JPS6126686A - Infrared-absorbing composition - Google Patents

Abstract

PURPOSE:To provide an infrared-absorbing composition containing a specific complex compound, and useful as an optical filter absorbing far infrared rays and near infrared rays with little loss of the transmission of visible light. CONSTITUTION:The objective composition contains the compound of formula I and/or formula II ([Cat1] and [Cat2] are cation necessary for neutralizing the complex; M1 and M2 are Ni, Cu, Co, Pd or Pt). Preferable examples of [Cat1] and [Cat2] are ions of formula III-VI [R<1>-R<11> are 1-20C (substituted) alkyl or 6-14C (substituted) aryl; Z<1> and Z<2> are non-metallic atom group capable of forming 5-6-membered ring with N or P).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an infrared absorbing composition. More specifically, it can be
The present invention relates to an infrared absorbing composition useful as an optical filter that absorbs far-red light to near-infrared light of 1 nm or less.

(Prior Art) A composition that selectively absorbs far-red light or near-infrared light with a wavelength of 900 nm has various possible uses and has been strongly desired, but until now there has been no suitable material. I couldn't get it. The main uses of conventional infrared absorbing compositions will be described below with reference to five examples.

■ Safelight filter for infrared-sensitive photosensitive materials In recent years, silver halide photosensitive materials (hereinafter referred to as ``sensitized materials'') are sensitive to far-red light or near-infrared light with a wavelength of 77-00 nm or more. Many things have been developed. °Black and white or crab for this! Not only the normal type but also Instagram 1. .

Silver halide photosensitive materials, including those of the print-type or heat-developable type, are equipped with infrared sensitivity to create pseudo-color photographs for use in resource surveys, etc., or they can be exposed using diodes that emit light in the infrared region. There is something that makes it wet.

A panchromatic safelight filter has conventionally been used for such infrared-sensitive materials.

■ Control of plant growth It has been known for a long time that the so-called morphogenesis related to plant growth and differentiation, such as seed germination, stem elongation, leaf expansion, flower bud and tuber formation, is influenced by light. It is being studied as a photomorphogenetic effect.

If a plastic film that selectively absorbs light with a wavelength of 700 nm or more can be obtained, for example, crops can be covered with a near-infrared absorbing film at a specific time to absorb light with a wavelength of 700 nm or more.
- By blocking the light, the heading period can be delayed,
It is expected to control and control growth (see Katsumi Inada, "Chemical Regulation of Plants", Vol. 6, No. 1 (1971)).

■ Blocking of heat rays Of the sun's radiant energy, light in the near-infrared and infrared regions with wavelengths of 800 nm and above is absorbed by objects and converted into thermal energy. Moreover, most of the energy distribution is concentrated in the near-infrared wavelength range of 800 to 2000 nm. Therefore, a film that selectively absorbs near-infrared rays is extremely effective in blocking solar heat, and can suppress the -L rise in indoor temperature while allowing in sufficient visible light. This can be applied not only to horticultural greenhouses but also to windows of houses, offices, stores, automobiles, airplanes, etc.

Conventionally, thermal gauze has been made of a plastic film with a very thin metal layer deposited on its surface, or a glass with an inorganic compound such as FeO dispersed therein.

■ Infrared rays that are harmful to human eye tissue Infrared rays contained in sunlight and infrared rays emitted during welding have a harmful effect on human eye tissue. .

One of the main uses of infrared cut filters is as eyeglasses that protect human eyes from such harmful infrared rays. For example, sunglasses, safety glasses for welders, etc.

■Infrared cut filter for semiconductor photodetector At present, silicon photodiodes (hereinafter referred to as
SPD) is used. FIG. 2 shows a graph of the relative luminous efficiency curve and the relative output value (spectral sensitivity) for each wavelength of the SPD.

