JPH0446186A - Azo metal chelate compound and optical recording medium using the same compound - Google Patents

Abstract

NEW MATERIAL:An azo metal chelate compound of a bisazo-based compound shown by formula I (P and P' together with C and N bonded form heterocyclic ring; Q and Q' together with 2C form aromatic ring; X and X' are active hydrogen-containing group; Y is bifunctional group) and a metal. USE:An optical recording medium. The compound has high solubility in organic solvents, can be coated by application, has excellent sensitivity, and improved light resistance and shelf stability. PREPARATION:For example, an amino compound shown by formula II (ring A and ring A' are replaceable) is diazotized, coupled with 2 equivalents of a substituted anilinecarboxylic acid derivative shown by formula III (ring B may contain substituent group; R<1> and R<2> are H, alkyl, aryl, etc.) to give a bisazo compound shown by formula IV. Then this compound is reacted with a metal salt to give an azo metal chelate compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel azo metal chelate compound of a bisazo compound and a metal, and an optical recording medium using the compound.

[Conventional technology]

Optical recording using lasers has been particularly developed in recent years because it enables high-density information recording storage and reproduction.

An example of an optical recording medium is an optical disc. In general, optical discs record high-density information by irradiating a thin recording layer provided on a circular base with laser light focused to about 1 μm. The record is created by absorbing the energy of the laser beam.
This is done by thermal deformation such as decomposition, evaporation, and melting occurring in the recording layer at that location. Further, recorded information is reproduced by reading the difference in reflectance between a portion where deformation has occurred and a portion where no deformation has occurred by laser light.

Therefore, as an optical recording medium, it is necessary to efficiently absorb the energy of laser light, and a laser-absorbing dye is used.

Various configurations of this type of optical recording medium are known.

For example, Japanese Patent Application Laid-Open No. 55-97033 discloses a single layer of a phthalonanine dye provided on a substrate. However, phthalocyanine dyes have problems such as low sensitivity, high decomposition point, and difficulty in vapor deposition.
Furthermore, it has a problem that it has extremely low solubility in organic solvents and cannot be used for coating by coating.

Also, JP-A-58-172790, JP-A No. 58-1149
No. 89, No. 51-85791 and No. 60-8323
Each publication No. 6 discloses a recording layer in which a cyanine dye is provided. However, although such dyes have the advantage of being highly soluble and can be coated by coating, they have the problem of poor light resistance. For this reason, Japanese Patent Application Laid-Open No. 59-55795 proposes adding a quencher to this cyanine dye to improve light resistance, but this is still at an insufficient level.

Regarding these problems, JP-A-62-30090 discloses a complex of a monoazo compound and a metal as a medium with improved solubility in organic solvents and light resistance. However, these compounds have problems in that they have short photosensitive wavelengths and poor sensitivity, and also have poor storage stability under high temperature and high humidity conditions.

[Problem to be solved by the invention]

An object of the present invention is to provide an azo metal chelate compound of a bisazo compound and a metal that has excellent sensitivity, storage stability, and light resistance and is suitable for spin coating, and an optical recording medium using the compound. It is.

[Means to solve the problem]

The present invention is based on the following formula (I), in which P and P'' each independently represent a residue that forms a heterocycle together with the carbon atom and nitrogen atom to which it is bonded, and Q and Q' each independently represent a residue that forms an aromatic ring together with the two carbon atoms to which it is bonded, and χ and X' each independently represent a group having an active hydrogen. , Y represents a divalent group) and an azo metal chelate compound of a bisazo compound and a metal, and an optical recording medium containing the compound in a recording layer.

As a preferable bisazo compound, the following general formula (II
)X represents a residue that forms an aromatic ring together with X, X and X independently represent a group having active hydrogen, and Y represents a divalent group. More preferable compounds include the following formula [■] (wherein, rings A, A'
, B and B' may each independently have a substituent <, R', R'', I?'' and Rg I each independently represent a hydrogen atom, an optionally substituted alkyl group, a substituted represents an optionally substituted aryl group, an optionally substituted alkenyl group, or an optionally substituted cycloalkyl group, and Y represents a divalent group. ) or the following formula: R1
and R2'' each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, or an optionally substituted cycloalkyl group, (Y represents a divalent group.) Examples include bisazo compounds represented by the following.

