JPH0569838B2 - - Google Patents

Description

[Detailed Description of the Invention] "Industrial Application Field" The present invention has (1) near-infrared absorption, (2) light resistance and heat resistance, which has the effect of stabilizing an organic base substance against light. A novel compound (dipyridyl) (cis-1,
2-Ethylenedithiolat)nickel derivative. "Prior art" In the present invention, near-infrared rays have a wavelength of approximately 500 nm.
Refers to electromagnetic waves with a wavelength of approximately 2000 nm. In addition, the term organic basic substance or base compound includes substances that appear colored or colorless to the human eye under irradiation with sunlight, and includes not only substances that have an absorption maximum in the visible range, but also, for example,
Also included are optical brighteners or substances with an absorption maximum in the infrared. In the present invention, the organic substrate material includes an organic material having an absorption maximum from about 300 nm in the ultraviolet region to about 2000 nm in the near-infrared region. As used herein, the term pigment or dye includes organic substances that appear colored to the human eye under sunlight. Conventionally, the following techniques have been known. () Substances that absorb near-infrared rays include infrared cut filters, such as safe light filters for near-infrared sensitive photosensitive materials, infrared cut filters that are harmful to human eyes, plastic films used for controlling plant growth, and silicone films. It is used in near-infrared cut filters for semiconductor photodetectors such as diodes (hereinafter referred to as SPDs). In addition, by taking advantage of the property of absorbing near-infrared rays and exchanging it for heat, it can be used for thermal coloring by laser, thermal recording, optical disk recording layer,
It is used to accelerate the drying of ink paint.
Furthermore, utilizing near-infrared absorption, it is applied and dispersed in various photosensitive materials to form an anti-halation layer to improve image quality. Attempts have also been made to add it to ink for readable cards and ink for inkjet printers. Various compounds have been developed as near-infrared absorbers used in these applications. For example, as organic compounds not containing transition metals, Japanese Patent Publication No. 36-6763, Japanese Patent Publication No. 25347-1972
Special Publication No. 1977-25335, Special Publication No. 13326, Special Publication No. 1972, Special Publication No. 5810, Special Publication No. 1972, Special Publication No. 11249, Special Publication No. 1972, Japanese Patent Publication No. 1973
-129532, JP-A-57-45509, U.S. Patent No.
There are compounds described in US Pat. No. 2,813,802 and US Pat. No. 2,895,955. Examples of materials containing transition metals include, for example, Japanese Patent Publication No. 46-3452, Japanese Patent Application Laid-open No. 49-22748,
U.S. Patent No. 3588216, U.S. Patent No. 3663089,
U.S. Patent No. 3806462, U.S. Patent No. 3875199,
U.S. Patent No. 3979583, U.S. Patent No. 4062867,
There are compounds described in US Pat. No. 4,152,332, US Pat. No. 4,432,595, etc. () Conventionally, organic basic substances such as pigments,
It is known that dyes, polymeric substances, etc. have a tendency to discolor, change color, decompose, or deteriorate when exposed to light.Therefore, methods to reduce this fading, discoloration, or decomposition deterioration, that is, prevent photodeterioration and improve light resistance. There are many reports on how to improve this. For example, in U.S. Patent No. 3,432,300, organic compounds such as indophenols, indoanilines, azo and azomethine dyes are made to be robust to visible and ultraviolet light by mixing them with phenolic-type compounds having fused heterocyclic ring systems. It is stated that the properties are improved. In addition, in the field of silver halide photographic materials,
“The Theory” by CEKMees and TH James
of the Photographic Process” (Macmillan)
(1976), azomethine dyes or indoaniline dyes are formed by the reaction of the oxidized product of an aromatic primary amine developing agent with a color former (Kuplar). Many methods are known for improving the light stability of images made from these dyes, ie, color images. For example, U.S. Pat.
No. 2360290, No. 2418613, No. 2675314, No. 2701197, No. 2704713, No. 2728659,
Same No. 2732300, Same No. 2735765, Same No. 2710801,
Hydroquinone derivatives described in British Patent No. 2816028, British Patent No. 1363921, etc., U.S. Patent No. 3457079
Gallic acid derivatives described in No. 3069262, Japanese Patent Publication No. 43-13496, etc., US Patent No. 2735765,
p-alkoxyphenols described in US Patent No. 3698909, US Patent No. 3432300, US Patent No. 3573050
No. 3574627, No. 3764337, No. 3764337, No. 3574627, No. 3764337, No.
