JPH07138493A - Metal complex compound and optical recording medium using the same - Google Patents

Abstract

PURPOSE:To obtain a compound which has at least one alkylsulfonamide group, arylsulfonamdie group and the like capable of linking with a metal atom in a part of the compound and is useful for the optical recording medium of high molar absorption coefficient as a pigment of high light fastness. CONSTITUTION:A novel metal complex which has, in its moiety of pigment structure, at least one group selected from alkylsulfonamides, arylsulfonamdies, heterocyclic sulfonamides, acylamino groups substituted with electron-attracting groups, groups of imidazolyl, sulfamoyl and carbamoyl, is shown by the formula (X is an alkylsulfonamide, an arylsulfonamide, a heterocyclic sulfonamide, an acylamino substituted with an electron-attracting group, imidazolyl, sulfamoyl, carbamoyl; R1-R3 each is H, a nonmetal atom group; Z is OH, an alkylamino, an alkoxy; M is Ni, Cu, Co, Zn, Fe, Pd, Pt), and is useful as a pigment of high light fastness and high molar absorption coefficient.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel metal complex compound having excellent properties as a dye and an optical recording medium using the compound as a light absorbing substance.

[0002]

2. Description of the Related Art Pigments known as dyes and pigments are
It is widely used in various applications such as dyeing materials for fibers, coloring materials for resins and paints, image forming materials for photography, printing, copying machines and printers, and light absorbing materials for color filters. Common problems of these dyes include optimization of absorption wavelength and waveform, improvement of molar absorption coefficient, and improvement of storage stability such as light resistance and heat resistance.

In order to form a full color or three primary colors, three kinds of dyes of yellow, magenta and cyan are required, and a cyan dye having particularly good absorption characteristics and storage stability is desired.

On the other hand, in recent years, with the rapid increase in the amount of information,
Large-capacity optical recording media are in the spotlight. A long-wavelength absorption dye that absorbs light in the red to near-infrared region is used for an organic optical recording medium that can easily and highly densely record information with an inexpensive semiconductor laser.

Conventionally, cyanine dyes having excellent absorption and reflection characteristics have been used for this purpose among various dyes.
Since the storage stability such as light resistance is low, there is a drawback that information is lost or writing becomes impossible with the passage of time.

In order to solve such a problem, for example, US Pat. Nos. 3,432,300, 4,050,938, JP Patent Publication Nos. 60-118748, 63-199248, and Hei 2-300288, light stabilizers, Alternatively, although a photostabilization method has been described, sufficient storage stability has not been obtained yet. In addition, published patent publications Sho 64-44786, Hei 2-76884, and No. 5-17701 describe metal chelate dyes having excellent storage stability.
Since the absorption wavelength is too long, it cannot be used for optical recording media.

[0007]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a subject of the above dye, especially a dye having a high molar extinction coefficient and excellent light resistance. The second object of the present invention is to obtain optical recording characteristics and storage stability by using a dye having an absorption suitable for a semiconductor laser used in an optical recording device, a high molar extinction coefficient, and excellent light resistance. To provide an excellent optical recording medium.

[0008]

The above object of the present invention can be achieved by the following constitutions.

1. At least one of an alkylsulfonamide group capable of binding to a metal atom, an arylsulfonamide group, a heterocyclic sulfonamide group, an acylamino group substituted with an electron-withdrawing group, an imidazolyl group, a sulfamoyl group, and a carbamoyl group is part of the dye structure. A metal complex compound having two (except when the dye structure is an imidazole azomethine dye).

2. 2. The metal complex compound as described in 1 above, wherein the dye structure is an azomethine dye synthesized from each derivative of naphthol, phenol, pyrazolotriazole, pyrazolone, acylacetamide and acylacetate.

3. The metal complex compound as described in 1 above, wherein the dye structure is represented by the following general formula I.

[0012]

[Chemical 2]

In the formula, X is an alkylsulfonamide group, an arylsulfonamide group, a heterocyclic sulfonamide group,
It represents an acylamino group substituted with an electron-withdrawing group, an imidazolyl group, a sulfamoyl group, or a carbamoyl group.
R ₁ , R ₂ and R ₃ represent a hydrogen atom or a non-metallic atomic group, and R ₁ and R ₂ and R ₃ and X can be linked to each other to form a ring. Z represents an aryl group or a heterocyclic group having a substituent selected from a hydroxyl group, an alkylamino group, an alkoxy group, an anilino group, an acylamino group and an alkylsulfonamide group in the para position. M is N
i represents a metal atom selected from Cu, Co, Zn, Fe, Pd, and Pt.