In order to use the SPD as a light meter, it is necessary to cut out light in the infrared region, which is invisible to the human eye, and to use the SPD shown in Figure 2.
It is necessary to make the spectral sensitivity curve of the PD similar to the specific luminous efficiency curve. In particular, the output of the SPD is large for light in the wavelength range of 700 to 1100 nm, and the light in this region is not perceptible to the human eye, which causes malfunction of the exposure meter.

Therefore, there is less absorption in the visible region, 700~1l10
It is clear that if an infrared absorbing plastic film that absorbs 0n infrared light over the entire range can be used, the light transmittance in the visible region will be large, the output of the SPD will be thicker, and the performance of the light meter can therefore be significantly improved. be.

Conventionally, this type of photodetection device has been put into practical use by attaching a glass infrared cut filter using an inorganic infrared absorbing agent to the front of the SPD.

(Problems to be Solved by the Invention) However, conventional general organic dye-based infrared absorbers have poor light resistance and heat resistance, and have hardly been practically satisfactory.

In addition, the filter materials used for each of the above applications are as follows.
It had the following drawbacks.

First of all, the conventional safelight filter for panchromatic use described in Application ① not only partially transmits green light, which has high visibility, but also causes optical fog because it transmits a large amount of infrared light. The purpose of use as a safelight for photosensitive materials could not be fully achieved.

In addition, the plastic film with a vapor-deposited metal layer or the glass with dispersed FeO used in the above application (2) strongly absorbs not only infrared light but also light in the visible region, resulting in a decrease in internal illuminance, especially for agricultural use. was unsuitable because it would lead to an absolute shortage of sunlight.

Furthermore, the glass infrared cut filter that uses an inorganic infrared absorber used in the above application (2) is relatively robust against heat and light, but has low light transmittance in the visible region, and as a result, SPD The sensitivity of the body was addressed by ``gero''.

Increasing the sensitivity of the SPD leads to an increase in leakage current, which causes malfunction of the photodetector and poses a major problem in terms of reliability. Furthermore, the fact that the infrared cut filter is a special product means that it lacks flexibility from the viewpoint of manufacturing the photodetector, and it is difficult to improve the manufacturing process. On the other hand, inorganic infrared cut filters have the drawback of being expensive to manufacture and significantly increasing the cost of the photodetector.

In this way, in conventional photodetecting devices using inorganic cut filters, although their spectral sensitivities are close to the specific luminous efficiency curve, the operating performance as a photodetecting device decreases, the manufacturing cost increases, and from the viewpoint of improving the manufacturing process, It had significant drawbacks.

Furthermore, near-infrared absorbing plastic films that use complexes as infrared absorbers lack the solubility of the infrared absorbers in organic solvents, which has been a major drawback when producing thin plastic films.

In other words, for the above-mentioned applications, such as SPD filters, an extremely thin film with high infrared absorption efficiency is desired, but in order to do so, a large amount of infrared absorbing agent must be dispersed in the resin. First, infrared absorbing agents with low solubility in organic solvents could not satisfy the purpose.
.

Furthermore, ・Near-infrared absorbing plastic films using conventional metal complexes as infrared absorbers have a short maximum absorption wavelength.1. In particular, it was unsuitable for applications such as light-receiving elements of semiconductor lasers, whose applications have been expanding in recent years.

Therefore, the first object of the present invention is to provide an infrared absorbent having an absorption maximum on the long wavelength side, particularly at a wavelength of 900 nm or more. The second object is to provide a near-infrared absorber that has high solubility in organic solvents and good compatibility with film-forming binders.

The inventors of the present invention have completed the present invention as a result of various studies to achieve the objective stated in -1=.
1,゛,' (Means for solving the problem) The above-mentioned various points are expressed by the following general formula [English] or [,,11]
The problem was solved by an infrared absorbing composition characterized by containing at least one kind selected from the complexes represented by the following.

(In the formula, [Cat ] and [Cat 2 ] represent cations necessary to make the complex neutral, and M
and M2 is nickel, copper, cobalt, para! Denotes dium or platinum. ) The present invention will be explained in further detail.

