JPS63126889A - (dipyridyl) (cis-1,2-ethyleneditholato)nickel derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1>-R<4> are H, alkyl, alkoxy, phenyl, alkoxycarbonyl or aryloxycarbonyl or two adjacent groups thereof many link to form a ring; R<5> and R<6> are H, alkyl, aryl or cyano or R<5> and R<6> may link to form a ring) except compounds expressed by formulas II-IV. EXAMPLE:A compound expressed by formula V. USE:A near infrared ray absorber and preventive agent for photodeterioration of organic substrate substances, having excellent heat, light resistance, a solubility in organic solvents as well as compatibility with film-forming binders and capable of being readily synthesized and producible at a low cost. PREPARATION:cis-1,2-Ethylenedithiol derivatives, etc., are dissolved in absolute methanol and a (dipyridyl)(dihalo)nickel(II) derivative complex is added to the resultant solution and stirred to filter the formed precipitates. The obtained precipitates are then extracted with dichloromethane, etc., and concentrated. Methanol is added thereto to afford the aimed complex crystals.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention has l) near-infrared absorbing properties, and -) an effect of stabilizing an organic substrate substance against -yt and vc.

The present invention relates to a novel compound (dipyridyl) (cis-1°-1 ethylene dithiolate) nickel enzyme conductor that has excellent light resistance, heat resistance, and solubility in organic solvents.

"Prior Art" In the present invention, near-infrared rays refer to electromagnetic waves having a wavelength of about 200 nm to about -00 nm.

In addition, the term organic base substance 'X or base compound is 1
Contains substances that appear colored or colorless to the human eye under sunlight, and have significant absorption in the visible range.
It includes not only negative substances but also, for example, optical brighteners or substances having an absorption maximum in the infrared region.

In the present invention, M@substrate negative, ultraviolet O approximately JO
Onm includes organic substances that have an absorption maximum in the near-infrared region of about 2,000 nm.

In this specification, ## for 1 pigment or dye is:
Contains organic substances* that appear M-colored to the human eye under 8 degrees of irradiation.

Conventionally, the following techniques have been known.

(1) Near-infrared-absorbing substances can be used as infrared-cut filters, such as safelight filters for near-infrared @ photosensitive materials, infrared edge cut filters that are harmful to human eyes, and plant growth control. It is used in plastic films and near-infrared cut filters for semi-dedicated receiving elements such as silicon photodiodes (hereinafter referred to as SPDs). In addition, it has the ability to absorb near-infrared rays and exchange them into heat.
Taking advantage of this, it has been used for g-thermal coloring with lasers, thermosensitive recording, original disk recording, and for ink studies. It is also being dispersed in various ultraviolet materials to form an antihalation layer to improve mfii, and it is also being added to ink for cards that can be read by laser sources, and by inkjet printers. Attempts have also been made to add it to commercial inks.

Near-infrared light absorbers used in these applications include:

Compounds for each building are being developed.

For example, as an organic compound that does not contain transition gold syh,
Special public Sho J6-674J, registered Sho uO-JjJμ7,
#! f Kosho 4cJ-ko JJJj issue, special public Shosan! -/JJ
No. 26, Special Public Shosan 4-J'' No. 110, Special Public Shoda 4-//
Kosan No. 2, JP-A No. 10-722332, JP-A No. 7-72-
μ! ! OP No., US 1% Permit No. 211310-, US 13!
There are compounds described in Patent No. λjrjr sr.

In addition, examples of materials containing transition metals include, for example, Tokko Shogei 4-JAS No. 2, Tokko Shogei No. 2-27 Kou 1,
U.S. Patent No. JJtt216, U.S. Patent No. J44JO
No. r, U.S. Patent No. JI06 No. 6-, U.S. Patent No. JI
7j/? ? No. 327-513, US t3!
% permission No. 4 cot number 147, American chiken san/! 2JJ Co., U.S. Patent No. 3-! ? There are some compounds that are known as No.J.

