JPH0532906A - New trisazo compound - Google Patents

Abstract

PURPOSE:To obtain a new trisazo compound useful as a medium for light recording, ink, filter, optical shutter, photoelectric conversion element, light modulation element and space modulation element because of excellent solubility and large absorption coefficient and reflectance. CONSTITUTION:A trisazo compound expressed by formula I (Cp is residue of coupling component). For example, the trisazo compound is obtained by dispersing a trisamino compound, preferably expressed by formula II into an inorganic acid such as hydrochloric acid or sulfuric acid and adding sodium sulfite thereto at -10-20 deg.C and subjecting the trisamino compound to diazotization to form a tris(diazonium) salt expressed by formula III (X<-> is anion functional group) and then dissolving the tris(diazonium) salt in an organic solvent such as N,N-dimethylformamide together with a coupler expressed by the formula H-Cp and adding dropwise an aqueous alkali solution thereto to carry out coupling reaction.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel trisazo compound.

[0002]

2. Description of the Related Art In recent years, an optical disk recording device has been actively developed as a means for accumulating information data at high density. The optical information recording medium, which is one of the recording media used for these, has the characteristics that the recording medium does not wear and deteriorate and the density can be increased because the writing or reading head to the medium is not in contact with it. Development of information recording media is in progress. Among such optical information recording media,
Development of heat mode optical recording media has been active.
This heat mode optical recording medium is an optical information recording medium that uses recording light as heat. As an example, recording light such as a laser melts and removes part of the medium to form small holes called bits. There is a bit formation type in which writing is performed, information is recorded by this bit, and this bit is detected by reading light to perform reading.

In addition to the above, one utilizing phase change,
Various recording methods such as those using a photochromic material have been proposed. The optical information recording material needs to absorb the energy of the laser light efficiently, so it has a large absorption for the laser light of the specific wavelength used for recording, and the specific wavelength used for the reproduction in order to accurately reproduce the information. It is necessary that the laser light has a high reflectance.

Most of the bit-forming type recording media are composed mainly of inorganic Se and Te. However, in recent years, inorganic materials have a problem of environmental pollution, and it is necessary to improve sensitivity. Therefore, recording media using an organic material mainly composed of an organic dye instead of an inorganic material in a recording layer is considered. Reports are increasing. As a dye used for this organic material, a cyanine dye (see, for example, Japanese Patent Laid-Open No.
8-114989), metal complexes (for example, JP-A-58-16888), phthalocyanine dyes (for example, JP-A-3-43461), and the like.

When using semiconductor lasers, some of these compounds have been obtained with satisfactory absorption wavelengths. However, in storage in air, materials which are not sufficiently satisfactory such as being unstable with respect to oxygen and humidity, low in solubility and low in sensitivity have not been obtained, and improvements are still being made.

[0006]

SUMMARY OF THE INVENTION The present invention aims to provide a novel trisazo compound and a method for producing the same.

[0007]

The present invention provides: A trisazo compound represented by the following general formula (1).

[0008]

[Chemical 3]

(Wherein C _P represents the residue of the coupling component) and 2. The method for producing the trisazo compound according to claim 1,

[0010]

[Chemical 4]

The gist is a method of diazotizing and then coupling to a coupling component of H--C _P (3) (where C _P represents a residue of the coupling component).

In the above equation (2)

[0013]

[Chemical 5]

Is

[0015]

[Chemical 6]

The following compound obtained by reacting triphenylamine of 1 with excess nitric acid in an acetic acid solvent

[0017]

[Chemical 7]

Obtained by reducing the trinitrotriphenylamine of.

Examples of the reduction reaction of compound (5) with trinitrohyriphenylamine include a hydrogenation method.

In this reaction, there are a system using a homogeneous catalyst and a system using a heterogeneous catalyst. As homogeneous catalysts, VI such as rhodium, ruthenium, iridium and cobalt
A complex compound of a Group I metal element is used, and as the heterogeneous catalyst, a platinum compound, Raney-nickel, or platinum supported on activated carbon, alumina, barium sulfate, etc., palladium, rhodium or ruthenium is used. .
In this case, it is preferable to use a heterogeneous catalyst whose post-treatment is simple.

In a system using a heterogeneous catalyst, the reaction system is a closed system and the gas phase part is replaced with hydrogen gas at 1 atm and the reaction is performed by vigorously stirring. Hydrogen gas is supplied through a pressure reducing valve to which hydrogen gas is supplied according to the absorbed amount. Since the absorption stops when the theoretical amount of hydrogen gas is absorbed, the reaction is terminated. In this case, the reaction temperature may be room temperature, but may be heated when hydrogen gas absorption is slow. The reaction solvent is methanol, ethanol, propanol, tetrahydrofuran, dioxane, ethyl acetate,
Examples thereof include N, N-dimethylformamide.