In the compounds represented by the general formulas [I] and [11], among the cations represented by [Cat] or [Cat2], the inorganic cations include alkali metals (for example, Li, Na, Ni, etc.) , alkaline earth metals (Mg, Ca, Ba, etc.) or NH4+e.

Examples of the organic cation include quaternary ammonium ions and quaternary phosphonium ions.

Cation [cat] and [Cat 2
], preferred are the following general formulas (m-a) and (m-
b), (m-c) or (m-d).

(In the formula, ul, R2, R3, R4, R5, R8, n?
,R8,u! 3, Rlo and R11 are each a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted 7 having 6 to 14 carbon atoms;
It represents a lyl group, and Zl and Z2 represent a group of nonmetallic atoms that combine with the nitrogen or phosphorus atom in each formula to form a 5- or 6-membered ring.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-butyl group, 1so-amyl group, n-dodecyl group, and n-octadecyl group. Carbon number 6 to 14
Examples of the aryl group include phenyl group, tolyl group, and α-naphthyl group.

These alkyl groups or aryl groups include cyano groups, 'hydroxyl groups, and alkyl groups having 1 to 20 carbon atoms (for example, methyl groups, ethyl groups, n-butyl groups, n-octyl groups, etc.).
, a 7-aryl group having 6 to 14 carbon atoms (e.g., phenyl group, tolyl group, α-naphthyl group, etc.), an acyloxy group having 2 to 20 carbon atoms (e.g., acetoxy group, benzoyloxy group, p-methoxybenzoyloxy group, etc.) ) C1-C6 alkoxy group (e.g. methoxy group, ethoxy group, propoxy group, butoxy group, etc.)
, aryloxy group (e.g., phenoxy group, triloxy group, etc.), aralkyl group (e.g., benzyl group, phenethyl group, or anisyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, n-butoxycarbonyl group, etc.), aryloxycarbonyl group groups (e.g., phenoxycarbonyl group, triloxycarbonyl group, etc.), acyl groups (e.g., acetyl group, benzoyl group, etc.), acylamino groups (e.g., acetylamino group, benzoylamino group, etc.),
Carbamoyl groups (e.g., N-ethylcarbamoyl group, N-phenylcarbamoyl group, etc.), alkylsulfonylamino groups (e.g., methylsulfonylamino group,
phenylsulfonylamine group, etc.) sulfamoyl group (
For example, N-ethylsulfamoyl group, N-phenylsulfamoyl group, etc.), sulfonyl group (eg, mesyl group, tosyl group, etc.), etc. may be substituted.

Further, Zl and Z2 represent a group of nonmetallic atoms necessary to form a 5-membered ring or a 6-membered ring as described above. These 5-membered rings or 6-membered rings include a pyridine ring, an imidazole ring, a pyrrole ring, a 2-pyrroline ring, a pyrrolidine ring,
Examples include a piperidine ring, a pyrazole ring, a pyrazoline ring, and an imidacilline ring. Examples of the cation represented by the general formula (m-b) include a dodecylpyridinium group, a hexadecylpyridinium group, and a dodecylimidazolium group.

As the cation represented by the general formula (III-c),
Examples include N-ethyl-N-hexadecylpiperidinium group and N-ethyl-N-dodecylpyrazolidinium group.

Among the cations represented by the above general formulas (■-a), (m-b), (m-C) and (Ill-d), those that are particularly preferably used in the present invention are In terms of ease of preparation and manufacturing cost, these are (■-a), (tn-b) and (m-d).

Konoyo y[Cat] and [Cat 2
] affects the solubility of the compounds represented by the general formulas [II and [II] in organic solvents.

