JPS6268856A - Camouflaging material - Google Patents

Abstract

PURPOSE:To provide a camouflaging material composed of an azo compound having a specific structure and a carrier material, exhibiting the same infrared radiation behavior as green vegetables of e.g. forest, grass land, etc., and indistinguishable from green vegetables by infrared detection. CONSTITUTION:The objective material contains the azo compound of formula III produced by coupling a diazonium salt of an aromatic amine of formula I (n is 1 or 2; when n is 1, R1 is phenyl which may have halogen, methyl, nitro, methoxy, phenoxy, phenylazo or benzoylamino as substituent group; when n is 2, R1 is biphenylene which may have halogen, methyl, methoxy, ethoxy or nitro as substituent group) with the coupling component of formula II (X is H or methyl). The crystal size of the azo compound is preferably 0.3-10mum. The compound is compounded to a binder resin to form a paint or used for the coloring of a synthetic fiber or resin to obtain a camouflaging material.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to camouflage materials, and more specifically,
The present invention relates to a camouflage material that has properties against infrared rays similar to those of green plants such as grasslands.

(Prior Art) Hitherto, it has been widely used militarily to apply camouflage that creates the illusion of objects in the environment for field camouflage. For example, soldiers' clothing, equipment, facilities, etc. in forests and grasslands are usually camouflaged with random patterns of dark and black colors.

(The problem that the invention is trying to solve) However,
Even with improvements in military technology, these camouflages have the disadvantage that they can be easily distinguished from plants and detected using infrared detectors and the like. This is because there is a clear difference between the infrared reflectance of pigments or dyes used as conventional green to black edge colors and the infrared reflectance of natural plants.

Therefore, as military and other camouflage pigments, there is a demand for pigments that have the same or similar infrared ray properties as plants.

(Means for Solving the Problems) As a result of intensive research in response to the above-mentioned demands of the prior art, the present inventor has discovered that an azo compound with a certain structure exhibits almost the same infrared ray properties as plants. The present invention was completed based on the discovery that by using the azo compound to make, for example, a coloring agent, paint, or resin molded product, a camouflage material that cannot be distinguished from green plants by infrared detection can be obtained. did.

That is, the present invention is a camouflage material comprising an azo compound represented by the following general formula (I) and a phase material.

[However, n in the above formula is 1 or 2, or is a hydrogen atom or a methyl group, and when n = 1, R1 is a halogen atom, methyl group, nitro group, methoxy group, phenoxy group, or phenylazo group. Alternatively, it is a phenyl group which may have a benzoylamino group, and when n=2, R1 is a biphenylene group which may have a halogen atom, a methyl group, a methoxy group, an ethoxy group, or a nitro group. ] To explain the present invention in more detail, the azo compound of the above general formula (I) used in the present invention and which mainly characterizes the present invention is a compound represented by the following general formula (II), which is a compound represented by the following general formula (II). It is obtained by a conventional method of coupling to a coupling component represented by formula (m).

R1(NH2)n (II)■ X and R1 in the above formula have the same meanings as above.

When n-1, the compound represented by the above general formula (II) is aniline, 2-nitro-4-methylaniline, 2
-(4”-chlorophenoxy)-5-chloroaniline,
2-Methyl-4-nitroaniline, 2-meth*C4-
Nitroaniline, 2-nitro-4-chloroaniline, 2
-Methyl-4-nitroaniline, 2-aminoanthraquinone, 2-ditro-4-methoxyaniline, 2-methoxy-4(2'-ditro-4'-methylphenyl)azo-
5-methylaniline, 2-chloro-4(benzoyl)amino-5-methoxyaniline, 2,5-dimethoxy-4
Aniline or aniline derivatives such as (4'-nitrophenyl)azoaniline, or aminoanthraquinone, and when n=2, 4,4'-diamino-2,2'
-dichlordiphenyl, 4,4'-diamino-3,3'
-dichlordiphenyl, 4,4'-diamino-3-3'
-dimethyldiphenyl, 4,4'-diamino-3,3'
-dimethoxydiphenyl, 4,4'-diamino-2-nitrodiphenyl, 4,4'-diamino-3-methyldiphenyl, 4,4'-diamino-3,3'-shedodiphenyl, 4,4'-diamino-3,3'-dimethyl-
6,6'-dinitrodiphenyl,4,4'-diamino-
2,2'-dichloro-5,5'-dimethoxydiphenyl,4,4'-diamino-2,2',5.5'-tetrachlorodiphenyl,4,4'-diamino-3,3', 5.
5'-tetramethyldiphenyl, 4,4'-diamino-
Octachlordiphenyl, 4,4'-diamino-diphenyl, etc. are used.

