JPS634992A - Metal-complex salt compound and near infrared absorber - Google Patents

Abstract

PURPOSE:To obtain a near infrared absorber excellent in light resistance and heat resistance and rich in solubility in various solvents and compatibility with various resins, by using a specified metal-complex salt compound. CONSTITUTION:A near infrared absorber using a metal-complex salt compound of general formula (1) can be effectively used as a main material of a recording element of an optical disk, a medium or a member for shielding light of a wavelength in a visible light range or near infrared region, namely, a filter. The compound can be obtained in a high yield by converting diazo components of general formulas (2) into a diazo compound by the usual method, coupling the diazo compound with azo components of general formulas (3) by the usual method to produce monoazo compounds of general formulas (4), (5), treating the monoazo compounds with an iron salt in water or an organic solvent and, optionally, subjecting the resultant product to a salt-forming treatment with an aliphatic amine (inclusive of substd. aliphatic amine) or an alicyclic amine.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a metal complex compound and a near-infrared absorber using this compound. In more detail, the general formula, kL! In formula 1, xl and X are a nitro group and/or a nologe: /21, phenylazo (including substituted phenylazo),
Represents naphthylazo (including substituted 7-tylazo), n
l and nl represent integers of 1 to 3, R1 and bird represent an amino group, monoalkylamino group, dialkylamino group, acetylamino group, benzoylamino group (including substituted benzoylamino groups), xl and R3, nl and n-1R,
and R1 may be the same or different, and Y
e represents hydrogen, sodium, potassium, ammonium, aliphatic ammonium (including substituted ammonium) or alicyclic ammonium. ) and a near-infrared absorber using this compound.

The metal complex salt compound represented by the general formula (1) can be produced by the following steps.

A diazo component represented by the following general formula (in the formula, xl and R1 and R: are the same as previously defined.) By coupling according to a conventional method with an azo component represented by is the general formula defined above), this monoazo compound is then treated with iron salts in water or an organic solvent, and optionally further treated with aliphatic amines (substituted aliphatic It can be obtained in high yield by salt-forming treatment with an alicyclic amine (including amines).

The diazo component represented by the above general formula (me) used in the present invention is, for example, 6-nitro-2-aminephenol, 4,6-cinitro-2-aminephenol, 4-chloro-5-nitro-2-aminophenol. , 5.4.6
-Dolichloro-2-aminophenol, 4-phenylazo-2-aminephenol, 4-naphthylazo-2-aminephenol, etc.;
For example, the coupling component represented by 8-
Amino-2-naphthol, 8-acetylamino-2-naphthol, 8-benzoylamino-2-naphthol, 5
-amino-2-naphthol, 5-dimethylamine-2-
naphthol, 8-n-butylamino-2-naphthol,
Examples include 8-propylamino-2-naphthol and 8-ethylamino-2-naphthol.

Next, a near-infrared absorber using the metal complex compound represented by the above general formula (1) will be described.

In recent years, the use of near-infrared rays has attracted attention in a wide range of fields. For example, in the field of optical recording in the information field, optical discs such as compact discs and video discs that use laser light as the light source have been developed.
be. A near-infrared absorber may be used as the main material or medium of the recording element in the optical disc. One of the principles is to form a laser beam absorption layer on the substrate,
Irradiates a laser beam that corresponds to light or sound,
A physical or optical change is caused in the irradiated part and recorded as a signal. This change in the absorption layer (recording layer) is again read as a signal using a laser beam, which is then converted into sound or light and reproduced. Therefore, the role of the near-infrared absorber present in this recording layer is one of the most important elements, which has the effect of efficiently absorbing laser light and enhancing thermal effects. The desired properties of the near-infrared absorber used as the recording layer material include: uniform composition and good reproducibility of thin films, high resolution and long-term stability (light emission, heat resistance, etc.), high sensitivity, and recording pit shape. If there is no uniformity, there is no wheat.

Known near-infrared absorbers used in conventional recording layers include To, In, Bi, and 08! -Te, Te
-0, inorganic metals such as TeOx, and
Examples of the metal complex described in Publication No. 5452 and dye-based ones include 5,3'-dimethyloxatricarbocyanine iodide, but in the case of inorganic metal-based ones, it is difficult to form a recording layer on the substrate. Thin film formation requires a vacuum evaporation method, which requires special equipment and is extremely inefficient in terms of workability. The issue of toxicity is also a major topic. Further, in the case of metal complexes, they have a small extinction coefficient and must be used in large quantities, and furthermore, they lack solubility or compatibility with solvents and resins, and have poor storage stability.

-Although the monochromatic pigments have a large extinction coefficient, they are extremely sensitive to light and heat, and are of no practical use.

Therefore, among conventionally known compounds, a near-infrared absorber that fully satisfies the various performances practically required as a recording material has not yet been found.

As a result of many years of research into metal complex compounds as pigments, the inventors discovered the compound described in Japanese Patent Publication No. 60-042269.

As a result of further deep investigation into peripheral compounds, the present inventors found that
It has been found that the absorption wavelength range is significantly longer than that of the above-mentioned compounds, and that it is extremely advantageous in practical terms, leading to the completion of the present invention.

That is, the metal complex salt compound represented by the above general formula (1) is 4
It has an absorption wavelength in the wavelength range of 00 to 11,000 nm, and currently it has an absorption wavelength of 80 nm, which is the wavelength of semiconductor lasers that require liquids for practical use.
It has a molecular extinction coefficient of 50,000 or more in the 0 to 900 nm range, has excellent light emission and heat resistance, and has high solubility with various solvents and compatibility with various resins, making it suitable as a material for recording layers in optical recording. It turned out to be very good.