Generally, when the substituent bonded to a quaternary heteroatom is an alkyl group, the longer the chain length, the higher the solubility.
This tendency is particularly remarkable in the case of tetraalkyl-substituted ammonium or phosphonium; in the case of ammonium cations, cations with a total number of carbon atoms of 17 or more, and in the case of phosphonium cations, cations with a total number of carbon atoms of 4 or more give high solubility. . Substituted alkyl and aralkyl groups also provide high solubility. The general formula [I
The compounds represented by I and [II] are preferably contained in a dispersed state in a binder as a composition, and are preferably highly compatible with the coating composition or the binder.

In the compounds represented by the general formulas [II and [II], the preferred order of M or M2 is nickel, cobalt, copper, palladium, and platinum. In the case of nickel, the oxidation state is preferably trivalent rather than divalent, and a nickel complex with a divalent central metal does not exhibit strong infrared absorption.

The metal complex of general formula [II or [TI] has a three-dimensional structure of planar circular coordination. In addition, in the compound of general formula [11], whether the thioketone group is symmetrical or asymmetrical with respect to the central metal is not uniquely determined, but in the present invention, for convenience, it is expressed as general formula [II].

The compounds represented by the above general formulas [II and [11]] can be synthesized as follows.

The compound of the general formula [II is zindiram-1,3-dithiol-2 obtained by reacting carbon disulfide and sodium.
-thione-4,5-dithiolate is first converted into a zinc complex, and this is reacted with enriched benzoyl to form a bisbenzoylthio compound. After decomposing this with an alkali, a metal salt is reacted with the precipitated complex, which is then oxidized.

Further, the compound of general formula [II] is first obtained by reacting carbon disulfide with sodium.
3-dithiol-2-thione-4,5-dithiolate is isomerized to disodium 1,2-dithiol-3-thione-4,5-dithiolate by heating to about 130°C. This is made into a zinc complex, and this is reacted with benzoyl chloride to form a bisbenzoylthio compound. It is obtained by decomposing this with an alkali, then reacting with a metal salt, and oxidizing the precipitated complex.

1,3-dithiol-2-thione-4,5, which is an intermediate for obtaining the compound of general formula ['I] or [II]
The -dithiolate anion can be obtained not only by the reduction method using N'a as described in -1- but also by electrochemical reduction.

Preferred examples of the compounds represented by the general formulas [I] and [■I] are as follows, but it goes without saying that the present invention is not limited to these exemplified compounds.

The infrared absorbing composition of the present invention is a composition in which a compound represented by the above general formula [I] or [11] is appropriately contained in a binder. There are no particular restrictions on the binder, and organic,
It can be used regardless of whether it is inorganic or not. Examples of such binders include polymeric materials such as plastics and inorganic materials such as glass.

Preferably, the binder used is one that forms a film with excellent transparency and mechanical properties. Examples of such film-forming binders include polyesters such as polyethylene terephthalate;
Cellulose diacetate, cellulose triacetate,
Cellulose esters such as cellulose acetate-1-butyrate, polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl compounds such as polystyrene, and acrylics such as polymethyl methacrylate. Examples include known film-forming binders such as addition polymers, polycarbonates made of polycarbonate esters, phenolic resins, urethane resins, and wood-philic binders such as gelatin.

As a method for forming a film by adding and retaining the compound of the general formula [I] or [TI] to the above-mentioned plastic ink material, there is a first method of blending it into the plastic at the time of film production. That is, if the compound of formula [I] or [11] is mixed with various additives into polymer powder or pellets, melted and extruded by a T-die method or an inflation method, or formed into a film by a calendar method, the compound can be obtained. A uniformly dispersed film is obtained. In addition, when producing a film from a polymer solution by a casting method, the general formula [I] or [I] is added to the solution.
I] may be contained.

Second, an infrared absorbing layer is formed by applying a polymer solution or dispersion containing the compound of the general formula [I] or [II] to the surface of various plastic films or glass plates produced by an appropriate method. There is a way to form. As the painter polymer used in the coating solution, one is selected that can dissolve the compound of general formula [I] or [11] as well as possible and has excellent adhesiveness to the plastic film or glass plate serving as the support. Polymethyl methacrylate, cellulose acetate butyrate, polycarbonate i. etc. are suitable for this purpose.

