JPH0133112B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel halogen-substituted benzenedithiol metal complex and a plastic composition containing the same as a near-infrared absorber. That is, the first invention of the present invention has general formula (1) (In the formula, X is a chlorine or bromine atom, Y and Z
When X is a chlorine atom, hydrogen or chlorine atom,
When X is a bromine atom, hydrogen or a bromine atom is
are nickel, palladium, and platinum atoms, and A is the fourth
It is a halogen-substituted benzenedithiol metal complex represented by a halogen-substituted benzenedithiol metal complex (indicating an ammonium group). Specifically, bis(1,2,4-trichloro-5,6-dithiophenolate)nickel-tetra-n-butylammonium, bis(1,4-dichloro-5,
6-dithiophenolate) nickel-tetra-n
-butylammonium, bis(1-chloro-5,
6-dithiophenolate) nickel-tetra-n
- Methyl ammonium, complexes in which the nickel atom of these metal complexes is replaced with palladium or platinum, and tetra- of quaternary ammonium groups
Complexes in which n-butylammonium group is replaced with tetra-n-propylammonium group or 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
These are complexes in which the tetra-n-butylammonium group of the class ammonium group is changed to a tetra-n-propylammonium group or a trioctylmethylammonium group. The novel halogen-substituted orthobenzenedithiol metal complex of 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, the resin will remain stable even after long-term use. No crystallization occurs. Already known, for example, bis(1,2-dithiophenolate)nickel-tetra-n-butylammonium, bis(1-methyl-3,4-diothiphenolate)nickel-tetra-n-butylammonium, bis( 1,2,3,4-tetramethyl-
(5,6-dithiophenolate) nickel-tetra-n-butylammonium and bis(1,2,
Orthobenzenedithiol 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−Dithiolene als
"Chelatbildner fiir Metalla", Monachieft Fuia Hemy vol. 102, pp. 308-320, 1971 and "Charactarization and Electronic Structures
of Metal Complexes Contain−ing Benzene−
1,2-dithiolate and Related Liga-nds, Journal of the American Society
88, pp. 4870-4875, 1966), and these metal complexes are important near-infrared absorbers because of their excellent thermal stability and weather resistance (JP-A-135551-1983). In other words, these can be kneaded into plastic films or plates as near-infrared absorbers, or a polymer solution containing them can be applied to a substrate to produce agricultural films for selective use of sunlight, glare, and eyeballs. Research is being conducted on its use in sunglasses, welding glasses, aircraft window and television filters to prevent fatigue. Furthermore, in recent years, research has been conducted on the use of optical filters to compensate for the wavelength height characteristics of optical conversion elements such as photodiodes and light-emitting diodes, and because the near-infrared absorption range of these devices matches 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 (Japanese Patent Application Laid-open No.
Except for the metal complexes derived from 56-135463), they are extremely expensive and their use is naturally limited because they are obtained through a complex several-step synthesis reaction. 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 with plastic or kneading it into plastic as a near-infrared absorber and using it as a film or plate, if the amount of tetrachlorobenzenedithiol metal complex added is increased, the tetrachlorobenzenedithiol metal complex will deteriorate over a long period of use. causes the phenomenon of crystallization from plastic.
For example, it is not suitable for imparting a high degree of near-infrared absorbing ability with a thin film formed by a coating method. On the other hand, the halogen-substituted benzenedithiol metal complex of the present invention has high compatibility with resins, etc., 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 of the present invention is extremely useful as a near-infrared absorber having extremely excellent compatibility with resins. The novel halogen-substituted benzenedithiol metal complex of the present invention is a novel halogen-substituted benzenedithiol that was first made possible to synthesize 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-dithiol, obtained by heating and reacting iron powder or iron salts in the presence of sulfur and a polar organic solvent. , 1,4-dichlorobenzene-5,6-dithiol, 1-chlorobenzene-5,6-dithiol, 1,2,4-tripromobenzene-5,6
-dithiol, 1,4-dibromobenzene-5,
6-dithiol, 1-bromobenzene-5,6-
It can be synthesized using dithiol or the like as a raw material. That is, 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,
When is a bromine atom, indicates hydrogen or a bromine atom)
