JPH0355511B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a plastic composition containing a novel halogen-substituted benzenedithiol metal complex as a near-infrared absorber. That is, the present invention is based on the general formula () (In the formula, X is a chlorine or bromine atom, Y and Z are hydrogen or a chlorine atom when X is a chlorine atom, hydrogen or a bromine atom when X is a bromine atom, and N is a nickel, palladium, or platinum atom. An object of the present invention is to provide a plastic composition that absorbs near-infrared rays, characterized in that it contains a halogen-substituted benzenedithiol metal complex represented by (A represents a quaternary ammonium group) as a near-infrared absorber. Specifically, the metal complexes used in the present invention include bis(1,2,4-trichloro-5,6-dithiophenolate)nickel-tetra-n-butylammonium, bis(1,4-dichloro-5,6-dithiophenolate) -dithiophenolate) nickel-tetra-n-butylammonium, bis(1-chloro-5,6-dithiophenolate)nickel-tetra-n-butylammonium and these metal complexes by changing the nickel atom to palladium or platinum. complexes in which the tetra-n-butylammonium group of the quaternary ammonium group is replaced with a tetra-n-propylammonium group or a trioctylmethylammonium group, and bis(1,2,4-tribromo-5, 6-dithiophenolate) nickel-tetra-n-butylammonium, bis(1,4-dibromo-5,6-dithiophenolate) nickel-tetra-n-butylammonium, bis(1-
Bromo-5,6-dithiophenolate) nickel-tetra-n-butylammonium and complexes in which the nickel atom of these metal complexes is replaced with palladium or platinum, and tetra-n-butylammonium groups of quaternary ammonium groups These are complexes in which the compound is replaced with a tetra-n-propylammonium group or a trioctylmethylammonium group. The novel halogen-substituted orthobenzenedithiol metal complex used in the present invention has excellent compatibility with various resins compared to the conventionally known tetrachlorobenzenedithiol metal complex, and even if the addition ratio is increased, it can be used for a long period of time. Does not cause crystallization from resin. Already known, for example, bis(1,2-dithiophenolate)nickel-tetra-n-butylammonium, bis(1-methyl-3,4-dithiophenolate)nickel-tetra-n-butylammonium, bis(1-methyl-3,4-dithiophenolate)nickel-tetra-n-butylammonium, ,2,3,4-tetramethyl-
(5,6-dithiophenolate) nickel-tetra-n-butylammonium and bis(1,2,
Ortho-benzenedithiol metal complexes such as nickel-tetra-n-butylammonium (3,4-tetrachloro-5,6-dithiophenolate) are known to exhibit a unique absorption spectrum in the near-infrared region. Toluene-3,4-dithiol
und verwandte 1,2−Di−thiolene als
"Chelatbildner fur Metalle", vol. 102, pp. 308-320, 1971 and "Characterization and Electronic Structures
of Metal Complexes Containing Benzene−
1,2-dithiolate and Related Ligands Journal of the American Society 88
Vol. 4870-4875, 1966), and these metal complexes are important near-infrared absorbers because of their excellent thermal stability and weather resistance (Japanese Patent Application Laid-Open No. 135551/1983). Therefore, these materials are kneaded into plastic films or plates as near-infrared absorbers, or polymer liquids containing these materials are applied to substrates to create pharmaceutical films for selectively utilizing sunlight and for reducing glare. Research is being conducted on its use in sunglasses, welding glasses, aircraft window and television filters to prevent eye fatigue. Furthermore, in recent years, research has been conducted to use photodiodes as optical filters to compensate for the wavelength sensitivity characteristics of optical conversion elements such as light-emitting diodes, and because these near-infrared absorbers match the oscillation wavelength of semiconductor lasers, It is also important as a laser light absorbing heat storage agent for semiconductor laser light recording, ie, laser heat mode recording. However, the conventionally known metal complexes of benzenedithiols are 1,2,3,4-tetrachlorobenzene-5,6-dithiol (JP-A-56
-135463), which are obtained through a complex several-step synthesis reaction, are extremely expensive, and their use is naturally limited. In addition, tetrachlorobenzenedithiol metal complexes have been put into practical use because of their excellent near-infrared absorption ability, thermal stability, and weather resistance, and because the manufacturing method of tetrachlorobenzenedithiol, which is its ligand, is economically advantageous. However, when coating it with plastic as a near-infrared absorber or kneading it into plastic and using it as a film or plate, increasing the amount of tetrachlorobenzenedithiol metal complex added will cause
When used for a long time, the tetrachlorobenzenedithiol metal complex will crystallize from the plastic. For example, it is not suitable for imparting high near-infrared absorption ability with a thin film formed by a coating method. On the other hand, the halogen-substituted benzenedithiol metal complex used in the present invention has high compatibility with resins and the like, and does not crystallize from the resin even when used for a long time even if the addition ratio is increased. In addition, the halogen-substituted benzenedithiol of the present invention can be produced industrially by the production method described below, and therefore can be economically advantageously used as a near-infrared absorber for various purposes. That is, the halogen-substituted benzenedithiol metal complex used in the present invention is very advantageous as a near-infrared absorber having extremely excellent compatibility with resins. The novel halogen-substituted benzenedithiol metal complex used in the present invention is a novel halogen-substituted benzenedithiol that was made possible to synthesize for the first time by the present inventors, that is, a polyhalogenated benzene and sodium or potassium hydrosulfide. A novel halogen-substituted benzenedithiol, specifically 1,2,4-trichlorobenzene-5,6, obtained by heating and reacting with iron powder or iron salts in the presence of sulfur and a polar organic solvent.