The support film may be previously coated with a suitable primer to improve adhesion.

The second method is to mix the compound of general formula [I] or [11] and a polymerizable polymer in the window frame of the element to which infrared rays are to be applied, and then add a suitable polymerization initiator. ,
One method is to polymerize by applying heat or light, and then use the resulting polymer to form a filter on the window frame. In this method, the entire device can also be embedded in plastics made from ethylenically unsaturated synthetic monomers or synthetic additive compositions such as epoxy resins.

The fourth method D is the compound [I] or [I] according to the present invention.
I] is vapor-deposited onto a suitable support. In this process, a suitable film-forming binder layer may also be provided as a protective layer at a position remote from the support.

A method of using the near-infrared absorber according to the present invention in a color solid-state image sensor is described below. After forming a layer of striped or mosaic color separation filters having a plurality of predetermined spectral characteristics, surface protection is provided on the layer of the filter. The layer contains a near-infrared absorber, or this absorber is vapor-deposited,
■The near-infrared absorber of the present invention may be used in combination with visible light-absorbing dye etc. in one layer of the color separation filter, or (■Transparent intermediate layer or surface provided in a multi-layered color separation filter). An embodiment in which the near-infrared absorber is contained in the smooth layer is also possible.An optical filter obtained from the infrared absorbing composition of the present invention is disclosed in Japanese Patent Application Laid-Open No. 57-5
No. 8107, No. 59-9317 and No. 59-305
It is particularly effective when used in combination with a color separation filter such as that described in No. 09.

In the infrared absorbing composition of the present invention, the general formula [I]
Alternatively, two or more compounds represented by [TI] may be used in combination. It can also be used in combination with known near-infrared absorbers of organic or metal complex type. In particular, when used in combination with absorbers having different absorption maximums, the absorption wavelength range can be expanded.

In the infrared absorbing composition of the present invention, in order to further improve the light resistance, it is effective to add an ultraviolet absorber, such as substituted or unsubstituted benzoic acid esters such as resorcin monobenzoate, methyl salicylate, 2-oxy-3 -cinnamate esters such as butyl methoxycinnamate, 2,4
-benzophenones such as dioxybenzophenone, α,β-unsaturated ketones such as dibenzalacetone, 5,7
-Coumarins such as cyoxycoumarin, l,4-dimethyl-7-oxycarbostyrylpostyryls, 2-phenylbenzimidazole, 2-
Azoles such as (2-hydroxyphenyl)benzotriazole and the like are used.

In addition, in the case of a film made by a coating method using the infrared absorbing composition of the present invention, a thin plastic film is pasted or coated on the surface of the coating layer for the purpose of protecting the coating layer, imparting droplet properties, etc. You can also set it up.

For example, by stacking polyvinyl chloride films with a thickness of 0.05 mm and heat-pressing them at 120 to 140°C, a laminated film can be obtained.

In the infrared absorbing composition of the present invention, the general formula [I
] or [TI] is contained in an amount of 0.1 to 50 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts of the binder. The optical filter obtained from the infrared absorbing composition of the present invention only needs to have a low transmittance in the wavelength range that should be blocked functionally to the extent that it can achieve the intended purpose. Adjust the amount added per binder and the thickness of the filter so that the transmittance is 10% or less, preferably 2.0% or less, particularly preferably 0.1% or less at the transmittance trough wavelength of 900 nm or less. It is essential to do so. Practical thickness is 0.002mm to 0.00mm.
Although the thickness of the filter is 5 mm, it is possible to design a filter with a thickness outside this range depending on the application.

(Effects of the Invention) According to the present invention, a near-infrared absorbing composition having a maximum absorption wavelength of about 900 nm or more can be obtained.

Further, an optical filter having excellent fastness to heat and light can be obtained, and a low-cost optical filter can be obtained.

