JPS6180106A - Infrared absorption composition - Google Patents

Abstract

PURPOSE:To obtain a composition capable of absorbing light in a range from a far infrared to a near infrared wavelength regions and having a good fastness against heat and light by incorporating a specific compd. to the composition. CONSTITUTION:The titled compd. contains the compd. shown by the formulas I-III (wherein [Cat1]-[Cat3] are a cation necessary to neutralizing a complex ion, M1-M3 are each Ni, Pd, or Pt, R<1> and R<2> are each a hydrogen atom, alkyl, aryl groups, R<3>-R<6> are each a hydrogenatom, a halogen atom, cyano, hydroxy groups and an alkyl and an aryl groups which may lie a bivalence binding radical between said group and the benzene nucleus R<3> and R<4>, R<4> and R<5>, and R<5> and R<6> are each non-metallic atom groups capable of forming a 5 or 6 membered ring by jointing with each other. A bonding agent usable for the titled composition may be either an inorg. or an org. compd. and is preferably used a transparent plastic film having a good mechanical property. The titled composition is the composition capable of absorbing the near infrared ray having >=about 900nm the absorption max. wavelength and is broadly used for an infrared absorption filter, an infrared shield filter for controlling a growth of plant and for shielding a heat ray, an infrared absorption paint and an infrared heat converter etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an infrared absorbing composition. For more details, see [Wavelength 900 without almost impairing the transmission of visible light].
The present invention relates to an infrared absorbing composition that is useful as an optical filter that absorbs far-red light or near-infrared light of nm or more.

(Prior Art) A composition that selectively absorbs far-red light or near-infrared light with a wavelength of 900 nm has been considered for various uses and has been strongly desired, but until now no suitable composition has been obtained. I couldn't. The main uses of conventional infrared absorbing compositions are
Let me explain with an example.

■Safelight filter for infrared-sensitive photosensitive materials In recent years, many silver halide photosensitive materials (hereinafter referred to as R-sensitive materials) that are sensitive to far-red or near-infrared light with a wavelength of 700 nm or more have been developed. It's coming. This includes providing infrared sensitivity to silver halide photosensitive materials, whether black-and-white or color, as well as regular types, instant types, or heat-developable types, to create pseudo-color photographs for use in resource surveys, etc. Alternatively, there are devices that can be exposed using diodes that emit light in the infrared region.

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 light affects the so-called morphogenesis of plant growth and differentiation, such as seed germination, stem elongation, development of buds, and formation of flower buds and tubers. It is being studied as a photomorphogenetic effect.

If a plastic film that selectively absorbs light with a wavelength of 700 nm or more could be obtained, for example, crops could be coated with a near-infrared absorbing film at a specific time to block light with a wavelength of 700 nm or more, thereby delaying the time of heading. , is expected to have the effect of controlling growth (see Katsufu Inada, "Plant Chemistry rAWJ" No. 68, No. 1 (1971)).

(2) Blocking of heat rays Of the solar radiant energy, light in the near-infrared and infrared regions with a wavelength of 300 nm or more is absorbed by objects and converted into thermal energy. Moreover.

Most of the energy distribution is in the wavelength range of 800 to 2000
It is concentrated in the near-infrared region of nm. Therefore, a film that selectively absorbs near-infrared rays is extremely effective in blocking solar heat, and can suppress the rise in indoor temperature while allowing in sufficient visible light. In addition to horticultural greenhouses, this
It can also be applied to the windows of houses, offices, two stores, automobiles, aircraft, etc.

Conventionally, to block heat rays, a plastic film with a very thin metal layer deposited on the surface, or a glass with an inorganic compound such as FeO dispersed therein have been used.

■ 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 major uses of infrared cut filters is as eyeglasses that protect humans from such harmful infrared rays. For example, sunglasses,
These include safety glasses for welders.

