JPS63165392A - Novel t-butyl-substituted benzenedithiol nickel complex and plastic composition containing said complex - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula (A represents quaternary ammonium salt). EXAMPLE:Bis(4-t-butyl-1,2-dithiophenolate)nickel-tetra-n-butylammonium. USE:A near infrared ray absorber used for agricultural films, sunglasses, filter of window, etc., wavelength sensitivity compensation filter of photoelectric conversion element, heat-mode recording medium by semi-conductor laser beams, etc., by being incorporated in plastics, and especially useful for sunglasses, etc. because light-colored plastics can be obtained. PREPARATION:For example, 4-t-butylbenzene-1,2-dithiol is initially dispersed in a solvent such as THF, etc., and nickel chloride is added thereto to form a nickel complex. Then, a quaternary ammonium halogenide is added thereto to carry out the reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel t-butyl-substituted benzenedithiol nickel complex and a plastic composition containing the same as a near-infrared absorber.

(Prior art) Already known, for example, bis(1,2-dithiophel-1.
) Nickel ~ Tetra n-butyl ammonium, bis(
4-Methyl-1,2-cuthiof1-root)nickel-tetra-n=butylammonium, bis(3,4,5,6
-tetramethyl-1,2-didiopherto)nickel-tetra-n-butylammonium and bis(3,4
゜5.6-tetrachloro-1,2-dithiofert)
Ortho-benzenedithiol metal complexes such as nickel-tetra-n-butylammonium are known to exhibit a unique absorption spectrum in the near-infrared region, and these metal complexes have excellent thermal stability d3 and weather resistance. It is important as a near-infrared absorber because of its excellent
5551).

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 create industrial films and glare absorbers for selectively utilizing sunlight. In order to prevent eye fatigue, research is being conducted on its use in sunglasses, welding glasses, aircraft windows, and VDT (visual display terminal) filters. In recent years, it has been used in optical filters to compensate for the wavelength height characteristics of optical conversion elements such as photodanoodes and light-emitting diodes. Furthermore, since these near-infrared absorption regions match the oscillation wavelength of a semiconductor laser, they are important as an absorbing heat storage agent at the tip of the sheath 11 for semiconductor laser light recording, that is, laser heat mode recording.

However, when conventionally known metal complexes of benzenedithiols are coated with plastics as near-infrared absorbers or kneaded into plastic snacks and used as films or plates, the metal complexes may turn into plastics after long-term use. The phenomenon of crystallization occurs. For this reason, PJII which has been given high near-infrared absorption ability through a coating method! It was impossible to make J. In view of this situation, the present inventors have already developed special penpine dithiols, namely 3,4.6-t-lichloro-1,2-dithiol, 3,6-cyclobenzene-1
, 2-dithiol and 3-chlorobenzene-1,2-
We would like to propose a method for increasing compatibility with resins by using metal complexes using dithiol as a ligand (Japanese Patent Application Laid-Open No. 58-105996).

(Problem to be Solved by the Invention) However, these complexes also have relatively strong absorption in the visible light region and exhibit dark colors, making them unsuitable for use in sunglasses and VDT filters where color tone is important. A near-infrared absorber that can absorb light is desired.

(Means for solving the problem) Therefore, as a result of further research, it was found that it is possible to lighten the color by using nickel complexes with 4-t-butylbenzene-1,2-dithiol as a ligand. This discovery led to the present invention. In other words, the novel t-butyl-substituted benzenedithiol metal complexes of the present invention have excellent compatibility with various resins compared to known complexes, and even when the addition ratio is increased, the resins remain stable for long periods of use. Not only does it not cause crystallization, but when compared with a constant absorbance in the near-infrared region, the absorption of visible light is weak, making it possible to lighten the color.

Specifically, the present invention provides a t-butyl-substituted (wherein A represents a quaternary ammonium group) benzenedithiol nickel complex represented by the general formula (I), and the present nickel complex is The present invention also provides a plastic composition that absorbs near-infrared rays and contains it as an infrared absorber.

A typical example of the novel t-butyl-substituted benzenedithiol nickel complex of the present invention is bis(11-t-butyl-1,2-didiophelto)nickel-tetra-n-butylammonium, which has a quaternary ammonium group. There are complexes in which the tetra-n-butylammonium group is replaced with a tetra-n-propylammonium group or a trioctylmethylammonium group. In addition, to produce the nickel complex of the present invention, 4-t-butylbenzene-1,2-didiol is dissolved or dispersed in a suitable solvent, and a metal W capable of supplying nickel ions, such as nickel chloride or nickel acetate, is added to the solution. After adding a predetermined amount of nickel to form a nickel complex, a desired quaternary ammonium halobnide is added to a predetermined amount, or
Alternatively, by reacting a desired quaternary ammonium halobide with an alkali, adding 1 quart of quaternary ammonium hydroxide and reacting the same, a desired novel t-butyl-substituted benzenedithiol nickel 111 substance can be obtained. I can do it.