(■) Conventionally, organic substrate substances, such as pigments.

It is known that dyes, polymeric substances, etc. have a tendency to discolor, discolor, decompose, or deteriorate due to light VC, and 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 it.

For example, in US Patent 9pIJ, ≠ 32,300,
It has been described that organic compounds such as indophenol, indoaniline, azo and azomethine dyes are improved in their fastness to visible light and ultraviolet sources by mixing them with phenolic type compounds having fused heterocyclic ring systems. has been done.

In addition, in the field of silver halide photosensitive materials, C, E,
, Mees ↓ and T , H , James arrival @The
Theory of the Photographer
aphicProcess” (Macmilfan Company 1
As described in Chapter 17 of 276, azomethine dyes or Indian azomethine dyes are formed by the reaction of an aromatic primary amine imaging agent with a color former (coupler). However, a number of methods are known for improving the light stability of images, ie, color images, made from these dyes. For example, U.S. Pat.
, No. 413, No. 2゜47! , J/Hiro issue, same number -, 70
/ , /ri No. 7.

Same%J, 70μ, 7/J No. 2, 7211, 4
No. J, No. 732.300, No. λ, 7J! T
, 71, No. 1, 18λ, yio, roi, No. 1,
tits, Oco No. 1, British Patent No. 1. J4J.

Hydroquinone conductor described in Octopus No. 7, etc., US 13
A special FfmJ, uj7.079, wIJ, 06ri,
Gallic acid derivatives described in No. 26-, Tokuko Sho μJ-/J, Kou No. 26, etc., U.S. Patent No. 2.73j, 761
p-alkoxyphenols described in No. 3, No. 3, No. 6, No. 1, No. J, UJ, JQO,
Tie rate 3. ! 7J, No. 010, same'fPI3. j74A
, 4λ7, 3.76.

No. 337, No. 3, 57μ, No. 626, No. J of the same.

Ferment derivatives such as chromans and coumarans as described in No. 491.90P, wIg, 0/j, and 9YO VC are known.

British Patent No. 1 discloses a method for improving the stability of lr aircraft compounds against light using an azomethine quenching compound whose absorption maximum is also bathochromic. ≠ji,oo.

listed in the number.

In addition, polymer compounds such as polyolefins,
It was previously known that Eri deteriorates due to light, but
To prevent this, UV absorbers such as benzophenone fat conductors and hindered amines have traditionally been used.

10,000, a method for stabilizing dyes with metal complexes is disclosed in British Patent No. 16, Rit6, U.S. Patent No. μ.Qjo, pJt and Research Disclosure.
a (i-76), and the use of metal complexes to prevent photodeterioration of polymers is described in 0. C1cche
tti, Adv, Polymer Sci.

ヱ70(/970)　;M,S　,A11en.

J,F,McKellar,Chem,Soc,Re
v, <c s Js (/97z); D, J, C
arlson, D.M.

Wiles+J, Macromol, Sci, Rev.

Macromol, Chem, C/44 4 j (tri 76); R, B, Walter + J, F, John
son, J, Polymer Sci, /j 29 (/
9103, etc.

"Problems to be Solved by the Invention" (1) All of the near-infrared absorbers that do not contain transition metals mentioned in the previous section (1) have a common drawback that they have poor heat resistance and light resistance. , it is not practical.

Furthermore, compounds containing transition metals have the disadvantage of poor solubility in organic bath agents, making them difficult to put into practical use. for example,
For the above-mentioned applications, such as SPD layer filters, an extremely thin film with good infrared absorption efficiency is desired.

For this purpose, a large amount of infrared absorber must be dispersed in the resin, and infrared absorber C, which has a low f8 solubility with respect to organic solvents, cannot satisfy the purpose.