■Semiconductor photodetector infrared cut filter cameras, etc.! Currently, a silicon photodiode (hereinafter referred to as SPD) is mainly used as a light receiving element of a photodetector used in a II exposure meter. FIG. 4 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 the infrared light that is invisible to the human eye.
It is necessary to make the spectral sensitivity curve of D similar to the specific luminous efficiency curve. Especially for light with a wavelength of 700 to 1l100n.

Since the output of the SPD is large and the light in this region is not perceptible to the human eye, it becomes a cause of malfunction of the exposure meter.

Therefore, there is less absorption in the visible region, 700~1l10
If an infrared absorbing plastic film 11 that absorbs 0n infrared light over the entire region can be used, the light transmittance in the visible region will be high.

It is clear that the output of the SPD can be increased and therefore the peak of the light meter can be significantly improved.

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.

Furthermore, the filter materials used for each of the above-mentioned applications also had the following drawbacks.

First of all, the conventional panchromatic safelight filter described in Application ① not only partially transmits green light, which has high visibility, but also creates a light power pre-filter that transmits a large amount of infrared light. It has not been possible to sufficiently couple the purpose as a safelight for externally photosensitive materials.

In addition, the plastic film with a vapor-deposited metal layer or the glass with dispersed FeO used in the above application (3) strongly absorbs not only infrared light but also light in the visible region, reducing internal illuminance, especially in agricultural fields. It was inappropriate for practical use because it would lead to an absolute shortage of direct light.

Furthermore, the glass red line cut filter using an inorganic infrared absorber used in the above application (2) is relatively robust against heat and light, but has a low light transmission rate in the visible region ( This problem was dealt with by increasing the sensitivity of the SPD.

Increasing the sensitivity of the SPD leads to an increase in leakage current, which causes malfunction as a photodetector, and becomes a major issue from the viewpoint of reliability. Furthermore, since the infrared cut filter is an inorganic material, it lacks flexibility from the viewpoint of manufacturing a photodetecting device, and it is actually difficult to improve the manufacturing process to the extent possible. Furthermore, inorganic infrared cut filters are expensive to manufacture and have the disadvantage of significantly increasing the cost of the photodetector.

In this way, in the conventional photodetection device using an inorganic cut filter, although its spectral sensitivity is close to the specific luminous efficiency curve, the operational performance as a photodetection device deteriorates. This method had significant drawbacks from the viewpoint of increasing manufacturing costs and improving the manufacturing process.

Furthermore, near-infrared absorbing plastic films using complex infrared absorbers have insufficient solubility of the infrared absorber in organic solvents, which has been a major drawback when producing thin plastic films.

That is, for the above-mentioned applications, 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.

In addition, near-infrared absorbing plastic films that use conventional metal complexes as infrared absorbers have short maximum absorption wavelengths, and their applications have been expanding in recent years, such as in light-receiving elements of conductor radars. It was inappropriate.

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 shim-forming binders.

The present inventors have conducted various studies to achieve the above object, and as a result, have completed the present invention.

(Means for solving the problem) Article 1111, 1^ The purpose is to solve the general formula [I] ~ [+1]
The problem was solved by an infrared absorbing composition characterized by containing at least la selected from the metal complexes represented by:

(In the formula, [Cat] to [Cat3] represent cations necessary to neutralize the complex, 1M1 to M,
represents nickel, palladium or platinum, R1 and R2 are a hydrogen atom, a substituted or unsubstituted alkyl group, or! ! ul and R2 may be the same or different from each other R3,
R4, R5 and R6 are hydrogen atoms/% rogen atoms,
A cyano group, a hydroxyl group, an alkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group, in which a divalent linking group may be interposed between the bonded benzene ring, or R3 and R
4, R4 and R5, or R5 and R6 are bonded together to form a 5 (1 or 60 ring),
R3-R6 may be the same or different.) The present invention will be explained in further detail.

Among the cations represented by -c and [Cat] to [Cat3] in the compounds represented by the general formulas [I] to [II[], inorganic cations include alkali metals (
For example, Li, Na, etc.), alkaline earth gold H (
(Mg, Ca, Ba, etc.) or NH4''t-.