In this production method, a solvent is required when reacting t-butyl-substituted benzenedithiol with nickel ions, but preferably te-1-rahydrofuran and absolute ethanol, which easily dissolve t-butyl-substituted benzenedithiol, are used, but methanol, The reaction may be carried out in a state in which t-butyl-substituted benzenedithiol is dispersed in an alcohol such as ethanol or isopropanol.

In addition, nickel, ions, and quaternary
As a theoretical base, the class ammonium ion is 0.5 mol equivalent per 1 mol equivalent of t-butyl-substituted benzenedithiol.
Requires.

Further, the present invention provides a new Q t-
A butyl-substituted benzenedithiol nickel complex is used as a near-infrared absorber, and a near-infrared absorbing plastic composition containing the same is also provided.
This lifting platform has transparency and r
JM It is possible to use plastics that have been immersed in the material. For example, polyesters such as polyethylene terephthalate, cellulose esters such as 21-0 cellulose and cellulose triacede, polyolefins such as polyethylene and polypropylene, and polyacrylic resins such as polymethyl acrylate and polymethyl methacrylate. , polyvinyl chloride, polynylidene chloride, vinyl chloride/vinyl acetate copolymer, polyvinyls such as polystyrene, and polycarbonate, and it is possible to select a plastic that matches the purpose of imparting near-infrared absorbing ability.

Further, t- represented by general formula (I) in this invention
The proportion of butyl-substituted benzenedithiol nickel complexes in plastics varies depending on the type of plastic desired, the thickness of the plastic, and the intensity of light absorption, but nickel complexes crystallize from the plastic during long-term use. In order to prevent the plastic from becoming oxidized and to maintain the mechanical properties of the plastic, it is desirable to add about 50% by weight or less.

Further, a method of molding using a plastic composition that absorbs near infrared rays according to the present invention, that is, a method of molding using a plastic composition that absorbs near infrared rays, that is,
Methods for adding and retaining the t-butyl-substituted benzenedithiol nickel complex represented by (1) into the plastic when creating a plastic molded article, that is, mixing the nickel complex into a plastic powder or pellet; A method for obtaining a plastic snack molded product in a desired shape by melting and compression or extrusion molding, and (2) a method for applying a nickel complex represented by general formula (I) on the surface of a base material to be imparted with near-infrared absorbing ability. There is a method of forming a near-infrared absorbing layer by applying a polymer solution or dispersion containing the above. In these methods, stabilizers, plasticizers, antioxidants, ultraviolet absorbers, etc. may be added as necessary.

(Function) Thus, the composition of the present invention allows the t-butyl-substituted benzenedithiol nickel complex represented by the general formula (I) to be contained in a plastic at a high Width value, and absorbs the resulting near-infrared rays. The composition is used in agricultural films for the selective use of sunlight, sunglasses to prevent glare and eye fatigue, welding glasses, aircraft window or VDT filters, photodiodes, light emitting diodes, etc. It can be used as a filter for compensating the wavelength sensitivity characteristics of photoelectric conversion elements, and also as a recording medium for P1 mode recording by semiconductor laser light whose oscillation wavelength is in the near-infrared region, especially for sunglasses and VDTs.
Suitable for use in filters that require light coloring in the visible light range.

(Example) Examples are shown below. In addition, the part in an Example shows a Sengoku part.

'Example 1 4.2 parts of 4-t-butylbenzene-1,2-didiol was dissolved in 200 parts of absolute ethanol, and while stirring,
When a solution prepared by dissolving 2.4 parts of nickel chloride 6 in water at 25 parts of ethanol is added, the color changes to yellow-green. Then tetra-n-
After adding 3.5 parts of butylammonium bromide and continuing stirring for 2 hours, the reaction solution was distilled under reduced pressure and concentrated to about 175%.

Then, filtration was performed to obtain 7.0 parts of solid. Next, reconsolidation is performed from a mixture of dichloromethane and methanol in a weight ratio of 1:2, and yellow-green bis(4-t-butyl-1,2-dithioferrate)nickel-te-1-ra-n-butylammonium 5. 8 parts were obtained (yield: 84 mol%).

