JP3361108B2 - Metal ion-containing indoaniline dye compound, optical recording material - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a metal ion-containing indoaniline-based dye compound, and to an optical recording medium using these dye compounds.

[0002]

[Prior art and technical problems to be solved by the present invention]
Image recording using a laser, high-density information recording preservation,
In recent years, their development has been particularly advanced as a reproducing means (for example, an optical disk) and a high-density image recording means (for example, a thermal transfer recording material using a laser as a heat mode).
In general, an optical disc is one in which a thin recording layer provided on a circular substrate is irradiated with a laser beam focused to about 1 μm ^{2 for} high density information recording.

In the recording, the absorption of the irradiated laser light energy causes a change in the recording layer at that location due to heat.
(Heat mode) or change by light (photon mode)
Is induced to generate shape changes and structural changes such as decomposition, evaporation, and dissolution. In addition, the reproduction of the recorded information is performed by reading the difference in reflectance between the portion where the deformation is caused by the laser light and the portion where the deformation is not caused by the laser light as an optical signal or a magnetic signal.

Therefore, since the optical recording medium needs to efficiently absorb the energy of the laser light, the absorption of the laser light of a specific wavelength used for recording is large, and the information can be reproduced accurately. It is necessary that the reflectance with respect to a laser beam of a specific wavelength used for reproduction is high.

Various types of optical recording media are known as this type of optical recording medium. For example, JP-A-55-97
Japanese Patent No. 033 discloses a substrate in which a single layer of a phthalocyanine dye is provided. However, phthalocyanine dyes have problems that they have low sensitivity, that they have a high decomposition point and are difficult to deposit, and that they have very low solubility in organic solvents and cannot be used for coating by coating. Was there.

Further, JP-A-58-83344 discloses a phenalene dye and JP-A-58-224793 discloses a naphthoquinone dye provided in a recording layer. However, although such a dye has the advantage of being easy to deposit, it has a problem of low reflectance. Further, Japanese Patent Application Laid-Open No. 63-227569 discloses a metal-containing indoaniline compound in order to improve these problems. However, the spectral absorption wavelength is still a short wavelength, and storage stability is also a problem. Was not enough.

The dyes disclosed in these known patents do not necessarily satisfy the following performances required for optical recording media. (1) Sufficient storage stability (2) Good solubility in a solvent (3) Coating by coating is possible (4) High reflectance for laser light of a specific wavelength (5) Spectral absorption wavelength is good (6) Manufacturing cost is low The present invention has been made based on the above circumstances.

That is, an object of the present invention is to provide a metal ion-containing dye compound excellent in the above-mentioned properties, particularly in storage stability (light resistance and heat resistance) and solubility in a solvent, and an optical recording medium using the dye. To provide.

[0009]

The invention according to claim 1 for achieving the above object is a metal ion-containing indoaniline dye compound represented by the following general formula (Formula 1),

[0010]

[Chemical 1]

[Wherein M ²⁺ represents a chelatable metal ion, and X and Y are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group,
Aryl group, alkenyl group, aralkyl group, alkoxy group, aryloxy group, cyano group, acylamino group, arylamino group, alkylthio group, arylthio group, sulfonylamino group, ureido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryl Oxycarbonyl group, sulfonyl group, acyl group, amino group,
A nitro group and at least one group selected from the group consisting of an alkyl group having these groups as a substituent and a phenyl group. l and m are integers from 1 to 4, Z ⁻ is tet
Represents a laphenylboron anion , respectively. Also, B
Represents a group of non-metal atoms forming a 5- or 6-membered ring with adjacent nitrogen atoms. (Non-metal atoms are carbon atoms, nitrogen atoms, and oxygen atoms .)]

[0015] ClaimTwoThe invention described in 1.,
The claim as formed on the bodyTo 1Listed
General formula (Formula 1)ofContains a metal ion-containing dye compound
An optical recording body having a recording layeris there.

The present invention will be described in more detail. - a metal ion-containing dye compound (a metal ion-containing indoaniline dye compound) - in general formula (1), M ²⁺ represents a chelatable metal ion. Preferable examples of this metal ion include binary transition metal ions, particularly Ni ²⁺ and C.
^Examples thereof include u ²⁺ , Fe ²⁺ , Co ²⁺ , Cr ²⁺ and Zn ²⁺ . Among these, Ni ²⁺ and Cu ²⁺ are preferable.

