JP2681699B2 - Metal-containing indoaniline compounds - Google Patents

Description

TECHNICAL FIELD The present invention relates to an optical recording material optically recorded with a metal-containing indoaniline compound.

BACKGROUND OF THE INVENTION Optical recording using laser light has been particularly developed in recent years because it enables high-density information recording and reproduction thereof.

As an optical recording method, for example, recording on an optical disc,
Recording on an infrared image forming recording material can be mentioned.

Generally, recording on an optical disc is performed by irradiating a thin recording layer provided on a circular substrate with a laser beam focused to about 1 μm. When the recording layer is irradiated with laser light, the recording layer absorbs the irradiated laser light energy, and thermal changes such as decomposition, evaporation, and dissolution occur at that portion, and information is recorded. Further, for recording on a recording material for infrared image formation, a dye capable of being image-wise chelated by specific light is formed, and this is reacted with a metal-donating substance,
This is done by allowing reading with laser light.

Since these recordings are generally reproduced by laser light, it is necessary for the optical recording medium to efficiently absorb or reflect the energy of laser light having a specific wavelength.

Various types of optical recording media are known as this type of optical recording medium.

For example, Japanese Unexamined Patent Publication (Kokai) No. 55-97033 discloses a structure in which a single layer of a phthalocyanine dye is provided on a substrate. However, phthalocyanine dyes have low sensitivity,
Further, it has a problem that it has a high decomposition point and is difficult to evaporate. Further, it has a problem that it cannot be dissolved in an organic solvent for coating because it has extremely low solubility in an organic solvent.

Further, JP-A-58-83344 discloses a phenalene dye, and JP-A-58-224793 discloses a naphthoquinone dye in a recording layer. However, these dyes have the advantage of being easily evaporated, but have the problem of low reflectance. When the reflectance is low, there is no difference in the intensity of the laser light reflected from the portion recorded by the laser light and the unrecorded portion, and it becomes difficult to reproduce the recorded information. Furthermore, organic dyes generally have a problem of poor storage stability.

Further, JP-A-63-227569 discloses a metal-containing indoaniline-based compound in which the above problems have been improved, but the disclosed metal-containing indoaniline-based compound has a short spectral absorption wavelength. However, the storage stability was still insufficient.

[Object of the Invention] Therefore, an object of the present invention is that the recording layer has high solubility in an organic solvent, can be coated by coating, has high reflectance, is excellent in storage stability, and has a long spectral absorption wavelength. An object is to provide an optical recording medium composed of a metal-containing indoaniline-based compound having a wavelength.

[Structure of the Invention] The above object of the present invention is achieved by an optical recording medium characterized in that the recording layer is composed of a compound represented by the following general formula [I].

General formula [I] In the formula, M represents a chelatable metal ion, R ¹ represents an alkyl group or an aryl group, R ² and R ³ represent a halogen atom or a monovalent organic group, and X represents -OR ⁶ or a hydroxy group, Z ^- represents an anion, R ⁴ , R ⁵ and R ⁶ represent an alkyl group, m and n represent an integer of 0 to 3,
When m and n are 2 or more, R ² and R ³ may be the same or different.

The above-mentioned compound of the present invention causes a state change by a laser beam for recording, and a dye used for an optical recording medium for reproducing the same, a dye capable of chelating in an imagewise manner with a specific light to form a metal. React with donor material,
It is useful as a dye used in an optical recording medium which forms a metal-containing indoaniline compound and enables reading by near infrared light.

In the general formula [I], M represents a chelatable metal ion. Examples of these chelatable metal ions include nickel ions, copper ions, cobalt ions, iron ions, and zinc ions. Of these, particularly preferable are nickel ions or copper ions.

R ¹ represents an alkyl group or an aryl group. These alkyl groups and aryl groups include those having a substituent.

Examples of the substituent include a halogen atom, (fluorine atom, chlorine atom, etc.), alkyl group, aryl group, heterocyclic group, nitro group, cyano group, alkoxy group, aryloxy group, alkylthio group, arylthio group, keto group. , Sulfonamide group, sulfamoyl group, acylamino group,
Examples thereof include a carbamoyl group, a sulfonyl group, a sulfinyl group, a hydroxy group, a carboxy group, an amino group, and a primary or secondary amino group.

The alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and the aryl group is preferably a phenyl group.

R ² and R ³ represent a halogen atom or a monovalent organic group.