In addition, the metal complex compound represented by the above general formula (1) has an absorption wavelength range that extends to the visible range, and therefore, by utilizing this characteristic property, it is possible to absorb light with wavelengths from the visible range to the near-infrared range. Another major feature of the present invention is that it has a shielding effect, that is, it can be usefully used as a filter. For example, for preventing malfunctions of light receiving elements in electrical products, especially remote control devices such as televisions, radios, and stereos, cameras and projectors, or gaming machines, automatic opening/closing doors, etc. due to visible range light, which has a particularly rapid change in light dose. It can be suitably used as a filter.

The present invention will be described in detail below with reference to Examples, where parts are parts by weight.

Example 1 15.4 parts of 5-nitro-2-aminephenol was prepared in a conventional manner, and 25 parts of concentrated hydrochloric acid and 6 parts of sodium nitrite were added to 200 parts of water.
Diazotized with 9 parts at 0-5°C to give 8-amino-2
- Coupling 15.9 parts of naphthol under alkaline conditions at 0 to 5°C to produce a monoazo compound 3 having the following structural formula:
Got 2 copies.

This monoazo compound was formed into a metal complex with ferric chloride in an aqueous solvent. Next, this iron complex was obtained at an octoki rate.

The maximum absorption wavelength of this compound in dimethylformamide was 680 nm, J', and the molecular extinction coefficient at 850 nm was 5.1×10'. On the other hand, the Tokuko Sho 6
In the case of the known compound described in Example 1 of Publication No. 0-42269, the maximum absorption wavelength is 730 nm under the same conditions, but 8
The molecular extinction coefficient at 30 nm is 4.7×10 3 , which has the disadvantage that the extinction coefficient in the required absorption range is small.

Next, Figure IK shows absorbance comparison data between the compound of the present invention and this known compound.

Next, the upper solution was applied onto a glass plate on which aluminum had been vapor-deposited using a spin coating machine. After drying, this disk was used to read the recorded disk using a GaAjAs semiconductor laser beam with the same low output power of the semiconductor laser used during recording. 87N (high signal relative to noise) regarding readout and recording sensitivity were compared with known compounds. The results are shown in Table 1 below.

Table 1 In addition, this disk was stable even after being left in an atmosphere of 50°C and 70% humidity for 6 months without any change in recording sensitivity or recording signal. An iron complex compound was obtained.

Comparing the above-mentioned present compound and the compound described in Example 7 of Japanese Patent Publication No. 60-42269 in the same manner as in Example 1, it was found that the compounds in Figure 2 and Table 2 below are excessive, indicating that the compound of the present invention is superior. Ta.

Table 2 Known compounds of Example 7 of Japanese Patent Publication No. 60-42269 (Comparison 3 80 (L
Example 9) O Compound of Example 2 of the present invention 1 125 α
3 Examples 3 to 14 The same operations as in Example 1 were performed except that the metal complex compounds, solvents, binders, and coated substrates shown in the table below were used. These results are also listed in the table below.

Example 15 1 part of the following gold complex salt compound synthesized according to Example 1 was added to 150 parts of Epicor) 82B (Shell Chemical Products) and kneaded. Next, 15 parts of Ebicure X61B (curing agent) was added and 20~ The mixture was mixed at 25° C., poured into a mold in which a light-emitting diode light-receiving element was installed, and cured at 80° C. for 2 hours to obtain a molded product containing an epoxy light-receiving element containing a metal complex compound. The light-receiving element obtained in this manner does not malfunction because it passes through the epoxy resin layer containing the metal complex compound and receives only the selected light.

Further, instead of the epoxy resin in this example, a heating wire 9 was added to A8 resin to make a filter molded product.

Examples 16 to 23 Using the metal complex compounds and kneading resins shown in the table below, the same procedure as in Example 15 was carried out to obtain molded products with embedded light-receiving elements. The light transmittance (%) values of these molded products are shown in the following table.

[Brief explanation of the drawing]

Figure 1 shows the compound of Example 1 of the present invention and the
This is absorbance comparison data with the compound described in Example 1 of Publication No. 42269. Figure 2 shows the compound of Example 2 of the present invention and the
This is absorbance comparison data with the compound described in Example 7 of Publication No. 42269. Hodogaya Chemical Industry Co., Ltd. Figure 1 Wavelength (nm)

Claims (1)

[Claims] 1. The following general formula, ▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, X_1 and X_2 are a nitro group and/or a halogen atom, phenylazo (including substituted phenylazo),
Represents naphthylazo (including substituted naphthylazo), n
_1 and n_2 represent integers from 1 to 3, and R_1 and R_2
represents an amino group, a monoalkylamino group, a dialkylamino group, an acetylamino group, a benzoylamino group (including a substituted benzoylamino group), and X_1 and X_2, n
_1 and n_2, R_1 and R_2 may be the same or different, and Y^■ represents hydrogen, sodium, potassium, ammonium, aliphatic ammonium (including substituted aliphatic ammonium) or alicyclic ammonium. A metal complex compound represented by 2. For near-infrared absorbers, there are the following general formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ (wherein,
Represents naphthylazo (including substituted naphthylazo), n
_1 and n_2 represent integers from 1 to 3, and R_1 and R_2
represents an amino group, a monoalkylamino group, a dialkylamino group, an acetylamino group, a benzoylamino group (including a substituted benzoylamino group), and X_1 and X_2, n
_1 and n_2, R_1 and R_2 may be the same or different, and Y^■ represents hydrogen, sodium, potassium, ammonium, aliphatic ammonium (including substituted aliphatic ammonium) or alicyclic ammonium. A near-infrared absorber characterized by using a metal complex compound represented by: