JPS585317B2 - Cellulose cellulose cellulose - Google Patents

Description

Detailed Description of the Invention The present invention represents the general formula (1), A is a benzene residue having no sulfonic acid group or a benzene or naphthalene residue having 1 to 2 sulfonic acid groups, and B is an azo It is a naphthalene residue that has one O-bond bonded to copper at the 2-position relative to the group and further has 1 to 3 sulfonic acid groups.

A may have a methoxy group, methyl group, hydroxyl group, carboxylic acid group, cyano group, chloro atom, or bromine atom, and B may have a nitro group.

Here R, R1, R2 are hydrogen atoms or methyl groups,
X represents an aliphatic group having 2 to 6 carbon atoms, or -N-X-N- represents a 1,4-piperazinylene group in the form of a free acid.

This invention relates to a method for dyeing cellulose fibers using a reactive tetrakisazo dye represented by the following formula in the presence of an acid binder.

Various dyes having a monohalogenotriazine group are conventionally known, and they react well with cellulose fibers in the presence of an acid binder such as sodium carbonate and fix thereon.

For example, in the case of dyeing with a relatively large bath ratio, a method of heating to 60 to 90° C. in the presence of a salt and acid binder to absorb the dye gives a durable and practical dyed product.

When used for textile printing or padding dyeing, due to its reactivity, it can be well fixed to cellulose fibers by short-term steaming or dry heat treatment in the presence of an acid binder.

However, dyes with monohalogenotriazine groups generally cannot fix all of the dye obtained on cellulose fibers, and a considerable amount of unfixed dye is always contained in cellulose fibers. Wet fastness, especially washing fastness (JIS L
0844) and water (JIS L 0846) tests.

Therefore, in order to obtain high wet fastness, washing with hot bath soaping containing an appropriate surfactant is an essential step as a means of removing those unfixed dyes after dyeing.

However, in practice, the washing process including hot bath soaping requires time and labor comparable to the dyeing process, and it has been pointed out that the biggest drawback is that the dyeing process is extremely impossible. The appearance of this type of dye with excellent wet fastness has been eagerly awaited.

As a result of intensive research, the present inventors have surprisingly found that the dye represented by the general formula (1) of the present invention can be used for washing cotton in a hot bath soap containing a surfactant at a practical dyeing concentration. It is possible to pass the harsh washing fastness test (JIS L 0) by simply washing with water after dyeing and then treating with a fixing agent that is usually commercially available.
844. A-4 (near 0°C), the most important feature is that it exhibits extremely excellent wet fastness of cotton stain grade 4 or higher, and it was also discovered that it gives a deep navy blue color with excellent light fastness and sweat fastness. Ta.

The dye represented by the general formula (1) contains 1 mole of cyanuric chloride in any order and an aminodisazo compound 1 represented by 2).
Mol and Formula (3) [Here, A, B, R, R1, R2 and X have the above meanings.

] is produced by reacting the diamine in a 1/2 molar ratio.

The amino disazo compound represented by the formula (2) used here is obtained by diazotizing the amine compound represented by the following formula (4), using a known method such as German Patent No. 807289.
Coupling with a monoazo compound represented by the following formula (5) obtained by the oxidative copperization step described in No. , represents an acetylamino group or an acetylmethylamine group.

[In the formula, B represents the same meaning as above.

] Next, the substituent Z can be converted into an amino group by hydrolysis or reduction.

Examples of amino represented by formula (4) include, but are not limited to, the following.

Namely, 4-acetylaminoaniline-2-sulfonic acid 5-acetylaminoaniline-2-sulfonic acid 5-acetylaminoaniline-2,4-disulfonic acid 4-acetylaminoaniline-2,5-disulfonic acid 2-amino-6 -acetylaminonaphthalene-4,8-
Disulfonic acid 2-amino-6-nidronaphthalene-4,8-disulfonic acid 4-acetylamino-5-methoxyaniline-2-sulfonic acid 2-methoxy-4-nitroaniline-5-4-methyl-5-sulfonate -acetylaminoaniline-2-sulfonic acid 2-amino-6-nidronaphthalene-8 -sulfonic acid 6-nitro-2-aminophenol-4 -sulfonic acid 4-nitro-2-aminophenol-6 -sulfonic acid 6 -acetylamino-2-aminophenol-4-sulfonic acid p-acetylaminoaniline m-acetylaminoaniline p-amino-N-acetyl-N -methylaniline 2.5-dichloro-4-acetylaminoaniline 5-acetylamino Anthranilic acid 4-acetylaminoanthranilic acid 2-acetylamino-5-aminobenzoic acid 3-chloro-
4-acetylaminoaniline 3-methoxy-4-acetylaminoaniline 4-methyl-3-acetylaminoaniline 2.5-dichloro-4-nitroaniline 2-cyano-4-nitroaniline 2-amino-5-nitrobenzoic acid Examples include 2-methoxy-4-nitroaniline, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, and the like.