As the halogen atom, chlorine atom or fluorine atom is preferable. In addition, as the monovalent organic group, an alkyl group which may have a substituent (for example, a methyl group, an ethyl group),
Alkoxy group which may have a substituent (eg methoxy group, ethoxy group), -CONR ⁷ R ⁸ , -NHCOR ⁹ , -NHCO
_{^{2 R 9, -NHSO 2 R 9}} , -NHSO 2 NR 7 R 8, -COOR 9, -SO 2 R 9, -
NHCONR ⁷ R ⁸ or cyano groups are preferred. Here, R ⁷ and R ⁸ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ⁹ represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, a heterocyclic group or an amino group. Represents Each group may have a substituent.

Examples of the substituent include a halogen atom, (fluorine atom, chlorine atom, etc.), alkyl group, aryl group, heterocyclic group, nitro group, cyano group, alkoxy group, aryloxy group, alkylthio group, arylthio group, keto group. , Sulfonamide group, sulfamoyl group, acylamino group,
Examples thereof include a carbamoyl group, a sulfonyl group, a sulfinyl group, a hydroxy group, a carboxy group, an amino group, and a primary or secondary amino group.

The alkyl group of R ⁴ , R ⁵ and R ⁶ is particularly preferably an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, n-propyl group, n-butyl group).

These alkyl groups also include those having a substituent. Preferred examples of the substituent include a hydroxy group, an alkoxy group (for example, a methoxy group, an ethoxy group), an alkylsulfonamide group (for example, a methanesulfonamide group), a sulfo group, a carboxy group, a sulfamoyl group, a carbamoyl group and the like.

Examples of the anion represented by Z ⁻ include commonly known anions.

Examples of anions represented by Z ⁻ include I ⁻ , Br ⁻ , C
_{^{l -, ClO 4 -, CH}} 3 COO -, Is preferred.

The metal-containing indoaniline-based compound represented by the general formula [I] exhibits absorption in the wavelength band of 750 nm to 900 nm, and has a molecular absorption coefficient of 10 ⁴ to 10 ⁵ cm ^-1 .

The metal-containing indoaniline compound represented by the general formula [I] of the present invention can be synthesized by the following route.

Specific examples of the metal-containing indoaniline-based compound of the present invention will be given below, but the present invention is not limited thereto.

[Examples] Examples of the present invention will be described below.

Example 1 (Synthesis of Compound No. 3) Synthesis of 5-chloro-7-nitro-8-quinolinol 25 g of 5-chloro-8-quinolinol was added to 230 cc of glacial acetic acid and cooled with ice water under dispersion stirring. After adjusting the temperature to 20 ° C. or lower, 9.8 ml of nitric acid (d = 1.42) was added dropwise. After dropping,
After stirring at the same temperature for 1 hour, 230 cc of water was added and the mixture was further stirred for 1 hour. The precipitated crystals were filtered, washed with water, washed with methanol and dried to obtain 25.6 g of orange crude crystals. The yield was 81.8%.

Synthesis of 7-amino-5-chloro-8-quinolinol 5-chloro-7-nitro-8-quinolinol 25.0 g
Was added to a mixed solution of 60 cc of ethanol and 60 cc of water and stirred for 1 hour. Add 100 cc of water and cool with ice water at 20 ℃.
After the following, sodium hydrosulfite 38.7g
Was added in small portions. The precipitated crystals were filtered, washed with water, washed with acetonitrile and dried to give 22.0 g of beige crude crystals.
I got The yield was 86.6%.

Synthesis of 5-chloro-7-iso-butanamide-8-quinolinol 15.0 g of 7-amino-5-chloro-8-quinolinol in 100 cc of ethyl acetate, sodium acetate trihydrate 13.7 g, water 40
The mixture was added to cc, cooled with ice water, adjusted to 20 ° C. or lower, and 10.7 g of isobutyric acid chloride was added dropwise. After the dropwise addition was completed, the mixture was stirred at the same temperature for 3 hours, the precipitated crystals were filtered, washed with water, washed with ethyl acetate and dried. Recrystallize from ethanol and crystallize 1
1.9 g was obtained. The yield was 58.1%. The structure was confirmed by NMR and MASS.