-dithiol, 1,4-dichlorobenzene-5,
6-dithiol, 1-chlorobenzene-5,6-
dithiol, 1,2,4-tribromobenzene-
5,6-dithiol, 1,4-dibromobenzene-5,6-dithiol, 1-bromobenzene-
It can be synthesized using 5,6-dithiol or the like as a raw material. That is, the general formula () (wherein, X represents a chlorine or bromine atom, Y and Z represent a hydrogen or chlorine atom when X is a chlorine atom, and hydrogen or a bromine atom when X represents a bromine atom) Dithiol is dissolved or dispersed in a suitable solvent, and a predetermined amount of metal salts capable of supplying nickel, palladium, or platinum ions, such as nickel chloride, palladium chloride, and potassium chloride diplatinate, is added to this solution to prepare halogen-substituted benzenedithiol. After the metal complex is generated, a predetermined amount of a desired quaternary ammonium halide is added, or a predetermined amount of a quaternary ammonium hydroxide obtained by reacting a desired quaternary ammonium halide with an alkali is added. In addition, a desired novel halogen-substituted benzenedithiol metal complex can be obtained by reacting. A solution is required when reacting halogen-substituted benzenedithiol with metal ions in this production method, but tetrahydrofuran or absolute ethanol, which easily dissolves halogen-substituted benzenedithiol, is preferably used, but alcohols such as methanol, ethanol, isopropanol, etc. The reaction may be carried out in a state in which halogen-substituted benzenedithiol is dispersed in the halogen-substituted benzenedithiol. In addition, the metal ions of nickel, palladium, or platinum and quaternary ammonium ions used in this production method are halogen-substituted benzenedithiol 1
Theoretically, 0.5 molar equivalents are required for each molar equivalent. The novel halogen-substituted benzenedithiol metal complex used in the present invention has excellent near-infrared absorption ability, thermal stability, and weather resistance as well as the conventionally known tetrachlorobenzenedithiol metal complex. It has been found that it has a high degree of compatibility with plastics, which cannot be expected with metal complexes. Therefore, the novel halogen-substituted benzenedithiol metal complex of the present invention can be incorporated into plastics at high concentrations as a near-infrared absorber, and will not crystallize from plastics even after long-term use. I understand. In this invention, all plastics with excellent transparency and mechanical properties can be used as the plastic composition material holding the metal complex represented by the general formula (). For example, polyesters such as polyethylene terephthalate, cellulose esters such as nitrocellulose and cellulose triacetate, polyethylene,
These include polyolefins such as polypropylene, polyacrylic resins such as polymethyl acrylate and polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, vinyl chloride, vinyl acetate copolymers, polyvinyls such as polystyrene, and polycarbonate. Plastics can be selected to suit the purpose of imparting infrared absorption capabilities. In addition, the blending ratio of the metal complexes represented by the general formula () to the plastic in this invention varies depending on the desired type of plastic, the thickness of the plastic, and the intensity of light absorption. It is desirable to add about 30% by weight or less to prevent the metal complex from crystallizing from the plastic and to maintain the mechanical properties of the plastic. In addition, the method of molding using a plastic composition that absorbs near-infrared rays in this invention, that is, the method of adding and retaining a metal complex represented by the general formula () to plastic, includes (1) forming a plastic molded product; (2) Near-infrared absorbing ability There is a method of forming a near-infrared absorption layer by applying a polymer solution or dispersion containing a metal complex represented by the general formula () onto the surface of a substrate to which a near-infrared absorbing layer is to be imparted. In these methods, stabilizers, plasticizers, antioxidants, ultraviolet absorbers, etc. may be added as necessary. Thus, the composition of the present invention makes it possible to incorporate the metal complex represented by the general formula () as a near-infrared absorber into plastic at a high concentration. Agricultural film for selective use, sunglasses to prevent glare and eye fatigue,
Welding glasses, aircraft window or television filters, optical filters for compensating the wavelength sensitivity characteristics of photoelectric conversion elements such as photodiodes and light emitting diodes, and heat mode recording of semiconductor laser light with an oscillation wavelength in the near-infrared region. It can be used as a medium for Next, Table 1 shows the melting points and light absorption characteristics of representative examples of metal complexes represented by the general formula (). The metal complex of the present invention is not limited to these.