Examples of the amine naphthalene used as component B of the monoazo compound represented by formula (5) include the following.

1 or 2-aminonaphthalene monosulfonic acid 1 or 2-amine naphthalene disulfonic acid 1 or 2-aminonaphthalene trisulfonic acid 6-nitro-2-amine naphthalene disulfonic acid 6-nitro-2-amine naphthalene monosulfonic acid, etc. .

Examples of diamines represented by formula (3) include, but are not limited to, the following.

Ethylenediamine N-Methylethylenediamine 1,2-Propylenediamine 1,3-Propylenediamine N-Methyl-1,3-diaminopropane 1,4-Diaminobutane Pentamethylenediamine Hexamethylenediamine Piperazine 1,2-Bis-(4'- Examples include amino-2'sulfophenylamino)ethane.

Further, in the dye represented by the general formula (1), 1 mole of cyanuric chloride is mixed with 1/! of the diamine represented by the formula (3)! Mol and formula (
7) is condensed with 1 mol of aromatic diamine represented by (8).
) [In the formula, A and R are the same as above] [In the formula, A, R, R1, R2 and X are as above.

] The diamine represented by formula (8) is tetrazotized,
It can also be produced by coupling with 2 moles of a monoazo compound represented by formula (5).

The aromatic diamine represented by the formula (7) used here can be obtained by reducing or hydrolyzing the amine compound represented by the formula (4), preferably 1,3-phenylenediamine-4-sulfonic acid. 1.4-phenylenediamine-2-sulfonic acid 1.3-phenylenediamine-4,6-disulfonic acid 1.4-phenylenediamine-2,5-disulfonic acid 1.4-phenylenediamine-2-methoxy-5- Sulfonic acid 1,3-phenylenediamine-4-methyl-6-sulfonic acid, 2,6-naphthylenediamine-4,8-disulfonic acid, and the like.

Furthermore, the dye represented by the general formula (1) is cyanuric chloride 1
mol is condensed with 1 mol of aromatic diamine represented by formula (7), and 1 mol of the thus obtained monoamino compound represented by formula (9) is converted into a monoazo compound represented by formula (5) [wherein and R are as described above] expresses the same meaning as

] Coupling with 1 mol of the resulting product is expressed by formula (3)
It is also produced by condensing a diamine represented by 1/2 molar ratio.

The method of the present invention uses a reactive tetrakisazo dye having a specific structure as described above in the presence of an acid binder to dye cellulose-based textile products or blends thereof, for example,
It performs dip dyeing, padding dyeing, and printing processes.

Acid binders used during dyeing include, for example, sodium bicarbonate, sodium ortho- or metasilicate, sodium carbonate, and sodium hydroxide.

When the present invention is applied to dyeing with a relatively large bath ratio such as batch dyeing, inorganic salts such as sodium chloride,
Or make a dye bath with sodium sulfate and dye30
After dyeing for 10 to 60 minutes while heating at 60 to 100 degrees Celsius, add an acid binder and continue dyeing at 60 to 100 degrees Celsius for 20 minutes.
Perform staining for ~60 minutes.

In this case, the acid binder may be added to the dye bath from the beginning, or a separate bath containing the acid binder may be used to fix the dye after neutral dyeing.

In addition, when the method of the present invention is applied to a dyeing process using a padding method such as continuous dyeing or semi-continuous dyeing, the dye bath is usually mixed with a dye, an acid binder, a penetrating agent, and if necessary urea to prepare the fabric. After being immersed in the dye bath for a short time, it is squeezed and left at room temperature or under heating, or it is subjected to a short steam or dry heat treatment.

In some cases, the fibers may be padded with a neutral dyebath after pre-soaking in a solution of an acid binder, or the fibers padded with a neutral dyebath may be padded with a solution of an acid binder saturated with an inorganic salt. It may be treated with water, left to stand, or treated with steam or dry heat for a short period of time.

Furthermore, when the method of the present invention is applied to textile printing, a color paste is usually printed on the fibers using sodium alginate or emulsion paste as the base paste, to which a dye, an acid binder, and if necessary, urea, etc. are added. Then, it is subjected to intermediate drying and subjected to short-time steaming or dry heat treatment, or it is left at room temperature or under heating without removing intermediate drying to fix the dye.

In this case, it is also possible to print a neutral color paste on the fibers which have been padded with an acid binder solution and dried, and then to fix them in the same manner as described above.

After the fibers colored by such dyeing, padding dyeing or printing are lightly washed with water, they are treated with a bath of a commercially available fixing agent for anionic dyes, preferably a polyethylene polyamine fixing agent.

In this case, fixing treatment can be performed immediately after dyeing without even a light washing with water.

The colored fibers dyed according to the invention exhibit a favorable navy blue color and are excellent in various fastness properties, especially in harsh washing fastnesses.