Next, as a method for diazotizing the aromatic amine represented by the above general formula (1'l), a conventional method for diazotizing aromatic amines can be used as is.
A method of obtaining an aqueous solution of a diazonium salt by adding a sodium nitrite solution to a cold aqueous solution of a mineral acid salt of an aromatic amine represented by
-18383 Publication, Publication No. 46-37189, Publication No. 5
6-2102 and Japanese Patent Application Laid-Open No. 49-120923.

As the coupling component represented by the general formula (m) used in the present invention, conventionally known coupling components can be used. For example, the compound represented by the general formula (m) is 2-hydroxy-1',2'- It is obtained by reacting benzocarbazole-3-carboxylic acid or its functional derivative with 0-methoxyaniline or 4-methyl-〇methoxyaniline at a molar ratio of about 1=1, and is obtained by reacting benzocarbazole-3-carboxylic acid or its functional derivative with 0-methoxyaniline or 4-methyl-〇methoxyaniline in a molar ratio of about 1=1, and naphthol AS-3R and naphthol It is commercially available as As-3G.

The azo compound used in the present invention has the above general formula (n)
A diazonium salt of an aromatic amine represented by the general formula (
It is obtained by coupling the coupling component represented by III) according to the conventional method for producing an azo compound.

That is, the double coupling component is added to an aqueous alkaline solution and dissolved by heating, then the solution is cooled to around 25°C, a buffer is added thereto, the pH is adjusted, and then the above general formula (II ) is added dropwise to carry out a coupling reaction in an alkaline environment at room temperature to produce a crude azo compound, which is then filtered, washed with water and dried to obtain the desired azo compound. Furthermore, in the present invention, the coupling reaction can also be carried out in an organic solvent.

According to detailed research by the present inventor, the above azo compound is
It has been found that the best camouflage material is provided when the crystal size is between 0.3 and 10 ILm.

The azo compound used in the method of the present invention produced as described above is dark to black in color and solvent resistant.

It has good light resistance, heat resistance, water resistance, and chemical resistance, and has high tinting power, so it can be used satisfactorily as an azo pigment.

The camouflage material of the present invention consists of a double azo compound and a carrier material. The carrier material in the present invention refers to binder resins conventionally used in pigment textile printing, printing inks, paints, etc., and synthetic fibers such as acetyl cellulose, vinylon, polyester, polyamide, polypropylene, etc. When dyed with a compound as a stock solution, these synthetic fibers are also included in the carrier material of the present invention. Furthermore, using the above azo compound, the above synthetic resins and other thermoplastic or thermosetting resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, polyimide, phenol resin, urea resin, melamine resin, etc. can be colored. When obtaining various colored molded products such as films, sheets, etc., these thermoplastic and thermosetting synthetic resins are also included in the carrier material in the present invention.

Therefore, one example of the camouflage material of the present invention corresponds to one in which the azo compound of general formula (I) is used in place of the conventional pigment in liquid materials such as conventional pigment printing agents, printing inks, and paints. However, in these examples, as in the prior art, the azo compound of formula (1) is generally used in a proportion of about 0.1 to 50 parts by weight based on 100 parts by weight of the liquid material. Generally, the carrier material is used in an amount of 1 to 30 parts by weight, and the medium is used in an amount of 10 to 95 parts by weight.