4. An optical recording medium comprising a substrate and at least one kind of the metal complex compound described in 1 to 3 as a recording layer.

5. 3. The optical recording medium as described in 2 above, wherein writing and reading are performed through a substrate by using a semiconductor laser as a light source.

The metal complex compound of the present invention will be described in detail below.

The dye structure forming the metal complex compound of the present invention may be any structure, for example, azo, azomethine, benzoquinone, naphthoquinone, anthraquinone, indigo,
Representative dye structures such as triphenylmethane, phenazine, stilbene, Schiff base, and cyanine can be mentioned. In order to realize the sharp absorption, high ε, and high durability, which are the advantages of the dye-based metal complex compound, the substituent capable of binding to the metal atom of the present invention must be positioned adjacent to the color forming system.

The dye structure is preferably an azo or azomethine dye, more preferably an azomethine dye. As the azomethine dye structure, naphthol, phenol, pyrazolotriazole, pyrazolone, acylacetamide,
An azomethine dye synthesized from each acylacetate derivative is preferred, and a naphthol or phenol dye is more preferred.

In the above general formula I, examples of the case where X is an alkylsulfonamide group include a methylsulfonamide group, an ethylsulfonamide group and an octylsulfonamide group. Examples of the aryl sulfonamide group include a phenyl sulfonamide group, a tosyl sulfonamide group and a naphthyl sulfonamide group. Examples of the heterocyclic sulfonamide group include a furyl sulfonamide group, an imidazolyl sulfonamide group, a thiazolyl sulfonamide group, a pyridyl sulfonamide group and a tetrazolyl sulfonamide group.

When X is an acylamino group substituted with an electron-withdrawing group, trichloroacetamide group, trifluoroacetamide group, heptafluoropropylamide group, 4-nitrobenzamide group and the like can be mentioned.

The electron-withdrawing group is a group showing a positive Hammett's σ value, and a fluorine atom is particularly preferable.

When X is an imidazolyl group, examples thereof include a 2-imidazolyl group and a 2-benzimidazolyl group.

When X is a sulfamoyl group, examples thereof include N-phenylsulfamoyl group and N-tolylsulfamoyl group. Examples of the case where X is a carbamoyl group include an N-phenylcarbamoyl group.

X is preferably an acylamino group substituted with an electron-withdrawing group, and an arylsulfonamide group.

When R ₁ and R ₂ , and R ₃ and X are connected to each other to form a ring, a naphthyl ring, a phenanthrene ring,
An anthracene ring, a quinolyl ring, etc. can be formed. A naphthyl ring is preferred when forming a ring by linking with each other.

When R ₁ , R ₂ and R ₃ are non-metallic atomic groups, examples thereof include a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkoxy group, an alkyl sulfonamide group, an aryl sulfonamide group, Examples thereof include anilino group, acylamino group, alkylureido group, arylureido group, alkoxycarbonyl group, alkoxycarbonylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, aryl group and heterocyclic group.

Examples of Z include 4-hydroxyphenyl group, 3,5-dichloro-4-hydroxyphenyl group, 4-aminophenyl group, 4- (N-methylamino) phenyl group and 4- (N-ethyl group. Amino) phenyl group, 4- (N-hexylamino) phenyl group, 4- (N-dodecylamino) phenyl group, 4- (N, N-dimethylamino) phenyl group, 4- (N, N-diethylamino) phenyl Group, 4- (N, N-dihexylamino) phenyl group, 4- (N-
Ethyl-N-methylsulfonamido) phenyl group, 4- (N, N-
Diethylamino) -2-methylphenyl group, 4- (N, N-dihexylamino) -2-methylphenyl group, 4- (N-ethyl-N-methylsulfonamido) -2-methylphenyl group, 4- (N -ethyl-
N-hydroxyethyl) -2-methylphenyl group, 4-methoxyphenyl group, 3,5-dichloro-4-methoxyphenyl group, 3,5
-Dichloro-4-octyloxyphenyl group, 4-anilinophenyl group, 4-acetamidophenyl group, 4-isopropylamidophenyl group, 4-benzamidophenyl group, 4-methylsulfonamidophenyl group, octylsulfonamido group, 3 Examples thereof include a-(2-methyl-6-N, N-diethylamino) pyridyl group and a 2- (3-methyl-5-N, N-diethylamino) pyridyl group.