Furthermore, in the infrared absorbing All-compound parabolite of the present invention, the solubility in solvents can be adjusted by appropriately selecting and combining the cation species for the complex ion of the infrared absorber made of a metal complex, so that various binders can be used. It has the advantage of being widely applicable.

The optical filter obtained from the infrared absorbing composition of the present invention can be used as an infrared absorbing material for the above-mentioned safelight filter for infrared sensitive materials, controlling plant growth, blocking heat rays, and for human eye tissue. Harmful infrared cut filters, infrared light cut filters for semiconductor photodetectors, color solid-state image sensors, and infrared light in optoelectronic integrated circuits that incorporate elements with both electrical and optical functions on the same substrate. In addition to being used as a cart filter, it can be used for a variety of other purposes.

Furthermore, the composition according to the present invention can be applied other than optical filters based on its infrared absorption properties. For example, when added to the inkjet printer ink described in JP-A-56-135568, the reading efficiency by near-infrared light can be improved by 1-1.
It can also be applied to the laser light recording/reading medium described in No. 1090. In addition, the composition of the present invention has the property of converting absorbed near-infrared light into heat. ! / Can also be used as a heat exchange agent. Typical examples include l) Japanese Patent Application Laid-Open No. 1983-14
095 or 57-14096 to enhance the mixed coloring reaction caused by the heat generated by irradiation with an infrared laser.2) For example, Japanese Patent Laid-Open No. 57-40
3) The present invention can be incorporated into a heat-drying or thermosetting composition as described in JP-A-56-1.43.2/42. The reaction can be accelerated by containing the compound.

The compound according to the present invention is further disclosed in Japanese Patent Application Laid-open No. 58-2.14.
As described in No. 162 No. 1, it can also be used as an electrophotographic photosensitive film for an electrophotographic printer using a semiconductor laser as a source. It can also be applied to coatings for optical discs that can be written and reproduced using a semiconductor laser.・
- It goes without saying that the above description does not limit the uses of the compounds according to the present invention.

(Examples) 1 Next, the present invention will be explained in more detail based on Examples.
, Reference Example 1 <Exemplary Compound,
Synthesis of (?)> (1-7J) bis(tetraethylammonium)-bis(1,3-dithiol-2-thione-
Synthesis of 4゜5-dithiolat) zinc complex.

All reaction operations were performed under an argon atmosphere.

Cut 23g of sodium into small pieces and add 180mu of carbon disulfide.
After being dispersed in the solution, 200 mJJ of dimethylformamide was slowly added dropwise to the solution while stirring. At this time, be careful not to cause excessive heat generation.

After dropping dimethylformamide, the mixture was carefully heated and refluxed for 24 hours. After the reaction was completed, unreacted sodium was filtered off. Then add 50% ethanol to the filtrate.
mJL was added and stirred at room temperature for 2 hours. , Carbon disulfide is distilled off from this solution under reduced pressure at room temperature. Then 300 mu of water
was added slowly dropwise and the resulting solution was filtered.

Next, add 20 g of zinc chloride to 500 g of methanol in advance.
Dissolve in mJ1 and add 50 Om of concentrated ammonia water to this.
, Q was prepared, and this was added to the above reaction solution and stirred for 5 minutes (at room temperature). When an aqueous solution of 53 g of tetraethylammonium bromide dissolved in 250 mM of water was added, a red precipitate appeared immediately. Analyze and bring out. This was filtered and air-dried to obtain a zinc complex.

, , , (,1,= 2 )4. , 5-bis(benzoinothio)-1l,;Synthesis of 3-dithiol-2-thione.

22 g of the zinc complex obtained in (,,,,,1,-1,) is dissolved in 500 mJ1 of acetone and filtered. While stirring the filtrate, add 1.50 mu of sodium chloride.

A yellow precipitate immediately separates out. Filter, wash with water, air dry, mark the compound, 16. I got g. -(1,-,3)bis(tetrabutylphos, honium).