Examples of organic cations include quaternary ammonium ions, iminium ions, and quaternary phosphonium ions.

The above cations [Cat] ~ [Cat 3]
Among them, the following general formula (rV-a), (
I'll -b), (rlT-c), (rV-
d) or (rv-e).

(In the formula R7, R8, R9, RIOlRll, R12゜13 +4 15 1 [i 1?
R, R, R, R, RJJ and R18 each have 1 carbon number
to 20 substituted or unsubstituted alkylno^, or a substituted or unsubstituted 7-aryl group having 6 to 14 IRJ numbers, and zl and Z2 are bonded to the nitrogen or phosphorus atom in each formula to form a 5-membered or 61+L ring. Represents a group of nonmetallic atoms that form .

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-butyl group, 1so-7mil group, n-dodecyl group, n-octadecyl group, etc. . carbon a6 to 1
Examples of the 4-7J)-yl group include a phenyl group, a tolyl group, and an α-naphthyl group.

These furkyl groups or aryl groups are cyanoA,
Hydroxyl group, alkyl group having 1 to 20 carbon atoms (e.g., methyl group, ethyl group, n-butyl group, n-octyl group, etc.), 7-aryl group having 6 to 14 carbon atoms (e.g., phenyl group, tolyl group, α -naphthyl group, etc.), 15Ja2
to 20 7-syloxy, ll1i (e.g. 7-cetoxy group, benzoyloxy group or p-methoxybenzoyloxy group, etc.) phenoxy group having 1 to 6 carbon atoms (
(e.g. methoxy, ethoxy, propoxy, butoxy); aryloxy (e.g. phenoxy, triloxy); aralkyl (e.g. benzyl, phenethyl or anisyl); alkoxycarbonyl (e.g. methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, triloxycarbonyl group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.),
Acylamino group (e.g., acetylamino group, henzoylamino group, etc.), carbamoyl group (e.g., N-
ethylcarbamoyl group, N-phenylcarbamoyl group, etc.), furkylsulfonylamino group (for example, methylsulfonylamino group, phenylsulfonylamino group, etc.), sulfonyl group (for example, +f, N-ethylsulfamoyl 1.N- It may be substituted with a phenylsulfate (T mo, f group, etc.), a sulfonyl group (eg, mesyl group, tosyl group, etc.), or the like.

In addition, 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 511 rings or 6-membered rings include a pyridine ring, an imidazole ring, a pyrrole ring, Examples include a 2-pyrroline ring, a pyrrolidine ring, a piperidinino ring, a pyrazole ring, a pyrazoline ring, and an imidacilline ring. General formula (tv-
Examples of the cation represented by b) include dodecylpyridinium group, hexadecylpyridinium group, and dodecylimidazolium group.

Examples of the cation represented by general formula (IV-c) include N-ethyl-N-hexadecylpiperidinium group and N-ethyl-N-dodecylbitezolidinium group.

The general formulas (ff-a), (ff-b), (
Among the cations represented by ff -C), (ff-d) and (ff-e), those particularly preferably used for Ipponra Ikou 11 are easy to obtain manufacturing raw materials, 5A manufacturing cost (rV-a), (rV-b), (rV-d
) and (rV-e).

The type of the cation 7[Cat]-[Cat3'] influences the solubility of the compound represented by the general formula [11-[ml] in the 11# medium.

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 a phosphonium cation, a cation with a total carbon number of 17 or more gives high solubility, and in the case of a phosphonium cation, a cation with a total carbon number of 4 or more gives high solubility. Substituted alkyl groups and aralkyl holes also impair high solubility.The compounds represented by the general formulas [I] to [ml according to the present invention are preferably contained in a dispersed state in a binder as a composition. , painting M
It is preferable that it has high compatibility with the first component or binder.