【table】

[Table] Hereinafter, the present invention will be explained in detail with reference to Examples.
Parts in Examples indicate parts by weight. Synthesis Example 1 When 9.0 parts of 1,2,4-trichlorobenzene-5,6-dithiol was dissolved in 500 parts of tetrahydrofuran and stirred, a solution of 4.2 parts of nickel chloride hexahydrate dissolved in 50 parts of ethanol was added, and the mixture turned dark green. Change. Next, 6.0 parts of tetra-n-butylammonium bromide was added, stirring was continued for 2 hours, and the reaction solution was concentrated to about 1/3 by distillation under reduced pressure.
Then, the weight ratio of dichloromethane and methanol was 1:
Recrystallize from the mixture of 3 and bis(1,2,4
Obtained 11.5 parts of nickel-tetra-n-butylammonium (trichloro-5,6-dithiophenolate) (yield 80 mol%) Melting point 138-140°C Elemental analysis value (%) (C ₂₈ H ₃₈ NCl ₆ S ₄ Ni) C H N Cl S Calculated value 42.66 4.86 1.78 26.99 16.27 Analytical value 42.59 4.92 1.72 27.52 16.77 Synthesis example 2 22 parts of 1,4-dichlorobenzene-5,6-dithiol were suspended in 800 parts of methanol and stirred. Meanwhile, add 12.4 parts of nickel chloride hexahydrate to methanol.
When 100 parts of the solution is added, the color changes to dark green.
Next, 18.3 parts of tetra-n-butylammonium bromide was added, and after continued stirring for 2 hours, the reaction solution was concentrated to about 1/5 by distillation under reduced pressure. Then, filtration was performed to obtain 31 parts of a green solid. Next, recrystallization was performed from a mixture of dichloromethane and methanol in a weight ratio of 1:1 to obtain 26 parts of bis(1,4-dichloro-5,6-dithiophenolate)nickel-tetra-n-butylammonium (yield rate 70 mol%). Melting point 204-205℃ Elemental analysis value (%) (as C ₂₈ H ₄₀ NCl ₄ S ₄ Ni) C H N Cl S Calculated value 46.75 5.60 1.95 19.71 17.83 Analysis value 46.25 5.73 1.89 19.88 18.01 Synthesis example 3 Synthesis example 2-1 ,4-dichlorobenzene-5,6
-Bis(1-dichloro-5,
6-dithiophenolate) nickel-tetra-n
-26 parts of butylammonium were obtained (yield 77 mol%). Melting point 125-127℃ Elemental analysis value (%) (as C ₂₈ H ₄₂ NCl ₂ S ₄ Ni) C H N Cl S Calculated value 51.70 6.51 2.15 10.90 19.72 Analysis value 51.55 6.67 2.13 11.02 20.10 Synthesis example 4 Chloride of Synthesis example 1 Bis(1,2,4-trichloro-5,6-dithiophenolate)nickel- 13 parts of tetra-n-butylammonium were obtained (yield: 80 mol%). Melting point 146-147℃ Elemental analysis value (%) (as C ₂₈ H ₃₈ NCl ₆ S ₄ Pt) C H N Cl S Calculated value 36.37 4.14 1.51 23.01 13.87 Analysis value 36.40 4.18 1.49 22.98 13.96 Synthesis example 5 Synthesis example 1-1 ,2,4-trichlorobenzene-
1,2,4 instead of 9.0 parts of 5,6-dithiol
The procedure was repeated in the same manner as in Synthesis Example 1 except that 13.3 parts of -tribromobenzene was used to obtain 14 parts of bis(1,2,4-tribromo-5,6-dithiophenolate)nickel-tetra-n-butylammonium ( yield
73 mol%). Sloring point 193-196 ° C element analysis values ( %) (C ₂₈ H ₃₈ NBR ₆ S ₄ Ni) C Hn Class calculation value 31.88 3.63 1.33 45.44 12.69 1.29 44.38 12.22 Examples Add 10 parts of polymethyl acrylate to 45 parts of mixed solvent, and add Synthesis Example 1 to this.