-bis(1,,,,,3-dithiol-2-thione-4
Obtained by synthesis of 5,-dithiolat)nickel (,II) complex (L-,,2,). Dissolve 9.2 g of bis(1benzoylthio) compound in 50 mJl of methanol. Add to this a 28% methanol solution of sodium and mumethoxide, 6
Add 1.3g and stir for 1.10 minutes. Add 2. nickel chloride (hexahydrate) to this solution. ．． 4g methanol 50m
Add the dissolved solution to J1 and stir at room temperature for 30 minutes. Add 8.5 g of tetrabutylphosphonium bromide to this solution.
When a solution of g dissolved in 9 mfL of methanol and lO is added, a black precipitate immediately precipitates out.・Another 20
Stir for a minute and filter. Washing with acetone, air drying, and recrystallization from acetone-isopropyl alcohol gave the title compound. Yield 3. 8g, ,, I (,1-4)tetrabutylphosphonium-bis(1,3
Synthesis of -dithiol-2-thione-4,5-dithiolato)nickel ([I) complex (exemplified compound (2)).

Add 1 g of the nickel complex obtained in (l-3) to acetone, 6
0. 30 rn4 of acetic acid was added to this, and the mixture was stirred for 31 hours and the solvent was distilled off to precipitate black crystals. This was recrystallized from acetone-methanol to obtain the target exemplary compound (2). Yield 0.4
g m, p, 185°C λmax: 1125 nm, ε
max: 2.51X10 (CH-2C text, medium), 1
．． , Reference Example 2 (Synthesis of Exemplified Compound (lO)) (,1-1)bis(tetraethylammonium)-bis,(1,,
2-dithiol-3-thione-14゜5-dithiolato)
Synthesis of zinc complexes.

All reaction operations were performed under an argon atmosphere.

Cut 23g of sodium into small pieces and add 180mf of carbon disulfide.
While stirring, 200 mfL of dimethylformamide was slowly added dropwise to the bag dispersed in L. Be careful not to generate too much heat at this time.

After dropping the dimethylformamide, carefully
The mixture was heated gently and refluxed for 24 hours. After the reaction was completed, unreacted sodium chloride was removed by filtration, and carbon disulfide was distilled off from the liquid under reduced pressure at room temperature. The solution thus obtained was stirred in an oil bath at 140°C for 2 hours, then allowed to cool to room temperature. 50mM of ethanol was added to this, stirred at room temperature for 2 hours, and then 300ml of water was slowly added to obtain the solution. The resulting solution was filtered.

Next, it was prepared in advance. Add 20g of zinc chloride and 5.0g of tanol. Q. A solution prepared by dissolving in OmfL and adding 500 ml of concentrated ammonia water to it; Add to the above reaction solution (room temperature) and stir for 5 minutes, then add an aqueous solution of 53 g of tetraethylammonium bromide dissolved in 250 ml of water. Immediately, a red precipitate begins to separate out. This was filtered and air-dried to obtain the title zinc complex.
1. -Synthesis of 1,1(1-2)4,5-bis(benzoylthio)-1,2-dithiol-3-thione.・
18g of the zinc complex obtained in ('1-1) was added to 50ml of acetone.
Dissolve in Jlj and filter. While stirring the filtrate, add benzoyl chloride 15'6' rn Jl to it.

A poor color precipitate immediately separates out. After filtration, washing with water, and air drying, 1-2 g of the title compound was obtained.

