JPS5819699B2 - Polyamide Keisen Ino Senshiyokuhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to formula (1) [where X represents CONH or NHCO, and benzene ring A is 1 to 2 CI or further 1 --SO
3M may be substituted, and benzene ring B has a substituent when X is C0NH,
When NHCO has SO3M, when benzene ring C and X are CONH, it is substituted with 803M, and NH
When CO has a substituent, benzene iD has CH3 at any position and 01 to C
2 alkyl, benzene ring E may be substituted with -CH3, M
H1 represents an alkali metal, alkaline earth metal or ammonium group.

This invention relates to a method for dyeing polyamide fibers using a disazo dye represented by the following.

Here, the polyamide fibers refer to natural or synthetic polyamide fibers such as wool, silk, nylon, and polyurethane.

The main idea is to apply a new water-soluble disazo dye represented by formula (1) to ordinary dyeing and printing,
This invention relates to coloring the above-mentioned fibers in a strong yellow color.

The dye used in the method of the present invention can be obtained, for example, by the production method shown below.

That is, the compound represented by formula (2) is diazotized, and equimolar amounts of the resulting bis-diazonium salt (in the formula
A compound represented by formula (3) (B and C have the same meanings as above) is coupled, and then a compound represented by formula (4) (wherein A, B and M have the same meanings as above) is coupled. represents.

) or by first coupling the bis-diazonium salt described above with equimolar moles of the compound represented by formula (4), and then coupling with the compound represented by formula (3). A disazo dye represented by 5) is obtained.

(In the formula, A, B, C, D, , X and M have the same meanings as above.

)・If necessary, the compound represented by Shishi 5) is mixed with Ha l -R' (6) l in the presence of the compound represented by formula (6) and an acid binder.
+ (Hal represents...a rogen atom, and R' is omitted.

) to obtain a compound represented by formula (7).

(In the formula, A, B, C, D, R' and M have the same meanings as above.

) The disazo dye represented by formula (1) can dye natural and synthetic polyamide fibers to a medium deep uniform yellow color, and the dyed products have excellent light fastness, washing fastness,
It has alkali sweat resistance, shrinkage resistance, and potting resistance.

Color Index: Acid Orange 63 is a high-grade yellow dye for synthetic and natural polyamides that has been known for a long time and is used in the largest quantities today, and the dyed products obtained with this dye have excellent light fastness, washing fastness, and shrinkage fastness. There are dyes that are very important as they exhibit excellent properties, good build-up properties, and high color value, but since the above dyes are made from benzidine-3-sulfonic acid, which is obtained by sulfonating benzine, most of the dyes covered by Imada are It is in a state where it cannot be manufactured.

This made the invention even more important.

i.e. Color Index: Acid, Orange 6
The various fastnesses of the dyed products obtained by the method of the present invention are far superior to those of the dyed products obtained using the dye No. 3.

Furthermore, while the former dyed product has a color tone closer to orange, the dyed product according to the method of the present invention has a moderate color tone, so it can be said that it has more versatility.

To carry out the method of the present invention, a dye bath in which a disazo dye represented by the formula (1) or a mixture of two or more disazo dyes is dissolved in an aqueous medium or a printing paste is prepared and dyed or dyed by a method known per se. Print.

For example, in the case of dip dyeing, the object to be dyed may be immersed in a dye bath made of an aqueous medium preferably kept acidic or neutral and heated.

The dyeing temperature at this time varies depending on the type of the object to be dyed, the presence or absence of additives, the type of dyeing equipment, etc., but it is usually best to start at room temperature and carry out the dyeing process at 80 to 130°C.

At this time, known slow-leveling dyes, accelerators, fasteners, etc. can also be used as appropriate.

In the case of textile printing, the dye represented by the formula (1) above is mixed with a base paste, a dye dissolving agent, a dye accelerator, a reduction inhibitor, etc. to prepare a color paste, and this is printed on the object to be dyed. After usually 90-11
Steam treatment is performed at a temperature of about 0°C.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

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

Example 1 1 part of the dye represented by the above formula was dissolved in hot water, water was added to the solution to make a total amount of 3000 parts, and then 5 parts of ammonium acetate was added to prepare a dye bath.

This is nylon processed yarn knitted fabric (6 nylon, chassis)
100 parts of the sample was immersed, the temperature was raised to 100°C over 40 minutes, and after 20 minutes at the same temperature, 1 part of acetic acid was added and held for an additional 20 minutes for dyeing.

After dyeing, it was thoroughly washed with water, squeezed, and dried.

A uniform medium yellow dyeing without flickering was thus obtained.

Moreover, its light fastness, washing fastness, and alkaline sweat fastness were 6th grade, 5th grade, and 4th grade, respectively.

Example 2 The dyeing process was carried out in exactly the same manner as in Example 1, except that wool cloth was used instead of the nylon processed yarn for the dyed object and 3 parts of acetic acid was used instead of 1 part of acetic acid. A very similar uniform medium yellow color was obtained.

