JPH0541666B2 - - Google Patents

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an infrared reflective material, and more specifically, the present invention relates to an infrared reflective material that has higher infrared rays than conventional colored materials using black pigments such as carbon black and aniline black. The present invention relates to an infrared reflective material having reflective properties.

(Prior art and problems to be solved by the invention) Conventionally, various articles have been colored black with black pigments such as carbon black, but these black colored products tend to absorb heat, that is, infrared rays. However, there is a problem in that it tends to become extremely hot due to direct sunlight.

Furthermore, if such a black-colored material is used as a heat insulating material, there is a problem that heat radiation due to infrared radiation is large and sufficient heat retention cannot be achieved.

Therefore, there is a need for a black material that reflects infrared rays without absorbing them even when sufficiently colored black.

(Means for Solving the Problems) As a result of intensive research in response to the demands of the prior art as described above, the present inventor discovered that an azo pigment with a certain specific structure has a significantly higher carbon black pigment than a conventional carbon black pigment. It was discovered that an infrared reflective material with excellent infrared reflective properties can be obtained by using the azo pigment to make, for example, a coloring agent, a paint, or a resin molded product. Based on this knowledge, the present invention was completed.

That is, the present invention is represented by the following general formula (),
It is an infrared reflective material consisting of an azo pigment with a crystal size of 0.3 to 10 μm and a carrier material.

[However, n in the above formula is 1 or 2, X is a hydrogen atom or a methyl group, and when n = 1, R ₁
is a phenyl group or anthraquinonyl group which may have a halogen atom, methyl group, nitro group, methoxy group, phenoxy group, phenylazo group or benzoylamino group, and when n=2, R ₁ is a halogen atom, methyl is a biphenylene group which may have a group, a methoxy group, an ethoxy group or a nitro group. ] To explain the present invention in more detail, the above general formula () used in the present invention and mainly characterizing the present invention
The azo pigment is obtained by coupling a compound represented by the following general formula () with a coupling component represented by the following general formula () according to a conventional method.

X and R ₁ in the above formula have the same meanings as above.

As a compound represented by the above general formula (),
When n=1, aniline, 2-nitro-4-methylaniline, 2-(4'-chlorophenoxy)-5
-Chloraniline, 2-methyl-4-vitroaniline, 2-methoxy-4-nitroaniline, 2-
Nitro-4-chloroaniline, 2-methyl-4-
Nitroaniline, 2-aminoanthraquinone, 2
-Nitro-4-methoxyaniline, 2-methoxy-4-(2'-nitro-4'-methylphenyl)azo-5-methylaniline, 2-chloro-4-(benzoyl)amino-5-methoxyaniline, 2, 5
-Aniline or aniline derivatives such as -dimethoxy-4-(4'-nitrophenyl)azoaniline or aminoanthraquinone, when n = 2,
4,4'-Diamino-2,2'-dichlorodiphenyl, 4,4'-diamino-3,3'-dichlorodiphenyl, 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'-diethoxydiphenyl enyl, 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'-tetrachlor Diphenyl, 4,4'-diamino-3,3',
5,5'-tetramethyldiphenyl, 4,4'-diamino-octachlordiphenyl, 4,4'-diamino-diphenyl, etc. are used.

Next, for the method of diazotizing the aromatic amine represented by the above general formula (), the conventional method for diazotizing aromatic amines can be used as is. For example, the aromatic amine represented by the general formula () A method for obtaining an aqueous solution of a diazodinium salt by adding a sodium nitrite solution to a cold aqueous solution of a mineral salt of an amine and stirring for a while under cooling to diazotize the solution; This can be carried out by the method disclosed in Japanese Patent Application Laid-Open No. 49-120923.

As the coupling component represented by the general formula () used in the present invention, conventionally known coupling components can be used. For example, the compound represented by the general formula () is 2-hydroxy-1',2'- Benzocarbazole-3-carboxylic acid or its functional derivative and 2-methoxyaniline or 2-methoxy-4-
It is obtained by reacting with methylaniline in a molar ratio of about 1:1, and is commercially available as naphthol AS-SR and naphthol AS-SG.

The azo pigment used in the present invention is produced by combining the diazonium salt of an aromatic amine represented by the above general formula () and the coupling component represented by the general formula () according to the conventional method for producing an azo pigment. Obtained by coupling.

