JPH057398B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a new dye material that exhibits absorption in the near-infrared light region, and more specifically, dyes for optical recording materials, dyes for infrared absorption filters, dyes for laser printers, and single-layer dyes. This invention relates to dye materials related to oxygen quenchers and anti-fading agents. (Prior art) The characteristics that the material should have differ for each application of dyes that absorb in the near-infrared light region, but the basic characteristics are that the material has large absorption in the near-infrared light region, and chemical It is necessary for the material to be stable. Furthermore, depending on the field of application, it is used in the form of a film, so it must be easy to form a film under given conditions. Several such materials have been developed so far. Examples include squarylium, cyanine dyes, metal phthalocyanines, platinum bis(dithio α-diketone) complex compounds, and the like. Squarylium has the problem of low absorption and poor film quality, while cyanine dyes have the problem of becoming chemically unstable when the molecular chain is lengthened to increase near-infrared light absorption. However, when metal phthalocyanine forms a film, it becomes amorphous and has problems with its long-term stability, that is, crystallization, and platinum bis(dithio-alpha-diketone) complex compounds have poor film-forming properties and are chemically unstable. There is a problem with that. As described above, the conventionally developed near-infrared light absorbing dyes have some problems and have not been put into practical use. (Problems to be Solved by the Invention) An object of the present invention is to provide a dye material that has large absorption in the near-infrared region, is chemically stable, and is easy to form into a film. (Means for solving the problem) That is, the present invention has the general formula [] (In the formula, R represents a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a halogen, an amino group, or a substituted amino group, X represents sulfur, selenium, or an imino group, and Y represents a hydrogen atom or an amino group. R' represents an alkyl group, m represents 1 or 2), and is a near-infrared absorbing 2:1 type nickel complex dye. The compound of the present invention can be produced, for example, as follows. That is, the general formula [] (In the formula, X, Y, R, and m have the same meanings as in the general formula ) By reacting with an ethanol solution of chloride hexahydrate and further stabilizing by adding tetrabutylammonium bromide, a deep green pigment can be obtained with the following general formula [] A compound represented by the formula (wherein R, X, Y, R', and m have the same meanings as in the general formula []) is produced. The above reaction is usually carried out in a polar solvent mainly consisting of alcohols such as methanol and ethanol. The reaction temperature can be smoothly carried out at room temperature or from 0°C to 50°C. The 2:1 type nickel complex of the present invention is a novel dye, which is characterized by a strong absorption spectrum in the near-infrared region, and can be used to color low-molecular substances and to form sheets, fibers, and other forms made of synthetic polymer substances. Useful for coloring things. Examples of the coloring method include kneading, coating, and sputtering. Further, the compounds of the present invention are valuable as various functional dyes, such as dyes for near-infrared absorption recording materials, dyes for infrared absorption filters, dyes for laser printers, singlet oxygen quenchers, and color mixture inhibitors. EXAMPLES Next, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples. Example 1 0.4 g of metallic potassium in 12 ml of absolute ethanol
(0.01 mol) [or 0.55 g (0.01 mol) potassium hydroxide] and add 0.005 mol (0.54 g) of orthophenylenediamine to the solution at room temperature. On the other hand, dissolve 0.0025 mol (0.58 g) of nickel () chloride hexahydrate in 5 ml of absolute ethanol,
When this solution is added to the above ligand solution while stirring, a green color develops. After stirring in this state for an additional 2 hours, a solution of 0.0025 mol (0.8 g) of tetrabutylammonium bromide in 10 ml of ethanol was added, and the mixture was stirred for an additional 3 hours. The formed precipitate is filtered, washed with ethanol, and dried to obtain the complex dye [] with a yield of 48%. The melting point of this dye is over 300℃, and the DMF solution has a wavelength of 783nm.
shows strong absorption with ε of 37400. When potassium hydroxide is used instead of metallic potassium, the above product can be synthesized in exactly the same manner with a yield of 48%. Example 2 In the same manner as in Example 1, the following compound [ ] can be synthesized when euaminobenzenethiol is used as a ligand. This dye has an absorption maximum of 894 nm in DMF, a melting point of over 300°C, and a yield of 85%. Example 3 In the same manner as in Example 1, the following compound [ ] can be synthesized when 2-aminobenzeneselenol zinc salt is used as a ligand. This dye has an absorption maximum of 858 nm in DMF, a melting point of over 300°C, and a yield of 80%. Example 4 When 3,4,5-triaminoethylbenzene is used as a ligand in the same manner as in Example 1, the following compound [ ] can be synthesized. This dye has an absorption maximum of 790 nm in DMF, a melting point of 300° C., and a yield of 75%. Since this dye is easily soluble in ethanol, it can be isolated by distilling off the reaction solvent. Using an ethanol solution of this dye, a thin dye film can be formed on a substrate such as glass or resin by a solution coating method. Example 5 A further compound was obtained by a method similar to Example 1.

[Table] (Effects of the invention) As described above, the 2:1 type nickel complex dye of the present invention exhibits large absorption in the near-infrared region and has high solubility, so it is useful in industrial applications such as being able to form thin films with a simple coating. It has many advantages.

Claims (1)

[Claims] 1. General formula [] (In the formula, R represents a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a halogen, an amino group, or a substituted amino group, X represents sulfur, selenium, or an imino group, and Y represents a hydrogen atom or an amino group. R' represents an alkyl group, and m represents 1 or 2.) A near-infrared absorbing 2:1 type nickel complex dye.