JP2920553B2 - Metal-containing indoaniline compounds - Google Patents

Description

The present invention relates to a metal-containing indoaniline compound useful for optical recording.

[Background of the Invention]

In recent years, optical recording using laser light has been particularly developed in order to enable high-density information recording and reproduction thereof.

Optical recording methods include, for example, recording on an optical disc,
Recording on a recording material for infrared image formation can be mentioned.

Generally, recording on an optical disc is performed by irradiating a thin recording layer provided on a circular base with laser light focused to about 1 μm. When the recording layer is irradiated with the laser light, the recording layer is irradiated and absorbs the laser light energy, and a thermal change such as decomposition, evaporation, or dissolution occurs at that location, and information is recorded. In addition, recording on a recording material for infrared image formation is performed by forming a dye which can be chelated imagewise by specific light, reacting the dye with a metal donor, and enabling reading with a laser beam. Will be

Since these recordings are generally reproduced by a laser beam, the optical recording medium needs to efficiently absorb or reflect the energy of the laser beam having a specific wavelength.

Various types of optical recording media are known.

For example, Japanese Patent Application Laid-Open No. 55-97033 discloses a structure in which a monolayer of a flotocyanine dye is provided on a substrate. However, phthalocyanine dyes have low sensitivity,
In addition, 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 and coated because it has extremely low solubility in an organic solvent.

JP-A-58-83344 discloses a recording layer provided with a phenalene-based dye, and JP-A-58-224793 discloses a recording layer provided with a naphthoquinone-based dye. However, these dyes have an advantage of being easily evaporated, but have a problem of low reflectance. If the reflectivity is low, there is no difference in the intensity of the laser light reflected from the portion recorded by the laser beam and from the unrecorded portion, making it difficult to reproduce the recorded information. Further, organic dyes generally have a problem that storage stability is inferior.

Japanese Patent Application Laid-Open No. 63-227569 discloses a metal-containing indoaniline-based compound in which the above problem is improved, but the disclosed metal-containing indoaniline-based compound has a short spectral absorption wavelength. Unnecessary absorption was large in the red part, and storage stability was still insufficient.

[Object of the invention]

Therefore, an object of the present invention is high solubility in an organic solvent, coating by coating is possible, and
It is an object of the present invention to provide a metal-containing indoaniline compound having high reflectance, excellent storage stability, a long spectral absorption wavelength, and a small unnecessary absorption of a red portion for optical recording.

[Configuration of the invention]

The above object of the present invention is achieved by a metal-containing indoaniline compound represented by the following general formula [I].

General formula [I] [Wherein, M represents a chelateable transition metal ion.

R ₁ and R ₂ represent a halogen atom or a monovalent organic group,
m and n represent an integer of 0 to 4, and when m and n are 2 or more, R ₁ and R ₂ may be the same or different.

—OR ₅ or a hydroxy group, and R ₃ , R ₄ and R ₅ represent an alkyl group.

Z represents an anion; L ₁ and L ₂ represent a coordination compound capable of forming a complex by coordinating with a transition metal ion; and l ₁ and l ₂ represent an integer of 0 to 3. The compound of the present invention is recorded by causing a state change by a laser beam, a dye used for an optical recording medium for reproducing the same, a dye capable of being image-wise chelated by a specific light to form a dye, This is reacted with a metal donor to form a metal-containing indoaniline compound, which is useful as a dye for use in an optical recording medium that can be read by near-infrared light.

In the general formula [I], M represents a chelatable transition metal ion, and is preferably a divalent transition metal ion;
Examples include nickel (II), copper (II), cobalt (II), iron (II), and zinc (II). Of these, nickel (II), iron (II) and copper (II) are particularly preferred.

R ₁ and R ₂ represent a halogen atom or a monovalent organic group.