Next, the method of the present invention will be explained with reference to examples, but the present invention is not limited to the following examples unless the gist of the invention is exceeded.

In the examples, "parts" indicate "parts by weight."

Example 1 represents.

] A dye bath was prepared using 3 parts of the dye represented by the above formula (10), 60 parts of anhydrous sodium sulfate, and 1000 parts of water, and 25 parts of cotton stockinette was immersed in this dye bath at 90°C and treated for 30 minutes. Add 20 parts of sodium carbonate and continue to 60 parts.
Staining was performed for minutes.

Next, after a light wash with water, treatment was performed at 60°C for 20 minutes in a separately prepared bath using 4 parts of Sunfix 555 (polyamine-based fixing agent manufactured by Sanyo Chemical Industries, Ltd.) and 1000 parts of water, and washed with water and dried to improve various fastness properties, especially Laundry (70
A deep navy blue dyed product was obtained which had excellent wet fastness of cotton staining grade 4 or higher in the fastness test (JIS L 0844 A-4).

Example 2 2 parts of the dye represented by formula (10) above, 1 part of Liponox RNA (nonionic penetrant manufactured by Lion Yushi Co., Ltd.), 40 parts of sodium chloride, and 1000 parts of water were placed in a dye bath at 30°C. After 50 parts of spun rayon yarn was immersed and treated for 30 minutes, 2 parts of sodium hydroxide was added, the temperature was raised to 95° C. over 20 minutes, and dyeing was continued for 40 minutes while maintaining that temperature.

Next, without washing with water, the liquid was directly dehydrated and treated in a bath prepared using 3 parts of Thiocet K (polyamine-based fixing agent manufactured by Asahi Dye Co., Ltd.) and 1000 parts of water at 60°C for 20 minutes, washed with water, and dried. Frequent washing (70℃)
In the fastness test (JIS L 0844 A-4), a navy blue dyed product with excellent wet fastness of cotton staining grade 4 or higher was obtained.

Example 3 Said parrot 0) [In the formula, Y is -NHCH2CH2NH-.

represents.

] 20 parts of the dye shown above, 200 parts of urea, and 740 parts of water, and 20 parts of 10% sodium alginate paste,
A cotton cloth was padded through a solution prepared by adding 20 parts of sodium carbonate, squeezed to twice the original fiber weight, and after intermediate drying, heat treatment was performed at 160° C. for 2 minutes.

Next, after washing lightly with water, apply 4 parts of Spraffix WF New (polyamine-based fixing agent manufactured by Nippon Tohoku Co., Ltd.) and 1000 parts of water.
By treating the prepared bath at 60°C for 20 minutes, washing with water and drying, it has excellent fastness properties, especially cotton staining grade 4 or higher in the washing (70°C) fastness test (JIS L 0844 A-4). A navy blue dyeing with wet fastness properties was obtained.

In this case, the same result can be obtained by fixing by padding the dyed cloth through a solution prepared with 30 parts of fixing agent and 1000 parts of water, squeezing it to twice the weight of the fiber, and heating it at 100°C for 2 minutes. It was done.

Example 4 represents.

] 20 parts of the dye shown in the formula, 2 parts of Liponox 0C8 (non-ionic penetrant manufactured by Lion Yushi Co., Ltd.), 2 parts of sodium carbonate
0 parts, 200 parts of urea were dissolved in 505 parts of water, and 10 parts of urea was dissolved in 505 parts of water.
% sodium alginate aqueous solution was added and stirred well to prepare colored paste.

Use this color paste to print on cotton cloth, and after intermediate drying,
℃ for 20 minutes, followed by light washing with water and drying in the same manner as in Example 3.
844A-4) gave a navy blue dyeing with excellent wet fastness of grade 4.

Examples 5 to 16 By using the dyes having the structures listed in the table below in the same manner as described in Examples 1 to 4, deep navy blue dyeings or prints having good wet fastness can be obtained. It was done.

w-y-W (10)

Claims (1)

[Scope of Claims] 1 General formula (1) [In the formula, W represents a free acid form, and A is a benzene residue having no sulfonic acid group or a benzene or naphthalene residue having 1 to 2 sulfonic acid groups. B is a naphthalene residue having one O-bond bonded to copper at the 2-position with respect to the azo group, and further having 1 to 3 sulfonic acid groups. A may have a methoxy group, a methyl group, a hydroxyl group, a carboxylic acid group, a cyano group, a chloro atom, or a bromine atom, and B may have a nitro group. Here, R, R1, R2 are hydrogen atoms or methyl groups, and X represents an aliphatic group having 2 to 6 carbon atoms, or -N-X-N- represents a 1,4-piperazinylene group or a free expressed in acid form. ] A dyeing method for cellulose fibers characterized by using a reactive tetrakisazo dye represented by the following in the presence of an acid binder.