The light fastness, washing fastness, and potting fastness of this dyed fabric were 5th grade, 5th grade, and 4th grade, respectively.

Examples 3 to 6 Instead of the dye used in Example 1, if one part of each of the dyes having the following structure is used and the dyeing process is carried out in exactly the same manner as in Example 1, a medium color similar to Example 1 can be obtained. A nylon textured yarn knitted fabric dyed yellow was obtained.

Moreover, the light fastness was 6th class.

A printing paste with the following composition was prepared using the dye having the above structure, printed on 6-nylon and desyne, and after intermediate drying at 60 to 65°C, steam treatment was performed at a temperature of 100 to 102°C for 30 minutes. Ta.

Next, the printed fabric was thoroughly washed with water, subjected to saw pink treatment at 60°C for 20 minutes, washed again with water, and dried.

In this way, an extremely uniform, slightly greenish-yellow print was obtained.

The light fastness, water fastness, and alkaline sweat fastness of the printed products were 6th grade, 5th grade, and 4th to 5th grade, respectively. Using this method, a printing paste was prepared and printed in exactly the same manner as described above, and a printed product with the color tone shown on the right was obtained.

The dye of Example 10 was prepared as follows:
-Diaminobenzanilide-3-sulfonic acid (30.7 parts) is diazotized by a known method.

Then 25.4 parts of 1-(4'-sulfophenyl)-3
- A solution of methylpyrazolone (5) in 150 parts of water at a pH of 5 or lower is added over a period of 1.5 hours.

Subsequently, the pH value of the reaction solution was adjusted to 4.0 with a 10% sodium carbonate solution.
It took 60 minutes to set it to zero.

Next, a suspension of 10 parts of phenol in 30 parts of water was added all at once, and a suspension of 20 parts of anhydrous soda carbonate in 30 parts of water was added and stirred overnight.

The compound thus obtained was a disazo compound having the following structure.

The entire press cake of the disazo compound thus obtained was charged into an autoclave, and then methanol 10
0 parts, anhydrous sodium carbonate 15 parts 47% caustic soda 13
After stirring and dispersing well, 11.5 parts of chloroethyl was added under pressure.

Subsequently, the autoclave was gradually heated, and when the temperature was raised to 95° C., the internal pressure showed 9/cvt between 8 and 9.

If you continue to adjust the temperature to maintain this internal pressure for 2 hours,
The target response progressed at a high rate.

After the reaction is complete, the chloroethyl and methanol are distilled and recovered, and then the dye is extracted.

One part of the above structural dye was dissolved in hot water, water was added to make a total amount of 3000 parts, and then 5 parts of ammonium acetate was added to prepare a dye bath.

100 parts of wool muslin fabric is soaked in this for 1 to 30 minutes. The temperature was raised to 100° C. in 30 minutes, and after 30 minutes at the same temperature, 3 parts of acetic acid was added and held for an additional 40 minutes to carry out dyeing.The resulting dyed product was thoroughly washed with water and dried.

The dyed products thus obtained showed a uniform medium yellow color, and the light fastness, washing fastness and potting fastness were 5th grade, 5th grade and 4th grade.

The above dye was produced as follows.

4.4'-diaminobe/tuanilide-2-sulfonic acid 3
0.7 part was diazotized by a known method.

To this was added 20 parts of urea to eliminate excess nitrous acid.

To this was added 9.4 parts of phenol dispersed in 30 parts of fishing rod, and 10% sodium carbonate water was added little by little to maintain the pH at 6.

If stirring is continued for 2 hours, the 1:1 reaction between bisdiazonium salt and phenol will proceed almost quantitatively, and unreacted bis-
Diazonium salts were almost no longer detected.

Next, 130 parts of a neutral aqueous solution containing 25.4 parts of 1-(2'-sulfophenyl)-3-methylpyrazolone (5) was added, and sodium carbonate was further added to make the mixture alkaline, and the mixture was stirred overnight to complete the reaction. I measured it.

After raising the temperature to 80° C., salting out, filtering and drying, a disazo compound having the following structure was obtained.

In the reaction solution of the disazo compound thus obtained, 28
．． 5 parts of P-toluenesulfonyl chloride and 8 parts of anhydrous sodium carbonate were added, the temperature was raised to 80'C, and the mixture was stirred at this temperature for 1 hour.

Subsequently, dye crystals were precipitated with common salt, P was separated from the crystals, and dried to obtain a dye having the above structure.

The λmax of typical dyes of the present invention is shown below.○

Claims (1)

[Claims] Formula 1 [where X represents C0NH or NHCO; benzene ring A may be substituted with 1 to 2 CIs or further 1 M; benzene ring B is such that X represents C0NH When , it has a substituent,
When NHCO has 803M, the benzene ring C is
When X is CONH, it is substituted with SO3M, and NHCO
When , it has a substituent, be/zen-iD has CH3 at any position and ~C2
represents an alkyl group, benzene WE may be substituted with -CH3, and M
For example, H, an alkali metal, alkaline earth metal or ammonium group. A method for dyeing polyamide fibers, characterized by using a disazo dye represented by ].