In addition, in colored synthetic fibers or colored resin molded articles, which is another example, the azo compound of the general formula (I) may be used to the extent that the fibers or molded articles can be substantially colored, for example, 0.
．． It is generally included in a proportion of 1 to 30% by weight.

The camouflage material of the present invention as described above may be a liquid material as described above, a colored fiber or a resin molded product as described above, and any of them may be made of conventionally known pigment printing agents, paints, and printing inks. It can be obtained by a manufacturing method, a method of coloring with a stock solution, or a method similar to the method of coloring and molding synthetic resins.

(Action/Effect) The camouflage material of the present invention as described above can be used as a conventional pigment printing agent,
It can be used in the same way as paints and printing inks, and is useful for printing woven and non-woven fabrics, painting various articles, and printing.
By imparting a black coloration, these colored articles can be made to have infrared ray properties similar to those of natural green plants.

The same applies when the camouflage material of the present invention is colored fibers or molded articles, and provides fibers or molded articles that have properties against infrared rays similar to those of green plants.

Therefore, by using the camouflage material of the present invention to camouflage various military equipment, equipment, and facilities, it is possible to camouflage them so that they are not detected by infrared detectors from green plants in the environment.

Next, the present invention will be explained in more detail with reference to Examples. In the text, parts and percentages are based on weight unless otherwise specified.

Example 1 0901 mol of 2-nitro-4-methylacholine was suspended in 11.3 parts of glacial acetic acid, and 3.7 parts of concentrated hydrochloric acid was added thereto and stirred. Add 2.6 parts of water to this, maintain the temperature at 0~5°C, add 2.0 parts of 40% sodium nitrite aqueous solution,
The mixture was stirred at the same temperature for about 30 minutes to obtain a yellow diazonium salt solution.

4.8 parts of sodium acetate trihydrate was added to this to prepare a diazonium salt solution.

Separately, 1 mol of naphthol AS7SGO,O was suspended in 250 parts of 0-dichlorobenzene; the above diazonium salt solution was added at 20 to 30°C, and 20 parts of glacial acetic acid was added while maintaining the temperature at 30 to 40°C. Coupling was performed by keeping at this temperature for 5 to 6 hours to obtain an azo compound. The azo compound has a black appearance.

Example 2. 0.01 mol of dianisidine is dissolved in 45 parts of dimethylpolamide and cooled to 0°C. 050 in this
6 mol of hydrochloric acid is added dropwise and stirred for 60 minutes to form a hydrochloride salt. Furthermore, 0.02 mol of sodium nitrite dissolved in 4 parts of water is added dropwise to carry out diazotization for 60 minutes.

On the other hand, 0.02 mol of naphthol AS-SG is dissolved in 60 parts of dimethylformamide, and 0.09 mol of sodium acetate is dissolved in 24.5 parts of methanol, and these are added to the above solution. While stirring this subsoaking solution, the above diazonium solution was slowly added dropwise at 20 to 30°C.
The coupling reaction was carried out at ℃ for 2 hours to obtain a black azo compound.

Examples 3 to 14 The following general formula (
The azo compound used in the present invention was obtained using the compound II) and the compound of general formula (m).