('1-3) B'7. (''y-trabutyldenmonium)-bis(4,'2'''didionoC23-chin-4
゜5-dithiolat) nickel 'CTI) 'm'form''
Bis^kezoyl□thio obtained by the union of (lff2)
Dissolve 9.2 g of the body in 50" mJl of methanol. To this, add 6.3 g of a 28% methanol solution of sodium methoxide.
g and stirred for 10 minutes. Next, a solution of 2.4 g of nickel chloride (hexahydrate) dissolved in 50 m of methanol was added to the rice flour solution, and after stirring at room temperature for 50 minutes, 7.5 g of tetraethylammonium bromide was added to the rice flour solution.
When a solution prepared by dissolving 1'0' OmKL in methanol was added, a black precipitate was immediately deposited. 2 more
The mixture was stirred for 0 minutes, filtered, washed with acetone, and air-dried. Recrystallization from acetone-isopropyl alcohol gave the title compound. Yield: 2.8 g (1-4) Tetrabutylammonium-bis(l,2-
Synthesis of dithiol-3-“thiyne-4,5-dithiolato)nickel(■) complex (side compound (10)).

(1-3) Y 1 g of the obtained nickel complex was added to 60 ml of acetone.
When the solution was dissolved in mM, 30 ml of vinegar was added thereto, stirred for 3 hours, and the solvent was distilled off, black crystals began to precipitate. When this was recrystallized from cisetone-methanol, the title exemplary compound (10) was obtained.゛ Yield 0.3gm, p, 207℃□ λmax:l
138 nm.

εmat: 2.50X, 1O (in CH2, C10) Example 1 Using exemplified compound 1 (2) synthesized in Reference Example 1, an infrared absorbing composition was prepared and an optical filter was created. That is, each component is mixed with the composition shown in the heavy parts section below, stirred thoroughly, and then filtered and applied onto a metal support by a casting method, and after film formation, it is peeled off and the desired product is obtained. An optical filter was obtained. Several types of optical filters were obtained with dry film thicknesses varying between 0.02 and 0.3 mm. The optical density of the optical filter thus obtained (thickness: 25 microns) is shown in FIG.

Composition example: 170 parts of j'T-A"C (cellulose triacetate), 800 parts of methylene chloride-1, 160 parts of methanol, 2 parts of exemplified compound (2) Example 2 In the same manner as in Example 1, ultraviolet light Thickness containing absorbent O
A 19 mm optical filter was created. The composition of the casting composition is shown below.

TAC (cellulose triacetate) 170 parts TPP (triphenyl phosphate) 10 parts methylene chloride 800 parts methanol
160 parts Exemplary compound (2)
2 parts 2-(5-tert-butyl-2
-Hydroxyphenyl)benzotriazole 0.2
Part application example 1 Optical filter manufactured in Example 1 (thickness 0.05 mm
) was attached to a silicon photodiode as a near-infrared cut filter, and the operating performance of the photodetector was significantly improved. Further, even after a forced aging test at 50°C, the operational reliability showed no change at all.

When a UV absorber is used in combination with the metal complex according to the present invention, the light resistance of the filter is significantly improved.

The light resistance of such a filter was determined by mixing the exemplary compound (2) and the ultraviolet absorber 2-(5-t-butyl-2-hydroxyphenyl)benzotriazole (compound (U)) in a heavy ratio of 10:1. The table below shows the change over time in the optical density of the filter under light irradiation when the filters are used in combination at different ratios.

As can be seen from the table below, when the compound according to the present invention and an ultraviolet absorber were used in combination, the light fastness of the optical filter material could be dramatically improved.

[Brief explanation of drawings]

FIG. 1 is a graph showing the optical density of an optical filter obtained from the infrared absorbing composition of the present invention, and FIG. 2 is a graph showing the relative sensitivity of the human eye and the relative sensitivity of SPD to the wavelength of light. FIG. 1 is an optical density curve of an optical filter (thickness: 25 microns) using Exemplified Compound (2) obtained in Example 1. Komabi Tsutomu 2 Procedural Amendment (Method) October 1, 1980

Claims (1)

[Scope of Claims] An infrared absorbing composition comprising at least one compound selected from the following general formulas (I) and (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼…[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼…[II] (In the formula, [Cat_1] and [Cat_2] are the values necessary to make the complex neutral. (M_1 and M_2 represent nickel, copper, cobalt, palladium or platinum.)