JPS6230166A - Camouflaging material - Google Patents

Abstract

PURPOSE:To provide a camouflaging material for military use, composed of a specific azo compound and a carrier material and indistinguishable from green vegetables of forest and grassland by an infrared detector. CONSTITUTION:The objective material is composed of (A) an azo compound of formula I (X and Y are H or halogen; l and m are 1-4; R1 is phenylene or biphenylene which may have halogen, methyl, methoxy, ethoxy or nitro group as substituent group; n is 1 or 2; when n is 1, R2 is phenyl which may have halogen, methyl, methoxy, ethoxy, nitro, acetylamino or benzoylamino as substituent group; when n is 2, R2 is phenylene or biphenylene which may have the substituent group similar to that of R2 wherein n is 1) and (B) a carrier material. The azo compound of formula I can be produced by coupling the compound of formula II to the coupling component of formula III.

Description

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

(Prior art) Traditionally, it has been widely practiced in the military to apply camouflage that creates the illusion of objects in the environment as a disguise for field battles.For example, soldiers' clothing in forests, grasslands, etc. Equipment, facilities, etc. are usually decorated with random green and black camouflage.

(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 CI) and a carrier material.

However, X and Y in the above formula are hydrogen atoms and halogen atoms, and m are integers of 1 to 4, and R1 is
A phenylene group or biphenylene group which may have a halogen atom, methyl group, methoxy group, ethoxy group, nitro group, n is 1 or 2, and when n is 1, R
2 is a phenyl group which may have a halogen atom, a methyl group, a methoxy group, an ethoxy group, a nitro group, an acetylamino group, or a benzoylamino group; when n is 2, n
has the same substituent as R2 when is 1, and is a fuzzy phenylene group or biphenylene 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 (11), which is a compound represented by the following general formula (11). It is obtained by coupling the coupling component represented by (m) according to a conventional method.

N-R1-Nl2 In the above formula, R1, X, m, R2, Y, l and n have the same meanings as above.

The compound represented by the above general formula (II) is conventionally known. For example, an example of the method for producing 5A is 3-imino-1-oxoisoindoline or 3,3-dichloro-1-oxoisoindoline. Per mole of isoindoline or its nuclear chlorinated derivative or nuclear chlorinated derivative,
Reacting about 1 mole of phenylenediamine or diphenylenediamine or its phenyl group with phenylenediamine or diphenylenediamine which may have a halogen atom, methyl group, ethyl group, methoxy group, ethoxy group, nitro group, etc. It can be easily obtained by Conventionally known diamines can be used as such diamines, such as l,4-diamino-2-chlorobenzene, 1,4-diamino-2-methylbenzene, and 1,4-diamino-2-methylbenzene.
Diamino-2,5-dimethylbenzene, 1.4-diamino-2-nitrobenzene, 1.4-diamino-2-methyl-5-methoxybenzene, 1.4-diamino-2-methoxybenzene, 1.4 -diamino-2,5-diethoxybenzene, 1,3-diamino-benzene, l,3-diamino-4-methylbenzene, l,3-diamino-4-
Chlorbenzene.

1.3-diamino-4-methoxybenzene, 1°3-diamino-2,4,5,6-titrachlorobenzene, 1.
4-diamino-2,3,5,6-titrachlorobenzene, 1,2-diamino-benzene, 1,2-diamino-4
-nitrobenzene, 1,3-diamino-2-methylbenzene, 1,4-diaminobenzene, 4,4'-diamino-2゜2'-dichlorodiphenyl, 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'-jethoxydiphenyl, 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'
-tetrachlororephenyl, 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 (II), a conventional method for diazotizing aromatic amines can be used as is.
), a sodium nitrite solution is added to a cold aqueous solution of a mineral acid salt of an aromatic amine, and the mixture is stirred for a while under cooling to form a diazonium salt, thereby obtaining an aqueous solution of a diazonium salt.
This can be carried out by the methods disclosed in JP-A No. 5-18383, JP-A No. 46-37189, JP-A No. 56-2102, and JP-A-49-120923.

As the coupling component represented by the general formula (III) 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'-benzocarbazole-3-carboxylic acid or its functional derivative and aromatic monoamine in a molar ratio of about 1:1.

or 2-hydroxy-11-H-
benzo[a]carbasoleic acid or its functional derivative and aromatic diamine in a mixture of about 2:
The aromatic monoamine used is an aniline derivative having a halogen atom, methyl group, methoxy group, ethoxy group, nitro group, acetylamino group, etc. in addition to aniline. , for example o. m. p-chloroaniline, 0, m.p. p-methylaniline, 0, I]]. p-methoxyaniline, 0, m, p
-Ethoxyaniline, o,m,p-nitroaniline, 0
, m. p-acetylaminoaniline, 2-methyl-4-
Chloraniline, 2-methyl-5-chloroaniline, 2
．． 4-xylidine, 2-methoxy-5-chloro2-leaniline, 2-methoxy-5-bromoaniline, 2-methyl-
4-Methoxyaniline, 2,5-dimethoxy-5-chloroaniline, 2,5-dimethoxy-4-chloroaniline, 2.

