JPH0811464B2 - Metal complex compound and near infrared absorber - Google Patents

Description

The present invention relates to a metal complex salt compound and a compound using this compound.
It relates to an infrared absorber. More specifically, the general formula,{In the formula, X₁And X₂Is a nitro group and / or a halogen source
Child, phenylazo (including substituted phenylazo), naphthi
Represents luazo (including substituted naphthylazo), n₁And n₂Is
Represents an integer of 1 to 3, R₁And R₂Is an amino group, monoalk
Ruamino group, dialkylamino group, acetylamino group,
Benzoylamino group (including substituted benzoylamino group)
Represents X₁And X₂, N₁And n₂, R₁And R₂Are the same
Or it may be different, Y Is hydrogen, sodium,
Lithium, ammonium, aliphatic ammonium (substituted ammonium
(Including monium) or represents alicyclic ammonium}
The metal complex salt compound represented by
It is an infrared absorber.

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

The following general formula (In the formula, X ₁ and X ₂ , n ₁ and n ₂ are as defined above.)
The diazo component represented by the formula (In the formula, R ₁ and R ₂ are as defined above.) By coupling with an azo component represented by the conventional method,
The following general formula (In the formula, X ₁ and X ₂ , n ₁ and n ₂ , and R ₁ and R ₂ are as defined above.) A monoazo compound represented by the following is synthesized, and the monoazo compound is then added to water or an organic solvent. It can be obtained in a high yield by treating with an iron salt, and optionally with an aliphatic amine (including a substituted aliphatic amine) or an alicyclic amine.

Examples of the diazo component represented by the general formula (2) used in the present invention include 5-nitro-2-aminophenol, 4,6-dinitro-2-aminophenol, 4-chloro-5-nitro-2- Aminophenol, 3,4,6-trichloro-2-aminophenol, 4-phenylazo-
2-aminophenol, 4-naphthylazo-2-aminophenol and the like can be mentioned. Examples of the coupling component represented by the general formula (3) include 8-amino-2-naphthol and 8-acetylamino-2. -Naphthol, 8-benzoylamino-2-naphthol, 5-amino-2-naphthol, 5-dimethylamino-2-naphthol, 8-n-butylamino-2-naphthol, 8-
Propylamino-2-naphthol, 8-ethylamino-
2-naphthol and the like can be mentioned.

Next, the near-infrared absorbing agent using the metal complex salt 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, regarding optical recording in the information field,
Optical disks such as compact disks and video disks have been developed by using laser light as the light source. As a main material or medium of the recording element in the optical disc, use of a near infrared ray absorbent can be mentioned. One of the principles is to form a laser beam absorption layer on a substrate, irradiate a laser beam corresponding to light or sound, cause a physical or optical change in the irradiated part, and record (write) as a signal. To do. This absorption layer (recording layer)
Is read again as a signal using the laser beam, and is converted into sound or light for reproduction. Therefore,
The role of the near-infrared ray absorbing agent existing in this recording layer is one of the most important elements having an action of efficiently absorbing a laser beam and enhancing a thermal effect and the like. Various properties required of the near-infrared absorber as a recording layer material are that a thin film can be formed with a uniform composition with good reproducibility, high resolution and long-term stability (light resistance, heat resistance, etc.), high sensitivity, and recording pit shape. It must have uniformity and the like.

Known near-infrared absorbing agent used in the conventional recording layer, Te, In, Bi, CS 2 -Te, Te-C, according to the inorganic metallic and JP-B 46-3452 discloses such TeOx Metal complex,
As the dye-based one, 3,3'-dimethyloxatricarbocyanine iodide can be mentioned.
In the case of the inorganic metal type, in any case, the thin film formation of the recording layer on the substrate must be a vacuum deposition method and a special apparatus is required, and the workability is extremely low. The problem of toxicity is also a major obstacle. Further, a metal complex has a small absorption coefficient and must be used in a large amount. Further, it is insoluble or incompatible in a solvent, a resin, etc. and has poor storage stability.

On the other hand, dye-based materials have a large extinction coefficient, but are extremely vulnerable to light and heat, and none of them are practical. Therefore, no known near-infrared absorber has hitherto been found out from the conventionally known compounds, which sufficiently satisfies various performances practically required as a recording material.

The present inventors have studied metal complex salt compounds as dyes for many years, and as a result, found the compound described in JP-B-60-042269. As a result of further deep investigation of the peripheral compounds, the present inventors have found that the absorption wavelength region is significantly extended as compared with the above-mentioned compounds and are extremely advantageous in practical use, and have completed the present invention.

That is, the metal complex salt compound represented by the general formula (1) is
It has an absorption wavelength in the wavelength range of 400 to 1000 nm, and has a molecular extinction coefficient of 50,000 or more in the 800 to 900 nm region of the wavelength of the semiconductor laser that is currently most required for practical use, and it has excellent light resistance and heat resistance. It was found that the material is excellent in solubility in various solvents and compatibility with various resins, and is extremely good as a material for a recording layer in optical recording.

In addition, the metal complex salt compound represented by the general formula (1) has an absorption wavelength range in the visible range as well, and by utilizing this characteristic property, it blocks light in the wavelength range from the visible range to the near-infrared range. It is one of the great features of the present invention that it has a function, that is, it can be usefully used as a filter. For example, electrical products, especially remote control devices such as televisions, radios, and stereos, speed distance measurement of cameras and projectors, and light receiving elements in game machines, automatic doors, etc. It can be suitably used as an optical filter.