X and Y each independently represent a hydrogen atom or a monovalent organic group. This monovalent organic group is
Kill group (methyl group, ethyl group, isopropyl group, n-butyl group
A straight-chain or branched alkyl group having 1 to 12 carbon atoms such as a chill group.
Kill group), cycloalkyl group (cyclopentyl group, cyclo)
Rohexyl group), aryl group (phenyl group, naphthyl)
Group), alkenyl group (2-propenyl group), aralkyl
Group (benzyl group, 2-phenethyl group), alkoxy group
(Methoxy group, ethoxy group, isopropoxy group, n-bu
A straight-chain or branched alkyl group having 1 to 12 carbon atoms such as a toxy group.
Lucoxy group), aryloxy group (phenoxy group),
Ano group, acylamino group (acetylamino group, propio
A straight-chain or branched alkyl group having 1 to 12 carbon atoms such as a nylamino group.
Rukylcarbonylamino group, phenylcarbonylamino
Group), arylamino group (phenylamino group), alk
Ruthio group (methylthio group, ethylthio group, n-butylthio group
O group), arylthio group (phenylthio), sulfonyl
Amino group (methanesulfonylamino group, benzenesulfo
Nylamino group), ureido group (3-methylureido group,
3,3-dimethylureido group, 1,3-dimethylureido
Group, carbamoyl group (methylcarbamoyl group, ethyl
Carbon source such as rucarbamoyl group and dimethylcarbamoyl group
Linear or branched alkylaminocarbo having 1 to 12 children
Nyl group), sulfamoyl group (ethylsulfamoyl)
Group, dimethylsulfamoyl group), alkoxycarbonyl
Group (methoxycarbonyl group, ethoxycarbonyl group
Group), aryloxycarbonyl group (phenoxycarbo group
Nyl group), sulfonyl group (methanesulfonyl group, butane)
Linear or branched chain having 1 to 12 carbon atoms such as sulfonyl group
Alkylsulfonyl group, phenylsulfonyl group),
Syl group (acetyl group, propanoyl group, butyroyl
Group), amino group (methylamino group, ethylamino group, di
Methylamino group), cyano group, nitro group, etc.
be able to.

The alkyl group or phenyl group may further have a substituent, and examples of the substituent include the above monovalent groups. Preferred X is a hydrogen atom, an alkyl group,
An alkylcarbonylamino group and an acetoxycarbonyl group, and preferable Y is a hydrogen atom, an alkyl group or an alkoxy group.

L and m are integers of 1 to 4, preferred 1 is 1, and preferred m is 1. B represents a non-metal atom group forming a 5- or 6-membered ring with an adjacent nitrogen atom, and a preferable heterocyclic group formed by B and the adjacent nitrogen atom is a pyrrolidino group, a piperidino group or a morpholino group. Can be mentioned. Z ^- is tetraphenyl
Represents a boron anion.

Specific examples of the metal ion-containing indoaniline compound represented by the general formula (Formula 1) are shown below.

[0022]

[Chemical 5]

[0023]

[Chemical 6]

[0024]

[Chemical 7]

[0025]

[Chemical 8]

[0026]

[Chemical 9]

[0027]

[Chemical 10]

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

[0031]

[Chemical 14]

[0032]

[Chemical 15]

[0033]

[Chemical 16]

[0034]

[Chemical 17]

[0035]

[Chemical 18]

[0036]

[0037]

[0038]

[Chemical 21]

[0039]

[Chemical formula 22]

[0040]

[0041]

—Method for Producing Metal Ion-Containing Dye Compound— A general synthesis example of the metal ion-containing indoaniline compound represented by the general formula (Formula 1) will be described.

(Synthesis Example) As the raw material compounds, the general formula (Formula 57) and the general formula (Formula 5)
8), a compound represented by the general formula (Formula 59), a general formula (Formula 60), or a general formula (Formula 61) is used.

[0083]

[Chemical 57]

[0084]

[Chemical 58]

[0085]

[Chemical 59]

[0086]

[Chemical 60]

[0087]

[Chemical formula 61]

By oxidatively coupling the compound represented by the general formula (Formula 57) with the compound represented by the general formula (Formula 57) under an alkaline condition using an oxidizing agent, the compound represented by the general formula (Formula 59) can be obtained. The dyes shown can easily be obtained. Next, the compound represented by the general formula (Formula 1) is produced by reacting the dye represented by the general formula (Formula 59) with the metal salt represented by the general formula (Formula 60). can do. In the general formula, M ²⁺ , Z ⁻ ,
X, Y, l, m and B are as described above.

A represents a coordination compound capable of forming a coordination bond with a metal ion, and these coordination compounds can be selected, for example, from the coordination compounds described in Chelate Chemistry (5) (Nankodo). .

[0100] -Optical recording body- The optical recording medium of the present invention basically comprises a substrate and a recording layer.
And a subbing layer on the substrate, if necessary.
A protective layer is provided on the recording layer. The recording layer is on both sides of the substrate
It may be provided on one side or only on one side. The above
The plate is transparent or opaque to the laser light used.
It may be clear. As the material of the substrate material,
General notes on glass, plastic, paper, plate or foil
Supports for recording materials are listed, but plastics are various
It is preferable from the point. Acrylic tree as plastic
Fat, methacrylic resin, vinyl acetate resin, vinyl chloride resin
Fat, nitrocellulose, polyethylene resin, polypropylene
Resin, polycarbonate resin, polyimide resin,
Examples thereof include poxy resin and polysulfone resin.

The recording layer can be formed from the metal ion-containing dye compound of the present invention and a binder. As the metal ion-containing dye compound contained in this recording layer,
The metal ion-containing dye compound represented by the general formula (Formula 1) is used.

