JP2879826B2 - New metal complex compounds - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel dithiolato metal complex compound expected to be useful as a near-infrared absorbing agent, a light stabilizer and the like.

[Conventional technology]

In recent years, in connection with the development of infrared filters, optical recording media, liquid crystal displays, laser printers, electrophotography, and the like, the development of stable dyes that efficiently absorb light in the infrared to near-infrared region has been desired. I have.

So far, as a dye that has absorption in the near infrared region,
Squarylium, cyanine dyes, metal phthalocyanines, platinum bis (dithio-α-diketone) complex compounds, and certain nickel complex compounds are known. However, in order for such dyes to be effectively used, characteristics such as compatibility and film formability are also often required.

One of the remarkable properties of the dithiolatonic nickel complex compound is the deactivation of singlet oxygen, which is useful as a light stabilizer and antioxidant for polyolefins, and is useful for photodegradation of organic dyes. Attention has been paid as an inhibitor (for example, JP-A-63-288786, JP-A-63-209890, JP-A-63-288785, etc.). Also in this case, properties such as solubility, compatibility, and film formability of the dye are often required.

[Problems to be solved by the invention]

However, the near-infrared light absorbing dyes that have been developed so far have some problems and have not yet been put to practical use. For example, squarylium has a problem of low absorptivity and poor formed film state, and cyanine dyes become chemically unstable when the molecular chain is lengthened to increase the absorptivity of near infrared light. There is a problem that.
In addition, since metal furocyanines have poor solubility in organic solvents and the like and cannot be formed into a thin film by solution coating or the like, their use is greatly restricted, and there is a problem of crystallization of an amorphous film. Bis (dithioα-diketone) complex compounds have problems that film formability is poor and that they are chemically unstable. Further, as the nickel complex compound, many benzenethiolato type nickel complexes and dithiolene type nickel complexes are known. Not.

Therefore, an object of the present invention is to be useful as a near-infrared absorber or a light stabilizer, yet chemically stable, having high solubility in general organic solvents, having high compatibility with resins and the like, and forming a film. An object of the present invention is to provide a novel dye material which is easy to use.

[Means for solving the problem]

According to the present invention, a dithiolato metal complex compound represented by the following general formula is provided.

(Wherein, R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group, or a cyano group, which may be the same or different, and R ¹ and R ² are bonded to each other to form an aromatic group. X may represent a halogen atom, M may represent a transition metal selected from Ni, Pd, Pt, Co, Cu, Mn,
A represents a cation species such as a quaternary ammonium salt, a quaternary phosphonium salt, or sodium, and n represents the number thereof, and takes an integer of 0 to 2 depending on the valence of the metal complex. In the general formula (I), specific examples of R ¹ and R ² include a hydrogen atom; a methyl group, an ethyl group, a propyl group, and n-
An alkyl group such as a butyl group and a tert-butyl group; an aryl group such as a phenyl group and a naphthyl group; a cyano group. The alkyl group and the aryl group may further have a substituent. Examples of the substituent in the alkyl group include a halogen atom (each atom of chlorine, bromine, and fluorine). , Halogen atoms (chlorine, bromine, fluorine atoms, etc.), lower alkyl groups (methyl, ethyl, propyl, n-butyl, te
rt-butyl group, etc.), halogen-substituted alkyl group (trifluoromethyl group, etc.), alkylamino group (monomethylamino group, dimethylamino group, diethylamino group, etc.).

Further, R ¹ and R ² may be bonded to each other to form, for example, an aromatic ring or a pyridine ring, and these rings may be a halogen atom (chlorine, bromine, fluorine atom, etc.), an alkyl group (methyl group, Substituents such as ethyl group, propyl group, n-butyl group, tert-butyl group, etc., halogen-substituted alkyl groups (trifluoromethyl group, etc.), alkylamino groups (monomethylamino group, dimethylamino group, diethylamino group, etc.) May be provided. Note that X includes a halogen atom such as chlorine, bromine, and fluorine atoms.