Synthesis of Compound No. 3 2-Amino-5- (N-ethyl-N-methoxyethyl)
Aminotoluene / p-toluenesulfonate (9.9 g) was added to water.
It was dissolved in a solution consisting of 100 cc, sodium bicarbonate 0.69 g and caustic soda 1.56 g, cooled with ice water to 5 ° C., and caustic soda 1.04 g and water 65 cc solution were added thereto, followed by 5-chloro-7.
3.4 g of -iso-butanamide-8-quinolinol was added. After stirring at the same temperature for 30 minutes, 5% sodium hypochlorite aqueous solution
40 ml was dropped slowly. After completion of dropping, the mixture was stirred at the same temperature for 1 hour, extracted with ethyl acetate, and washed with water. The oil layer was separated, concentrated to dryness, and then purified using silica gel column chromatography to obtain 2.5 g of blue crystals.

Yield: 44.2%, λmax; 645nm (dichloromethane), εma
x; 1.95 × 10 ⁴ .

The obtained dye (0.87 g) was dissolved in ethanol (435 cc), and a solution of 1.8 g of nickel perchlorate in pure water (435 cc) was added dropwise over 3 hours under a nitrogen gas stream. After completion of dropping, the reaction was carried out at the same temperature for 1 hour, and then ethanol was distilled off under reduced pressure. The precipitated crystals were filtered, washed with water and dried.

Yield: 0.9 g (79%), λmax; 820 nm (dichloromethane), εmax; 1.71 × 10 ⁵ .

The light resistance and heat resistance of the compound of the present invention were examined as follows.

Polyvinyl chloride (n = 1.100, manufactured by Wako Pure Chemical Industries, Ltd.) mixed with the compound No. 3 of the present invention was coated on a photographic baryta paper so that the coating amount of polyvinyl chloride was 15.0 g / m ² and the sample No. 1 was produced. In the above, compound No. 3 of the present invention was added so that the coating film had a Dmax of 2.0.

The compounds No. 3 of the present invention were changed to the compounds shown in Table 1 and Sample Nos. 2 to 6 were prepared in the same manner.

These sample Nos. 1 to 6 were irradiated with a xenon lamp for 24 hours, and the concentrations before irradiation (D ₀ ) and after irradiation (D) were measured (D / D ₀ ) × 100, and the residual ratio (%) was measured. Then, the light resistance was evaluated. Further, the sample was left for 7 days under the conditions of a relative temperature of 70% and a temperature of 60 ° C., and similarly, the residual rate was measured from the maximum concentration before and after the standing to evaluate the heat resistance. The results are shown in Table 1.

Comparative compound-A: Compound described in JP-A-63-227569 As is clear from Table 1, all of the compounds of the present invention are recognized to have improved light resistance and are excellent in storage stability.

Further, the compound No. 3 of the present invention and the comparative compound-A were dissolved in methylene chloride and the absorbance was measured.

The absorbance of Compound No. 3 of the present invention is shown in FIG. 1, and the absorbance of Comparative Compound-A is shown in FIG.

In the figure, the vertical axis represents absorbance and the horizontal axis represents wavelength (nm).

It can be seen from FIGS. 1 and 2 that the spectral absorption wavelength of the compound No. 3 of the present invention is longer than that of the comparative compound-A, and is suitable for recording and reproducing by laser light.

[Effect of the Invention] The metal-containing indoaniline compound of the present invention has a long spectral absorption wavelength, high solubility in an organic solvent,
Coating by coating is possible, high reflectance,
The effect of the compounds of the present invention is surprising and unexpected, as it provides high contrast, allows reading by an optical reader, and greatly improves storage stability.

[Brief description of the drawings]

FIG. 1 shows the spectral absorption spectrum of compound No. 3 of the present invention,
FIG. 2 is a diagram showing a spectral absorption spectrum of Comparative Compound-A.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-1-99040 (JP, A) JP-A 64-44786 (JP, A) JP-A 63-227569 (JP, A)

Claims (1)

(57) [Claims] 1. An optical recording medium, wherein the recording layer is composed of a compound represented by the following general formula [I]. General formula [I] (In the formula, M represents a chelatable metal ion, R ¹ represents an alkyl group or an aryl group, R ² and R ³ represent a halogen atom or a monovalent organic group, and X represents -OR ⁶ or a hydroxy group, Z ^- represents an anion, R ⁴ , R ⁵ and R ⁶ represent an alkyl group, m and n represent an integer of 0 to 3,
When m and n are 2 or more, R ² and R ³ may be the same or different. )