(n) Photodegradation inhibitors, which are organic compounds mentioned in the previous section (■), are effective, but are not sufficient, and photodegradation inhibitors containing metals do not have high solubility in organic solvents, so they are not photodegradable. It is not possible to add enough amount to have a sufficient preventive effect. Moreover, since these compounds themselves have a large coloration, when a large amount of 1ivC is added, the presence of the substrate substance increases by %.
However, it has the drawback that the hue of the dye or pigment and the quality of the dye may cause negative shadows.

Therefore, the object of the present invention is, first of all, to have extremely high heat resistance and light resistance, *high compatibility with organic #4 media (and near-infrared absorbing properties with good compatibility with film-forming binders, etc.). Second, it is possible to form an optical filter that has a large near-infrared light blocking ability per unit thickness, has high visible light transmittance, and is robust against heat and radiation. The object of the present invention is to provide a near-infrared absorbing substance, and thirdly, to provide a substance that improves stability against organic substrates.

Fourth, it is an object to provide compounds that improve the light stability of organic substrate materials, especially pigments or dyes, without deteriorating their hue and purity.

The present inventor has conducted various studies to achieve the above object, and as a result has completed the present invention. (dipyridyl)(cis-1,-1ethylenedithiolat)nickel a
! It provides four bodies.

In the formula, R1 to R4 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 may be Two matching substituents may be combined to form a ring.Also, two R'fl
They may be bonded to each other to form a ring.

R%R represents a hydrogen atom, an alkyl group, an aryl group, or a cyano group, and these may be the same or different. R and R may be combined to form a ring.

However, in the above general formula Furthermore, the substituents will be explained in detail.

In the compound represented by the above general formula, the alkyl group represented by R1-R4 preferably has a carbon number of 1 to λO
This alkyl group includes, for example, methyl group, ethyl group, n-butyl group, n-octyl group,
Examples include n-dodecyl group and n-octadecyl group.

In this case, the alkyl group may be substituted with *vcfi1.

The alkoxy group represented by R1 to R preferably represents an alkoxy group having 7 to -20 carbon atoms, and examples of the alkoxy group include methoxy group, ethoxy 4 n
-7'toxy group, n-hekypdecyloxy7 group, etc. can be mentioned.

In this case, the alkoxy group has the history K[j! may have been done.

The alkoxycarbonyl group represented by R1 to R is preferably an alkoxycarbonyl group having 1 to 1 carbon atoms, and examples of the alkoxycarbonyl group include methoxycarbonyl group and n-butoxycarbonyl group.

In this case, the alkoxycarbonyl group may be substituted.

The aryloxycarbonyl group represented by RR preferably represents a phenoxycarminyl group or a t-phthoxycarbonyl group, and these phenyl or naphthyl groups may be further substituted.

fIII when R1 to R are an alkyl group, an alkoxy group, an al; I! Examples of the group include a halogen atom (e.g., chlorine atom, bromine atom, etc.), an alkyl group having 1 to 7 carbon atoms (e.g., methyl group, ethyl-ihbn-butyl group, n-octyl group, etc.), Examples include alkoxy groups (eg, methoxy group, ethoxy group, n-butoxy group, etc.).

In addition, in the case of an alkyl group, alkoxy fi and alkoxy 7 carbonyl group, water t1! It may be substituted with a group.

Two adjacent #s among R1-R4! 14 groups may be combined to form a ring (this ring is preferably a square, !-membered ring or 6-membered ring, and may be a fused ring. Also, two R4 groups may be combined with each other to form a ring). and this ring is preferably 6j[.

The alkyl group represented by R' and R is preferably an alkyl group having 7 to -20 carbon atoms, and examples of the alkyl group include methyl group, ethyl As, n-butyl group, n-hexyl group, n-octyl group, etc. % n-dodecyl group, n-hekypdecyl group, etc.

In this case, the alkyl group may be further substituted with
For example, an alkyl group having 1 to 1 carbon atoms (for example,
methyl group, ethyl group, n-butyl group, n-octyl group, etc.), or an alkoxy group having 7 to 1 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, etc.).