Z is preferably 4- (N, N-diethylamino) -2
-Methylphenyl group and 4- (N-ethyl-N-methylsulfonamido) -2-methylphenyl group.

The above R ₁ , R ₂ , R ₃ and Z can be optionally substituted with other substituents.

M is preferably Ni or Cu, and Ni
Atoms are more preferred.

Since the metal complex compound of the present invention is advantageous in that it has a high absorbance per molecular weight, it has a molecular weight of 18%.
It is preferably 00 or less, more preferably 1300 or less.

The metal complex compound of the present invention is formed by bonding two dye molecules and one divalent metal. Although the details of the bond are not necessarily clear, in the general formula I, the bond between the metal atom and the dye molecule is a covalent bond between the anion obtained by removing one hydrogen atom from the substituent represented by X and M, and It is considered that a tetradentate metal chelate is formed by the lone electron pair of the main ring ketone and a coordinate bond by M, and a hexadentate metal chelate is formed when other bonds are included. Depending on the compound, water molecules may be coordinated.

Specific examples of the organometallic complex compound of the present invention are shown below.

[0034]

[Chemical 3]

[0035]

[Chemical 4]

[0036]

[Chemical 5]

[0037]

[Chemical 6]

In the compound of the present invention, a substituent capable of binding to M is introduced into a generally known dye raw material, the dye raw material is dissolved in a suitable solvent, and then a metal salt such as Ni chloride or Cu chloride is added.
Inorganic salts such as Ni acetate, Cu acetate, diketone N
The metal complex compound of the present invention can be obtained by adding an organic salt such as i.

The synthesis examples of the organometallic complex compound of the present invention are shown below.

Synthesis Example 1 (Synthesis of Exemplified Compound (2)) (Reaction Scheme)

[0041]

[Chemical 7]

6 g of coupler (1) and 10 g of 4- (N-
Ethyl-N-methylsulfonamidoethyl) -2-methylaniline was dissolved in 200 ml of ethyl acetate. Potassium carbonate 2
A solution of 0 g dissolved in 100 ml of water was added, and then 50 ml of an aqueous solution containing 20 g of ammonium persulfate was added dropwise. After reacting for 1 hour, the aqueous layer was separated, the solvent was distilled off, and the residue was purified by column chromatography to obtain 5 g of the objective dye (2). It was confirmed to be the desired product by NMR and MASS spectra.

5 g of the dye (2) was dissolved in 30 ml of methanol, 1.8 g of Ni acetate tetrahydrate was further added and stirred, and the precipitated crystals were filtered under reduced pressure to obtain 3.5 mg of the desired compound of the metal complex (2). g was obtained. It was confirmed to be the target by IR and elemental analysis.

Synthesis Example 2 (Synthesis of Exemplified Compound 11) (Reaction Scheme)

[0045]

[Chemical 8]

8 g of coupler (3) and 10 g of 4- (N-
Ethyl-N-methylsulfonamidoethyl) -2-methylaniline was dissolved in 200 ml of ethyl acetate. Potassium carbonate 2
A solution of 0 g dissolved in 100 ml of water was added, and then 50 ml of an aqueous solution containing 20 g of ammonium persulfate was added dropwise. After reacting for 1 hour, the aqueous layer was separated, the solvent was evaporated, and the residue was purified by column chromatography to obtain 3.8 g of the objective dye (4). It was confirmed to be the desired product by NMR and MASS spectra. 2.5 g of dye in 30 ml of methanol (4)
Was dissolved, 0.8 g of Ni acetate tetrahydrate was further added and stirred, and the precipitated crystals were filtered under reduced pressure to obtain 1.1 g of Exemplified Compound (11) of the target metal complex. It was confirmed to be the target by IR and elemental analysis.

[0047]

EXAMPLES The spectral absorption characteristics of the metal complex compounds of the present invention are shown below.

Example 1 (Spectral Absorption Characteristics) Table 1 shows the spectral absorption characteristics in methanol of the metal complex compound of the present invention and, for comparison, the azomethine dye not forming a metal complex.

[0049]

[Table 1]

[0050]

[Chemical 9]

As is apparent from Table 1, the exemplified compounds of the present invention are excellent dyes having absorption maximums in the wavelength range preferable for cyan dyes and large ε, as compared with the comparison.