Derivatives such as chromans and coumarans as described in No. 3574626, No. 3698909, and No. 4015990 are known. In addition, the stability of organic base compounds against light,
A method of improvement using an azomethine quenching compound whose absorption maximum is more bathochromic than that of the base compound is described in GB 1451000. It has also been known for some time that polymeric compounds such as polyolefins deteriorate when exposed to light.To prevent this, UV absorbers such as benzophenone derivatives and hindered amines have traditionally been used. . On the other hand, methods for stabilizing dyes using metal complexes are disclosed in British Patent No. 869986, US Patent No. 4050938 and
Research Disclosure 15162 (1976), and the use of metal complexes to prevent photodegradation of polymers is described in O.Cicchetti.Adv.Polymer Sci. 7.
70 (1970); MS Allen, JFMckellar, Chem.
Soc.Rev. 4 533 (1975); DJ Carlson, DM
Wiles, J. Macromol. Sci. Rev. Macromol. Chem.
C14 65 (1976); RBWalter, JFJohnson, J.
Polymer Sci. 15 29 (1980), etc. "Problems to be Solved by the Invention" () The common drawbacks of all the near-infrared absorbers that do not contain transition metals listed in the previous section () are:
It has extremely poor heat resistance and light resistance, and is not suitable for practical use. Further, compounds containing transition metals have a disadvantage that they have poor solubility in organic solvents, making them difficult to put into practical use. For example, for the applications mentioned above, such as SPD filters, an extremely thin film with high infrared absorption efficiency is desired, but for this purpose a large amount of infrared absorber must be dispersed in the resin. However, infrared absorbers with low solubility in organic solvents could not satisfy the purpose. () Although the photodegradation inhibitors, which are organic compounds mentioned in the previous section (), are effective, they are not sufficient, and photodegradation inhibitors containing metals do not have high solubility in organic solvents, so they are not effective in preventing photodegradation. It is not possible to add enough amount to fully exert the effect. Moreover, these compounds themselves have a large coloring property, so if they are added in large amounts, they may cause organic base substances,
In particular, it has the disadvantage of adversely affecting the hue and purity of dyes and pigments. Therefore, the first object of the present invention is to provide a near-infrared absorbing substance that has extremely high heat resistance and light resistance, and also has high solubility in organic solvents and good compatibility with film-forming binders. Second, we need a near-infrared absorbing material that has a large ability to block near-infrared light per unit thickness, has high light transmittance in the visible region, and can form an optical filter that is robust against heat and light. Thirdly, to provide a substance that improves the stability of organic substrates to light; and fourthly, to provide substances that impair the hue and purity of organic substrates, especially pigments or dyes. The object of the present invention is to provide compounds that improve the light stability of these substances. The present inventor has completed the present invention as a result of various studies to achieve the above object. "Means for Solving the Problems" That is, the present invention provides a (dipyridyl)(cis-1,2-ethylenedithiolat)nickel derivative represented by the following general formula. [Formula] In the formula, R ¹ to ^{R 4} represent a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and these may be the same or different, and Two adjacent substituents among these may be combined to form a ring. Furthermore, two R ⁴ may be bonded to each other to form a ring. R ⁵ and R ⁶ are hydrogen atoms, alkyl groups, aryl groups,
It represents a cyano group, which may be the same or different, and R ⁵ and R ⁶ may be combined to form a ring. However, in the above general formula, [formula] [formula] and [formula] are excluded. Furthermore, the substituents will be explained in detail. In the compound represented by the above general formula, R ¹ ~
The alkyl group represented by R ⁴ is preferably an alkyl group having 1 to 20 carbon atoms, and examples of the alkyl group include methyl group, ethyl group, n-butyl group, n-octyl group, n-dodecyl group, n- −
Examples include octadecyl group. In this case, the alkyl group may be further substituted. The alkoxy group represented by R ¹ to ^{R 4} preferably represents an alkoxy group having 1 to 20 carbon atoms, and examples of the alkoxy group include a methoxy group,
Examples include ethoxy group, n-butoxy group, and n-hexadecyloxy group. In this case, the alkoxy group may be further substituted. The alkoxycarbonyl group represented by R ¹ to ^{R 4} is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and examples of the alkoxycarbonyl group include a methoxycarbonyl group and an n-butoxycarbonyl group. . In this case, the alkoxycarbonyl group may be further substituted. The aryloxycarbonyl group represented by R ¹ to ^{R 4} is preferably a phenoxycarbonyl group or a naphthoxycarbonyl group, and these phenyl groups or naphthyl groups may be further substituted. When R ¹ to ^{R 4} are an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and these are further substituted, the substituents include, for example, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), Alkyl group having 1 to 20 carbon atoms (e.g. methyl group, ethyl group, n-butyl group, n-octyl group, etc.), 1 to 20 carbon atoms
alkoxy groups (eg, methoxy group, ethoxy group, n-butoxy group, etc.). Further, in the case of an alkyl group, an alkoxy group, or an alkoxycarbonyl group, it may be further substituted with a hydroxyl group. Two adjacent substituents among R ¹ to ^{R 4} may be combined to form a ring, and this ring is preferably a 5-membered ring or a 6-membered ring, and may be a fused ring. Further, two R ⁴ may be bonded to each other to form a ring, and this ring is preferably a 6-membered ring. The alkyl group represented by R ⁵ and R ⁶ is preferably
Represents an alkyl group having 1 to 20 carbon atoms, such as methyl group, ethyl group, n
-butyl group, n-hexyl group, n-octyl group,
Examples include n-dodecyl group and n-hexadecyl group. In this case, the alkyl group may be further substituted, for example, an alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, n-butyl group,
C1-C20 alkoxy groups (e.g. methoxy, ethoxy, n-octyl, etc.)