The present invention will be explained in detail below.

The bisazo compound of the present invention is represented by -a formula (1), where P and Po together with the carbon atom and nitrogen atom to which they are bonded form a heterocycle. It is not particularly limited as long as it is formed.

for example, general formula [1) The following may be mentioned.

In the formula, ring A may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and M is a hydrogen atom, an alkyl group,
Examples include halogen atoms and aryl groups.

- Q and Q' in formula (1) together with the two carbon atoms to which they are bonded represent a benzene ring,
Examples include residues forming aromatic rings such as naphthalene rings.

In the general formula (1), Y may be any divalent group capable of connecting two azo compounds, and examples thereof include the following.

+ CHz→T, -←CHz→T-0+ CI(2-)
7.

-0,000CH2-) 70 10,000CHZ+To (1+cHz-+-To, C
H=CH+CI(z+pe0ushiCHr+- (In the above formula, n is an integer from 1 to 6.) - Formula (i
), X is not particularly limited as long as it is a group having active hydrogen, but for example, -0! (.

-5H-COOH, -5O□H, 5O3H, B (OB)
2-NHK, -NHR, -po(on)z,
-NtlCOR (wherein R represents an optionally substituted alkyl group or phenyl group), -NIISO
, R (wherein R is the same as defined above), and the like. In addition, X is -Coo)l.

If the group is dissociable into an anion, such as SO, H, etc., it may be used as is in the production of an azo metal chelate compound, but it may also be used in the form of a salt with a cation. The cations include inorganic cations such as Na"Li" and K".

In general formula (II), substituents for rings A and A'' include a nitro group, a cyano group, an alkyl group, an alkoxy group,
Examples include an alkylsulfonyl group, an alkoxycarbonyl group, a thiocyanato group, a perfluoroalkyl group, and a halogen atom.

- In the formulas (Il and (TV)), R', R''R
2 and Rz' are hydrogen atoms or carbon atoms 1 to 2
0 alkyl groups, aryl groups, alkenyl groups or cycloalkyl groups, and these groups may be substituted. Examples of this substituent include an alkoxy group,
Examples include alkoxyalkoxy groups, alkoxyalkoxyalkoxy groups, allyloxy groups, aryl groups, aryloxy groups, cyano groups, nitro groups, hydroxyl groups, tetrahydrofuryl groups, alkylsulfonylamino groups, halogen atoms, etc. In addition, aryl groups, Examples of substituents for the cycloalkyl group include an alkyl group and a vinyl group.

In the general formulas [I[[] and [IV], substituents for rings B and B' include a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkylsulfonyl group, an alkoxycarbonyl group, a thiocyanato group, and a perfluoroalkyl group. , a halogen atom, and the like.

Specific examples of bisazo compounds that form chelate compounds with metals in the present invention include the following, which may be used alone or in combination.

In the present invention, the metal that forms a chelate compound with a bisazo compound is generally not particularly limited as long as it has the ability to form a chelate compound with the bisazo compound, but examples include Ni, Co, Fe, and Ru.

Transition elements such as Rh, Pd, Os, Ir, and Pt are preferred, and Ni and Co are particularly preferred.

A general synthesis of the azo metal chelate compounds of the present invention is described, for example, by Furukawa; Analytica Chimica.
Acta 140 (1982) 281-289. For example, an amino compound represented by the formula (V) [V] (wherein, rings A, A' and Y are the same as defined above) is diazotized according to a conventional method, and the amino compound represented by the following formula (Vll (wherein, the ring B, R' and R2 are the same as defined above.

Coupling with 2 equivalents of the substituted aniline carboxylic acid derivative represented by formula (II) to obtain the bisazo compound represented by formula (II []), and then the bisazo compound, metal salt, water and/or dioxane, tetrahydrofuran, acetone, ethanol, etc. The ab-metal chelate compound of the present invention can be produced by reacting in an organic solvent.

