JPH064939B2 - Infrared reflective woven fabric manufacturing method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for printing a woven fabric, and more particularly to a method for producing a woven fabric which is substantially black and has good infrared reflectivity.

(Prior Art) Conventionally, a method of applying various printing patterns to various woven fabrics by a pigment printing method has been widely performed. Among them, in order to obtain a black printed material, carbon is used as a coloring agent in the printing agent. Black is widely used.

(Problems to be Solved by the Invention) Of course, a printed material with a printing agent using the carbon black as a colorant is black, but these black printed woven fabrics easily absorb infrared rays, When black clothes must be used in the summer, the body temperature is prevented from being dissipated, and infrared rays are absorbed and heat is stored in direct sunlight, which often gives a hotter feeling. There is a similar problem in other industrial fields using black woven fabrics other than clothing.

Therefore, there is a demand for a black woven cloth which is colored black and has a low heat storage effect or a low infrared absorption property.

(Means for Solving Problems) As a result of earnest research to meet the above-mentioned demands of the prior art, the present inventor adjusted a printing agent using a certain specific black azo compound, thereby producing a black printed material. The present invention has been completed by finding that by obtaining it, it is possible to obtain a printed woven fabric having a good heat dissipation property inside and reflecting well without absorbing infrared rays in sunlight and the like.

That is, the present invention provides a method of printing a woven fabric using a printing agent comprising a colorant, a binder resin and a liquid medium, wherein the main component of the colorant is an azo compound represented by the following general formula (I). A method for producing a characteristic infrared reflective woven fabric.

However, X in the above formula is a hydrogen atom or a halogen atom, m is an integer of 1 to 4, and R ₁ may have a halogen atom, a methyl group, a methoxy group, an ethoxy group, or a nitro group. A good phenylene group or biphenylene 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. , N is 2, a phenylene group or a biphenylene group which may have the same substituent as R ₂ when n is 1, and Y is an atomic group forming a benzocarbazole ring.

The present invention will be described in more detail. The azo compound represented by the general formula (I), which characterizes the present invention, is mainly represented by the following general formula (I
It is obtained by a method of coupling the compound represented by I) with the coupling component represented by the following general formula (III) according to a conventional method.

R ₁ , X, m, R ₂ , Y and n in the above formula have the same meanings as described above.

The compound itself represented by the general formula (II) is conventionally known, and, for example, when an example of the production method thereof is described, 3-imino-1-oxoisoindoline or 3,
About 1 mol per mol of 3-dichloro-1-oxoisoindoline or its nuclear chlorinated derivative or nuclear brominated derivative.
Easily by reacting a mole of phenylenediamine or diphenylenediamine or its phenyl group with a phenylenediamine or diphenylenediamine which may have a halogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a nitro group or the like. Is what you get.

As such a diamine, any conventionally known one can be used, for example, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2-methylbenzene, 1,4-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-diaminobenzene, 1,3-diamino-4-methylbenzene, 1,3-diamino-4-chlorobenzene, 1,3-diamino-4-methoxybenzene, 1,3- Diamino-2,4,5,6-tetrachlorobenzene, 1,4-diamino-2,3,5,6-tetrachlorobenzene, 1,2-diamino-benzene, , 2-diamino-4-nitrobenzene, 1,3-diamino-2-methylbenzene, 1,4-diaminobenzene, 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, 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-octachlorodiphenyl, 4,4'-diamino-diphenyl and the like are used.

Next, as the method for diazotizing the aromatic amine represented by the general formula (II), the conventional diazotization method for aromatic amines can be used as it is, and for example, the aromatic amine represented by the general formula (II) can be used. A method in which a sodium nitrite solution is added to a cold aqueous solution of an amine mineral salt, and the mixture is stirred for a while under cooling to obtain a diazonium salt solution to obtain an aqueous solution of a diazonium salt, is disclosed in JP-B-45-18.
No. 383, No. 46-37189, No. 56-2.
No. 102 and Japanese Patent Laid-Open No. 49-120923.

As the coupling component represented by the general formula (III) used in the present invention, conventionally known compounds can be used. For example, the compound represented by the general formula (III) is 2-hydroxy-1 ′, 2 ′. -Benzocarbazole-3
-Carboxylic acid, 2-hydroxy-2 ', 3'-benzocarbazole-3
-Carboxylic acid, 2-hydroxy-3 ', 4'-benzocarbazole-3
Reacting a carboxylic acid or a halogen-substituted product thereof or a functional derivative thereof with an aromatic monoamine in a molar ratio of about 1: 1 (n = 1), or reacting an aromatic diamine with a molar ratio of about 2: 1. It is obtained by reacting (n = 2) with.