As the above-mentioned binder, polyvinyl chloride resin, polyvinyl acrylate resin, polyvinyl pyrrolidone resin, nitrocellulose, cellulose acetate,
Known resins such as polyvinyl butyral and polycarbonate are used. The weight ratio of the metal ion-containing dye compound to the binder is preferably 0.01 or more.

In order to improve the stability and light resistance of the recording material, the recording layer has a transition metal chelate compound (eg, acetylacetonate chelate, bisphenyldithiol, salicylaldehyde oxime, bisdithio-) as a singlet oxygen quencher. (alpha-diketone etc.) may be contained. Further, other dyes can be used in combination if necessary. The other dye may be another type of the same type of compound, or may be a dye of another type such as a triarylmethane type dye, an azo dye, a cyanine type dye, and a squarylium type dye.

The thickness of the recording layer in the optical recording medium of the present invention is usually 0.0001 to 5 μm, preferably 0.001.
It is 1 to 3 μm. As the film forming method, a vacuum deposition method,
Sputtering method, doctor blade method, casting method,
The film can also be formed by a commonly used thin film forming method such as a spinner method, a dipping method, and a solvent dissolution coating method.

In the case of the solvent dissolution coating method, a coating film can be easily formed by evaporating the solvent and drying after coating. As a coating solvent for forming the recording layer by a solvent dissolution coating method, tetrachloroethane, bromoform, dibromoethane, ethyl cellosolve, methyl ethyl ketone, tetrahydrofuran, xylene, chlorobenzene, cyclohexanone or the like having a boiling point of 50 to 160 ° C. is preferably used. To be done.

Recording on the optical recording material obtained as described above is carried out in a recording layer of 1 μm on both sides or one side of the substrate.
^It is carried out by shining a laser beam focused on about ² , preferably a semiconductor laser beam. The part irradiated with laser light is decomposed by absorption of laser energy,
Thermal deformation of the recording layer such as evaporation and melting occurs. The recorded information is reproduced by reading the difference in reflectance between the portion where the laser beam is thermally deformed and the portion where the laser beam is not thermally deformed.

The laser light used for the optical recording medium is N
₂ laser, He-Cd laser, Ar laser, He
-Ne laser, ruby laser, semiconductor laser, dye laser and the like can be mentioned, but the semiconductor laser is particularly preferable from the viewpoints of lightness, easy handling, compactness and the like .

[0160]

EXAMPLES Specific examples using the metal ion-containing dye compound of the present invention are shown below, but the present invention is not limited thereto. (Examples 1 to 6, Comparative Example 1) Polyvinyl chloride [n = 1100, manufactured by Wako Pure Chemical Industries, Ltd.] and a metal ion-containing dye compound of the present invention (compound number in Table 3 The coating composition of the above) was applied so that the coating amount would be 15.0 g / m ² and the light absorption density = 2.0 to obtain an optical recording material.

Further, instead of the above-mentioned metal ion-containing dye compound, a compound other than the present invention, that is, comparative compound- (a)
An optical recording material was prepared in the same manner as described above except that (Chemical Formula 76) was used.

[0162]

[Chemical 76]

These optical recording materials were replaced with a xenon lamp.
Irradiation was carried out for 4 hours, the concentration before irradiation (D ₀ ) and after irradiation (D) was measured, and the value of (D / D ₀ ) × 100 was determined as the residual ratio (%)
The light resistance was evaluated as. The results are shown in Table 3.

Further, the optical recording material was allowed to stand for 7 days in an environment of relative humidity 70% and temperature 60 ° C., and similarly the density before and after the standing was measured to evaluate the heat resistance. As is clear from Table 3, it is understood that the optical recording materials of the present invention are improved in light resistance and heat resistance and are excellent in storage stability.

[0165]

[Table 3]

[0198]

The metal ion-containing dye compound of the present invention is
It has excellent storage stability such as light resistance and heat resistance, and high solubility in organic solvents. Therefore, when an optical recording material is prepared, a coating solution containing the metal ion-containing dye compound can be prepared smoothly and quickly, and the obtained optical recording material of the present invention can be used for recording layers and images. It has excellent storage stability.

Since the optical recording material of the present invention has a high reflectance and a high contrast, recording and reproduction can be surely performed.

Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A metal ion-containing indoaniline dye compound represented by the following general formula (Formula 1). [Chemical 1] [ ^Wherein M ²⁺ represents a chelatable metal ion, and X and Y are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group,
Alkenyl group, aralkyl group, alkoxy group, aryloxy group, cyano group, acylamino group, arylamino group, alkylthio group, arylthio group, sulfonylamino group, ureido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group Represents a sulfonyl group, an acyl group, an amino group, a nitro group, and at least one group selected from the group consisting of an alkyl group having these groups as a substituent and a phenyl group. l and m are integers from 1 to 4 and z ^- is tetraphene.
Represents each boron anion . B represents a group of non-metal atoms that form a 5- or 6-membered ring with adjacent nitrogen atoms (the non-metal atoms are carbon atoms, nitrogen atoms , and
And oxygen atoms . )] 2. A support, and a recording layer formed on the support and containing the metal ion-containing dye compound of the general formula (Formula 1) described in claim 1. An optical recording body.