JPH0672147B2 - Quaternary phosphonium bis (cis-1,2-ethylenedithiolato) nickelate derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION “Industrial field of application” The present invention is 1) having near-infrared absorbing properties, 2) having a function of stabilizing an organic substrate material against light, and having light resistance and heat resistance. The present invention relates to a novel compound quaternary phosphonium bis (cis-1,2-ethylenedithiolato) nickelate derivative which is excellent and has excellent solubility in an organic solvent.

"Prior Art" In the present invention, near infrared light has a wavelength of about 500 nm to about 2,0
Says an electromagnetic wave of 00 nm.

The term organic substrate substance or substrate compound includes substances that appear colored or colorless to the human eye under the irradiation of sunlight, and not only substances that have an absorption maximum in the visible region but also, for example, optical enhancement. It also includes a white agent or a substance having an absorption maximum in the infrared region.

In the present invention, the organic substrate material is about 300 n in the ultraviolet region.
m includes organic substances having an absorption maximum at about 2,000 nm in the near infrared region.

As used herein, the term dye or dye includes organic substances that appear colored to the human eye under sunlight.

Conventionally, the following technologies have been known.

(I) The substance that absorbs near infrared rays is an infrared cut filter, for example, a safe light filter for a near infrared sensitive photosensitive material, an infrared cut filter harmful to human eyes,
Plastic film used for controlling the growth of plants,
It is used for near infrared cut filters of semiconductor photo detectors such as silicon photodiodes (hereinafter referred to as SPD). Also, by utilizing the property of absorbing near infrared rays and exchanging them with heat, they are used for heat-sensitive color development by laser, heat-sensitive recording, use for optical disc recording layer, and acceleration of drying of ink paint. It is also possible to coat and disperse in various light-sensitive materials to form an anti-halation layer to improve the image quality and improve the image quality by utilizing the absorption property of the. Additions to inks, inks for ink jet printers, etc. have also been tried.

Various compounds have been developed as near-infrared absorbers used for these.

For example, as the organic compound containing no transition metal, Japanese Patent Publication Nos. Sho 36-6763, Sho 40-25347 and Sho 43-25335 are available.
No. 4, Japanese Patent Publication No. 45-13326, Japanese Patent Publication No. 46-5810, Japanese Patent Publication No. 46
-11249, JP-A-50-129532, JP-A-57-45509,
There are compounds described in US Pat. No. 2813802, US Pat. No. 2,895,955 and the like.

Examples of compounds containing a Δ transition metal include, for example, Japanese Patent Publication No. 46-3452, Japanese Patent Publication No. 49-22748, and U.S. Pat. No. 3,588,216.
U.S. Pat.No. 3663089, U.S. Pat.No. 3806462, U.S. Pat.No. 3875199, U.S. Pat.No. 3979583, U.S. Pat.
There are compounds described in 62867, U.S. Pat. No. 4,153,332, U.S. Pat. No. 4,432,595 and the like.

(II) Conventionally, organic substrate materials such as dyes, dyes,
It is also known that polymer materials tend to discolor, discolor, or decompose due to light.A method to reduce this discoloration, discoloration, or decomposition and deterioration, that is, prevent light deterioration and improve light resistance. There are many reports on how to blame them.

For example, in U.S. Pat. It is stated that the robustness is improved.

In the field of silver halide photographic light-sensitive materials, CEK, M
“The Theory of the Photograph” by ees and TH James
As described in Chapter 17 of "ic Process" (published by Macmillan Co. in 1976), an azomethine dye or an indoaniline dye can be obtained by a reaction between an oxidized product of an aromatic primary amine developing agent and a color developing agent (Kuppler). There are many known methods of improving the light stability of images formed from these dyes, i.e., color images, such as U.S. Pat. Nos. 2,360,290 and 2,4.
No. 18,613, No. 2,675,314, No. 2,701,197, No. 2,
No. 704,713, No. 2,728,659, No. 2,732,300, No. 2
2,735,765, 2,710,801, 2,816,028, hydroquinone derivatives described in British Patent 1,363,921, U.S. Pat.No. 3,457,079, 3,069,262, gallic acid described in Japanese Patent Publication No. Derivatives, p-alkoxyphenols described in US Pat. Nos. 2,735,765 and 3,698,909, and US Pat. Nos. 3,432,300 and
Derivatives such as chroman and coumaran as described in 3,573,050, 3,574,627, 3,764,337, 3,574,626, 3,698,909, and 4,015,990 are known.