As the halogen atom, a chlorine atom or a fluorine atom is preferable. Further, as the monovalent organic group, an alkyl group which may have a substituent (for example, a methyl group, an ethyl group),
An optionally substituted alkoxy group (eg, methoxy group, ethoxy group), -CONR ₆ R ₇ , -NHCOR ₈ , -NHCO
_{2 R 8, -NHSO 2 R 8} , -NHSO 2 NR 6 R 7, -COOR 8, -SO 2 R 8, -
NHCONR ₆ R ₇ or a cyano group is preferred. Here, R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₈ 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 (a fluorine atom,
Chlorine atom), an alkyl group, an aryl group, a heterocyclic group,
Nitro group, cyano group, alkoxy group, aryloxy group, alkylthio group, arylthio group, keto group, sulfonamide group, sulfamoyl group, acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, hydroxy group, carboxy group, amino group, Or a primary or secondary amino group.

R ₁ is a halogen atom, -CONR ₆ R ₇ , -NHCOR ₈ , -N
HCO ₂ R ₈ , -NHSO ₂ R ₈ , -NHSO ₂ NR ₆ R ₇ , -COOR ₈ , -SO
_It is particularly preferred that ₂ R ₈ , -NHCONR ₆ R ₇ or a cyano group is substituted at the 2- or 7-position. More preferably, -NH
This is the case where COR ₈ is substituted at the 7-position.

As the alkyl group for R ₃ , R ₄ and R ₅ , an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group, an n-butyl group) is particularly preferable.

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

Z ^- is any negative ions, anions and the like that are commonly known as Z, e.g. ^{I -, Br -, Cl -} , ClO 4 -, C
H ₃ COO ^-, Are preferred.

L ₁ and L ₂ each represent a coordination compound capable of forming a complex by coordinating with a transition metal ion (each of which may be the same or different); For example, it can be selected from the coordination compounds described in Chelate Chemistry (5), edited by Nankodo.

l ₁ and l _{2 each} represent an integer of 0 to 3, depending on whether the complex represented by the general formula [I] is tetradentate to hexadentate and / or L ₁ and L ₂ Determined by the number of ligands.

Preferred examples of L ₁ and L ₂ include (1) NH ₂ CH ₂ (NHCH ₂ CH ₂ ) _n NH ₂ (n = 0 or 1) (2) NH ₂ (CH ₂ ) _n NH ₂ (n = 2 Or 3) (3) C ₂ H ₅ NHCH ₂ CH ₂ NHC ₂ H ₅ And the like, but more preferably, It is.

Hereinafter, specific examples of the compound of the present invention are shown, but the present invention is not limited thereto.

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these.

Example 1 [Synthesis of Exemplified Compound No. 2] Compound 1 25 g was added to glacial acetic acid 230 cc, a distributed stirring, ice-cooled, after a 20 ° C. or less, was added dropwise nitric acid (d = 1.42) 10ml. After completion of the dropping, the mixture was stirred at the same temperature for 1 hour.
Was added, and the mixture was further stirred for 1 hour. The precipitated crystals were filtered, washed with water, and dried to obtain 26.1 g of crystals. This was recrystallized from methanol to obtain 25.3 g of Compound 2 .

25 g of Compound 2 was added to a mixture of 60 cc of ethanol and 60 cc of water and stirred for 1 hour. Further, 100 cc of water was added, and the mixture was cooled with ice water to 20 ° C. or lower, and then 39 g of sodium hydrosulfite was added little by little. The precipitated crystals were filtered, washed with water and dried to obtain 230 g of Compound 3 .

15 g of compound 3 was added to 100 cc of ethyl acetate and sodium acetate.
14 g of water salt and 40 cc of water were added, and the mixture was ice-cooled to 20 ° C. or less, and 7.9 g of acetyl chloride was added dropwise. After completion of the dropwise addition, the mixture was stirred at the same temperature for 3 hours, and the precipitated crystals were filtered, washed with water, washed with ethyl acetate and dried. Recrystallization from methanol gave 10.8 g of compound 4 .