The novel dithiolato metal complex compound represented by the general formula (I) of the present invention has an absorption capacity in the near-infrared region and has a pyridine skeleton and can be hydrogen-bonded. It has excellent solubility in polar solvents, good compatibility with resins, etc., and high stability, so it is a safelight filter for photosensitive materials, an infrared cut filter harmful to human eyes, and a plant growth control. Plastic film, heat ray blocking plastic film, infrared cut filter for semiconductor light receiving element such as silicon photodiode, singlet oxygen quencher, anti-fading agent, lightfastness improver for optical disk dye, recording dye for optical disk, heat of laser light Conversion materials, ink for inkjet printers, barcode inks, infrared absorbing dyes for soundtracks Infrared couplers formed, filters for optical converter, industrial thermal label, utility as such solid ink, such as thermal transfer ribbons are expected.

The metal complex compound according to the present invention is a metal complex having at least one skeleton (II) shown below as a ligand.

(In the formula, X represents a halogen atom.) When the metal complex is asymmetric, a conventionally known ligand is used as another ligand. Further, a monovalent metal complex is desirable in order to have both solvent solubility and large absorption in the near infrared region, and a cation species such as a quaternary ammonium salt or a quaternary phosphonium salt is used as a counter ion at that time. .

Specific examples of the metal complex compound represented by the general formula according to the present invention include a zero-valent complex shown below,
Examples of the complex include a combination of an anion of the complex and a complex cation, but the present invention is not limited to these.

(1) Specific examples of complexes Bis (2,5,6-trichloropyridine-3,4-dithiolato)
nickel (2,5,6-trichloropyridine-3,4-dithiolato)-
(1,2-dicyanoethylenedithiolato) nickel (2,5,6-trichloropyridine-3,4-dithiolato)-
(1,2,4-trichloro-5,6-dithiolato) nickel (2,5,6-trichloropyridine-3,4-dithiolato)-
(Tetrachlorodithiolato) nickel (2,5,6-trichloropyridine-3,4-dithiolato)-
[Bis (4-chlorophenyl) ethylene-1,2-dithiolato] nickel (2,5,6-trichloropyridine-3,4-dithiolato)-
(4-trifluoromethyl-1,2-dithiolato) nickel (2,5,6-trichloropyridine-3,4-dithiolato)-
[Bis (4-dimethylaminophenyl) ethylene-1,2
-Dithiolat) nickel (2,5,6-trichloropyridine-3,4-dithiolato)-
(4-octene-4,5-dithiolato) nickel (2,5,6-trichloropyridine-3,4-dithiolato)-
(4-tert-butyl-1,2-dithiolato) nickel In the above example of the complex anion, the case where M represents Ni is shown.
Is also included.

(2) Specific examples of the complex cation (counter cation A) Tetraethylammonium cation Tetra n-butyl ammonium cation Benzyl-tri-n-butylammonium cation N-laurylpyridinium cation N-benzylpicolinium cation Trimethyl-hexadecane ammonium cation Tetra-n-butylphosphonium cation Trihexylethyl phosphonium cation Tetraoctylphosphonium cation Tetraethylphosphonium cation The compound of the present invention can be produced, for example, as follows. First, 2,5,6-trihalogenated pyridine-3,4-dithiol is synthesized from pentahalogenated pyridine by a method similar to the method for synthesizing benzenedithiol disclosed in Japanese Patent Application Laid-Open No. 58-105960. . When this compound is reacted with a transition metal salt such as nickel chloride, a bis (2,5,6-trihalogenated-3,4-pyridinethiolato) metal complex is mainly divalent or a mixture of divalent and monovalent metals. The body is obtained as a hydrochloride and / or hydrate and / or solvate without the stable cationic species (hereinafter simply abbreviated as hydrochloride), and some have monovalent stable cationic species Obtained as is. The latter can be obtained as a stable monovalent metal complex by adding a stable cationic species. The former hydrochloride is well dissolved in a mixed solvent of acetone / water or a mixed solvent of alcohol / water, and air is blown into the solution to oxidize the solution. It can be. Further, a stable divalent metal complex can be obtained by adding a stable cation species after neutralizing the solution of the hydrochloride with an alkali. Incidentally, the can be converted into a monovalent body 2 Ataitai with an oxidizing agent such as iodine, it can be converted into divalent body 1 Ataitai with a reducing agent such as NaBH _4.