A halogen-substituted benzenedithiol represented by 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 chloroplatinate, is added to this solution. After producing a metal complex of halogen-substituted benzenedithiol, a predetermined amount of a desired quaternary ammonium halide is added, or a quaternary compound obtained by reacting a desired quaternary ammonium halide with an alkali. A desired novel halogen-substituted benzenedithiol metal complex can be obtained by adding a predetermined amount of ammonium hydroxide and causing a reaction. In this production method, a solvent is required when reacting halogen-substituted benzenedithiol with metal ions, and preferably tetrahydrofuran or absolute ethanol, which easily dissolves halogen-substituted benzenedithiol, is used, but alcohols such as methanol, ethanol, isopropanol, etc. The reaction may be carried out in a dispersed state using 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 of the present invention has the same excellent near-infrared absorption ability, thermal stability, and weather resistance as the conventionally known tetrachlorobenzenedithiol metal complex, and also has excellent near-infrared absorption ability, thermal stability, and weather resistance. It was found that it has a high degree of compatibility with plastics, which is not expected with complexes. Therefore, the novel halogen-substituted benzenedithiol metal complex of the present invention is
It has been found that it is possible to incorporate it into plastics at high concentrations as a near-infrared absorber, and that it does not crystallize from plastics even after long-term use. That is, the second invention of the present invention has the general formula ()
A novel halogen-substituted benzenethiol metal complex represented by (hereinafter simply referred to as metal complex) is used as a near-infrared absorber, and a plastic composition that absorbs near-infrared absorption lines is also provided. It is something. 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 complex represented by the general formula () to the plastic in this invention varies depending on the type of plastic desired, the thickness of the plastic, and the intensity of light absorption. Additions of up to about 30% by weight are desirable to prevent metal complexes 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 the present invention, that is, the method of adding and retaining a metal complex represented by the general formula () to plastic, includes (1) when creating a plastic molded article; A method of blending the metal complex into plastic, that is, a method of mixing the metal complex with plastic powder or pellets, melting it, and compressing or extruding it to obtain a plastic molded article of the desired shape;
In addition, (2) there is a method of forming a near-infrared absorbing layer by applying a polymer solution or dispersion containing a metal complex represented by the general formula () to the surface of a base material to which near-infrared absorbing ability is to be imparted. . In these methods, stabilizers, solubilizers, 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. The wavelength sensitivity characteristics of photoelectric conversion elements such as photodiodes and light emitting diodes can be applied to agricultural films for use in sunglasses, welding glasses, aircraft window or television filters to prevent glare and eye fatigue. It can be used as a compensation optical filter and as a heat mode recording medium for semiconductor laser light having an oscillation wavelength in the near-infrared region. Next, Table 1 shows the melting point 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] Examples are shown below. Note that parts in the examples indicate parts by weight. Example 1 9.0 parts of 1,2,4-trichlorobenzene-5,6-dithiol was dissolved in 500 parts of tetrahydrofuran, and while stirring, a solution of 4.2 parts of nickel chloride hexahydrate dissolved in 50 parts of ethanol was added, resulting in a dark green color. 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. Next, reconsolidation was performed from a mixture of dichloromethane and methanol in a weight ratio of 1:3, and bis(1,
(2,4-trichloro-5,6-dithiophenolate) nickel-tetra-n-butylammonium
11.5 parts were obtained (yield 80 mol%). Melting point 138-140℃ Elemental analysis value C (%) H (%) N (%) Cl (%) Calculated value 42.66 4.86 1.78 26.99 (as C ₂₈ H ₃₈ NCl ₆ S ₄ Ni) Analysis value 42.59 4.92 1.72 27.52 S( %) Calculated value 16.27 Analytical value 16.77 Example 2 22 parts of 1,4-dichlorobenzene-5,6-dithiol was suspended in 800 parts of methanol and while stirring, 12.4 parts of nickel chloride hexahydrate was added 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 stirring was continued for 2 hours, after which the reaction solution was concentrated to about 1/5 by distillation under reduced pressure. The mixture was then filtered to obtain 31 parts of a green solid. Next, recrystallization is performed from a mixture of dichloromethane and methanol in a weight ratio of 1:1 to form bis(1,4-dichloro-
26 parts of nickel-tetra-n-butylammonium (5,6-dithiophenolate) were obtained (yield: 70 mol%). Melting point 204-205℃ Elemental analysis value C (%) H (%) N (%) Cl (%) Calculated value 46.75 5.60 1.95 19.71 (as C ₂₈ H ₄₀ NCl ₄ S ₄ Ni) Analysis value 46.25 5.73 1.89 19.88 S( %) Calculated value 17.83 Fractional value 18.01 Example 3 1,4-dichlorobenzene-5,6 of Example 2