Examples include 5-dimethoxy-4-benzoylaminoaniline. The aromatic diamine is as mentioned above. The coupling components, such as the two legs, are all well-known compounds in the art.

The azo compound used in the present invention has the above general formula (I
It can be obtained by coupling a diazonium salt of an aromatic amine represented by I) with a coupling component represented by general formula (m) according to a conventional method for producing an azo compound.

That is, the above coupling component is added to an aqueous alkaline solution and dissolved by heating, and then the solution is cooled to around 25 ° C.
A buffer was added thereto, the pH was further adjusted, and then an aqueous solution of the diazonium salt of the aromatic amine represented by the above general formula (II) was added dropwise to carry out a coupling reaction in an alkaline environment at room temperature, resulting in a crude azo compound. 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.

The azo compound used in the method of the present invention produced as described above has vS green to . It is black, solvent resistant, light resistant,
It has good heat resistance, water resistance, and chemical resistance, and has high coloring power, so it can be used satisfactorily as an azo pigment.

The camouflage material of the present invention consists of the above azo compound and a carrier material. Here, the carrier material in the present invention refers to binder resins conventionally used in pigment textile printing, printing inks, paints, etc., and synthetic fibers 1 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. hand,
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 (I) 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 the case of colored synthetic fibers or colored resin molded articles, which is another example, the azo compound of the general formula CI) 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 fabrics, non-woven fabrics, painting various articles, and printing.It gives a dark green to black color and improves the infrared rays of these colored articles to a natural green color. It can have properties against infrared rays similar to those of 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 addition, unless otherwise specified, ``parts'' or ``%'' in the text are ¥3,000 unless otherwise specified.
It is a standard.

Example 1 3.75 parts of 3-(4-7minophenylimino)-1-
Oxo-4,5,6,7-titrachloroisoindoline was suspended in 11.3 parts of glacial acetic acid, and 3.7 parts of concentrated hydrochloric acid was added to the suspension.
1 part and stirred. Add 2.6 parts of water to this and the temperature θ~
The temperature was maintained at 5°C, 2.0 parts of a 40% aqueous sodium nitrite solution was added, and the mixture was stirred at the same temperature for about 30 minutes to obtain a yellow diazonium salt solution. Add to this 4. sodium acetate trihydrate.
A solution of diazonium salt was prepared by adding 8 parts.

On the other hand, 2-hydroxy-N-(4-methoxyphenyl)
-11 Taidenzo(a)-Carbazole-3-carboxamide (3.82 parts) was dissolved in 9.9 parts of 0-dichlorobenzene (250 parts). The above diazonium salt solution was added at 5.20 to 30°C, and 20 parts of glacial acetic acid was added while maintaining the temperature at 30 to 40°C. Keep at this temperature for 5 to 6 hours to perform coupling.
An azo compound was obtained. The azo compound exhibits a black color and 3
It has a decomposition point of 73°C.

Example 2 Diazotized 3-(3'-7minophenylimino)-
3.7 parts of a diazo compound prepared by reacting 1-oxo-4,5,6,fuchtrachloroisoindoline with piperidine in an alkaline medium and 1,4-bis-[2-hydroxy-11-H- Benz [a] - Rubazol - 3
6.3 parts of -carbonylaminocobenzene and 6.3 parts of 0-dichlorobenzene were suspended in 300 parts of 0-dichlorobenzene, and the mixture was heated to 70 to 75°C and 20 parts of glacial acetic acid was added thereto. Then heat the mixture to 120-130℃
When the mixture was stirred for 2 hours, coupling proceeded and an azo compound was obtained. The azo compound exhibits a slightly reddish black color, and
It has a decomposition point of 42°C.

Examples 3 to 11 The following general formula (
The azo compound used in the present invention was obtained using the compound II) and the compound of general formula (III).