butoxy group, etc.). The aryl group represented by R ⁵ and R ⁶ is preferably a phenyl group, and in this case, the phenyl group is
It may be further substituted, for example, a halogen atom (chlorine atom, bromine atom, etc.) having 1 to 20 carbon atoms.
Alkyl groups (e.g. methyl, ethyl,
n-butyl group, n-octyl group, n-decyl group), alkoxy groups having 1 to 20 carbon atoms (e.g. methoxy group, ethoxy group, n-butoxy group,
n-dodecyloxy group, etc.). R ⁵ and R ⁶ may be combined with each other to form a ring, but in this case, it is preferably a 5-membered ring or a 6-membered ring, and the constituent elements of the ring are elements other than carbon (for example, oxygen atoms, nitrogen atoms, sulfur atoms, etc.). Further, these rings may be substituted with a halogen atom, an alkyl group, an alkoxy group, or an aryloxy group, or may be fused with another ring. All of the complexes excluded from the scope of the claims have low solubility in organic solvents and have little practical value. The (dipyridyl)(cis-1,2-ethylenedithiolat)nickel derivative represented by the above general formula can generally be produced as follows. A cis-1,2-ethylenedithiol derivative or an alkali metal salt thereof is dissolved in anhydrous methanol. To this solution (which may be prepared from a precursor) is added the (dipyridyl)(dihalo)nickel() derivative complex as a powder or methanol solution, stirred, and the formed precipitate is filtered. This precipitate is extracted with an organic solvent such as dichloromethane, concentrated and slowly added with methanol to obtain crystals of the desired complex. Preferred examples of the compounds represented by the above general formula are as follows.
Of course, the present invention is not limited to these exemplified compounds. [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] ] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] [Table] Some of these compounds Absorption maximum (λmax) and molar extinction coefficient (εmax, l・mol ^-1・
The cm ^-1 units and melting points (decomposition points) are as shown in Table 1 below. [Table] [Table] [Table] [Table] "Effects of the Invention" The (dipyridyl)(cis-1,2-ethylenedithiolat)nickel derivative of the present invention has high solubility in organic solvents and is a film-forming binder. It has excellent properties such as excellent compatibility with other substances, high near-infrared light blocking ability, and high light transmittance in the visible region. Furthermore, these complexes have an excellent effect of preventing deterioration of organic base materials, especially dyes, pigments, and polymeric substances due to light, and since they themselves are less colored, they do not adversely affect the hue and purity of the organic base materials. Additionally, this compound has excellent heat resistance and light resistance.
In addition, since there are many positions for introducing substituents, the maximum absorption wavelength can be easily selected by combining them. Furthermore, these complexes have excellent practical advantages in that they are easy to synthesize and can be produced at low cost. Therefore, the complex of the present invention can be used as a near-infrared cut filter that utilizes light absorption as a near-infrared absorber;
In addition to ink, it can be used for a variety of purposes, including heat-sensitive coloring by laser using light->heat exchange, heat-sensitive recording, use in optical disk recording layers, and use as a photodegradation inhibitor for organic base materials. "Example" Next, the present invention will be explained in more detail based on an example. Various (dipyridyl)(dihalo)nickel derivatives which are the starting materials used in the present invention are described in J.Inorg.Nucl.
It was prepared according to the method described in Chem. 29 1047 (1967). Therefore, the respective preparation methods will be omitted in the following examples. Example 1 Synthesis of compound (2) 4,5-dimethyl-1,3-dithiol-2-
Disperse 0.002 mol of ion in 20 ml of absolute methanol.
Add 0.004 mol of sodium methoxide (a methanol solution may be used) and stir at room temperature for 2 hours. Add 0.002 mol of dipyridyldichloronickel to this solution, and stir for an additional hour at room temperature. The deposited precipitate is filtered, washed with methanol, and air-dried. Dissolve this in 200ml of dichloromethane,
Filter. Concentrate the filtrate, add isopropanol and leave for 1 hour. The precipitated crystals are filtered, washed with isopropanol, and air-dried. Yield 0.3g. Example 2 Synthesis of compound (30) 4,5-di-p-methoxyphenyl-1,3-
Disperse 0.002 mol of dithiol-2-one in 20 ml of anhydrous methanol, and add sodium methoxide to this.