The aromatic monoamine used is, in addition to aniline, an aniline derivative having a halogen atom, a methyl group, a methoxy group, an ethoxy group, a nitro group, an acetylamino group or the like, and examples thereof include o, m, p-chloroaniline and o. , M, p-methylaniline, o, m, p-methoxyaniline, o, m, p-ethoxyaniline, o, m, p-nitroaniline, o, m, p-acetylaminoaniline, 2-methyl-4 -Chloroaniline, 2-methyl-5-chloroaniline, 2,4-xylidine, 2-methoxy-5-chloroaniline, 2-methoxy-5-bromoaniline, 2-methyl-4-methoxyaniline, 2,5- Dimethoxy-5-chloroaniline, 2,5-dimethoxy-4-chloroaniline, 2,5-dimethoxy-4-benzoylaminoaniline Aniline derivatives fine formula are exemplified.

The aromatic diamine is the aromatic diamine as described above.

The coupling components as described above are all compounds known in the art.

The azo compound used in the present invention comprises a diazonium salt of an aromatic amine represented by the general formula (II) and a coupling component represented by the general formula (III), and a conventional method for producing a compound of the azo compound. It can be obtained by coupling according to.

That is, the above coupling component is added to an alkaline aqueous solution to be heated and dissolved, and then the solution is cooled to near 25 ° C.,
A buffer is added to this to further adjust the pH, and then an aqueous solution of a diazonium salt of the aromatic amine represented by the general formula (II) is added dropwise to the mixture to carry out a coupling reaction at room temperature in an alkaline manner, A compound is produced, and then filtered, washed with water and dried to obtain the desired azo compound. Furthermore, in the present invention, the coupling reaction can be carried out even in an organic solvent.

The azo compound used in the present invention produced as described above is dark purple to black, and has solvent resistance, light resistance, heat resistance,
It also has good water resistance and chemical resistance, has high coloring power, and can be sufficiently used as an azo pigment.

The above-mentioned azo compound occupies the main component of the colorant of the textile printing agent used in the present invention, and in the present invention, as long as the above-mentioned azo compound is the main component, in addition to the azo compound, a conventionally known aqueous solution is used. The organic pigments, inorganic pigments and various dyes used in the printing agent can be used in combination, and these colorants are about 1 to 100 parts by weight in total of the printing agent.
It is generally used in a ratio of 40 parts by weight.

As the binder resin used in the present invention, any of the binder resins used in conventional printing agents can be arbitrarily used.

For example, polyester resin, acrylic ester resin,
Examples thereof include vinyl acetate resin and ethylene-vinyl acetate resin.
These binder resins are preferably used in a ratio of about 0.4 to 20 parts by weight per 1 part by weight of the colorant.

The medium used in the printing agent of the present invention is water as a main component, and a petroleum-based sizing agent such as terpen in the prior art is used to make an O / W type or W / O type emulsion.

Although the above are the essential components in the printing agent of the present invention, for the purpose of improving various fastnesses of a print pattern to be formed,
Various kinds of crosslinking agents such as epoxy type, ethyleneimine type, methylol type, isocyanate type and the like can be added in a necessary amount according to need. Of course, other various surfactants, antifoaming agents, pigment dispersants, and other various additives may be added.

As described above, the printing agent used in the present invention has the above-mentioned general formula (I).
Other than the main component of the colorant of the azo compound represented by, for example, the binder used, sizing agent such as terpen,
The catalyst and other additives may be those of the prior art, and the liquid medium is not limited to the oil-in-water type and may be a water-in-oil type liquid medium.

In addition, the woven fabric printed with the above-mentioned printing agent is also cotton,
Natural fibers such as hemp, wool and silk, woven fabrics made of synthetic or semi-synthetic fibers such as cellulose acetate, viscose rayon, nylon, polyester, polypropylene and acrylonitrile (including non-woven fabrics, the same below), and It may be a mixed-spun woven fabric and is not particularly limited.

Further, as the printing method, any one of screen printing, spray printing and roll printing may be used.
There is no particular limitation.

Further, the core conditions at the time of printing, the dry-curing treatment and the post-treatment after printing, etc. may be the same as in the prior art.

(Operation / Effect) The black printed woven fabric according to the present invention as described above is compared with a conventional black printed woven fabric using carbon black as a coloring agent.
Since the black colorant used has a property of not absorbing infrared rays, when used for clothing, for example, it is possible to reflect infrared rays from the outside even in the summer, and Since the heat can be easily dissipated, the feeling of heat can be significantly reduced.

In addition, the meaning of infrared reflectivity in the present invention means that the azo compound itself does not absorb infrared rays and reflects, and the azo compound does not absorb infrared rays, and a printing agent containing the azo compound is added. It also includes the case where the underlying substrate, that is, the woven fabric, reflects infrared rays.