Hereinafter, the present invention will be described in detail with reference to Examples, but "parts" means "parts by weight".

Example 1 5-Nitro-2-aminophenol (15.4 parts) was diazotized at a temperature of 0.5 to 5 ° C with 25 parts of concentrated hydrochloric acid and 6.9 parts of sodium nitrite in 200 parts of water by a conventional method to give 8-amino-2-naphthol. By coupling 15.9 parts under alkaline conditions at 0 to 5 ° C, 32 parts of a monoazo compound having the following structural formula was obtained.

This monoazo compound was metal-complexed with ferric chloride in a water solvent. Next, this iron complex product was subjected to salt formation treatment with octoxypropylamine hydrochloride to obtain a black powder of the iron complex salt compound represented by the following formula in a high yield of 44 parts.

The maximum absorption wavelength of this compound in dimethylformamide was 680 nm, and the molecular absorption coefficient at 830 nm was 5.1 × 10 ⁴ . In contrast, Japanese Patent Publication No. 60-42269, Example 1
In the case of the known compounds described, the maximum absorption wavelength is
Although it has a molecular absorption coefficient of 730 nm, the molecular absorption coefficient at 830 nm is 4.7 × 10 ³ , which has a drawback that the absorption coefficient in the required absorption region is small.

Next, FIG. 1 shows the absorbance comparison data of the compound of the present invention and this known compound.

Next, a 2% methyl ethyl ketone solution of the iron complex salt compound was applied on a glass plate on which aluminum was vapor-deposited by a spin coater. After drying this as a disk GaAlAs
Recording was possible in the recording layer of the disk, that is, the above iron complex salt compound composition film, by using the semiconductor laser beam. The recorded disk could be read with the same low output of the semiconductor laser as at the time of recording. S / for reading
N (high signal against noise) and recording sensitivity were compared with known compounds. The results are shown in Table 1 below.

Further, this disk was stable with no change in recording sensitivity or recording signal even when left for 6 months in an atmosphere of 50 ° C. and 70% humidity.

Example 2 According to Example 1, an iron complex compound having the following structure was obtained.

When the above compound and the compound described in Example 7 of JP-B-6042269 are compared in the same manner as in Example 1, the results are shown in FIG. 2 and Table 2 below, which shows that the compound of the present invention is excellent. It was

Examples 3 to 14 Operations were performed in the same manner as in Example 1 except that the metal complex salt compound, solvent, binder and coated substrate shown in the table below were used. These results are also shown in the following table.

Example 15 The following metal complex compound synthesized according to Example 1 1 part was added to 150 parts of Epicote 828 (Ciel Chemical),
Knead, then add 15 parts of Epikiure K61B (hardening agent), mix at 20-25 ° C, pour into a mold incorporating the light-receiving element of the light-emitting diode, cure at 80 ° C for 2 hours, and metal complex salt An epoxy light receiving element embedded molded product containing the compound was obtained. The light-receiving element obtained in this manner passed through the epoxy resin layer containing the metal complex salt compound and received only the selected light, so that no malfunction occurred.

Further, a filter molded product could be obtained by heating and kneading into an AS resin instead of the epoxy resin in this example.

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

[Brief description of drawings]

FIG. 1 shows the compound of Example 1 of the present invention and JP-B-60-42.
269: Absorbance comparison data with the compound described in Example 1 of No. 269 publication. FIG. 2 shows the compound of Example 2 of the present invention and JP-B-60-42.
9 is data of comparison of absorbance with the compound described in Example 7 of JP-A No. 269.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-11385 (JP, A)

Claims (2)

[Claims] 1. The following general formula,{In the formula, X₁And X₂Is a nitro group and / or a halogen source
Child, phenylazo (including substituted phenylazo), naphthi
Represents luazo (including substituted naphthylazo), n₁And n₂Is
Represents an integer of 1 to 3, R₁And R₂Is an amino group, monoalk
Ruamino group, dialkylamino group, acetylamino group,
Benzoylamino group (including substituted benzoylamino group)
Represents X₁And X₂, N₁And n₂, R₁And R₂Are the same
Or it may be different, Y Is hydrogen, sodium,
Lithium, ammonium, aliphatic ammonium (substituted fat
Group containing ammonium) or alicyclic ammonium
A metal complex salt compound represented by 2. A near-infrared absorber having the following general formula:{In the formula, X₁And X₂Is a nitro group and / or a halogen source
Child, phenylazo (including substituted phenylazo), naphthi
Represents luazo (including substituted naphthylazo), n₁And n₂Is
Represents an integer of 1 to 3, R₁And R₂Is an amino group, monoalk
Ruamino group, dialkylamino group, acetylamino group,
Benzoylamino group (including substituted benzoylamino group)
Represents X₁And X₂, N₁And n₂, R₁And R₂Are the same
Or it may be different, Y Is hydrogen, sodium,
Lithium, ammonium, aliphatic ammonium (substituted fat
Group containing ammonium) or alicyclic ammonium
Characterized by using a metal complex compound represented by
And near-infrared absorber.