Shimuki 1" Compound of formula H; 2-(4'-chlorophenoxy)
-5-Chloraniline- ■ H: Naphthol AS-SR Color-1; Slightly reddish black color - General (■ Compound: 2-methyl-4-nitroaniline - ■ H; Naphthol AS- , SR death-1; black support 1J - ■: 2-methoxy-4-nitroaniline- (■; naphthol AS-3R color-1; black color - I■; 2-nitro- 4-Methylaniline-m Noshi: Naphthol AS-5G color-1; Slightly bluish black color 11-■ Hi; 2-nitro-4-chloroaniline-■ Noshi; Naphthol AS-5G color-1; Slightly greenish black color J - ■ 2-Methyl-4-nitroaniline - ■ Naphthol AS-5G - 1; Slightly reddish black color - H; 2- Methoxy-4-nitroaniline - ■ H; Naphthol As-5G -1; Slightly greenish black branch m General (Compound H; Compound of "Flavored black fruit" 2 "I: 2-nitro-4-methoxyaniline - Naphthol As-5G";
Slightly bluish black color ■Yu λ-II; 2-methoxy-4(2'-nitro-4'-methylphenyl)azo-5-methylaniline; Naphthol AS-5G; 1; Slightly greenish black color J-I■: 2-chloro-4-benzoylamino-5-methoxyaniline-■; Naphthol AS-5G color-1; Slightly greenish black color 2,5-dimethoxy-(
4'-nitrophenyl)azoaniline-■ Nohi;
Naphthol AS-SG - 1; slightly greenish black Example 15 30 parts of acrylic acid ester emulsion (active agent free type, solid content 40%) Example 1
Azo compound obtained in 35 parts antifoaming agent
0.5 part powder 1 part Daimonex E H-6 (manufactured by Dainichiseika)
3 parts turpentine 15 parts methanol 8 parts A paste-like black paste containing an azo compound dispersed in the above recipe was combined with 1% ethyleneimine crosslinking agent, and was silk screened onto entrance cloth (manufactured by Toshi). Print, 120℃,
A black print is obtained by curing for 15 minutes. When the infrared reflectance of the printed portion of this printed product was measured, as shown in FIG. 1, it was similar to the infrared reflectance of a green plant.

Example 16 Azo compound obtained in Example 2 17 parts Thermoplastic acrylic resin 70 parts Doluol
6.8 parts pheasant roll
3.2 parts butanol 2.
Two parts of the above composition were dispersed in a ball mill to obtain a black paint. When this was applied to a steel plate to form a coating film and the infrared reflectance of the coating film was measured, the same results as in Example 15 were obtained.

Example 17 Flashed color of the azo compound obtained in Example 3 (purity 5
0%) 38.0 parts Mixed varnish for offset lithographic ink 60.0 parts 5% cobalt dryer 0.2 parts 8% manganese dryer 1.0 parts The above components were thoroughly mixed within the mixing line to obtain an offset printing ink. When solid printing was performed on high-quality paper using this printing ink and the infrared reflectance thereof was measured, the same results as in Example 15 were obtained.

Example 18 0.5 part of the azo compound obtained in Example 4 and Pansolve H1,
The kneaded mixture of θ part and 50 parts of polyvinyl chloride resin compound was mixed with 50 parts of polyvinyl chloride resin compound, and heated at 155 to 160°C using a 6-inch roll.
The mixture was roll-kneaded for 3 minutes to form a sheet, and this sheet was press-molded at 170° C. and a pressure of 50 kg to a thickness of 5 m to obtain a colored sheet with black edges. When the infrared reflectance of this sheet was measured, the same results as in Example 15 were obtained.

The same results as in Example 15 were obtained when the azo compounds obtained in Examples 6 to 14 were colored in the same manner as in Examples 15 to 18.

[Brief explanation of drawings]

Figure 1 shows the infrared reflectance curve (dashed line) of natural green plants.
and shows the infrared reflectance curve (solid line) of the camouflage material obtained in Example 15.

Claims (2)

[Claims] (1) A camouflage material comprising an azo compound represented by the following general formula (I) and a carrier material. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [However, n in the above formula is 1 or 2, X is a hydrogen atom or a methyl group, and when n = 1, R1 is a halogen atom, A phenyl group which may have a methyl group, a nitro group, a methoxy group, a phenoxy group, a phenylazo group or a benzoylamino group, and when n=2, R1 is a halogen atom, a methyl group, a methoxy group, an ethoxy group or a nitro group. It is a biphenylene group which may have a group. ] (2) The crystal size of the azo compound is 0.3 to 10 μm
A camouflage material according to claim (1).