JPS6042269B2 - Near infrared absorber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a near-infrared absorber using a metal complex compound.

More specifically, the general formula (wherein X1 and X2 represent a nitro group and/or a halogen atom, and n1 and f are 1 to
represents an integer of 3, R1 and R2 are an amino group, a monoalkylamino group, a dialkylamino group, an acetylamino group,
Benzoylamino group (including substituted benzoylamino group)
, and X1 and X2, nl and N2, Rl and R2 are that. They may be the same or different.

M represents a chromium or cobalt atom, Y1 is hydrogen,
Represents sodium, potassium, ammonium, aliphatic ammonium (including substituted ammonium), or alicyclic ammonium. ) metal represented by! This is a near-infrared absorber that uses a complex salt compound. The metal complex salt compound represented by the general formula (1) can be produced by the following steps.
The following general formula (wherein, X1, X2, and nl are as defined above.

) is diazotized by a conventional method, and the diazotized product is formed by the following general formula (wherein R1 and R2 are as defined above).

) by coupling with the azo component represented by the following general formula (where X1 and X2, nl and N2
, Rl and R2 are as defined previously.

) is synthesized, and then this monozoa compound is heat-treated in water or an organic solvent with a chromation-imparting agent or a cobalt-imparting agent by a conventional method. It can be obtained in high yield by salt-forming treatment with an alicyclic amine) or an alicyclic amine. The above general formula used in the present invention (
Examples of the diazo component represented by 2) include 5-nitro-2-aminophenol, 4,6-dinitro-2-aminophenol, 4-chloro-5-nitro-2-aminophenol, and 3,4,6-trichloro-2-aminophenol. Examples of the azo component represented by the above general formula (3) include 8-amino-2-naphthol, 8-acetylamino-2-naphthol, 8-benzoylamino-2-naphthol, and 5-amino-2-naphthol. -naphthol, 5-dimethylamino-2-naphthol, and the like.

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 been attracting attention in a wide range of fields. For example, regarding optical recording in the information field, optical discs such as compact discs and video discs that use laser light as the light source are being developed. .

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, irradiate it with a laser beam corresponding to light or sound, cause a physical or optical change in the irradiated area, and record it as a signal (write). do. 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 performance of the near-infrared absorber used as the recording layer material is that it has a uniform composition and can form a thin film with good reproducibility, high resolution and long-term stability (light resistance, heat resistance, etc.), high sensitivity, and recording bit shape. It must have uniformity, etc. Known near-infrared absorbers used in conventional recording layers include Te, In, Bi, and C.
Examples of inorganic metal complexes such as S2-Te, Te-C, TeOx, metal complexes described in Japanese Patent Publication No. 46-3452, or dye-based ones include 3,3''-dimethyloxatricarbotanine iodide. However, in the case of inorganic metals, the thin film formation of the recording layer on the substrate must be performed by vacuum evaporation, which requires special equipment and is extremely inefficient in terms of workability.

The issue of toxicity is also a major obstacle. Furthermore, in the case of metal complexes, they have a small extinction coefficient and must be used in large quantities, and they also lack solubility or compatibility in solvents, resins, etc., and have poor storage stability. On the other hand, dye-based materials have a large extinction coefficient, but 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 that
Among these compounds, we have found a compound that is satisfactory as a near-infrared absorber and completed the present invention.

That is, the metal complex compound represented by the above general formula (1) is 7
It has a maximum absorption wavelength in the wavelength range of 00 to 900 r1m, has a molecular extinction coefficient of 50,000 or more, and has excellent light resistance and heat resistance of 5.
Good solubility with various solvents and compatibility with various resins,
It was found that it is extremely suitable as a material for recording layers in optical recording.

In addition, the metal complex compound represented by the above general formula (1) has an absorption wavelength range that extends to the visible range, so by utilizing this characteristic property, it is possible to absorb wavelengths from the visible range to the near-infrared range. Another major feature of the present invention is that it has a light shielding effect, that is, it can be usefully used as a filter.

For example, it can be used to measure the speed and distance of electrical products, especially remote control devices such as televisions, radios, and stereos, cameras and projectors, or to prevent malfunctions of light receiving elements in game machines, automatic opening/closing doors, etc. due to light in the visible region, where the light dose changes significantly. It can be suitably used as an optical filter. The present invention will be explained in detail below with reference to Examples, where parts are by weight.

Example 1 5-nitro-2-aminophenol was diazotized with hydrochloric acid and sodium nitrite at 0 to 5°C in a conventional manner to give 8
-Amino-2-naphthol was coupled under alkaline conditions at 0 to 5°C to obtain a monoazo compound having the following structural formula.

This monoazo compound was chromated with sodium chromium salcylate in an aqueous solvent.

Next, this chromium compound was subjected to salt formation treatment with octoxypropylamine hydrochloride to obtain a black powder chromium complex salt compound represented by the following formula in high yield. The maximum absorption wavelength of this compound in dimethylformamide was 730 r1m, and the molecular extinction coefficient was 5.6 x 101.

Next, a 2% solution of the chromium complex compound in methyl ethyl ketone was applied onto the glass plate on which aluminum had been vapor-deposited using a spin coater.

After drying, this material was used as a disk, and by using a GaAlAs semiconductor laser beam, recording was made in the recording layer of the disk, that is, the chromium complex compound composition film.
This recorded disk could be read using the same low output power of the semiconductor laser used during recording. S/N for reading
(high signal relative to noise) was 55 dB, and recording sensitivity was 0.8 rT]J/CFlf. Further, this disk remained 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. Examples 2 to 6 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 12 1 part of the following metal complex compound synthesized according to Example 1 was added to 15 parts of Epicure 828 (Shell Chemical Products) and kneaded. Next, 15 parts of Epicure K61B (curing agent) was added and the mixture was heated at 20 to 25°C. The mixture was mixed and poured into a mold in which a light-receiving element of a light emitting diode 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 thus obtained passes through the epoxy resin layer containing the metal complex compound and receives only the selected light, thereby preventing malfunction. Furthermore, instead of using the epoxy resin in this example, a filter molded product could be made by heating and wire-wiring AS resin.

Examples 13 to 15 Using the metal complex compounds and kneading resins shown in the table below, the same procedure as in Example 7 was carried out to obtain molded products with embedded light-receiving elements.

Claims (1)

[Claims] 1. Near-infrared absorbers include the following general formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼{In the formula, X_1 and X_2 represent a nitro group and/or a halogen atom, and n_1 and n
_2 represents an integer from 1 to 3, R_1 and R_2 represent an amino group, molar alkylamino group, dialkylamino group, acetylamino group, benzoylamino group (including substituted benzoylamino group), X_1 and X_2, n_1 and n_2, R_1 and R_2 may be the same or different. M represents a chromium or cobalt atom, Y■ represents hydrogen,
A near-infrared absorber characterized by using a metal complex salt compound represented by sodium, potassium, ammonium, aliphatic ammonium (including substituted aliphatic ammonium), or alicyclic ammonium.