Examples of the anion of the metal salt used for producing the azo metal chelate compound include 5CN- and SbF.

C1-, Br-, F-, Cl2O--, BF.

Examples include P Fb -CHz COO-, T I F b''-valent or divalent anions.

The optical recording medium of the present invention is basically composed of a substrate and a recording layer containing a metal chelate compound of the bisazo compound, but if necessary, an undercoat layer may be further formed on the substrate. can be provided. In addition, as a preferable layer structure, a metal reflective layer such as gold or aluminum and a protective layer are provided on the recording layer to create a high reflectance medium, and a write-once type C
It can be used as D media.

The substrate in the present invention may be transparent or opaque to the laser beam used, and examples include supports of general recording materials such as glass, plastic, paper, plate-shaped or foil-shaped metal, etc. is preferable from various points of view. Plastics include acrylic resin, methacrylic resin, vinyl acetate resin, vinyl chloride resin, nitrocellulose, polyethylene resin, polypropylene resin, polycarbonate resin, polyimide resin, epoxy resin,
Examples include polysulfone resin. Among these, an injection-molded polycarbonate resin substrate is particularly preferable from the viewpoint of high productivity, cost, and moisture absorption resistance.6 The recording layer containing a chelate compound of a bisazo compound and a metal in the optical recording medium of the present invention has a film thickness of 100 mm. human~5μm, preferably 1000
It is 3 μm for humans.

The film can be formed using commonly used thin film forming methods such as vacuum evaporation, sputtering, doctor blade method, casting method, spinner method, and dipping method, but the spinner method is preferred from the viewpoint of mass production and cost. is preferred.

Moreover, a binder can also be used if necessary. As the binder, known binders such as polyvinyl alcohol, polyvinylpyrrolidone, ketone resin, nitrocellulose, cellulose acetate, polyvinyl butyral, and polycarbonate can be used. In the case of film formation by the spinner method, the rotation speed is preferably 500 to 5000 rpm, and after the spin code, treatment such as heating or exposure to solvent vapor may be performed as the case requires.

In addition, to improve the stability and light resistance of the recording layer, transition metal chelate compounds (e.g., acetylacetonate chelate, bisphenyldithiol, salicylaldehyde oxime, bisdithio-α) are used as heavy oxygen quenchers.
-diketone, etc.). Furthermore, other dyes can be used in combination if necessary. Other dyes may be other types of compounds of the same type, or other types such as triarylmethane dyes, azo dyes, cyanine dyes, squarylium dyes, metal complexes of monoazo compounds, Ni-indoaniline dyes, etc. The dye may also be used.

When forming a recording layer by a coating method such as a doctor blade method, a casting method, a spinner method, or a dipping method, especially a spinner method, the coating solvent may include tetrafluoropropanol, octafluoropentanol, tetrachloroethane, bromoform, dibromo, etc. Ethane, diacetone alcohol, ethyl cellosolve, xylene, 3-hydroxy-3
-Methyl 2-butanone, chlorohenzene, cyclohexanone, methyl lactate and the like having a boiling point of 120 to 160°C are preferably used.

Among these, diacetone alcohol, 3-hydroxy-3-methyl- Ketone alcohol solvents such as 2-butanone; Cellosolve solvents such as methyl cellosolve and ethyl cellosolve; Perfluoroalkyl alcohol solvents such as tetrafluoropropanol and octafluoropentanol; Hydroxyester solvents such as methyl lactate and methyl isobutyrate Examples include solutions.

The recording layer of the optical recording medium of the present invention may be provided on both sides of the substrate or only on one side.

Recording on the recording medium obtained as described above is carried out by irradiating the recording layer provided on both sides or one side of the substrate with laser light, preferably semiconductor laser light, focused to about 1 μm. In the portion irradiated with the laser beam, thermal deformation of the recording layer such as decomposition, evaporation, and melting occurs due to absorption of laser energy.