Further, the above-mentioned hydrochloride is combined with another kind of complex and an appropriate organic solvent (eg, acetonitrile, acetone, ethyl acetate, 1,2-
By heating and stirring in dichloroethane and the like, ligand exchange is performed and an asymmetric metal complex is synthesized.

In particular, when producing a monovalent asymmetric dithiolato metal complex, two kinds of symmetric dithiolato metal complexes having the same transition metal and counter cation are reacted with each other in an organic solvent to form a ligand. The method of exchanging is preferable. That is,
A symmetric metal complex represented by the following general formula (III): (In the formula, X, M and A are the same as those in the general formula (I).) A symmetric metal complex represented by the following general formula (IV) (Wherein, M and A are the same as those in the general formula (I).) By reacting in an organic solvent, the following general formula (V)
An asymmetric metal complex represented by the following formula is obtained.

(In the formula, X, M and A are the same as those in the general formula (I).) In this case, the organic solvent may be a commonly used organic solvent, and in particular, acetone, acetonitrile, ethyl acetate, 1,2, -Dichloroethane and the like have good solubility. Tetrahydrofuran and dioxane are not preferred because they cause the decomposition of the complex. A reaction at 50 to 120 ° C. for about 5 hours is sufficient. According to this method, there is an advantage that the yield of the target substance is high and only a small number of by-products are produced.

In the case of an asymmetric metal complex, salts of transition metals such as nickel in a solution containing a 2,5,6-trihalogenated-3,4-pyridinedithiol ligand and another type of dithiol ligand are used. May be employed. In addition, the dithiol can be converted into an alkali metal salt at the time of complexation and reacted with a salt of a transition metal such as nickel. In this case, sodium is generally used as the alkali metal, but other metals may be used, and one of the dithiols may be in the form of an alkali metal salt.

〔The invention's effect〕

The novel metal complex represented by the general formula (I) of the present invention itself has an absorptivity in the near infrared region and has a pyridine skeleton and can form a hydrogen bond. Since it has excellent solubility in solvents, excellent compatibility with resins and the like, and high stability, it is useful as a near-infrared absorbing agent or light stabilizer.

〔Example〕

Next, the present invention will be described in more detail by way of examples. The percentages and parts shown below are based on weight.

Example 1 20 parts of pentachloropyridine, 16 parts of 70% NaSH, 3.4 of iron powder
Parts, 1.6 parts of sulfur powder and 70 parts of N, N-dimethylformamide while heating at 130 ° C while passing nitrogen gas slowly.
After reacting for 0 hour, the mixture was cooled, 200 parts of water was added, and the mixture was filtered to remove a black solid by filtration and air-dried. Next, the total amount of the solid was mixed with an aqueous solution in which 100 parts of methanol, 8 parts of zinc oxide and 20 parts of sodium hydroxide were dissolved in 100 parts of water, and the mixture was refluxed for 1 hour. After cooling, perform filtration,
The filtrate was poured into an acidic aqueous solution obtained by mixing 200 parts of water and 100 parts of 98% sulfuric acid to obtain a brown solid. This was extracted with chloroform, washed with water several times, and dried up in chloroform phase to give yellow 2,5,6-trichloropyridine-
10 parts of 3,4-dithiol were obtained. 137.5-138.0
° C.

The 2,5,6-trichloropyridine-3,4-dithiol 10
Was dissolved in 350 parts of chloroform, and a solution of 4.8 parts of nickel chloride hexahydrate dissolved in 100 parts of ethanol was added to obtain a red bis (2,5,6-trichloropyridine-3,4-dithiolato) nickel complex Of hydrochloride was obtained. Melting point
300 ° C or higher. FIG. 1 shows the infrared absorption spectrum (KBr method).