In the compounds represented by the general formulas [I] to [ml, M1 to M3 are listed in order of preference: nickel, palladium, and platinum. In the case of nickel, the oxidation state is RF or trivalent rather than divalent.

A nickel complex with a divalent central metal does not exhibit strong infrared absorption.

The compounds of the general formulas [I] to [ml] contain complexes whose formal oxidation numbers of the central metal are divalent and tetravalent, in equal moles I4. Organic solvent (
For example, it can be obtained by mixing and refluxing in acetone).

Preferred examples of the compounds represented by the general formulas [11 and [■] of 1111 are as follows: 1
It goes without saying that the present invention is not limited to these exemplified compounds.

In addition, in Tables 1 to 3, a to f in (cat+] to [CaL3] represent the following cations.

a: [("C4H9), N] b: [CC4H,), P]" c: ["CH(CH3)3Nl" d: ["C,, H33("C, H3) 3F]
”f: [((@卜丁P) 2Nl ” Table 1 (Continued from Table 1) (Continued from Table 1) (Continued from Table 1) (Continued from Table 1) (Continued from Table 1! Table 2 (Continued from Table 2) (Continued from Table 2) (Continued from Table 2) (Continued from Table 2) (Continued from Table 2) (Continued from Table 3-1) (Continued from Table 3-1) (Continued from Table 3-1) (Continued from Table 3-2) (Continued from Table 3-2) (Continued from Table 3-2) Table 3-2 continued) (Table 3-2 continued) (Table 3-2 continued) Table 3-3 (Table 3-3 continued) (Table 3-3 continued) (Table 3-3 continued) (Continued) (Continued from Table 3-3) (Continued from Table 3-3) The metal complexes represented by the general formulas [I] to [ml] containing the above-mentioned exemplified compounds can be prepared by the method shown in the reference examples below or similar thereto. It can be synthesized by a method.

The infrared absorbing composition of the present invention has the general formulas [I] to [m
This is a composition in which a compound represented by 1 is appropriately contained in a binder. There are no particular restrictions on the binder.
Any material can be used regardless of whether it is organic or inorganic as long as it exhibits infrared absorbing properties. Such binders include polymeric materials such as plastics, inorganic materials such as glass, and the like.

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 butyrate, polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl compounds such as polystyrene, and acrylic addition polymers such as polymethyl methacrylate. Examples include known film-forming binders such as hydrophilic binders such as polycarbonates, phenolic resins, urethane resins or gelatin.

As a method for forming a film by adding and retaining compounds of the general formulas [1] to [ml] to the above-mentioned plastic material, there is a first method of blending them into the plastic at the time of film production. That is, if compounds of formulas [1] to [ml] are 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 above compounds can be obtained. A film with uniformly dispersed particles is obtained.

When a film is produced from a polyethylene solution by a casting method, a compound of the general formula [11 to [ml] may be contained in the solution.

Second, the surface of various plastic films or glass plates manufactured by a suitable method (V) is coated with the general formula [I
] to [ml] There is a method of forming an infrared absorbing layer by applying a polymer solution or dispersion containing the compound. The /<inner polymer used in the coating solution has the general formula [11 to [ml] dissolved as well as possible,
In addition, a material with excellent adhesion to the plastic film or glass plate serving as the support is selected. Polymethyl methacrylate, cellulose acetate butyrate, polycarbonate, etc. are suitable for this purpose.

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

The third method is to mix a compound of general formula [I] to [ml] with a polymerizable monomer in the light incident window frame of an element whose infrared rays are to be cut, add a suitable polymerization initiator, and heat or light. There is a method in which the polymer is added and polymerized, and the resulting polymer is used to form a filter on the window frame. In this method, the entire device can also be embedded in a plastic made from an ethylenically unsaturated polymerizable monomer or an additive composition such as an epoxy resin.

The fourth method is a method in which 1 to ml of the compound [I] according to the present invention 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.