The recorded information is reproduced by using a laser beam to read the difference in reflectance between a portion where thermal deformation has occurred and a portion where no thermal deformation has occurred.

The laser beams used for the optical recording medium of the present invention are Nt, He-Cd, Ar He-Ne.

Examples include ruby, semiconductor, and dye lasers, and semiconductor lasers are particularly preferred from the viewpoint of lightness, ease of handling, and compactness.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by the Examples unless the gist thereof is exceeded.

Example 1 9.35 g of ammonium thiocyanate and 4.95 g of a diamino compound represented by the following structural formula were added to 237 g of acetic acid.
．． It was dissolved in a mixed solution of 5 g and 12.5 g of water at room temperature. After the solution was cooled to 10''C, a solution of 25g of bromine in acetic acid was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 5 hours.

Next, the resulting reaction solution was stirred at 80°C for 30 minutes,
The mixture was added to hot water 250a+42, stirred at 90-95°C for 1 hour, and then filtered while hot. The filtrate was cooled to room temperature, adjusted to pH 5 using sodium carbonate, filtered and dried to obtain a pale yellow powder of a diaminothiazole compound represented by the following structural formula.4.
46 g was obtained.

Live blood value Melting point: 217-219°C (decomposed) Mass spectrum: 312 (M”), 279252.
209,183,163.13G103.63,39.
27 2.50 g of the obtained diaminothiazole compound was mixed with 50 mj2 of phosphoric acid, 50 mff1 of acetic acid, and 16+ propionic acid.
It was dissolved in a mixed solution of wff and diazotized using 5.42 g of 45% nitroturosulfuric acid at 0 to -3°C.

2.64 g of 3-dimethylaminobenzoic acid and 0.2 g of urea
g to methanol 150+/! The resulting diazo solution was added dropwise to the solution at 0 to 5''C, and neutralized with an aqueous ammonia solution.

The precipitated crystals were filtered and dried to obtain 5.21 g of black-green crystals of a bisazo compound represented by the following structural formula.

0.30 g of the obtained bisazo compound was added to 25++/! of tetrahydrofuran. And water 25 deposit! 0.07 g of sodium acetate and 0.14 g of nickel acetate were added. After stirring at room temperature for 1 hour, the precipitated crystals were filtered and dried to give 0.22 kg of black crystals of the nickel chelate compound.
I got g. The maximum absorption wavelength (λ□X) of the obtained compound in chloroform solution was 552 nm and 582 nm.
Met.

Example 2 (a) Compound Production Example The procedure was repeated in the same manner as in Example 1 except that 5.3 g of a diamino compound represented by the following structural formula was used in place of the diamino compound used in Example 1, and a compound represented by the following structural formula was produced. 4.82 g of a pale yellow powder of a diaminothiazole compound was obtained.

Material melting point: (250°C or higher) Mass spectrometry 326 (M”), 163°136
．． 109,77.51 Obtained diaminothiazole compound 1.63 g -i
Phosphate 16 Shin! , acetic acid 16+/! , propionic acid jII
! ! , and diazotized using 3.39 g of 45% trosyl fL acid at 0 to -3°C. Add 1.65 g of dimethylaminobenzoic acid and 0.15 g of urea to 100+J of methanol! The diazo solution prepared in the solution was added dropwise at 0 to 5°C, and neutralized with an aqueous ammonia solution. The precipitated crystals were filtered and dried in the field to obtain 2.28 g of blackish brown crystals of a bisazo compound represented by the following structural formula.

The λsix (in a chloroform:t9ol=1:1 solution) of the obtained compound was 602 nm and 642 nm.

0.30 g of the obtained bisazo compound was dissolved in a mixed solution of 25 ml of tetrahydrofuran and 25 ml of water, and 0.07 g of sodium acetate and 0.14 g of nickel acetate were added. After stirring at room temperature for 1 hour, the precipitated crystals were filtered and dried to give 0.23% black crystals of the nickel chelate compound.
I got g.

The absorption spectrum data (in chloroform:methanol-9:l solution) of the obtained compound were as follows.