Also, a method of improving the light stability of an organic substrate compound by using an azomethine quenching compound whose absorption maximum is bathochromic than the absorption maximum of the substrate compound is described in British Patent No. 1,451,000. ing.

In addition, high molecular compounds, such as polyolefin,
It has been known for a long time that light deteriorates,
In order to prevent this, a UV absorber such as a benzophenone derivative or a hindered amine has been widely used.

On the other hand, a method for stabilizing a dye with a metal complex is a British patent.
869,986, U.S. Pat.No. 4,050,938 and Research Disc
losure15162 (1976), and the use of metal complexes to prevent photodegradation of polymers is described by O. Cicchett.
i, Adv.Polymer Sci. 7 70 (1970); MSAllen, JFMck
ellar.Chem.Soc.Rev. 4 533 (1975); DJ Carlson, D.
M.Wiles, J.Macromol.Sci.Rev.Macromol.Chem.C14 65
(1976); RBWalter, JF Johnson, J. Polymer Sci. 15
29 (1980); NS Allen, Chem. Soc. Rev., 15 373 (1986).

[Problems to be Solved by the Invention] (I) A common drawback of all the near-infrared absorbers containing no transition metal mentioned in the above (I) is that heat resistance and light resistance are extremely poor, It means that they cannot bear it.

Further, the compound containing a transition metal has poor solubility in an organic solvent and has a drawback that it is difficult to put into practical use. For example,
As described above, for example, as a SD filter,
An extremely thin film having a good infrared absorption efficiency is desired, but for that purpose, a large amount of the infrared absorbent must be dispersed in the resin, and the infrared absorbent having a small solubility in an organic solvent satisfies the purpose. I couldn't do it.

(II) The photodeterioration inhibitor, which is an organic compound mentioned in (II) above, is effective, but it is not sufficient, and the photodegradation inhibitor containing a metal has high solubility in an organic solvent, so photodegradation It is not possible to add a sufficient amount to exert the preventive effect. Moreover, these compounds are highly colored in their own right, so if added in large amounts, organic substrate materials, especially
It has the drawback of adversely affecting the hue and purity of dyes and pigments.

Therefore, firstly, the object of the present invention is to provide a near-infrared absorbing material having extremely high heat resistance and light resistance, high solubility in an organic solvent, and good compatibility with a film-forming binder and the like. Second, a near-infrared absorbing material that has a large ability to block near-infrared light per unit thickness, has a high light transmittance in the visible region, and can form an optical filter that is robust against heat and light. Third, to provide a substance that improves the stability of the organic substrate material to light, and fourth, to deteriorate the hue and purity of the organic substrate material, especially a dye or dye. The need is to provide compounds that improve the stability of these materials to light, without the need to do so.

The present inventor has completed the present invention as a result of various studies in order to achieve the above object.

"Means for Solving Problems" That is, the present invention provides a quaternary phosphonium bis (cis-1,2-ethylenedithiolato) nickelate derivative represented by the following general formula.

(In the formula, R ^{1 to} R ⁴ represent an alkyl group or a phenyl group, which may be the same or different, and n represents 2 or 3.) Further, the substituent will be described in detail.

The alkyl group represented by R ^{1 to} R ⁴ in the compound represented by the above general formula is preferably an alkyl group having 1 to 20 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group and an n-butyl group, n-octyl group, n-
Examples thereof include dodecyl group, n-octadecyl group, 2-ethylhexyl group and the like.

The alkyl group and phenyl group represented by R ^{1 to} R ⁴ may be further substituted with another substituent such as a halogen atom (fluorine, chlorine, bromine, etc.) cyano group, alkyl group, aryl group, etc. Alternatively, it may be substituted with another alkyl group, an aryl group or the like via a divalent linking group (eg, —O—, —S—, —CO ₂ — and the like).