Add 0.004 mol (methanol solution may be used),
Stir at room temperature for 5 hours. Add 0.002 mol of dipyridyldichloronickel to this solution, and stir for an additional hour at room temperature. Locate the precipitate that has separated out,
Wash with methanol and air dry. Dissolve this in 200 ml of dichloromethane and filter. Concentrate the filtrate and
Add methanol and leave at 5°C overnight. The precipitated crystals are filtered, washed with methanol, and air-dried. yield
0.6g Example 3 Synthesis of compound (65) 4,5-dimethyl-1,3-dithiol-2-
Disperse 0.002 mol of ion in 20 ml of absolute methanol.
Add 0.004 mol of sodium methoxide (a methanol solution may be used) and stir at room temperature for 2 hours. Add 0.02 mol of (1,10-phenanthroline)dichloronickel to this solution, and stir further at room temperature for 1 hour. The deposited precipitate is filtered, washed with methanol, and air-dried. Dissolve this in 200 ml of dichloromethane and filter. Concentrate the filtrate, add methanol, and leave overnight.
The precipitated crystals are filtered, washed with methanol, and air-dried. Yield 0.3g. Example 4 Synthesis of compound (86) 4,5-di-p-methoxyphenyl-1,3-
0.002 mol of dithiol-2-one is dispersed in 20 ml of anhydrous methanol, 0.004 mol of sodium methoxide (a methanol solution may also be used) is added thereto, and the mixture is stirred at room temperature for 5 hours. 0.002 mol of (4,7-diphenyl-1,10-phenanthroline)dichloronickel was added to this solution, and the mixture was further stirred at room temperature for 1 hour. Locate the deposited precipitate, wash with methanol, and air dry. Dissolve this in 200 ml of dichloromethane and filter. Concentrate the filtrate and
Add methanol and leave overnight. The precipitated crystals are filtered, washed with methanol, and air-dried. Yield: 0.2g Example 5 An infrared absorbing composition was prepared using the exemplary compound (86) synthesized in Example 4, and an optical filter was created. That is, after mixing each component with the composition shown in parts (meaning parts by weight) below and stirring well,
After filtration, it was coated onto a metal support by a casting method, and after film formation, it was peeled off to obtain the desired optical filter. The optical density of the optical filter thus obtained (thickness 60 microns after drying) is approximately 970 nm.
It was a filter with maximum absorption at . When optical filters were similarly prepared using other compounds shown in Table 1, optical filters having absorption in the near-infrared region were obtained. [Composition] TAC (cellulose triacetate) 170 parts TPP (triphenyl phosphate) 10 parts Methylene chloride 800 parts Methanol 160 parts Exemplary compound (86) 4 parts Example 6 The compound synthesized in Example 1 (2 parts) was added to polypropylene powder. ) was added 0.2% (by weight) and pressurized at 190℃ for 1 minute to make a film (200μ), which was then attached to a xenon weather meter [Atlas Weather
Using an O-meter (xenon 6.5KW, illuminance 100,000 lux)], the panel was exposed to light at a temperature of 60℃ and relative humidity of 50%, and the carbonyl index was measured according to the exposure time to investigate the deterioration of propylene. .
Additive-free polypropylene was used as a control. The results are shown in FIG. Here, the carbonyl index is calculated by tracking the carbonyl groups generated as polypropylene photodegrades using the infrared spectrum of the sample, and dividing the absorbance at 1710 ^-1 cm by the thickness (microns) of the sample. It is something. As is clear from FIG. 3, compound (2) was effective in preventing photodeterioration of polypropylene.

[Brief explanation of the drawing]

Figures 1 and 2 show compounds (2) and (86), which are complexes of the present invention obtained in Examples 1 and 4.
The electron spectra in CH ₂ Cl ₂ are shown respectively.
FIG. 3 is a graph showing changes in the carbonyl index of polypropylene measured in Example 6 using Compound (2), which is the complex of the present invention obtained in Example 1. In the figure, the solid line indicates polypropylene to which the compound of the present invention has not been added, and the dotted line indicates polypropylene to which the compound (2) of the present invention has been added.

Claims (1)

[Scope of Claims] 1. A (dipyridyl)(cis-1,2-ethylenedithiolat)nickel derivative represented by the following general formula. [Formula] In the formula, R ¹ to ^{R 4} represent a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and these may be the same or different, and Two adjacent substituents among these may be combined to form a ring. Furthermore, two R ^4s may be bonded to each other to form a ring. R ⁵ and R ⁶ are hydrogen atoms, alkyl groups, aryl groups,
It represents a cyano group, which may be the same or different, and R ⁵ and R ⁶ may be combined to form a ring. However, in the above general formula, [formula] [formula] and [formula] are excluded.