λ□*; 602 nm, 642 nm Molecular extinction coefficient (ε); 14. lX10'15.6X10
(b) Recording Medium Production Example 0.15 g of the nickel chelate compound Th of the bisazo compound obtained in the above compound production example was dissolved in 5 g of octafluoropentanol and filtered through a 0.22 μm filter to obtain a solution. Add 5 ml of this solution to a depth of 700 mm and a width of 0 mm.
．． The mixture was dropped onto an injection molded polycarbonate resin substrate (5 inches in diameter) with grooves (groups) of 7 μm, and coated using a spinner at a rotation speed of 500 rpm. After application, 60
It was dried for 10 minutes at "C". The λ and □ of the coating film were 617 nm.
and 673 nm.

Next, a gold film having a thickness of 2000 was formed on this coating film by sputtering to form a reflective layer. Furthermore, after spin-coding an ultraviolet curable resin on this reflective layer, it was cured by irradiation with ultraviolet rays to form a protective layer with a thickness of 10 μm.

(C) Optical recording example While rotating the above recording medium at 1.2 m/s,
Recording power of semiconductor laser light with a center wavelength of 780 nm is 7.
．． Irradiation was performed at 0 mW and the EFM signal was recorded.

Next, when this recorded portion was reproduced by a CD player having a semiconductor laser with a center wavelength of 780 nm, a good reproduced signal was obtained.

Also, light resistance (xenon fade meter acceleration test);
60 hours) and storage stability (70°C, 585%RH, 5
As a result of the test (00 hours), no deterioration in sensitivity or reproduction signal was observed compared to Hatsuho, and it was found to be extremely excellent as an optical recording medium.

Example 3 Using 1.63 g of the diaminothiazole compound obtained in the compound production example of Example 2, 3-dibutylaminobenzoic acid 2 was used instead of 3-dimethylaminobenzoic acid of Example 1.
．． The procedure was carried out in the same manner as in Example I, except that 49 g was used, to obtain 2.9.6 g of dark brown crystals of a bisazo compound represented by the following structural formula.

0.30 g of the obtained bisazo compound was mixed with 25 mff of tetrahydrofuran and 2511 i! of water. , dissolved in a mixed solution of 0.07 g of sodium acetate and 0.14 g of nickel acetate.
g was added. After stirring at room temperature for 1 hour, the precipitated crystals were separated by filtration and dried to obtain 0.0% black crystals of the nickel chelate compound.
23 g was obtained.

The absorption spectrum data (in chloroform:methanol-9=1 solution) of the obtained compound was as follows.

λ□x; 612 nm, 655 nm Molecular extinction coefficient (ε); 16.7X10'20, lXl0
(b) Recording Medium Production Example 0.15 g of the nickel chelate compound of the bisazo compound obtained in the complex production example above was dissolved in 5 g of diacetone alcohol, and filtered through a 0.22 μm filter to obtain a solution. This solution was prepared using 5 vans with a depth of 700 mm and a width of 0.7 μm.
The grooves (groups) were wiped, the drops were placed on an injection molded polycarbonate resin substrate (5 inches in diameter), and the spinner method
Coating was performed at a rotation speed of 00 rpm. After coating, 10 at 60℃
Dry for a minute.

The maximum absorption wavelengths of the coating films were 619 nm and 673 nm.

Next, a gold film W-2000 was formed on this coating film by sputtering to form a reflective layer.

Furthermore, after spin-coding an ultraviolet curable resin on this reflective layer, it was cured by irradiation with ultraviolet rays to a thickness of 10 μm.
A protective layer was formed.

(C) Optical recording example While rotating the above recording medium at 1.2 m/s, a semiconductor laser beam with a center wavelength of 780 nm was emitted at a recording power of 7.0 m.
It was irradiated with W and the EFM signal was recorded.

Next, when this recorded portion was reproduced with a CD player having a semiconductor laser with a center wavelength of 780 nm, a good reproduced signal was obtained.