That is, the above coupling component is added to an alkaline aqueous 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 solution expressed by the above general formula () is added. An aqueous solution of a diazonium salt of an aromatic amine is added dropwise to perform a coupling reaction in an alkaline environment at room temperature to produce a crude azo pigment, which is then filtered, washed with water, and dried to obtain the desired azo pigment. Furthermore, in the present invention, the coupling reaction can also be carried out in an organic solvent.

According to detailed research conducted by the present inventors, it has been found that the above-mentioned azo pigment exhibits the best infrared reflectivity when the crystal size thereof is 0.3 to 10 μm.

The azo pigment used in the method of the present invention produced as described above is dark to black in color, has good solvent resistance, light resistance, heat resistance, water resistance, and chemical resistance, and has high coloring power. It can be fully used as

The infrared reflective material of the present invention consists of the above azo pigment and 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,
In the case of coloring polypropylene or the like with the above-mentioned azo pigment, these synthetic fibers are also included in the carrier material of the present invention. Furthermore, the azo pigment described above can be used to color synthetic resins such as those described above, and other thermoplastic or thermosetting resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, polyimide, phenolic resin, urea resin, melanin resin, etc. When producing 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 infrared reflective material of the present invention is:
The above general formula () can be used instead of conventional pigments in liquid materials such as conventional pigment printing agents, printing inks, and paints.
In these examples, as in the prior art, liquid materials are used.
About 100 parts by weight of the azo pigment of the general formula ()
It is generally used in a proportion of 0.1 to 50 parts by weight. 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.

Furthermore, in the case of colored synthetic fibers or colored resin molded articles, which is another example, the azo pigment of the general formula () is used in an amount that can substantially color the fibers or molded articles, for example, 0.1 to 30% by weight. Generally, it is included by percentage.

The infrared reflective 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 the above-mentioned pigment printing agents, paints, printing materials, etc. It can be obtained by a method similar to an ink manufacturing method, a undiluted solution coloring method, or a synthetic resin coloring molding method.

(Action/Effect) The infrared reflective material of the present invention as described above can be used in the same way as conventional pigment printing agents, paints, and printing inks, and is useful for printing woven fabrics and nonwoven fabrics, coatings for various articles, and printing. The infrared reflectance of these colored articles is significantly higher than that of colored articles using conventional carbon black pigments.

Further, the same applies when the infrared reflective material of the present invention is a colored fiber or a molded article, and a fiber or a molded article having the same infrared reflective properties as a green animal is provided.

Therefore, by obtaining various articles using the infrared reflective material of the present invention, it is possible to obtain articles that are black but do not absorb infrared rays and do not excessively increase in temperature due to direct sunlight, etc. Moreover, if these articles are used as a heat insulating material, it is possible to suppress heat dissipation due to infrared radiation of the contents.

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

Example 1 0.01 mol of 2-chloro-4-methylaniline 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 and the temperature is 0.
Keep at ~5℃, 40% sodium nitrite aqueous solution 2.0
of the solution and 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, 0.01 mole of naphthol AS-SG was suspended in 250 parts of o-dichlorobenzene, the above diazonium salt solution was added at 20 to 30°C, the temperature was maintained at 30 to 40°C, and 20 parts of glacial acetic acid was added. The mixture was maintained at this temperature for 5 to 6 hours and coupled to obtain an azo pigment of the following formula.
The azo pigment exhibits a black color.

Example 2 0.01 mol of dianisidine is dissolved in 45 parts of dimethylformamide and cooled to 0°C. in this
0.06 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 liquid, heat it at 20-30℃.
The above diazonium solution was slowly added dropwise, and a coupling reaction was carried out at 20 to 30°C for 2 hours to obtain a black azo pigment represented by the following formula.

Examples 3 to 14 In the same manner as in Example 1 or Example 2, the azo pigments used in the present invention represented by the structural formulas are prepared using the following compounds of the general formula () and the compound of the general formula (), respectively. Obtained.

