JPS5855273B2 - Cellulose cellulose - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention can be used generally in the form of a free acid 1) [wherein X represents a hydrogen atom, a chloro atom, a methyl group, a methoxy group, a carboxyl group or an acetylamino group, and R
represents a hydrogen atom or a methyl group.

2 represents a methyl group or a methoxy group, and m represents a number of 1.2 or 3.

The present invention relates to a method for dyeing cellulose fibers, which is characterized by using a novel azo dye represented by ] in the presence of an acid binder.

Conventionally, dyes synthesized from the aminoazide compound represented by the general formula (2) have the drawback that due to their increased affinity, the washability of non-fixed dyes and the wet fastness of the resulting dyed products are extremely poor. Therefore, the appearance of this type of dye that has improved these drawbacks has been eagerly awaited.

As a result of extensive studies, the inventors of the present invention found that the aminoazo compound represented by the general formula (2) and the diamine represented by the general formula (3) [wherein X and R represent the same as described above].

] Obtained monohalogenotriazine dye (general formula (2)
It is known that cellulose fibers are dyed using dyes obtained by condensing cyanuric chloride, amines, alcohols, etc. with compounds of have been used mainly in the dyeing and padding dyeing of cellulosic fibers, and those of the group in which R corresponds to a methyl group have been mainly used in the printing and padding dyeing of cellulosic fibers, but these dyes have a halogenotriazine reactive group. Due to the side reaction in which the dye reacts with water instead of cellulose molecules, a considerable amount of the dye does not stick to the fiber, and the washing process to remove such unfixed dye from the fiber has poor cleaning performance, and therefore, it is difficult to use in textile printing. It has the disadvantage of poor hot water stain resistance and poor wet fastness of the resulting dyed products, especially in dip dyeing and padding dyeing.

Furthermore, there are problems such as loss of dye due to the production of such non-fixed dye and pollution caused by coloring of dyeing wastewater.

In addition, it is generally known to react two molecules of dihalogenotriazine dye with one molecule of diamine to obtain a bis-(monohalogenotriazine) dye in order to improve the fixation rate of monohalogenotriazine dye. Formula (2
) In the case where the aminoazo compound represented by the formula and ordinary diamines are combined, [in the formula, Z and m represent the same as above.

] When cellulose fibers are dyed using a bis-(monochlorotriazine) type dye represented by the general formula 0) obtained by the combination and dyeing conditions as described below are appropriately selected, a surprisingly high fixation rate and a high fixation rate can be obtained. Its main characteristics are that it has high fixation efficiency (the proportion of dye that reacts with the fiber) and excellent washability, as well as high build-up properties and excellent wet fastness.It also has light fastness and chlorine resistance. It has been found that dyed products with excellent fastness and color yield can be obtained.

The dye represented by the general formula (1) used in the present invention is itself a novel dye, and can be obtained by various methods.

For example, 2 molar proportions of cyanuric chloride, 2 molar proportions of the aminoazo compound of general formula (2) and 1 molar proportion of diamine of general formula (3)
Either molar proportions are reacted in any order, or 2 molar proportions of cyanuric chloride are reacted with aminonaphtholsulfonic acid of the general formula (4) [wherein R represents the same as described above].

2 molar proportions and 1 molar proportion of the diamine of general formula (3) in any order, and then reacted with the amine of general formula (5) [wherein X represents the same as described above].

] It is obtained by campfringing a 2 molar proportion of the obtained diazonium compound.

Furthermore, 2 molar proportions of cyanuric chloride are reacted with 2 molar proportions of aminonaphtholsulfonic acid of general formula (4), and a diazonium compound 2 obtained from amino of general formula (5) is added to this.
After coupling the molar ratio, this and general formula (3)
It can also be obtained by reacting 1 molar proportion of diamine.

The amine of general formula (5) used in this process (and the general formula (
Examples of the diasocomponent in 2) include aniline sulfonic acids (aniline-2-sulfonic acid, aniline-3-sulfonic acid, aniline-4-sulfonic acid).
Anisidine sulfonic acid (4-methoxyaniline-2-sulfonic acid, 2-methoxyaniline-4-sulfonic acid, etc.) Toluidine sulfones I (4-methylaniline-2-
sulfonic acid, 2-methylaniline-4-sulfonic acid, etc.) Chloraniline sulfonic acids (4-chloroaniline-2
-sulfonic acid, 2-chloroaniline-4-sulfonic acid, etc.) carboxyaniline sulfonic acids (5-sulfoanthranilic acid, 4-carboxyaniline-3-sulfonic acid, etc.) acetylaminoaniline sulfonic acids (4-acetylaminoaniline- Examples of aminonaphtholsulfonic acid of general formula (4) (and coupling fraction of general formula (2)) include 2-sulfonic acid, 5-acetylaminoaniline-2-sulfonic acid, etc. Amino-5-naphthol-7-sulfonic acid 2-N-
Methylamino-5-naphthol-7-sulfonic acid is mentioned.