The method of using the near-infrared absorber according to the present invention in a color solid-state image sensor is as follows: 1. After forming a striped or mosaic color separation filter layer having a plurality of predetermined spectral characteristics, a surface is provided on the filter layer. Incorporating a near-infrared absorber into the protective layer, vapor-depositing this absorber,
■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 smoothness provided in a multilayer color separation filter. An embodiment in which this near-infrared absorber is contained in the 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. 57-58.
No. 107, No. 59-9317 and No. 59-3050
It is particularly effective when used in combination with color separation filters such as IVL described in 9-'j.

In the infrared absorbing composition of the present invention, the general formula [I] ~
[Two or more compounds expressed in ml 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 21- or unsubstituted benzoic acid esters such as resorcinol monobenzoate, salicyl-ugly methyl, 2-oxy -Cinnamate esters such as butyl 3-methoxycinnamate, 2,
4-dioxybenzophenone, penzophenols,
α, β-unsaturated ketones such as dibenzalacetone, 5,
Coumarins such as 7-cyoxycoumarin, carbostyrils such as 1,4-dimethyl-7-oxycarbostyryl, azoles such as 2-phenylbencyimidazole, 2-(2-hydroxyphenyl)benzotriazole, etc. etc. 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 I film is pasted on the surface of the coating layer for the purpose of protecting the coating layer and imparting droplet properties. It can be painted or painted.

For example, by stacking polyvinyl chloride films of 0.05 mmN 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
] to [m] The optical filter obtained from the infrared absorbing composition of the present invention contains 0.1 to 50 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts of the binder. It is sufficient that the transmittance in the wavelength range to be functionally blocked is low enough to achieve the intended purpose, and in order to use the composition of the present invention, the transmittance in the wavelength range of 900 nm or more at the valley of the transmittance is preferably 10% or less. It is important to adjust the amount added per binder and the thickness of the filter so that the transmittance is 2.0% or less, particularly preferably 0.1% or less. Practical thickness is 0.002mm to 0.5mm
However, depending on the application, it is possible to design a filter with a thickness outside this range.

(Effects of the Invention) According to the present invention, a near-infrared absorbing composition having a maximum absorption wavelength of about 900 am 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 Jg product 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 a wide variety of binders can be used. It has the advantage of

The optical filter obtained from the infrared-absorbing composition of the present invention can be used as an infrared-absorbing material such as the above-mentioned safelight filter for infrared-sensitive photosensitive materials, a control of plant life 1'Y, heat ray blocking, and Iruma. [41 Infrared rays harmful to tissues/) filter, semiconductor photodetector, color solid-state image sensor infrared cut filter, optoelectronic device that incorporates elements with both electrical and optical functions on the same substrate. In addition to being used as an infrared light cut filter in integrated circuits, it can be used for a variety of other applications.

Further, 1 Sesame seeds 5 The composition according to the present invention can be used not only for optical filters but also for applications based on its infrared absorbing properties, such as infrared absorbing paints.
When added to the inkjet printer ink described in No. 6-125568, it can improve the reading efficiency by near-infrared light, and it can also be applied to the laser beam recording/reading medium described in JP-A-57-11090. . Furthermore, the composition of the present invention has the property of converting absorbed near-infrared light into heat, and can also be used as an infrared/heat exchange agent. Typical examples include l) JP-A-57-140953 or JP-A-57-140953;
It can be added to a laser heat-sensitive recording material such as that described in No. 14096 to enhance the mixed color reaction caused by the heat generated by irradiation with an infrared laser.2) Dissolution due to the action of heat generated by laser light. It can be included in resist materials that change the properties, for example, as described in JP-A No. 57-40256. 3) JP-A-56-1
When the compound of the present invention is included in a heat-drying or thermosetting composition such as that described in No. 43242, the reaction can be accelerated.

The compound according to the present invention is further disclosed in Japanese Patent Application Laid-Open No. 58-2141.
As described in No. 62, it can also be used as a photosensitive film for electrophotography A of an electrophotographic printer using a semiconductor laser as a light source. It can also be applied to an optical disc cover 11g that can be written and reproduced using a semiconductor laser.