The metal complex compound of the present invention can be made into a polymer by introducing a polymerizable substituent, if necessary, and an LB film is formed by introducing an oil-soluble group or a hydrophilic group, or an oil is used. It can be dispersed or processed into various forms such as microcapsules. The compound of the present invention, alone or in combination with other dyes, is an image forming material for optical recording media, dyeing agents for fibers, coloring materials for resins and paints, printing inks, color copying machines, color printers, thermal recording materials and the like. It can be used in various applications such as solid-state image pickup tubes and color liquid crystal filter dyes.

It is possible to further improve the storability by adding various storability improvers to the metal complex compound of the present invention.
For example, an ultraviolet absorber such as benztriazolylphenol derivative, β-carotene, tocopherol derivative, hydroquinone derivative, spiroindane derivative, phenol derivative, amine derivative, thioether derivative, Ni dithiol derivative, Ni phenanthroline derivative, Ni benzylidene aniline derivative And antioxidants and light stabilizers, and may be added alone or in admixture of two or more.

An optical recording medium using the metal complex compound of the present invention will be described below.

As the substrate constituting the optical recording medium of the present invention, the wavelength region of laser light used for recording / reproducing, for example,
Substantially transparent at 650-900 nm (transmittance of 80% or more)
Is required to be. Regarding the shape of the substrate, the thickness when used as an ordinary compact disc
The diameter is about 1.2 mm and the diameter is about 80 to 120 mm. Examples of the material forming the substrate include polymethylmethacrylate resin, acrylic resin, polycarbonate resin, epoxy resin, polysulfone resin, transparent resin such as methylpentene polymer, and glass.

If necessary, an oxygen barrier film may be formed on the outer surface, inner surface, and inner / outer peripheral surface of the substrate. Further, it is preferable that a tracking groove is formed on the substrate on which the recording layer is formed. The recording layer using the metal complex compound of the present invention has an extinction coefficient k in the wavelength region of laser light that is preferable as a recording layer of an optical recording medium, and is suitable for light absorption suitable for recording and reproduction. It has a high reflectance.

Here, if the extinction coefficient k of the recording layer in the wavelength region of the laser light is excessively large, the reflectance is lowered, and the reproduction by the reflected light cannot be sufficiently performed. Further, if the extinction coefficient k is too small, it becomes difficult to perform recording with normal recording power. The extinction coefficient k of the recording layer is preferably 0.1 or less, more preferably 0.05 or less. On the other hand, the refractive index n (real part of complex refractive index) of the recording layer in the wavelength region of laser light is preferably 1.8 to 4.0.

The recording layer constituting the optical recording medium of the present invention contains other kinds of dye compounds, various resins, surfactants, antistatic agents, dispersants, antioxidants, crosslinking agents and the like. May be.

The recording layer may be formed on one surface of the substrate or may be formed on both surfaces of the substrate. Also,
Generally, the thickness of the recording layer is preferably 500 to 3000A.

The method for forming the recording layer on the substrate is not particularly limited, and examples thereof include spin coating method, dip coating method, spray coating method, blade coating method, roller coating method, bead coating method and Meyer. Coating method,
Various methods such as a curtain coating method can be applied.

The solvent used for forming the recording layer is, for example, a ketone solvent such as cyclohexanone,
Examples thereof include ester solvents such as butyl acetate, ether solvents such as ethyl cellosolve, alcohol solvents, aromatic solvents such as toluene, and alkyl halide solvents.

A reflective layer may be formed on the recording layer. Examples of the reflective layer include Au, Al-Mg alloy, A
It can be formed by means of vapor deposition, sputtering or the like, using a metal having a high reflectance such as 1-Ni alloy, Ag, Pt and Cu. The thickness of the reflective layer is preferably 500 A or more.

A protective film made of, for example, an ultraviolet curable resin may be formed on the reflective layer. The thickness of the protective film is about 0.1 to 100 μm, and the pencil hardness thereof at 25 ° C. is preferably H to 8H. The dye in the recording layer may be used alone, or may be mixed with the present invention or several kinds of dyes other than the present invention.
It is also possible to mix various materials such as an improving agent for absorption wavelength.

An adhesive layer may be provided between the recording layer and the reflective layer to bring them into close contact with each other. The thickness of the adhesive layer is preferably 10 to 300A.

Solid-state lasers, gas lasers, dye lasers, and semiconductor lasers are conceivable as light sources for recording and reproducing data on the optical recording medium of the present invention, but they are inexpensive, small in size, low in power consumption, etc. as seen in compact discs. From the viewpoint, a semiconductor laser is preferable.

Since the compound of the present invention has a particularly high recording sensitivity, a semiconductor laser of 650 nm to 830 nm is suitable.

Examples of optical recording media using the metal complex compound of the present invention will be shown below.