The aryl group represented by R%R is preferably a phenyl group, and in this case, the phenyl group may be further substituted, for example, a halogen atom (chlorine atom, bromine atom, etc.) having a carbon number of 1 to λO. Alkyl group (t#i,
Methyl group, ethyl group, n-butyl group (% n-octyl group, n-defluoride, etc.), R8 alkoxy group (e.g., methoxy group, ethoxy group, n-butoxy group, n-dodecyloxy group) It does not work even if it has been changed to fit such as "base etc."

R5 and R may be combined with each other to form a ring,
In this case, preferably j! A ring or a 6-membered ring is preferable, and the constituent elements of the ring are elemental FA other than carbon (e.g., oxygen atom,
Nitrogen atoms, sulfur atoms, etc.] may also be used. Also, these lumps are halogen atoms.

It may be substituted with an alkyl group, an alkoxy group, or an aryloxy group, or it 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, co-ethylenedithiolat) nickel enzyme conductor represented by the above general formula can generally be produced as follows.

Cis-7,λ-ethylenedithiol # in anhydrous methanol
Bathing with S4 form or its alkali metal salt.

(sometimes prepared from precursors) to this solution.

Add the (dipyridyl)(dihalo)nickel (■) spinner complex as a powder or methanol solution, stir, and filter the formed precipitate. This precipitate was extracted with an organic solvent such as dichloromethane, and then extracted with Sa.

Add methanol slowly to obtain crystals of the desired complex.

Preferred examples of the compounds represented by the above general formula are as follows, but it goes without saying that the present invention is not limited to these exemplified compounds.

(3s(38) ←l) (8s) The absorption maximum (λmaX) and extinction coefficient (gmaX I l-mol-' ・cm of some of these compounds)
-1 unit and melting point (decomposition point) are as shown in Table 1 below.

"Effects of the Invention" The (dipyridyl)(cous7.coethylenediteorato)nickel derivative of the present invention has high solubility in organic solvents (,
It has excellent compatibility with film-forming binders, etc., and has excellent 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 are less colored by themselves, they do not adversely affect the hue and purity of the organic base materials.

This compound also has 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 the advantage 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 absorber for near-infrared cut filters and inks that utilize light absorption, as well as for thermal coloring by laser using light → heat exchange, thermal recording, and optical disk recording layers. In addition, it can be used for various purposes such as use as a photodegradation inhibitor for organic substrate substances.

[Kyosei - Moon Next, the present invention will be explained in more detail based on examples.

Various starting materials used in this invention 94 (, Giviridi K)
(Dihalo) Nickel M4 body t! J, I no r
g.

Nucl, Chem, J? 10447 (/ri67)
vI4 was produced according to the method described in . Therefore, in the following examples, the respective preparation methods are omitted.

Example 1. Synthesis of compound (2), J-dimethyl-/, J-dithiol-1-one 0.
00 λ moles are dispersed in 20 ml of absolute methanol. Add 0.00 mol of sodium methoxide (methanol bath solution) to this solution and let it stand at room temperature for 2 hours. Add 0.002 mol of dipyridyldichloronickel to this solution and let it sit at room temperature for 1 hour. Filter the precipitate, wash with methanol, and air dry. Dissolve this in dichloromethane and filter. Concentrate the filtrate.
Add isopropanol and leave for 1 hour. The precipitated crystals are filtered, washed with isopropanol, and air-dried. Yield 0. J9゜Example 1 Synthesis of compound (30) 0.00 λ mol of j-di-p-methoxyphenyl-7,3-dithiol-coon was added to 20 WL of anhydrous methanol.
tVc is dispersed, and sodium methoxide o, oo is added to this.
Add a mol (methanol bath solution may also be used) and incubate at room temperature for 3
Add 0.00 mole of dipyridyl dichloronickel to this solution and stir for 1 hour at room temperature. Locate the precipitate, wash with methanol, and air dry.
Filter down.