Examples of the diamine of general formula (3) include diaminomesitylene sulfonic acid, 2,6-diamino-1,3-xylidine-4- or -5-sulfonic acid, and 2,6-diamino-1,4-xylidine- 3-sulfonic acid, 2,4-diaminotoluene-5- or -6-sulfonic acid, 2,6-diamittoluene-4-sulfonic acid, 2,4-diaminoanisole-5-sulfonic acid, 2,6-diamino 7 tri-/1/-4-sulfonic acid and the like.

Examples of cellulosic fibers used in the method of the present invention include cellulose fibers such as cotton, hemp, viscose human silk, viscose cotton, and benbelb, as well as blended, interwoven, and interwoven products thereof.

The dyeing according to the present invention is applied to cellulose fibers using the general formula (
In 1), those in the group in which R corresponds to a hydrogen atom are preferably subjected to conventional methods such as dip dyeing and padding dyeing, and those in the group in which R corresponds to a methyl group are preferably subjected to conventional methods such as textile printing and padding dyeing. It can be applied more widely.

Examples of acid binders used in dyeing include sodium hydrogen carbonate, sodium metaphosphate, trisodium phosphate,
Examples include sodium ortho- or metasilicate, sodium carbonate, and sodium hydroxide.

When the present invention is applied to dyeing processes with relatively large bath ratios, such as batch dyeing, the dyebath is usually prepared with an inorganic salt such as sodium chloride or sodium sulfate and a dye.
After dyeing for 10 to 60 minutes at 0 to 100°C, add an acid binder and dye for 20 to 60 minutes at 60 to 100°C.
Perform staining for 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 and an inorganic salt may be used to fix the dye after dyeing.

Further, when the present invention is applied to a dyeing process in which the bath ratio is relatively small, such as continuous dyeing or semi-continuous dyeing, the dye bath is usually prepared by adding a dye, an acid binder, a penetrating agent and, if necessary, urea. The fibers are immersed in the dyebath for a short time and then squeezed and either left at room temperature or under heating, or subjected to a short steam or dry heat treatment.

In some cases, the fibers may be padded with a neutral dye bath after pre-soaking with a solution of an acid binder, or the fibers may be padded with a neutral dye bath using a solution of an acid binder saturated with an inorganic salt. It may be left to stand or heat treated.

Furthermore, when the method of the present invention is applied to textile printing, the base paste is usually sodium alginate or emulsion paste, and a dye, an acid binder, urea, etc. are added to the base paste, and a color paste is printed on the fibers, followed by intermediate drying. Either heat-treat it or leave it as it is at room temperature or under heat to fix the dye.

If necessary, it is also possible to print a neutral color paste on a fiber that has previously been impregnated with an acid binder solution, and then leave it to stand or heat-treat it.

The fibers colored by such dyeing, padding dyeing or printing are washed with water and, if necessary, soaked in a solution containing a surfactant and subjected to hot bath soaping.

When cellulose fibers are dyed by the method of the present invention using the new azo dye represented by general use 1) in the presence of an acid binder, extremely high fixation rate and efficiency and excellent washability are exhibited. A deep orange to scarlet dyed or black print with excellent light fastness, chlorine fastness, and especially wet fastness can be obtained.

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 it exceeds the gist thereof.

In the examples, "1 part" means "1 part by weight."

The structural formula of the dye is as follows (in the formula, X represents a hydrogen atom, a chloro atom, a methyl group, a methoxy group, a carboxyl group, or an acetylamino group, and R
represents a hydrogen atom or a methyl group.

Z represents a methyl group or a methoxy group, and m represents a number of 1.2 or 3.

) Although it is written in an abbreviated form, it formally represents a dye with the following structure.

(In the formula, X, R1 1 m represents the above.

) Prepare a dye bath using 2 parts of the dye represented by the above formula (6) in the form of free acid, 80 parts of anhydrous sodium sulfate, and 1000 parts of water,
Dip 50 parts of cotton stockinette into this dye bath and dye at 80°C for 30 minutes.
After treatment for 0 minutes, 20 parts of sodium carbonate is added and dyeing is continued for 60 minutes at the same temperature.