Quaternary phosphonium bis (cis-) represented by the above general formula
The 1,2-ethylenedithiolato) nickelate derivative can be generally synthesized as follows.

Dissolving an alkali metal salt of a cis-1,2-ethylenedithiol derivative obtained by ring-opening 4,5 (alkylenedithio) -1,3-dithiol-2-thione with a base in anhydrous methanol,
To this, a solution of nickel salt in methanol is added, and air (or oxygen) is blown therein.

A quaternary phosphonium salt is added to this solution and the deposited precipitate is localized. Inorganic salts produced as by-products (alkali metal salts, etc.)
After removing the solvent with an organic solvent such as dichloromethane, the solvent is distilled off to obtain crude crystals. This is recrystallized from, for example, dichloromethane-isopropanol.

The preferred compounds among the compounds represented by the above general formula are shown below, but it goes without saying that the present invention is not limited to these exemplified compounds.

The absorption maximum (λmax), molar extinction coefficient (εmax, .mol ^-1 cm ^-1 unit) and melting point of these compounds are as follows.

However, the absorption maximum and the molar extinction coefficient are values in dichloromethane.

"Effect of the Invention" The quaternary phosphonium bis (cis-1,2-ethylenedithiolato) nickelate derivative of the present invention has high solubility in an organic solvent, excellent compatibility with a film-forming binder and the like, and has a near red color. It has excellent properties that it has a large ability to block external light and a high light transmittance in the visible region.

Further, these complexes have an excellent effect of preventing deterioration of organic base materials, particularly dyes, pigments and polymer materials by light, and do not adversely affect the hue and purity of the organic base materials because they are less colored.

Furthermore, these complexes have the practical advantage that they are easy to synthesize and can be produced at low cost.

Therefore, the complex of the present invention can be applied to a near infrared ray cut filter using light absorption as a near infrared ray absorbent, an ink, etc., as well as a heat sensitive color development by a laser utilizing light → heat exchange, a heat sensitive recording, an optical disc recording layer. It can be utilized for various purposes such as utilization and use as an organic photo-deterioration preventing agent.

[Examples] Next, the present invention will be described in more detail based on examples.

Example 1 Synthesis of Exemplified Compound (2) 4,5-Synthesized according to a conventional method in 20 ml of absolute ethanol.
(Ethylenedithio) -1,3-dithiol-2-thione 1.0
Add 2.0 g of potassium hydroxide and stir at 50 ° C for 2 hours. When the reaction solution is left to cool at room temperature, yellow crystals are precipitated. Decant and drain the supernatant. Add 30 ml of ethanol, decant again, and drain the supernatant.

Next, 20 ml of methanol is added to dissolve the crystals. A solution of 0.3 g of nickel chloride (hexahydrate) in 20 ml of methanol is added to this solution under nitrogen with stirring at room temperature, and the solution immediately becomes a dark red color. Stir at room temperature for 2 hours.

Then, when air is blown into it, the reaction liquid becomes dark green immediately. Stir while blowing air for 30 minutes. When 2 g of tetrabutylphosphonium chloride was added as powder to this, a precipitate was immediately formed. Stir at room temperature for 30 minutes.

The deposited precipitate is washed with rocker and methanol and air dried. Dissolve this in dichloromethane and lock. Concentrate the liquid,
Add hot methanol and allow to cool to room temperature overnight. The crystals precipitated the next day are washed with rocker and methanol and air dried. 0.7 g of black crystals are obtained.

The electronic spectrum of this complex (2) is shown in FIG.

Example 2 Synthesis of Exemplified Compound (6) 4,5-Synthesized according to a conventional method in 20 ml of absolute ethanol.
(Trimethylenedithio) -1,3-dithiol-2-thione 1,1 g and potassium hydroxide 2.0 g are added, and the mixture is stirred at 55 ° C. for 2 hours. When the reaction solution is left to cool at room temperature, yellow crystals are precipitated. Decant and drain the supernatant. Next, 20 ml of methanol is added to dissolve the crystals. To this solution, a solution of 0.3 g of nickel chloride (hexahydrate) in 20 ml of methanol is added under nitrogen with stirring at room temperature, whereupon a red and colored precipitate immediately forms. Stir at room temperature for 1 hour and then stir for 1 hour while blowing air.