Of course, the description in Section L does not limit the uses of the compound related to undeveloped Il+.

(Examples) Next, the present invention will be described in more detail with reference to Examples.

Reference J15 Example 1 Synthesis of small compound (27)> (1-1)
(hexadecyltrimethylammonium)bis1.2-
Synthesis of dicyano-112-ethylenedithiorad) nickelate (if).

Q, 8ihr and G, 5chleitzer (F
) Method (Chew.

1 g of sodium cyanodithioformate (having 3 molecules of dimethylform 7mide as the crystallizing solvent) prepared by J. Ber., 90438 (1957)) was
Dissolve in 6mJ1 and heat in water bath-F for 20 minutes. The precipitated sulfur was filtered off, and after the filtrate was cooled to room temperature, 30 ml of ethanol was added thereto. First, a solution of 1.73 g of nickel chloride (hexahydrate) dissolved in 11 mJL of water is added to the obtained solution, and the mixture is stirred at room temperature for 5 minutes. When a solution of 6.08 g of hexadecyltrimethylammonium bromide dissolved in 18 ml of ethanol is added to this, a precipitate is immediately formed. After stirring at room temperature for 10 minutes, the precipitate was filtered, washed with water, and air-dried. 7 Recrystallization from setone-n-hexane gave 6 g of red crystals of the title nickel (II) M substance.

(1-2) dithio(p-methoxybenzyl)nickel (
rV) Synthesis of the complex.

50g of anisoin and 50g of phosphorus dioxide to 35g of dioxane
The mixture was refluxed in 0ml for 2 hours. After cooling and filtering, a solution of 25 g of nickel chloride (hexahydrate) dissolved in 100 mJL of water is added to the filtrate, and a precipitate immediately forms. This was heated on a water bath for 1.5 hours and allowed to cool. The reaction solution was filtered to obtain a black precipitate. This precipitate was filtered, washed with water, and air-dried.
Next, this was extracted with toluene using a Soxhlet extractor, and 36 g of black crystals of the title nickel (rV) 2a were obtained.

(L-3) Synthesis of exemplary compound (27).

(1-1)? ! ) nickel(II) complex 0.55g
0.40 g of the nickel (rV) complex obtained in (1-2) is poured into 150 ml of acetone for 12 hours. Fever 11'?
Filter and reduce the filtrate.

Mature methanol was added to this and the mixture was allowed to cool overnight, whereby dark orange crystals of Exemplified Compound (27) were precipitated. Yield 0.50g,
Melting point 231-232°C (λwax: 927nta: E
maw: 0.72XLO' (in CHC exchange 3)) Reference example 2 <Synthesis of exemplified compound (Ll, l)> (2-1)
Synthesis of bis(tetrabutylammonium)his(l,3-dithiol-2-thione-4,5-dithiolato)nickelate C11).

(2-1-1) Synthesis of bis(tetraethylammonium)-bis(1,3-dithiol-2-thiono-4,5-dithiolato)zinc complex.

All reaction operations were performed under an argon atmosphere.

Cut 23g of sodium into small pieces and add 180mQ of carbon disulfide layer.
After being dispersed in 1. - 200 mJl of dimethylformamide was slowly added dropwise to the mixture while stirring. Be careful not to generate too much heat at this time.

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

Next, 20g of zinc chloride was added in advance to 500ml of methanol.
Prepare a solution by adding 500 m of concentrated ammonia water to this solution, and add this to the reaction solution described in (h).
After stirring for 5 minutes (at room temperature), an aqueous solution of 53 g of 1.I-laethylammonium bromide dissolved in 250 ml of wood is added, and a red precipitate immediately precipitates out. This was filtered and air-dried to obtain a zinc complex.

(2-1-2)4.5-bis(hensoylthio)-1,
Synthesis of 3-1,000-2-thione.