3-(4'-aminophenylimino)
-1-year-old xo4,5゜6.7-titrachlorisointhrin- ヱ■ nohi ;2-hydroxy-N-(2'-
Methyl-4'-methoxyphenyl)-11-H-benzo(a)-rubazole-3-carboxamide Color-1: Slightly reddish black External temperature: 359°C H ;3-(2',5'-dichloro-4'-7minophenylimino)-1-oxo-4,5
, 6,7-titrachloroisoindoline-■;2-hydroxy-N-(2'-methyl4'-methoxyphenyl)-11-H-benz
)-Carhezol-3-Lupoxyamide Color-11 Black Vertical MΔ; 341"0Xh1" -E II H ;3-(2'+5'-dimethyl-4'-aminophenylimino)-l-oxo4. 5
, 6.7-titrachloroisoindoline-■;2-hydroxy-N-(2'-
ethyl phenyl)-11-H-benzo(a)-rubazole-3-carboxyamide-1; Slightly reddish black. Methyl-5'-chloro-
4'-7minophenylimino)-1-oxo-4,5,
6,7-titrachloroisoindoline-m:2-hydroxy-9-chloro-
N-(4'-methoxyphenyl)=11-H-benzo(
a) -Rubazole-3-carboxamide color-1, black 汰鼠Δ;369℃夾电舊1-II的磷;3-(3',3″-dimethyl-4
″-aminobiphenyl-4-ylimino)-1-oxo-4,5,6,7=tetrachloroisoindoline-■: Bis-2-hydroxy-N-(3'-
methylphenyl)-11-H-benzo[a]-carboxyamide color-1; black Note: 347°C 3”-dichlor-4
″-aminobiphenyl-4-ylimino)-1-oxo-4,5,6,7-titrachloroisoindoline- ■ 1,4-bis[2′-hydroxy-11-H-benza(a) -Carbazole-3-carbonylaminocobenzene Color-1; Black Curtain Δ; 342°C Fruit" 11 Temperature-1II Heat; 3-(3'-aminophenylimino)-1-oxo-4,5°6 .7-Titrachlorinindoline - ■ Chemical composition: 2-Hydroxy-N-(4'-methoxyphenyl)-11-H-benzo(a)-rubazole-3-carboxamide Color-1; Black Meng; 359℃ flame sub-II; 3-(5'-chloro-3'aminophenylimino)-1-year-old xo 4.5,6.7-titrachloroisoindoline; ■; 2 -Hydroxy-N-(2'-
Methyl-4'methoxyphenyl)-11-H-benz(
a) -Carbazole-3-carboxyamide color-1; Slightly bluish black Tachime J; Heat at 345℃ ■
Compound of ~■: 2-hydroxy-N-(2'-
Ethylphenyl)-11-H-benzo[a]-rubazole-3-carboxamide color; slightly reddish black Note 4: 375°C Example 12 Acrylic acid ester emulsion (activator-free type, solid content: 40 %) 30 copies Example 1
35 parts of the azo compound obtained as an antifoaming agent
0.5 part dispersant
Part 1 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 and heat at 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 13 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 12 were obtained.

Example 14 Flushed water 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 12 were obtained.

Example 15 0.5 part of the azo compound obtained in Example 4 and Pannrup H1,
The mixture was mixed with 50 parts of polyvinyl chloride resin compound, and rolled into a 155-160"
A sheet was formed by roll kneading for 3 minutes at 170" C!, and this sheet was press-molded into a 5-part thick sheet at 170" C! under a pressure of 50 kg to obtain a colored sheet with a black border.Infrared reflection of this sheet When the ratio was measured, the same results as in Example 12 were obtained.

Example 16 10 parts of the azo compound obtained in Example 5, 1 part of the dispersant and 89 parts of ethylene glycol were ground in a ball mill, and 15 parts of this ground product was obtained from 1 mole of dimethyl terephthalate and 2 moles of ethylene glycol. transesterified product 1
00 parts and heated and polymerized at about 280° C. for 4 hours under reduced pressure to obtain a uniformly and beautifully colored black polyester. When we measured the infrared reflectance of a woven fabric made of black fibers obtained by spinning this colored polyester according to a conventional method, we found that
Similar results as in Example 12 were obtained.

In addition, those colored in the same manner as Examples 12 to 16 using the 1-liquid azo compounds in Examples 6 to 12 showed excellent infrared reflectance.

[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 12. (%)

Claims (1)

[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, in the above formula, X and Y are hydrogen atoms or halogen atoms, l and m are integers from 1 to 4, and R
1 is a phenylene group or biphenylene group which may have a halogen atom, methyl group, methoxy group, ethoxy group, or nitro group, n is 1 or 2, and when n is 1, R2 is a halogen atom , a phenyl group which may have a methyl group, a methoxy group, an ethoxy group, a nitro group, an acetylamino group, a benzoylamino group, and when n is 2, the same substituent as R2 when n is 1 is a phenylene group or biphenylene group which may have ]