Since it has high light absorption and light reflectivity at wavelengths of 700 nm or less, it is possible to record and reproduce with laser light in the wavelength range of 700 nm or less, which enables high-density recording, and has excellent light resistance and storage stability. Are better.

The optical recording medium according to claim 2 is a recording layer containing at least one compound represented by the general formula (I), (II) or (III) and an organic dye having a maximum absorption wavelength at 680 to 750 nm. Since it is contained in the medium, it is possible to record and reproduce with the current system, and it is possible to reproduce the recorded information even with the next-generation high-density optical disc system.

The optical recording medium according to claim 3 is 680 to 750.
Since at least one of a cyanine dye of pentamethine, a phthalocyanine dye, and an azo metal chelate dye is selected as the organic dye having a maximum absorption wavelength in nm, high-quality signal characteristics can be recorded.

In the optical recording medium of the fourth aspect, the recording layer has a wavelength of 6
Since the recording is performed with a laser beam of 30 to 720 nm, a high density write-once write-once optical recording medium having a density of 1.6 to 1.8 times that of an optical recording medium compatible with 770 to 830 nm can be obtained.

In the optical recording medium according to the fifth aspect, since the reflection layer is made of aluminum or gold, high reflectivity and CD-R media with good productivity can be realized.

In the optical information recording medium according to the sixth aspect, since the protective layer is made of an ultraviolet curable resin, it is possible to form a medium with a protective layer having high productivity.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a layer configuration as a general write-once optical recording medium applicable to a recording medium of the present invention.

FIG. 2 is a diagram showing a layer configuration example for a CD-R applicable to the recording medium of the present invention.

[Explanation of symbols]

 1 substrate 2 recording layer (organic dye layer) 3 undercoat layer 4 protective layer 5 hard coat layer 6 reflective layer

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yasunobu Ueno 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd.

Claims (6)

[Claims] 1. An optical recording medium in which a recording layer is provided on a substrate directly or via an undercoat layer, and if necessary, a reflective layer and a protective layer are further provided on the substrate, the following recording layer is provided in the recording layer. An optical recording medium comprising at least one compound represented by formula (I), (II) or (III). Embedded image Embedded image Embedded image ^{Wherein, R 1 ~R 7, 1,} m, n, Z, X, and Q represents the following, respectively. R ^{1 to} R ³ each independently represent an amino group, a dialkylamino group having 1 to 6 carbon atoms which may be substituted, a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group; group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted carboxylic acid ester group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted arylthio group, R ⁴ to R ⁶ : each independently a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted dialkylamino group,
O ⁻ , COO ⁻ , or SO ₃ ⁻ , 1, m, n: each independently an integer of 0 to 4, R ⁷ : halogen atom, nitro group, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted Alkoxy group, substituted or unsubstituted alkylthio group, amino group,
Dialkylamino group, O ⁻ , COO ⁻ , or SO ₃ ⁻ , Z: heterocyclic residue, X: acid anion or metal complex anion, Q: 0 or 1. ] 2. The recording layer has the general formulas (I) and (II).
Or at least one compound represented by (III) and 680
The optical recording medium according to claim 1, further comprising an organic dye having a maximum absorption wavelength in the range of nm to 750 nm. 3. An organic dye having a maximum absorption wavelength in the range of 680 nm to 750 nm is a pentamethine cyanine dye,
The optical recording medium according to claim 2, which is at least one of a phthalocyanine dye and an azo metal chelate dye. 4. The optical recording medium according to claim 1, wherein the recording layer is recorded by laser light having a wavelength of 630 to 720 nm. 5. The optical recording medium according to claim 1, wherein said reflection layer is made of aluminum or gold. 6. The optical recording medium according to claim 1, wherein the protective layer is made of an ultraviolet curable resin.