Then, after washing with water, 100 g of an aqueous solution containing 2 parts of anionic activator
0 parts at 95 to 100°C for 10 minutes, washed with water, and dried to test light fastness, chlorine fastness, and especially washing fastness test (JIS LO844A
An intense scarlet dyeing having an excellent wet fastness of grade 4 to 5 or above with cotton staining at -4 (near 0 DEG C.) is obtained.

Example 2 A dye bath was prepared using 2 parts of the dye represented by the above formula (7) in the form of free acid, 40 parts of anhydrous sodium sulfate, and 1000 parts of water, and 50 parts of spun rayon yarn was immersed in this dye bath. , 8
After treatment at 0° C. for 30 minutes, 10 parts of sodium carbonate are added and dyeing is continued for 60 minutes at the same temperature.

Then, in the same manner as in Example 1, the light fastness, chlorine fastness, especially washing fastness test (JIS LO844: A-4 near 0°C) was carried out by washing with water, no-punching, washing with water, and drying.
A deep orange dyeing with excellent wet fastness of cotton stain grade 4 or above is obtained.

Examples 3 to 7 If the dyes having the structural formulas listed in the table below are used in the same manner as described in Examples 1 to 2, dyes with excellent light fastness, chlorine fastness, especially wet fastness can be obtained. A dyed product is obtained.

Its structural formula and color tone on cellulose fibers are shown below.

Mix 20 parts of the dye represented by the above formula (8) in the form of a free acid with 10 o35 of urea, add 380 parts of warm water to dissolve the dye, and add 20 parts of Polymin L New (reduction inhibitor: manufactured by Nippon Kayaku) with bicarbonate. ) Add this dye solution to 500 parts of a 5% sodium alginate aqueous solution containing 40 parts of IJum, and stir well to adjust the color paste.

Printing was performed on cotton cloth using a screen, and after intermediate drying at 50 to 60°C, steaming treatment was performed at 100 to 103°C for 10 minutes, followed by washing with soaping, washing with water, and drying in the same manner as in Example 1, resulting in very little hot water contamination. (Class 4 to 5 or higher in hot water staining test under the following conditions) Light fastness, chlorine fastness, especially washing fastness test (JIS LO84
4A-4 (near 0 DEG C.), a deep orange dyeing with excellent wet fastness of cotton stain grade 4-5 or higher is produced.

Hot water contamination test conditions The printed surface that has been printed, intermediately dried, and steamed and a white cloth of the same weight and quality are placed in the same container and heated in a water bath with a bath ratio of 1:20.
Treat at 0°C for 10 minutes.

After dehydrating each sample with plain paper, both were placed together in a separately prepared container and treated in a hot water bath at a bath ratio of 1:20 at 95°C for 10 minutes. After dehydrating each sample with P paper, they were dried and used for testing. Comparing the degree of contamination of the white cloth with the original white cloth, gray scale (JI
S0805).

Examples 9 to 14 If dyes having the structural formulas listed in the table below are used in the same manner as described in Example 8, light fastness, chlorine fastness, especially hot water stain resistance and wet fastness can be improved in the same manner as above. An extremely excellent print can be obtained.

Its structural formula and color tone on cellulose fibers are shown below.

20 parts of the dye represented by the above formula (9) in the form of free acid, 100 parts of urea, 1 part of sodium alginate, carbonic acid) IJ
Prepare 1,000 parts of a dye solution containing 20 parts of umum, pass a cotton cloth through this pad bath, squeeze it using a padder until the fiber weight is 1.7 times the original fiber weight, and dry for 2 minutes at 100°C, then dry at 170'C. Perform dry heat treatment for 2 minutes.

Then, in the same manner as in Example 1, washing with water, soaping, washing with water and drying was performed to obtain an excellent color fastness to light, chlorine fastness, especially washing fastness test (JIS LO844A-4 near 0°C) with cotton staining level 4 to 5 or higher. An intense scarlet dyeing with wet fastness is obtained.

Examples 16 to 21 If dyes having the structural formulas listed in the table below are used in the same manner as described in Example 15, dyes with extremely good light fastness, chlorine fastness, and especially wet fastness can be obtained. A dyed product is obtained.

Its structural formula and color tone on cellulose fibers are shown below.

The λmax (mμ: pure water) of the dye of the present invention is reduced below.

Claims (1)

[Scope of Claims] 1 In the form of a free acid, the general formula (1) [wherein X represents a hydrogen atom, a chloro atom, a methyl group, a methoxy group, a carboxyl group or an acetylamino group, and R
represents a hydrogen atom or a methyl group. 2 represents a methyl group or a methoxy group, m represents a number of 1.2 or 3] A method for dyeing cellulose fibers, characterized in that a novel azo dye represented by * is used in the presence of an acid binder. .