Example 3 Compound of general formula (); 2-(4'-chlorophenoxy)-5-chloroaniline Compound of general formula (); Naphthol AS-SR Color tone: Slightly reddish black Example 4 Compound of general formula (); 2-methyl-4-nitroaniline Compound of general formula (); Naphthol AS-SR Color tone: black Example 5 Compound of general formula (); 2-methoxy-4-nitroaniline Compound of general formula (); Naphthol AS-SR Color tone: Black Example 6 Compound of general formula (); 2-nitro-4-methylaniline Compound of general formula (); Naphthol AS-SG Color tone: slightly blue black Example 7 Compound of general formula (); 2-nitro-4-chloraniline Compound of general formula (); Naphthol AS-SG Color tone: slightly greenish black Example 8 Compound of general formula (); 2-methyl-4-nitroeaniline Compound of general formula (); Naphthol AS-SG Color tone: Slightly reddish black Example 9 Compound of general formula (); 2-methoxy-4-nitroaniline Compound of general formula (); Naphthol AS-SG Color tone: slightly greenish black Example 10 Compound of general formula (); 1-aminoanthraquinone Compound of general formula (); Naphthol AS-SG Color tone: Slightly reddish black Example 11 Compound of general formula (); 2-nitro-4-methoxyaniline Compound of general formula (); Naphthol AS-SG Color tone: Slightly bluish black Example 12 Compound of general formula (); 2-methoxy-4-
(2'-nitro-4'-methylphenyl)-azo-5
-Methylaniline Compound of general formula (); Naphthol AS-SG Color tone: slightly greenish black Example 13 Compound of general formula (); 2-chloro-4-benzoylamino-5-methoxyaniline Compound of general formula (); Naphthol AS-SG Color tone: slightly greenish black Example 14 Compound of general formula (); 2,5-dimethoxy-4
-(4′-nitrophenyl)-azo-aniline Compound of general formula (); Naphthol AS-SG Color tone: Black with a slight greenish tinge Example 15 Acrylic acid ester emulsion (activator-free type, solid content 40%) 30 parts Azo pigment obtained in Example 1 35 parts Antifoaming agent 0.5 parts Powder 1 part Daimonex EX-6 (manufactured by Dainichiseika) 3 parts turpentine 15 parts methanol 8 parts water 15.5 parts total 100 parts A paste-like black paste with azo pigment dispersed in the above formulation was combined with 1% ethyleneimine crosslinking agent, and was coated on Entrance (Toray brand) cloth. A black print can be obtained by printing with a silk screen and curing at 120℃ for 15 minutes. When the infrared reflectance of the printed portion of this printed article was measured, as shown in FIG. 1, it was found to be significantly higher than the infrared reflectance of the same article made of carbon black pigment.

Example 16 Azo pigment obtained in Example 2 17 parts Thermoplastic acrylic resin 70 parts Toluene 6.8 parts Xylol 3.2 parts Butanol 2.2 parts Cellosolve 0.8 parts Total 100 parts The above composition was 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 Fluid color of the azo pigment obtained in Example 3 (purity 50%) 38.0 parts Mixed varnish for offset lithographic ink 60.0 parts 5% Cobalt dryer 0.2 parts 8% Manganese dryer 1.0 parts Inksol belt 0.8 parts Total 100 Part The above components were sufficiently mixed and kneaded 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 azo pigment obtained in Example 4 and Pansolve
Mix 1.0 part of H with 50 parts of polyvinyl chloride resin compound and roll it into a 6-inch roll.
Form a sheet by roll kneading at 155-160℃ for 3 minutes, and roll this sheet to a thickness of 5mm at 170℃ with a pressure of 50Kg.
A black-green colored sheet was obtained by press molding. Example of measuring the infrared reflectance of this sheet
15 obtained similar results.

In addition, those colored in the same manner as Examples 15 to 18 using the azo pigments obtained in Examples 6 to 14,
It showed excellent infrared reflectance.

[Brief explanation of the drawing]

FIG. 1 shows an infrared reflectance curve (dashed line) of the colored product with carbon black and an infrared reflectance curve (solid line) of the infrared reflective material obtained in Example 13.

Claims (1)

[Claims] 1. It is represented by the following general formula (), and the size of the crystal is
An infrared reflective material consisting of an azo pigment having a diameter of 0.3 to 10 μm and a carrier material. [However, n in the above formula is 1 or 2, X is a hydrogen atom or a methyl group, and when n = 1, R ₁
is a phenyl group or anthraquinonyl group which may have a halogen atom, methyl group, nitro group, methoxy group, phenoxy group, phenylazo group or benzoylamino group, and when n=2, R ₁ is a halogen atom, methyl is a biphenylene group which may have a group, a methoxy group, an ethoxy group or a nitro group. ]