Melting point 154-155℃ Elemental analysis value C (%) 1 (%) N (%) S (
%) Calculated value 62.32 8.72 2.0
218.48 (as C36H6oN S 4 N i ) Analysis value 61.55 8.93 1.991
8.14 Absorption characteristics (acetone solvent) Maximum absorption wavelength 878 parts m Molar extinction coefficient 14400 Example 2 Instead of 3.5 parts of tetra-n-butylammonium bromide in Example 1, 7 parts of caustic potassium was added in advance to 25 parts of ethanol.
．． A yellow-green bis(4- 6.3 parts of t-butyl-1゜2-dithioferrate) nickel-trioctylmethylammonium (yield: 78
mole%).

Melting point 148-151℃ Elemental analysis value C (%) H (%) N (%) S (%
) Calculated value 65.91 9.59 1.71
15.64 (as C45H76N S 4 N!) Analysis (ii 65,37 9.73 1.
6815.53 absorption characteristics (acetone solution W) Maximum absorption wavelength 875 parts m Molar specific extinction coefficient 13800 Example 3 10 parts of polymethyl acrylate was added to a mixed solvent of 45 parts of acetone and 45 parts of toluene, and Examples 1 and 2 were added.
and the known bis(3,4,5,6-tetrachloro-1,2-dithioph 1
Root) Nickel-tetra-n-butylammonium 3
Each portion was dissolved. The above solution was coated on the surface of a polyvinyl chloride film with a thickness of 0.2 m using a small gravure coater so as to have a dry film thickness of 7 microns, and then 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(3,4,5,6-tetrachloro-1,2-didiophyl-h)nickel-tetra-n-butylammonium The film containing the bis(
4-1-butyl-1,2-dithioferrate) nickel-tetra-n-butylammonium and bis(4-
No crystals were observed in the film containing nickel-trioctylmethylammonium (t-butyl-1,2-dithioferlate). Furthermore, the appearance of all the films is pale yellow-green, while the
, 5,6-tetrachloro-1,2-dithiophelate)
The film containing nickel-tetra-n-butylammonium had a dark green color.

Example 4 In a solution prepared by dissolving 5 parts of nitrocellulose and 50 parts of methylethylcane, the 17 nickel complexes of Examples 1 and 2 and the known bis(3°4.5.6-tetrachloro-1) were added for comparison. , 2-dithiofert), nickel-tetra-n-butylammonium, and 3 parts of polyethylene terephthalate using a spinner coater.
~ It was applied onto a film and dried to form a coating film of about 1 μm. After placing the 19-treated film in a constant temperature bath at 60°C for 7 days, the test piece was observed with an optical microscope.
In the test piece containing bis(3,4,5,6-tetrachloro-1,2-dithioferrate)nickel-tetra-n-butylammonium, minute crystals were observed scattered, whereas No crystals were observed in the test pieces containing the nickel complexes obtained in Examples 1 and 2, and the coated surfaces had a pale yellow-green appearance. On the other hand, the coated surface containing bis(3,4,5,6-tetrachloro-1,2-dithioferto)nickel-tetra-0-butylammonium had a dark green color.

Reference Example 1 Among the films obtained in Example 4, bis(4-t-butyl-1,2-dithioferrate)nickel-tetra-n
-butylammonium and bis(4-t-butyl-1
, 2-dithioferrate) nickel-trioctylmethylammonium) were focused on the coated surface of the film (GaA IAS laser,
830 nm, optical output 5 mW) was illuminated in a straight line.

As a result of observing the laser irradiated area with an electron microscope, it was found that the trajectory of the laser beam was extremely clear in all films, and the area that was irradiated with the laser beam was groove-shaped. It turned out that it was possible to record.

Example 5 Bis(4-t-butyl-1,2-dithiofert)
Nickel complex 1 Heller n-butyl ammonium 0.15
and 100 parts of polymethyl methacrylate resin at a pressing temperature of 150°C and a pressing pressure of 280 kg/cff.
A test piece with a thickness of 1.0 m++ was obtained by compression molding using a pressurizer. The obtained test piece exhibited a slight ζζ green color and had a 350 to 1 l10
In the 0n wavelength range, the maximum transmittance in the visible region is 85% or more, and is below 400 nm and from 800 to 950 nm.
The transmittance was 10% or less, and an optical filter having spectral characteristics close to the visibility was obtained.

Claims (2)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, A represents a quaternary ammonium group) t-butyl-substituted benzenedithiol nickel complex. (2) As a near-infrared absorber, t-butyl-substituted benzenedithiol nickel is represented by the general formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, A represents a quaternary ammonium group) A plastic composition that absorbs near-infrared rays and is characterized by containing a complex.