Next, the present invention will be described more specifically with reference to Reference Examples and Examples. In the text, “part” or “%” is based on weight unless otherwise specified.

Reference Example 1 3.75 parts of 3- (4'-aminophenylimino) -1
-Oxo-4,5,6,7-tetrachloroisoindoline was suspended in 11.3 parts of glacial acetic acid, to which concentrated hydrochloric acid 3.7 was added.
Parts were added and stirred. 2.6 parts of water is added to this and the temperature is 0-
The temperature was kept at 5 ° C., 2.0 parts of a 40% sodium nitrite aqueous solution was added, and the mixture was stirred at the same temperature for about 30 minutes to obtain a yellow diazonium salt solution. Sodium acetate trihydrate 4.
A solution of the diazonium salt was prepared by adding 8 parts. On the other hand, 2-hydroxy-N- (4'-methoxyphenyl)
3.82 parts of 11-H-benzo [a] -carbazole-3-carboxamide was suspended in 250 parts of o-dichlorobenzene, the above diazonium salt solution was added at 20 to 30 ° C, and 30 to 40 ° C. 20 parts of glacial acetic acid was added. Coupling was carried out at this temperature for 5 to 6 hours to obtain the azo compound of the present invention. The azo compound has a black color and is 3
It has a decomposition point of 73 ° C.

Reference Example 2 Diazotized 3- (3'-aminophenylimino)-
3.7 parts of a diazo compound prepared by reacting 1-omiso-4,5,6,7-tetrachloroisoindoline with piperidine in an alkaline medium and 1,4-bis- [2'-
Hydroxy-11'-H-benzo [a] -carbazole-3'-carbonylamino] benzene 6.3 parts and o-
Suspended in 300 parts of dichlorobenzene, 70-75 ° C
20 parts of warm glacial acetic acid was added. Then mix the mixture from 120-
When the mixture was stirred at 130 ° C. for 2 hours, the coupling proceeded and the azo compound of the present invention was obtained. The azo compound has a slightly reddish black color and has a decomposition point of 342 ° C.

Reference Examples 3 to 11 In the same manner as in Reference Example 1 or Reference Example 2, the following general formula (I
An azo compound of the present invention was obtained using the compound of I) and the compound of general formula (III).

Reference Example 3 Compound of general formula (II); 3- (4'-aminophenylimino) -1-oxo-4,5,6,7-tetrachloroisoindoline Compound of general formula (III); 2-hydroxy- N- (2'-
Methyl-4′-methoxyphenyl) -11-H-benzo [a] -carbazole-3-carboxamide Color tone; slightly reddish black Decomposition point; 359 ° C. Reference Example 4 Compound of general formula (II); 3- (2 ', 5'-dichloro-
4'-aminophenylimino) -1-oxo-4,5,5
6,7-Tetrachloroisoindoline Compound of general formula (III); 2-hydroxy-N- (2'-
Methyl 4′-methoxyphenyl) -11-H-benzo [a] -carbazole-3-carboxamide Color tone; Black Decomposition point; 341 ° C. Reference Example 5 Compound of general formula (II); 3- (2 ′, 5) ′ -Dimethyl-
4'-aminophenylimino) -1-oxo-4,5,5
6,7-Tetrachloroisoindoline Compound of general formula (III); 2-hydroxy-N- (2'-
Ethylphenyl) -11-H-benzo [a] -carbazole-3-carboxamide Color tone; slightly reddish black decomposition point; 346 ° C Reference Example 6 Compound of general formula (II); 3- (2'-methyl) -5'-chloro-4'-aminophenylimino) -1-oxo-4,
5,6,7-Tetrachloroisoindoline Compound of general formula (III); 2-hydroxy-9-chloro-
N- (4'-methoxyphenyl) -11-H-benzo [a] -carbazole-3-carboxamide Color tone; Black Decomposition point; 369 ° C Reference Example 7 Compound of general formula (II); 3- (3 ' , 3 "-dimethyl-
4 "-aminobiphenyl-4'-ylimino) -1-oxo-4,5,6,7-tetrachloroisoindoline Compound of general formula (III); bis-2-hydroxy-N-
(3'-Methylphenyl) -11-H-benzo [a]-
Carbazole-3-carboxamide Color tone; Black Decomposition point; 347 ° C Reference Example 8 Compound of general formula (II); 3- (3 ', 3 "-dichloro-
4 "-aminobiphenyl-4'-ylimino) -1-oxo-4,5,6,7-tetrachloroisoindoline compound of general formula (III); 1,4-bis- [2'-hydroxy-11- H-benzo [a] -carbazole-3-carbonylamino] benzene Color tone; Black Decomposition point; 342 ° C Reference Example 9 Compound of general formula (II); 3- (3'-aminophenylimino) -1-oxo- 4,5,6,7-Tetrachloroisoindoline Compound of general formula (III); 2-hydroxy-N- (4'-
Methoxyphenyl) -11-H-benzo [a] -carbazole-3-carboxamide Color tone; Black Decomposition point; 359 ° C Reference Example 10 Compound of general formula (II); 3- (5'-chloro-3'amino) Phenylimino) -1-oxo-4,5,6,7-tetrachloroisoindoline Compound of general formula (III); 2-hydroxy-N- (2'-
Methyl-4'methoxycyclophenyl) -11-H-benzo [a] -carbazole-3-carboxamide Color tone; slightly bluish black Decomposition point; 345 ° C Reference Example 11 Compound of general formula (II); 3- ( 4'-aminophenylimino) -1-oxo-4,7-dichloroisoindoline compound of general formula (III); 2-hydroxy-N- (2'-
Ethylphenyl) -11-H-benzo [a] -carbazole-3-carboxamide Color tone; slightly reddish black Decomposition point; 375 ° C Example 1 30 parts of the azo compound of Reference Example 1 above, polyoxyethylenenonylphenyl 100 parts of a mixture consisting of 10 parts of an ether-based dispersant and 60 parts of water was stirred and mixed with a dissolver, 300 parts of otter sand with a diameter of 3 mm was put into a paint shaker, and dispersed for 4 hours, and a 100 μm filter cloth was used. Coarse particles were removed by using an aqueous color base.