22 g of the zinc complex obtained in (1-1) is dissolved in a solution of 500 m thick and filtered. While stirring the filtrate, add 150 mM of benyl JU.

A precipitate of a different color immediately separates out. After filtration, washing with water, and air drying, 16 g of the title compound was obtained.

(2-1-3)Bis(tetrabutylammonium)-bis(1,3-dithiol-2-thione-4.5-7thiolat)dinkeret)(II) &j compound obtained in synthesis (1-2) Dissolve 9.2 g of bis(benzylthio) in 50 mJL of methanol, add 6.3 g of a 28% methanol solution of sodium methoxide, and make 1
Stir for 0 minutes. Add nickel chloride (hexahydrate) to this solution.
2.4 g was dissolved in 50 mft of methanol. Add the solution and stir at room temperature for 30 minutes. Add 8.5 g of tetrabutylammonium bromide to this solution in 100 ml of methanol.
When a solution dissolved in is added, a black precipitate immediately precipitates out. The mixture was further stirred for 20 minutes and filtered. Washing with acetone, air drying, and recrystallization from acetone-isopropyl alcohol gave the title compound. Yield: 3.8 g (2-2) Synthesis of bisdithiobenzylnickel (IV) complex.

50g of benzoin and 5g of phosphorus pentasulfide to 35g of dioxane
Flow at 0 mg gL for 2 hours. Cool and filter.

When a solution of 25 g of nickel chloride (hexahydrate) dissolved in 100 m of water is added to the filtrate, a precipitate is formed. Heat this on a water bath for 1 hour at 7 P and let it stand. Filter the reaction solution. A black precipitate was obtained. This was filtered, washed with water, and air-dried. Extracted with toluene using a Soxhlet BL+ extractor to obtain 43 g of black crystals of the title compound.

0.57 g of nickel (■) complex obtained in (2-1) and 0.33 g of nickel (rV) complex obtained in (2-2)
were mixed and dissolved in 77 tons of 150 mJl, refluxed for 5 hours, and filtered.

The filtrate was concentrated, hot methanol was added, and the mixture was allowed to stand at -25°C overnight to obtain 0.30 g of russet-colored crystals of the title complex.

Melting point 280-281"C.

(λwax: 11015n; εsat: 1.31X10
(See CHC. Middle)) Reference Example 3 (Synthesis of Exemplified Compound (203)) Synthesis of (3-1) Tetrabutylammonium bis(quinoxaline dithiolate) 2-Keley) (H).

14.4 g of quinoxaridge thiol is added to and dissolved in a solution prepared by diluting 48.4 g of a 28% solution of sodium methoxide with 300 mM methanol. This is combined with nickel chloride (
A solution of 5.8 g of hexahydrate dissolved in methanol roomjL is added little by little. Stir at room temperature for 30 minutes after addition. To this, tetrabutylammonium bromide
A solution of 7.2 g dissolved in 100 mJL of methanol is added, and the mixture is stirred at room temperature for 30 minutes. Add 900 m of water to this and filter out insoluble matter. The obtained precipitate is thoroughly washed with water and air-dried. Dissolve this in a small amount of hot acetone, add ethanol, and allow to cool.

The precipitated crystals were filtered to give 8.6 black crystals of the title compound.
gt-obtained.

(3-2) Synthesis of hisdithiohensylnickel (IV).

This was the one synthesized in (2-2).

(3-3) Synthesis of exemplary compound (203).

0.57 g of the nickel (11) complex obtained in (3-1) and (
0.33 g of the nickel (■) complex obtained in 2-2) was
The mixture was refluxed for 5 hours in -y150mJL and then filtered, the filtrate was concentrated, hot ethanol was added thereto, and the mixture was allowed to cool. 0.43 g of dark reddish-purple crystals of the title compound were obtained. Melting point 26
3 to 264°C (λsag: 972n scale: εmat: 1.
Example 1 Using the exemplary compound (27) synthesized in Reference Example 1, 2 g of an infrared absorbing composition was prepared to prepare an optical filter. That is, after mixing each component with the composition shown in the jut part and stirring well, after filtering, it is coated on a metal support by a casting method, and after film formation, it is peeled off, and the desired optical filter is obtained. I got it. Several types of optical filters with dry film thicknesses varying between 0.02 and 0.3 mm were used. The optical density of the optical filter thus obtained (thickness: 95 microns) is shown in FIG.