Example 2 (Evaluation as an optical recording medium) The absorption maximum in a thin film, light resistance, optical recording characteristics, etc. were evaluated by the following procedure.

(1) Formation of Recording Layer 1 g each of the exemplified compounds (2), (9) and (11) of the present invention and comparative compounds (B) and (C) were weighed and dissolved in 50 ml of cyclohexanone. Apply the coating solution on a glass substrate (thickness 1.1 mm, diameter 80 mm) by spin coating, and
A recording layer having a thickness of about 1000 A was formed on the glass substrate by drying at 0 ° C. for 30 minutes.

(2) Light resistance test Using a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.), the recording layer of each sample was irradiated with xenon light, and the dye residual ratio after irradiation was measured. Here, as the irradiation conditions, the illuminance on the surface of the recording layer was 70,000 lux, the temperature during irradiation was 43 ° C., and the irradiation time was 30 hours. Further, the dye residual ratio was obtained from the following formula by measuring the light transmittance of the dye at the maximum absorption wavelength before and after irradiation with xenon light.

Formula) Percentage of remaining dye (%) = [(100-
T) / (100−T ₀ )] × 100 [where T ₀ is the transmittance before irradiation with xenon light and T is the transmittance after irradiation with xenon light]. The results are shown in Table 2.

[0072]

[Table 2]

[0073]

[Chemical 10]

As is clear from the results shown in Table 2, Sample Nos. 1 to 3 which are recording media using the metal complex compound of the present invention have absorption maximums equivalent to those of Comparative Sample 4 using the cyanine dye. It is also found that the residual ratio of the dye is higher than that of the comparison, and that it has excellent light resistance. On the other hand, it can be seen that Sample 5 using a metal complex compound different from that of the present invention has an absorption maximum at a long wavelength and is not suitable as an optical recording medium.

(3) Production and Evaluation of Optical Recording Medium A recording layer was coated with the metal complex compound (1) of the present invention on a grooved polycarbonate substrate having a diameter of 5 inches, and a reflective layer (Au, thickness 1000A) was applied. ) And a protective film (ultraviolet curable resin, thickness: 5 μm) were sequentially formed according to a conventional method to produce an optical recording medium of the present invention. When the reflectance was measured, it showed 70% or more. When information was recorded / reproduced on / from the recording layer using a 780 nm semiconductor laser, good reproduction satisfying the CD standard was achieved, and stable recording characteristics particularly excellent in light resistance were obtained. It became clear to have.

[0076]

INDUSTRIAL APPLICABILITY The metal complex compound of the present invention is an excellent dye having a maximum absorption in the preferred wavelength range as a cyan dye and a large ε, and an optical recording medium using these dyes has an absorption maximum in the preferred wavelength range. It can be seen that the dye has a high dye residual ratio and excellent light resistance.

Claims (5)

[Claims] 1. An alkylsulfonamide group, an arylsulfonamide group, a heterocyclic sulfonamide group, an acylamino group substituted with an electron-withdrawing group, an imidazolyl group, and a sulfamoyl group capable of binding to a metal atom in a part of a dye structure. A metal complex compound having at least one carbamoyl group (excluding cases where the dye structure is an imidazole azomethine dye). 2. The metal complex compound according to claim 1, wherein the dye structure is an azomethine dye synthesized from naphthol, phenol, pyrazolotriazole, pyrazolone, acylacetamide and acylacetate derivatives. 3. The metal complex compound according to claim 1, wherein the dye structure is represented by the following general formula I. [Chemical 1] [In the formula, X represents an alkylsulfonamide group, an arylsulfonamide group, a heterocyclic sulfonamide group, an acylamino group substituted with an electron-withdrawing group, an imidazolyl group, a sulfamoyl group, or a carbamoyl group. R ₁ , R ₂ , R ₃
Represents a hydrogen atom or a non-metallic atomic group, and R ₁ and R ₂ , and R ₃ and X can be connected to each other to form a ring. Z represents an aryl group or a heterocyclic group having a substituent selected from a hydroxyl group, an alkylamino group, an alkoxy group, an anilino group, an acylamino group and an alkylsulfonamide group in the para position. M is Ni, Cu, Co, Z
It represents a metal atom selected from n, Fe, Pd and Pt. ] 4. An optical recording medium having at least one metal complex compound according to claim 1 as a recording layer on a substrate. 5. The optical recording medium according to claim 2, wherein writing and reading are performed through a substrate by using a semiconductor laser as a light source.