Example 2 10 parts of the nickel complex hydrochloride obtained in Example 1 was mixed with 140 parts of water.
The mixture was dissolved in a mixed solvent of 500 parts of ethanol and 500 parts of ethanol, and the mixture was stirred at room temperature for 4 hours while blowing air thereinto.
6.1 parts of butyl ammonium were added to obtain 12.4 parts of a green precipitate. This is silica gel (trade name: Wakogel C-20)
Using 0), purification was performed by column chromatography using 1,2-dichloroethane as a developing solvent. As a result, 11 parts of bis (2,5,6-trichloropyridine-3,4-dithiolato) nickel-tetra-n-butylammonium [II] was obtained.

The melting point of this compound was 197 to 199 ° C, and its elemental analysis value was as follows as C ₂₆ H ₃₆ N ₃ S ₄ Cl ₆ Ni.

C% H% N% S% Cl% Calculated 39.51 4.59 5.31 16.23 26.91 Found 39.52 4.30 5.19 16.02 26.91 This compound had an absorption maximum at 854 nm in a methanol solution and had a molar extinction coefficient of 8,900. FIG. 2 shows the infrared absorption spectrum (KBr method).

Example 3 10 parts of a bis (2,5,6-trichloropyridine-3,4-dithiolato) nickel complex hydrochloride synthesized in the same manner as in Example 1 and 15 parts of a divalent nickel complex represented by the following formula Was refluxed for 5 hours in 520 parts of 1,2-dichloroethane. After cooling, it was dried up, and 5 parts of the following nickel complex [III] was taken out by column chromatography using chloroform and 1,2-dichloroethane as a developing solvent.

The melting point of this compound was 127.5 to 128 ° C., and its elemental analysis value was as follows as C ₂₅ H ₃₆ N ₄ S ₄ Cl ₃ Ni.

C% H% N% Calculated 43.77 5.29 8.16 Found 43.51 5.19 7.92 This compound had an absorption maximum at 850 nm in a methanol solution, and the molar extinction coefficient was 9600. The infrared spectrum (KBr method) is shown in FIG.

Example 4 31 parts of commercially available bis (3,5,6-trichlorobenzene-1,2-dithiolato) nickel-tetra-n-butylammonium complex (trade name: PA1006; manufactured by Mitsui Fine Chemical Co., Ltd.) are dispersed in 270 parts of methanol. Then, 12 parts of a 50% aqueous sodium hydroxide solution was added. Then, 1.5 parts of NaBH ₄ was added, and
Stirred at 40 ° C. for 2 hours. To the portion that turned red and transparent, 25.4 parts of tetra-n-butylammonium bromide was added, and the mixture was stirred at room temperature for 2 hours. Thereafter, the precipitate was removed by filtration,
After washing with water and drying, 36 parts of a divalent form of PA1006 were obtained. This 2
10 parts of bis (2,5,6) synthesized in the same manner as in Example 1.
5.3 parts of -trichloropyridine-3,4-dithiolato) nickel complex hydrochloride was refluxed for 5 hours in 320 parts of 1,2-dichloroethane. After cooling, it was dried up, and 6.5 parts of the following nickel complex [IV] was taken out by column chromatography using chloroform and 1,2-dichloroethane as a developing solvent.

This compound had a melting point of 141 to 142.5 ° C., had an absorption maximum at 860 nm in a methanol solution, and had a molar extinction coefficient of 12,800. FIG. 4 shows the infrared absorption spectrum (KBr method).

Example 5 As a divalent nickel complex, the following formula was used. In the same manner as in Example 3 except that the compound represented by the following formula was used, 1.5 parts of a nickel complex represented by the following [V] was obtained.

This compound had a melting point of 245 to 247 ° C, had an absorption maximum at 850 nm in a methanol solution, and had a molar extinction coefficient of 9600. FIG. 5 shows the infrared absorption spectrum (KBr method).

Example 6 15 parts of the hydrochloride of the bis (2,5,6-trichloropyridine-3,4-dithiolato) nickel complex obtained in Example 1 was
It was dissolved in a mixed solvent of 500 parts of acetone and 200 parts of water, and a 0.1 N aqueous solution of sodium hydroxide was added dropwise to the solution until the pH reached 7 (about 490 parts). Thereafter, 18 parts of tetra-n-butylammonium bromide was added, and the mixture was stirred for 1 hour. A tan precipitate was deposited, which was collected by filtration and washed with water to obtain 24 parts of the following nickel complex [VI].