When 3.0 g of tetrabutylphosphonium bromide was added to this reaction solution at room temperature, a red and colored precipitate was immediately deposited. Stir at room temperature for 30 minutes and start rocking. Wash with methanol and air dry.

The crude crystals are dissolved in dichloromethane to give a locus. The solution was concentrated, hot isopropanol was added, and the mixture was allowed to cool at room temperature overnight. The next day, the precipitated dark red crystals are localized, washed with isopropanol and air dried.

Reference Example 1. The infrared absorbing composition was prepared using the exemplified compound (2) synthesized in Example 1 to prepare an optical filter. That is, the components shown below in parts (meaning parts by weight) are mixed and stirred well, filtered, and then coated on a metal support by a casting method and peeled off after film formation. The desired optical filter was obtained. The optical density of the optical filter (60 μm thickness after drying) thus obtained is about 1,180 nm.
Atta has a filter with maximum absorption.

〔composition〕

TAC (cellulose triacetate) 170 parts TPP (triphenyl phosphite) 10 parts Methylene chloride 800 parts Methanol 160 parts Exemplified compound (2) 4 parts Reference example 2. Compound (2) synthesized in Example 1 on polypropylene powder 0.2% (by weight) and pressurizing at 190 ° C for 1 minute to make a film (200μ), and use this for xenon weather meter [Atlas Weather O. Meter (Xenon 6.
5KW, illuminance 100,000 lux)] at a panel temperature of 60 ° C. and a relative humidity of 50%, and the carbonyl index was measured according to the exposure time to examine the deterioration of propylene.
Additive-free polypropylene served as a control. The results are shown in FIG.

Here, the carbonyl index is a carbonyl group produced as polypropylene is photo-deteriorated by tracing the infrared spectrum of the sample, and the absorbance at 1,710 ^-1 cm is divided by the thickness (micron) of the sample. It is a thing.

As is clear from FIG. 3, the compound (2) had the effect of preventing the photodegradation of polypropylene.

Reference Example 3. The solubility of the compound of the present invention in an organic solvent was measured.

The test compound has the formula Where [Cat] is the Cat of Test Nos. 2 and 4 in Table 2.
The quaternary phosphonium ion shown in the column is shown.

For comparison, a test was conducted using quaternary ammonium as [Cat], and the results are shown in Test Nos. 1 and 3 in Table 2.

Acetone or methylene chloride was selected as the organic solvent.

To measure the solubility, 10 ml of solvent and 1 g of sample were placed in a 20 ml glass test tube with a fitting stopper and placed in a constant temperature bath (15
The mixture was shaken for 24 hours at (° C.), allowed to stand, then placed in a locomotive, the solvent of the filtrate was distilled off, and then the residue was weighed.

As is clear from the results in the above table, the phosphonium complex of the present invention (even test No.) has significantly higher solubility in organic solvents than the ammonium complex (odd test No.). Therefore, the composition for film formation or coating can be concentrated.

Further, the phosphonium complex of the present invention has excellent compatibility with the plastic binder used for film formation and can easily produce a uniform filter.

[Brief description of drawings]

FIG. 1 and FIG. 2 show electronic spectra in CH ₂ Cl ₂ of the compounds (2) and (6), which are the complexes of the present invention obtained in Examples 1 and 2, respectively. FIG. 3 is a graph showing changes in the carbonyl index of polypropylene measured according to Reference Example 2 using the compound (2) of the present invention obtained in Example 1. In the figure, the solid line shows the case of polypropylene to which the compound of the present invention was not added, and the dotted line shows polypropylene to which the compound (2) of the present invention was added.

Claims (1)

[Claims] 1. A general formula A quaternary phosphonium bis (cis-1,2-ethylenedithiolato) nickelate derivative represented by: (In the formula, R ^{1 to} R ⁴ represent an alkyl group or a phenyl group, which may be the same or different, and n represents 2 or 3.)