On the other hand, acrylic ester emulsion (solid content 46.5
%) 25 parts of water, 25 parts of water, 4 parts of Daimonex ER-H (Emulsifier for Dainichi purification printing) are mixed uniformly at a low speed, and then 46 parts of mineral spirit (kerosene) is gradually added to the homogenizer. And agitate to obtain a viscosity of 30,000-
A printing table paste of 40,000 cps was prepared.

Next, the above-mentioned aqueous color base and the above printing base paste were mixed in the following formulation (parts) to prepare dark, medium and light color printing pastes.

Using the above-mentioned three kinds of printing pastes, # 60 cotton broad cloth was printed on 80 mesh silk screen, dried at 110 ° C., and baked at 130 ° C. for 5 minutes to make three kinds. Black prints with different densities were obtained.

Examples 2 to 11 Instead of the azo compound of Reference Example 1, the azo compounds of Reference Examples 2 to 11 were used, and the other processes were performed in the same manner as in Example 1 to obtain black printed matters. The infrared reflectivity of these prints was similar to the infrared reflectivity of the prints of Example 1.

Comparative Example A black printed matter was obtained in the same manner as in Example 1 except that the same amount of carbon black was used instead of the azo compound of Example 1.

When the infrared reflectance and the surface temperature of the solid printed matter of the printed matter of Example 1 and the comparative example were measured,
The infrared reflectance curves (A: invention, B: comparative example) and temperature rising curves (A: invention, B: comparative example) as shown in FIGS. 1 and 2 were obtained.

[Brief description of drawings]

FIG. 1 shows an infrared reflectance curve, and FIG. 2 shows a temperature rise curve. A: Printed product of the present invention B: Printed product of Comparative Example

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yoshiyuki Zama 4-2-30 Saginumadai, Narashino City, Chiba Prefecture (72) Inventor Shirou Yamamiya 3-24-1, Fujimidai, Nerima-ku, Tokyo (72) Inventor Nishikatsu Hiroaki 2-176-1, Akayama-cho, Koshigaya-shi, Saitama (72) Inventor Atsushi Nogami 4-2-8 Ryoke, Kawaguchi-shi, Saitama

Claims (4)

[Claims] 1. A method for printing a woven fabric using a printing agent comprising a colorant, a binder resin and a liquid medium, wherein the main component of the colorant is an azo compound represented by the following general formula (I). And a method for producing an infrared reflective woven fabric. [Wherein, X in the above formula is a hydrogen atom or a halogen atom, m is an integer of 1 to 4, and R ₁ has a halogen atom, a methyl group, a methoxy group, an ethoxy group, or a nitro group. Is also a phenylene group or a biphenylene 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. , N is 2, a phenylene group or a biphenylene group which may have the same substituent as R ₂ when n is 1, and Y is an atomic group forming a benzocarbazole ring. ) 2. The production method according to claim 1, wherein X is a chlorine atom, m is 4, and Y is an atomic group forming a 1,2-benzocarbazole ring. 3. The method according to claim 1, wherein n is 1. 4. The method according to claim 1, wherein n is 2.