The melting point of this compound was 207-208.5 ° C. FIG. 6 shows the infrared absorption spectrum (KBr method).

Example 7 Bis (2,5,6-trichloro-3,4-pyridinethiolato)
Bis (cis-1,2-dicyano-1,2-) equimolar to 2 parts of nickel / tetra-n-butylammonium complex (monovalent)
1.47 parts of (ethylenedithiolato) nickel-detra-n-butylammonium complex (monovalent) was charged into 200 parts of 1,2-dichloroethane, and the mixture was heated under reflux for 5 hours. afterwards,
After allowing to cool and evaporating the solvent, the main component is 2,5,6-trichloropyridine-3,4-dithiolato)-(1,2-dicyanoethylenedithiolato) nickel-tetra-n-butylammonium complex. A reaction mixture was obtained. When the obtained mixture was analyzed by high performance liquid chromatography, the yield of the target compound was 53.1%, and the number of components other than the target compound was 2.

Example 8 An asymmetric dithiolatonic nickel complex was produced in the same manner as in Example 7 except that acetone was used instead of 1,2-dichloroethane as the solvent, and the reaction mixture was analyzed. The yield of the target product was 55.0%, and the number of components other than the target product was 3.

Application Example 1 The following formula is formed on a PC (polycarbonate) substrate having a thickness of 1.25 mm by injection molding, and grooves having a half width of 0.3 μm and a depth of 950 mm are provided at a track pitch of 1.6 μm and a radius of 45 to 94 mm at a radius of 45 to 94 mm. And the nickel complex [II] obtained in Example 2 were dissolved at a weight ratio of 85/15 in a mixed solvent of methanol and 80 parts by weight of 1,2-dichloroethane: 20 parts by weight, and spin-coated with a spinner to obtain a thickness. A 700 記録 recording layer was provided.

Information is written and reproduced from the substrate side at a recording frequency of 0.5 MHz and a linear velocity of 1.5 m / sec using a semiconductor laser beam with a wavelength of 790 nm on the produced recording medium, and the reproduced waveform is subjected to spectrum analysis (scanning filter, bandwidth 30 KHz). ) To measure C / N. Furthermore, the same recording medium was irradiated with tungsten light of 54000 lux for 20 hours, and the reproduction degradation acceleration experiment and 60
The reflectance and the C / N were measured after an accelerated storage deterioration experiment was conducted for 1000 hours at 90 ° C. and 90% RH. Table 1 shows the results.

Application Example 2 A recording medium was prepared in the same manner as in Application Example 1, except that the nickel complex [III] obtained in Example 3 was used instead of the nickel complex obtained in Example 2. ,
evaluated. Table 1 shows the results.

Comparative Example 1 In the same manner as in the application example 1, except that the nickel complex obtained in the example 2 was replaced with a nickel complex having the following structure (trade name: PA1006; manufactured by Mitsui Toatsu Co., Ltd.). To prepare a recording medium and evaluate it. Table 1 shows the results.

From the results shown in Table 1, it can be seen that by using the metal complex compound of the present invention, a recording medium having high stability to heat and light, having excellent storage stability, and having little reproduction deterioration can be obtained.

[Brief description of the drawings]

1 to 6 show infrared absorption spectra of the respective nickel complexes obtained in Examples 1 to 6 of the present invention.

Claims (1)

(57) [Claims] 1. A dithiolato metal complex compound represented by the following general formula. (Wherein, R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group, or a cyano group, which may be the same or different, and R ¹ and R ² are bonded to each other to form an aromatic group. X may represent a halogen atom, M may represent a transition metal selected from Ni, Pd, Pt, Co, Cu, Mn,
A represents a cation species such as a quaternary ammonium salt, a quaternary phosphonium salt, or sodium, and n represents the number thereof, and takes an integer of 0 to 2 depending on the valence of the metal complex. )