In addition, light resistance (xenon fade meter accelerated test;
60 hours) and storage stability (70'C185%RH, 5
As a result of testing (00 hours), there was no deterioration in sensitivity or reproduced signal compared to the initial stage, and it was found to be extremely excellent as an optical recording medium.

〔Effect of the invention〕

The metal chelate compound of the bisazo compound of the present invention has high solubility in organic solvents, can be coated by coating, has good sensitivity, and has excellent light resistance and storage stability. Optical recording media using compounds are extremely useful.

[Brief explanation of drawings]

FIG. 1 is a drawing showing the visible region absorption spectrum of the nickel chelate compound of the bisazo compound obtained in Example 2 of the present invention, and FIG. FIG. 3 is a drawing showing the absorption spectrum of the coated thin film obtained in Example 2 of the present invention.

Claims (10)

[Claims] (1) The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [I] (In the formula, P and P' each independently represent the carbon atom and nitrogen atom to which they are bonded. X and X' each independently represents a group having active hydrogen, and Y represents a divalent group.) An azo metal chelate compound of a bisazo compound and a metal. (2) The bisazo compound has the following general formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... [II] (In the formula, rings A and A' each independently have a substituent. Q and Q' each independently represent a residue that forms an aromatic ring together with the two carbon atoms to which it is bonded;
each independently represents a group having active hydrogen, and Y represents a divalent group. ) The azo metal chelate compound according to claim 1, characterized in that it is represented by: (3) The bisazo compound has the following general formula [III]▲mathematical formula,
There are chemical formulas, tables, etc. ▼... [III] (In the formula, rings A, A', B and B' may each independently have a substituent, R^1, R^1^ ', R^
2 and R^2^' each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, or an optionally substituted cycloalkyl group. Y represents a divalent group. ) The azo metal chelate compound according to claim 1, characterized in that it is represented by: (4) The bisazo compound has the following general formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... [IV] (In the formula, rings A, A', B and B' are each independently a substituent. may have R^1, R^1^', R^
2 and R^2^' each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, or an optionally substituted cycloalkyl group. Y represents a divalent group. ) The azo metal chelate compound according to claim 1, characterized in that it is represented by: (5) Writing information on the board by laser and/or
Or, in an optical recording medium provided with a readable recording layer, the recording layer has the following general formula [I] ▲ Numerical formula, chemical formula, table, etc.▼ ...[I] (In the formula, P and P ' each independently represents a residue that forms a heterocycle together with the carbon atom and nitrogen atom to which it is bonded, and Q and Q' each independently represent the two carbon atoms to which it is bonded. (represents a residue that forms an aromatic ring together with an atom, X and X' each independently represent a group having active hydrogen, and Y represents a divalent group) An optical recording medium characterized by containing an azo metal chelate compound of and a metal. (6) The bisazo compound has the following general formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... [II] (In the formula, rings A and A' each independently have a substituent. Q and Q' each independently represent a residue that forms an aromatic ring together with the two carbon atoms to which it is bonded;
each independently represents a group having active hydrogen, and Y represents a divalent group. ) The optical recording medium according to claim 5, characterized in that: (7) The bisazo compound has the following general formula [III]▲mathematical formula,
There are chemical formulas, tables, etc. ▼... [III] (In the formula, rings A, A', B and B' may each independently have a substituent, , R^2
and R^2' each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, or an optionally substituted cycloalkyl group. where Y represents a divalent group. ) The optical recording medium according to claim 5, characterized in that: (8) The bisazo compound has the following general formula [IV] ▲ Numerical formula, chemical formula, table, etc. ▼... [IV] (In the formula, rings A, A', B and B' are each independently a substituent. may have R^1, R^1', R^2
and R^2' each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, or an optionally substituted cycloalkyl group. where Y represents a divalent group. ) The optical recording medium according to claim 5, characterized in that: (9) The optical recording medium according to any one of claims 1 to 8, wherein the metal is a transition element. (10) The optical recording medium according to any one of claims 5 to 9, characterized in that a metal reflective layer and a protective layer are provided on the recording layer.