The diazotization of the thus obtained triamino compound is carried out by dispersing the triamino compound in an inorganic acid such as hydrochloric acid or sulfuric acid and then adding sodium nitrite at a temperature of -10 to 20 ° C. The reaction is completed in about 2 hours.

By this reaction, a tris (diazonium) salt represented by the following general formula (6) is obtained.

[0024]

[Chemical 8]

Further, the triazo (diazonium) salt of the general formula (6) can be obtained by adding an aqueous solution of borofluoric acid, sodium borofluoride or the like to the diazotization reaction solution and exchanging the salt.

The couplers used in the coupling reaction for producing the bisazo compound of the present invention include acylacetoarylamides, phenols, pyridones, quinolones, pyrazoles, indoles, diphenylamines, anilines. , Aminopyridines, pyrimidines, pyrimidones, naphthols, naphthylamines, hydroxyanthracenes, aminothiazoles,
Examples thereof include thiophenes and hydroxypyridines.

Further, these coupling components are unsubstituted, or are alkyl group, aryl group, hydroxy group, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, hydroxyalkylamino group, halogen atom. ,, alkoxy group, aryloxy group, alkylaminocarbonyl group, arylaminocarbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, sulfonyl group, alkylaminosulfonyl group, arylaminosulfonyl group, alkylsulfone group, arylsulfone group, It may be substituted with a nitro group, a cyano group or the like.

Tris (diazonium) thus obtained
To produce the trisazo compound of the present invention using a salt,
First, a tris (diazonium) salt is isolated from the reaction solution, and then this is dissolved in an organic solvent such as N, N-dimethylformamide, dimethylsulfoxide and 1,4-dioxane together with the coupler represented by the general formula (3). Then, an alkaline aqueous solution such as an aqueous sodium acetate solution may be added dropwise thereto at a temperature of −10 to 4 ° C. to cause a coupling reaction. The reaction is completed in about 5 minutes to 3 hours. After the reaction was completed, the reaction mixture was poured onto ice, and the precipitated crystals were filtered off,
The desired trisazo compound can be obtained by purification by an appropriate method such as recrystallization or silica gel column chromatography. The trisazo compound can be produced by directly acting a coupler on the diazotization reaction solution.

Preferred specific examples of the trisazo compound of the present invention produced as described above are listed, but the scope of the present invention is not limited thereto.

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical 12]

[0034]

[Chemical 13]

When the trisazo compound (I) of the present invention is used as a recording medium, it basically comprises a substrate and a recording layer containing the trisazo compound (1).

The substrate used in the present invention can be arbitrarily selected from various materials used as substrates for conventional information recording media. From the viewpoints of optical properties, flatness, processability, handleability, temporal stability and manufacturing cost of the substrate, examples of the substrate material include glass such as soda lime glass; cell cast polymethyl methacrylate, injection molded polymethyl methacrylate. Acrylic resins such as; polyvinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers; epoxy resins; and polycarbonate resins, amorphous polyolefins and polyesters. Among these, polymethyl methacrylate, polycarbonate resin, epoxy resin, amorphous polyolefin, polyester and glass are preferable from the viewpoints of dimensional stability, transparency and flatness. Note that these materials can be used as a film or as a rigid substrate.

When the trisazo compound (1) is used, the film thickness is 100Å to 5 μm, preferably 1000Å to 3 μm.
Is. As the film forming method, a generally used thin film forming method such as a vacuum vapor deposition method, a sputtering method, a doctor blade method, a casting method, a spinner method, and a dipping method can be used. Further, a binder can be used if necessary. Known binders such as PVA, PVP, nitrocellulose, cellulose acetate, polyvinyl butyral, and polycarbonate are used, and the amount of the trisazo compound (1) relative to the resin is 0.1.
It is desirable that it be 01 or more. In the case of film formation by the spinner method, the rotation speed is preferably 500 to 5000 rpm, and after spin coating, treatment such as heating or applying to solvent vapor may be performed depending on the case.

When the recording layer is formed by a coating method such as a doctor blade method, a casting method, a spinner method, a dipping method, or a spinner method, the coating solvent is tetrachloroethane, bromoform, dibromoethane, ethyl cellosolve, xylene or chlorobenzene. , Chloroform, toluene, acetone, ethylenediamine, pyridine and the like are preferably used.