Composition example TAC (-acid-resistant cellulose) 170 parts TPP () liphenyl phosphate) 10 parts methylene chloride 800 parts methanol
160 parts Exemplary compound (27)
Part 2 Example 2 Using the exemplary compound (111) synthesized in Reference Example 2, an infrared absorbing composition was prepared and an optical filter was made. That is, each component is mixed with the composition shown below in parts by weight, stirred well, and after filtering, it is applied onto a metal support by a casting method, and after the film is formed, it is peeled off. We obtained an optical filter that 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: 60 microns) is shown in FIG.

Composition example TAC (orthosulfate cellulose) 170 parts TPP (triphenyl phosphate) toe methylene chloride 800 parts methanol
160 parts exemplified compound (l l
1) Two-part Example 3 An infrared absorbing composition was prepared using the exemplary compound (203) synthesized in Reference Example 3, and an optical filter was created. That is, each component is mixed with the composition shown below in parts by weight, stirred thoroughly, and then filtered and cast onto a metal support by a casting method.
After forming a film using F5 cloth, it was peeled off to obtain the desired optical filter. Optical filters from several companies were obtained with dry film thicknesses varying between 0.02 and 0.3 mm. The optical Ml of the optical filter (thickness 60 microns) thus obtained
Composition example AC ("EP#, acid cellulose) 170 parts TPP (
triphenyl phosphate) 10 parts methylene chloride aOO parts methanol
180 parts Exemplary compound (203)
2 Parts Example 4 Same as Example 1, 0 thickness containing ultraviolet absorber.
．． A 19 mm optical filter was created. The composition of the casting composition is shown below.

TAC (cellulose triacetate) 170 parts TPP (triphenyl phosphate) ion methylene chloride 800 parts methanol
180 parts Exemplary compound (27)
Part 2 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole 0.2 City Center I11
Example 1 Optical filter manufactured in Example 1 (thickness 0.05 mm
) When attached to a silicon photodiode as a near-infrared cut filter, the operating performance of the photodetector was significantly improved. Further, a forced aging test at 50'C also showed no change in operational reliability.

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 the example compound (27)
and the ultraviolet absorber 2-(54-butyl-2-hydroxyphenyl)benzotriazole (compound (U)) at a ratio of 10:l. The changes over time are shown in the table below.

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

[Brief explanation of the drawing]

Figures 1 to 3 are graphs showing the optical density of an optical filter obtained from the infrared absorbing composition of the present invention, and Figure 4 is a graph showing the relative sensitivity of the human eye and the relative sensitivity of SPD to the wavelength of light. . 1 to 3 are optical density curves of optical filters using exemplified compounds (27), (ill), and (203) obtained in Examples 1 to 3, respectively. Figure 1 Figure 2 One-pronged table (nm)

Claims (1)

[Scope of Claims] An infrared absorbing composition characterized by containing at least one compound selected from the following general formulas [I], [II] and [III]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[III] (In the formula, [Cat_1] to [Cat_3] indicates the cation necessary to make the complex neutral, and M_1 to M_
3 indicates nickel, palladium or platinum. R^1 and R^2 represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R^
1 and R^2 may be the same or different. R^3, R^4, R^5 and R^6 are a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, or an alkyl group in which a divalent linking group may be interposed between the benzene ring and the benzene ring. group, aryl group, cycloalkyl group or heterocyclic group, or R^3 and R^4, R^4 and R^5, or R^5
and R^6 represent a group of nonmetallic atoms that combine with each other to form a 5- or 6-membered ring, and R^3 to R^6 may be the same or different from each other. )