Concentrate the filtrate, add methanol, and leave at 0C overnight. The precipitated crystals are filtered, washed with methanol, and air-dried.

Yield o, tg Example 3. Synthesis of compound (65), j-dimethyl-1,3-diteol-one 0.
00λ moles are dispersed in anhydrous methanol 2Q1. Add 0.00 φ mol of sodium methoxide (a methanol solution may be used) and stir at room temperature for 2 hours.

Add (/, 10-phenanthroline)/Roronickel 01QQ2mo) to this Q bath solution, and further stir for 1 hour at room temperature. Filter the deposited precipitate, wash with methanol,
Air dry. This was filtered using 200 ml of dichloromethane/IC/g. Concentrate the filtrate, add methanol,
- Set up at night. The precipitated crystals are filtered, washed with methanol, and air-dried. Yield o, sg0 Example 4. Compound (8
Synthesis of 6), 0.00 λ mol of j-di-p-methoxyphenyl-1,3-dithiol-2-one was added to anhydrous methanol 2 (NL
Dispersed in I, sodium methoxide o, oou
mol (a methanol solution may also be used) and incubate at room temperature for 3 hours.
, 10-phenanthroline) dichloronickel 0.0
Add 0-mol.

Stir for an additional hour at room temperature. Precipitate! Wash with methanol and air dry. Dissolve this in diku aa methane 00dyC and filter. Concentrate the filtrate, add methanol, and incubate overnight. The precipitated crystals are filtered, washed with methanol, and air-dried.

Yield O0λI0 Example 5 An infrared absorbing composition was prepared using the exemplary compound (86) synthesized in Example 4, and an optical filter was created. After mixing each component with the composition indicated by λ, which means parts by weight, stirring thoroughly, passing through a filtration, and coating it on a metal support by a casting method to form a film. It was peeled off to obtain the desired optical filter.

The optical density of the optical filter thus obtained (thickness after drying: AOi cm) is approximately 70 nm, with maximum absorption at 70 nm!
It was a filter that had.

When optical filters were similarly prepared using other compounds shown in Table 7, optical filters having absorption in the near-infrared region were obtained.

[Composition] TAC (cellulose triacetate) / 70 parts TPP
() Riphenyl phosphate) 10 parts methylene chloride too parts methanol
ibo part exemplified compound (86)
Main part Example 6 The compound (2) synthesized in Example 1 was added to polypropylene powder.
) 917, add 1 marrow (1 marrow), pressurize for 1 minute, make a film (coop), and add this to a xenon weather meter [Atlas Weather 0 Meter (
Xenon 4. Additive-free polypropylene was exposed to light at a panel temperature of 40'C and a relative humidity of 10% using a 10000000000000000000000 sKW, illuminance 10,000 lux), and the deterioration of propylene was investigated by adding 1 orchid to the carbonyl index according to the exposure time. This was used as a control object. The results are shown in FIG.

Here, the carbonyl index is boli at? Carbonyl produced as len photodegrades fig
, traced in the infrared spectrum of the sample, its i, yio
It is the absorbance at Cm divided by the depth of the sample (ξ chron).

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 C12cg of compounds (2) and (86), which are the complexes of the present invention obtained in Examples 1 and 4.
The electron spectra in z are shown respectively. FIG. 3 is a graph showing the change in the carbonyl index of polypropylene measured using Compound (2), which is the complex of the present invention obtained in Example 1, using an IC. In the figure, 1 point f! indicates the case of polypropylene to which the compound of the present invention is not added. indicates polypropylene added with the compound (2) of the present invention. Patent applicant: Fuji Photo Film Co., Ltd. 1st figure [1 (nm) 2nd figure plate length (nm)

Claims (1)

[Claims] (Dipyridyl) (cis-1,2) represented by the following general formula
- ethylene dithiolat) nickel derivative. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 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 they may be the same or They may be different, and two adjacent substituents among these may be combined to form a ring. Also, 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 formulas, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ are excluded.