The trisazo compound of the present invention is excellent in solubility and has a large molecular extinction coefficient and reflectance, so that it is not only used as an optical recording medium, but also as an ink, a filter, an optical shutter, a photoelectric conversion element, an optical modulation element, It can be suitably used as a spatial modulation element.

[0040]

EXAMPLES The present invention will be described below with reference to examples.
This does not limit the embodiment of the present invention.

Example 1 {Production of tris (diazonium salt)} 4,4 ', 4 "-triaminotriphenylamine 10.
80 g of concentrated hydrochloric acid and 80 g of water in 00 g (0.034 mol)
After adding ml and heating to 70 ° C. to give the hydrochloride salt, the solution is cooled to −5 ° C. with salt-ice. Then 7.40 g (0.1
A solution of sodium nitrite (07 mol) dissolved in 20 ml of water was added dropwise to the solution of the hydrochloride over 20 minutes while maintaining the temperature at -5 ° C or lower. After stirring at the same temperature for 3 hours, the temperature was further adjusted to 17.50 at a temperature of -5 ° C or lower.
A solution of g (0.159 mol) of sodium fluoroborate dissolved in 25 ml of water is added dropwise. After keeping the temperature at 0 ° C. and stirring for 1 hour, the precipitated yellow crystals are filtered off. The crystals were washed with cold water and dried under reduced pressure at room temperature in the dark to give tris (diazonium) salt as a yellow powder in an amount of 17.95 g.
(Yield 90%) was obtained.

Example 2 (Production of trisazo compound of compound No. 1) 1.88 g (0.013 mol) of β-naphthol was DM
Dissolve in 100 ml of F and add tris (diazonium) to it.
After adding 2.24 g (0.0038 mol) of salt, a solution of 2.14 g of sodium acetate dissolved in 10 ml of water was reacted dropwise at room temperature over 20 minutes. Next, after stirring at the same temperature for 3 hours, the reaction mixture was poured into ice and stirred for further 1 hour, and the precipitated crystals were separated by filtration. This crystal was recrystallized with 100 ml of toluene, and the obtained crystal was dried by heating under reduced pressure to give the trisazo compound of Compound 1 as a green powder.2.
18 g (yield 70%) was obtained. FIG. 1 shows the infrared absorption spectrum (KBr method) of this trisazo compound.

Example 3 (Production of Trisazo Compound of Compound No. 2) 2.16 g of m-N, N-diethylaminophenol
(0.013 mol) is dissolved in 100 ml of DMF and cooled to 3 ° C. with ice water. To this, 2.24 g (0.0038 mol) of tris (diazonium) salt was added, and then a solution of 2.14 g of sodium acetate dissolved in 10 ml of water was reacted dropwise at the same temperature over 20 minutes. Then, after stirring at 4 ° C. for 2 hours, the reaction mixture was poured into ice and stirred for further 1 hour, and the precipitated crystals were separated by filtration. The crystals were purified by silica gel column chromatography using chloroform as a developing solvent, recrystallized with 200 ml of ethanol, and the obtained crystals were dried by heating under reduced pressure to give the trisazo compound of Compound No. 2 as green glossy crystals. 51 g (yield 50
%)Obtained. FIG. 2 shows the infrared absorption spectrum (KBr method) of this trisazo compound.

Examples 4 to 8 (Production of Trisazo Compounds of Compound Nos. 3 to 7) A method for producing the trisazo compound of Example 2 (Compound No. 1) using a coupler corresponding to Compounds No. 3 to 7 or Compounds 3 to 7 were produced in the same manner as in the production method of the trisazo compound (Compound No. 2) of Example 3. The melting points or decomposition points, elemental analysis results, absorption maximum wavelengths, and molecular extinction coefficients of these substances are as shown in Tables 1 and 2.

[0045]

[Chemical 14]

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

INDUSTRIAL APPLICABILITY The trisazo compound of the present invention is useful as an optical recording medium because it is excellent in solubility and has a large extinction coefficient and reflectance.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum (KBr method) of compound No. 1 according to the present invention.

FIG. 2 Infrared absorption spectrum of compound No. 2 according to the present invention (KBr method)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C07D 213/84 6701-4C 231/06 6701-4C G11B 7/24 7215-5D

Claims (2)

[Claims] 1. A trisazo compound represented by the following general formula (1). [Chemical 1] (In the formula, C _P represents a residue of the coupling component) 2. The method for producing a trisazo compound according to claim 1, wherein: Is diazotized and then coupled to a coupling component of H-C _P (3) (where C _P represents a residue of the coupling component).