Compound 5 10 g, water 100 cc, sodium hydrogen carbonate 0.7 g,
It was dissolved in a solution of 1.6 g of sodium hydroxide, cooled on ice, and adjusted to 5 ° C. A solution of 1 g of sodium hydroxide and 65 cc of water was added thereto, and then 3.4 g of Compound 4 was added. After stirring at the same temperature for 30 minutes, 5
A 40% aqueous solution of sodium hypochlorite was dropped in about 30 minutes. After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour, extracted with ethyl acetate, and washed with water. The organic layer was separated, the solvent was distilled off, and the residue was purified by column chromatography to obtain Compound 6 ( 2.3 g).

0.9 g of the obtained dye was dissolved in 435 cc of ethanol, and a solution of 1.8 g of nickel perchlorate in 435 cc of pure water was added dropwise over 3 hours under a nitrogen gas stream. After completion of the dropwise addition, the mixture was reacted at the same temperature for 1 hour, and then ethanol was distilled off under reduced pressure. After filtering the precipitated crystals,
After washing with water and drying, 0.9 g of the target product was obtained.

 All the confirmation of the structure of the intermediate was performed by NMR and MS.

Example 2 The light resistance and heat resistance of the compound of the present invention were examined as follows.

On a photographic baryta paper, polyvinyl chloride (n = 1.100, manufactured by Wako Pure Chemical Industries, Ltd.) mixed with the compound No. 3 of the present invention was applied so that the coating weight of polyvinyl chloride was 15.0 g / m ^2, and the sample No. 1 was produced. In the above, Compound No. 2 of the present invention was added so that _Dmax of the coating film was 2.0.

Sample Nos. 2 to 5 were prepared in the same manner except that the above compound No. 3 of the present invention was changed to the compounds shown in Table 1.

The concentrations of the sample Nos. 1 to 5 at 850 nm (D ₈₅₀ ) and 700 nm (D ₇₀₀ ) were measured, and the value of (D ₇₀₀ / D ₈₅₀ ) × 100 was shown in the table.
It is shown in FIG.

Sample Nos. 1 to 6 were irradiated with a xenon lamp for 24 hours, and the concentrations at 850 nm before (D ₀ ) and after irradiation (D) were measured, and the value of (D / D ₀ ) × 100 was determined as the residual ratio. (%), And the light resistance was evaluated. In addition, it was left for 7 days under the conditions of a relative temperature of 70% and a temperature of 60 ° C., and similarly, the residual ratio was measured from the maximum concentration before and after being left, and the heat resistance was evaluated. Table 2 shows the results.

Comparative compound-A: Compound described in JP-A-63-227569 As is clear from Table 1, the compound of the present invention has a long spectral absorption, a small absorption in the red part, and is excellent in both light resistance and heat resistance.

〔The invention's effect〕

The metal-containing indoaniline compound of the present invention has a long spectral absorption wavelength, high solubility in organic solvents,
Coating by application is possible, high reflectance,
It provides high contrast, allows reading by an optical reader, and has greatly improved storage stability.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C09B 53/02 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A metal-containing indoaniline compound represented by the general formula [I]. General formula [I] [Wherein, M represents a chelateable transition metal ion. R ₁ and R ₂ represent a halogen atom or a monovalent organic group. However, as the monovalent organic group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, -CONR ₆ R ₇ , -NHCOR ₈ , -NHCO ₂ R ₈ , −NHSO ₂ R ₈ , −N
_{HSO 2 NR 6 R 7, -COOR} 8, -SO 2 R 8, a -NHCONR ₆ R ₇ or cyano group, wherein R ₆ and R ₇ are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or R ₈ represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, a heterocyclic group, or an amino group. Each group may have a substituent. As the substituent, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
It is a keto group, a sulfonamide group, a sulfamoyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfinyl group, a hydroxy group, a carboxy group, an amino group, or a primary or secondary amino group. m and n represent an integer of 0 to 4, and when m and n are 2 or more, R ₁ and R ₂ may be the same or different. —OR ₅ or a hydroxy group, and R ₃ , R ₄ and R ₅ represent an alkyl group. Z represents an anion; L ₁ and L ₂ represent a coordination compound capable of forming a complex by coordinating with a transition metal ion; and l ₁ and l ₂ represent an integer of 0 to 3. ]