One of the novel halogen-substituted benzenedithiol metal complexes obtained in Steps 5 to 5 or the known bis(1,2,3,4-tetrachloro-5,6-dithiophenolate)nickel-tetra-n-butyl for comparison. Three parts of ammonium was added and dissolved. Thickness 0.2
The above solution was applied to the surface of a polyvinyl chloride film of mm size using a small gravure coating machine to a dry film thickness.
After coating to a thickness of 7 μm, it was dried with hot air at 70°C. After leaving this film in a constant temperature bath at 60°C for 7 days, it was observed under a microscope.
In the film containing nickel-tetra-n-butylammonium (2,3,4-tetrachloro-5,6-dithiophenolate), fine needle-like crystals were observed scattered, whereas in the synthesis example No crystals were observed in the films containing the novel halogen-substituted benzenedithiol obtained in Examples 1 to 5. Example 2 New halogen-substituted benzenedithiols obtained in Synthesis Examples 1 to 5 and, for comparison, the known bis(1,2,3,4-tetrachloro-5,6-dithiophenolate)nickel-tetra-n - A composition prepared by dissolving 3 parts of a type of butylammonium and 5 parts of nitrocellulose in 50 parts of methyl ethyl ketone is applied onto a polyethylene terephthalate film using a spinner and dried under specified conditions to form a coating surface of approximately 1 μm. was formed. After the obtained film was left in a constant temperature bath at 60℃ for 7 days, the test piece was observed with an optical microscope, and it was found that screws (1, 2,
In the test piece containing nickel-tetra-n-butylammonium (3,4-tetrachloro-5,6-dithiophenolate), fine needle-like crystals were observed scattered, whereas in Synthesis Example 1 No crystals were observed at all in the test piece containing the novel halogen-substituted benzenedithiol obtained in Steps 5 to 5. Reference Example 1 (Infrared blocking effect) Among the films obtained in Example 1, bis(1, 2,
4-trichloro-5,6-dithiophenolate)
Using a film made of nickel-tetra-n-butylammonium (hereinafter referred to as film A), the film was placed on the screen and top of a wooden frame measuring 90 cm long, 120 cm wide, and 90 cm high. We installed a Toshiba No. 5 illuminance meter, a Gorchinski solar irradiance meter, and an integrated illuminance meter (Toyo Rika Kogyo, model PH-11).Illuminance (unit: lux), amount of sunlight (unit: cal), and ultraviolet, visible, and infrared radiation. Amount (unit: mW・
min/cm ² ) was calculated and converted into a relative value with the value when not covered (in the field) as 100. The results obtained are shown in Table 2. Film A of the present invention reduced visible light by only 22%, but was effective in reducing the amount of sunlight to about 1/2.

[Table] Reference Example 2 Films prepared by the method of Example 2 Among the films obtained in Example 2, bis(1,4-
Semiconductor laser light (GaAlAs-based laser,
830 nm, optical output 5 mW) linearly swept irradiation.
Observation of the laser irradiated area with an electron microscope showed that the trajectory of the laser beam was extremely clear, and observation with an optical microscope showed that the unirradiated area was green, while the irradiated area turned yellow. It was found that recording with laser light was possible with Film B. Example 3 Bis(1-chloro-5,6-dithiophenolate)nickel-tetra-n-butylammonium
A mixture of 0.15 parts and 100 parts of polymethyl methacrylate resin was pressed at a temperature of 150 degrees and a pressure of 280 kg/
A test piece with a thickness of 1.0 mm was obtained by compression molding in ^cm2 . The obtained test piece has a green color, and the maximum transmittance in the visible region in the wavelength range of 350 to 1100 nm is 70% or more, and the transmittance in the wavelength range of 400 nm or less and 800 to 950 nm is 10%.
% or less, and an optical filter having spectral characteristics close to the visual sensitivity was obtained.

Claims (1)

[Claims] 1. As a near-infrared absorber, the general formula () (In the formula, X is a chlorine or bromine atom, Y and Z are hydrogen or a chlorine atom when X is a chlorine atom, hydrogen or a bromine atom when X is a bromine atom, and N is a nickel, palladium, or platinum atom. A plastic composition that absorbs near-infrared rays, characterized in that it contains a halogen-substituted benzenedithiol metal complex represented by the formula (A represents a quaternary ammonium group).