-1-chlorobenzene instead of 22 parts of dithiol-
In the same manner as in Example 2 except that 18.5 parts of 5,6-dithiol was used, bis(1-dichloro-5,6
-dithiofrate) 26 parts of nickel-tetra-n-butylammonium were obtained (yield 77 mol%). Melting point 125-127℃ Elemental analysis value C(%) H(%) N(%) Cl(%) Calculated value 51.70 6.51 2.15 10.90 (as C ₂₈ H ₄₂ NCl ₂ Ni) Analysis value 51.55 6.67 2.13 11.02 S(%) Calculated value: 19.72 Analytical value: 20.10 Example 4 Bis(1,2,4 13 parts of platinum-tetra-n-butylammonium (trichloro-5,6-dithiophenolate) were obtained (yield
80 mol%). Melting point 146-147℃ Elemental analysis value C (%) H (%) N (%) Cl (%) Calculated value 36.37 4.14 1.51 23.01 (as C ₂₈ H ₃₈ NCl ₆ S ₄ Pt) Analysis value 36.40 4.18 1.49 22.98 S( %) Calculated value 13.87 Analyzed value 13.96 Example 5 1,2,4-trichlorobenzene of Example 1
1,2,4 instead of 9.0 parts of 5,6-dithiol
14 parts of bis(1,2,4-tribromo-5,6-dithiophenolate)nickel-tetra-n-butylammonium were obtained in the same manner as in Example 1 except for using 13.3 parts of -tribromobenzene ( yield
73 mol%). Melting point 193-196℃ Elemental analysis value C (%) H (%) N (%) Br (%) Calculated value 31.88 3.63 1.33 45.44 (as C ₂₈ H ₃₈ NBr ₆ S ₄ Ni) Analysis value 31.75 3.69 1.29 44.38 S( %) Calculated value 12.16 Analysis value 12.22 Application example 1 Add 10 parts of polymethyl acrylate to a mixed solvent of 45 parts of acetone and 45 parts of toluene, and add Example 1 to this.
- One of the novel halogen-substituted benzenedithiol metal complexes obtained in 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 coated on the surface of a polyvinyl chloride film with a dry film thickness of 7 mm using a small gravure coating machine.
After applying it to a micron thickness, 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 and found that bis(1,2,3,4-tetrachloro-5,6-dithiophenolate)nickel-tetra-n-butylammonium It was observed that fine needle-like crystals were scattered in the film containing Example 1.
No crystals were observed at all in the film containing the novel halogen-substituted benzenedithiol obtained in steps 5 to 5. Application Example 2 The novel halogen-substituted benzenedithiol obtained in Examples 1 to 5 and the known bis(1,
A composition prepared by dissolving 3 parts of one type of nickel-tetra-n-butylammonium (2,3,4-tetrachloro-5,6-dithiophenolate) and 5 parts of nitrocellulose in 50 parts of metal ethyl ketone was prepared using a spinner. It is coated on polyethylene terephthalate film using
A coating surface of 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,
3,4-Tetrachloro-5,6-dithiophenolate) nickel-tetra-n-butylammonium was observed to have scattered fine needle-like crystals, whereas Examples 1 to No crystals were observed in the test piece containing the novel halogen-substituted benzenedithiol obtained in step 5. Reference Example 1 (Infrared blocking effect) Among the films obtained in Example 6, bis(1, 2,
The side of a wooden frame with a length of 90 cm, a width of 120 cm, and a height of 90 cm was prepared using a film using nickel-tetra-n-butylammonium (3,4-trichloro-5,6-dithiophenolate) (hereinafter referred to as film A). A film was placed on the top surface, and an illumination meter (Toshiba, No. 5 illuminance meter), Gorchinski sunshine meter, and integrated illuminance meter (Toyo Rika Kogyo, model PH-11) were installed inside. Illuminance (unit: lux), amount of sunlight (unit: cal), and ultraviolet light. Visible and infrared radiation (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 obtained crystals are as 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.

Reference Example 2 Film prepared by the method in [Table] Among the films obtained in Example 7, bis(1,4-
Semiconductor laser light (GaAlAs-based laser, 830n
m, optical output 5 mW) was swept in a straight line. As a result of observing the laser irradiated area with an electron microscope, the trajectory of the laser beam was extremely clear, and when observed with an optical microscope, the unirradiated area was green, while the irradiated area turned yellow. It was found that recording with laser light was possible with film B. Application example 3 Bis(1-chloro-5,6-dithiophenolate), 0.15 part of nickel-tetra-n-butylammonium and polymethyl methacrylate resin 100
Press the mixture at a temperature of 150℃ and a pressure of 280℃.
A test piece with a thickness of 1.0 mm was obtained by compression molding at Kg/cm ² .
The obtained test piece exhibits 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 the visibility is low. An optical filter with spectral characteristics close to that of the above was obtained.

Claims (1)

[Claims] 1 (1) General formula (1) (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,
is a bromine atom, M is a nickel, palladium or platinum atom, and A is a quaternary ammonium group), a halogen-substituted benzenedithiol metal complex.