JPS60377B2 - Disazo reactive dye - Google Patents

Description

[Detailed description of the invention] The present invention relates to blue to black disazo-reactive dyes.

Conventionally, 2 moles of 1-aminobenzene-4-8-sulfatoethylsulfone were diazotized as a reaction material for dyeing cellulose fiber materials blue to black to gray, and 1 mole of 1-amino-8-hydroxy naphthalene-3,6-
C. obtained by coupling with disulfonic acid. 1. Re
activeBlack5 is known. However, the fastness of dyed products using this dye is not sufficient, and improvements in texture are also desired. Tsubaki Publication No. 43-1529y discloses disazo-reactive dyes that dye cellulose fibers to give blue or black dyes with good moisture resistance and light resistance. Improvements are expected in terms of chlorine fastness, solubility, exhaustion rate, fixation rate, or build-up property.

For example, the dye represented by the following formula described in Example 1 of the same publication has a chlorine fastness (ISO method) of 1st to 2nd class, and a solubility in water of 30 μg/k or less.

C. in trouble. 1. The solubility of Reacive Black 5 in water is 300 μm/so or more. Furthermore, although the dye represented by the formula below described in Example 5 of the same publication has improved solubility to some extent, C.I. 1. ReactiveBlack
Compared to No. 5, a larger amount of dye is required for dyeing to the same density, and the build-up property is still inferior to No. 5.

Furthermore, similar disazo anti-oxidants are disclosed in Japanese Patent Publication No. 45-4337.
*Although reactive dyes have been developed, these dyes still have practical problems in terms of fastness other than light fastness and moisture fastness, such as fastness to chlorine in particular.

For example, the dye of the formula below described in the same publication has first class chlorine fastness, and the dye of the formula below also has problems in practical use.

The present inventors conducted intensive studies to solve this problem, and as a result, in the form of a free acid, the following general formula (1) [wherein, X represents a hydrogen atom or a sulfonic acid group, and X is bonded to a naphthalene] It is assumed that the azo group and the sulfonic acid group bonded to the ring are in adjacent positions.

] It was found that the disazo-reactive dye represented by the following was found to be suitable for the purpose, and the present invention was completed. The disazo reactive dye represented by the general formula (1) is a monoazo dye represented by the formula (0) and the general formula (m) [wherein, X has the above meaning, and the amino group and the sulfonic acid group are located at adjacent positions It shall be assumed that

It can be produced by coupling a diazo compound of a naphthylamine sulfonic acid converter shown in ].

The manufacturing method will be explained in more detail below.

A naphthylamisosulfonic acid derivative represented by the general formula (m) is dissolved or suspended in water and diazotized using sodium nitrite under key acid acidity at 20 oC or less.

After removing excess nitrous acid with sulfamic acid, the formula (0
) is coupled with a monoazo dye. In this method, the diazo compound may be added to a solution or suspension of the monoazo dye, or the latter may be added to the diazotization solution.
The coupling reaction is carried out at pH 2 to 8 and below 30 oo until the diazo compound is no longer detected.
After the obtained disazo-reactive dye is once removed by salting out or as a reaction solution, an auxiliary agent such as a stabilizer may be added as the case may be, and the dye of the present invention is obtained by drying. The following compounds can be exemplified as naphthylamine sulfonic acid derivatives of general formula (m) that can be used in the present invention.

2-naphthylamine-1-sulfonic acid, 2-naphthylamine-1,5-disulfonic acid, 2-naphthylamine-3
, 6-disulfonic acid, especially 2-naphthylamine-
1-sulfonic acid is preferred.

The dyes of the invention include a wide range of substances having hydroxyl groups,
In particular, textile materials, such as natural or regenerated cellulose, such as cotton or viscose lace materials, can be dyed according to the customary methods carried out with water-drop reactive dyes.

For example, in the case of cellulosic fibers, dyeing is carried out using the dye of the present invention and an acid binder such as caustic soda or sodium carbonate.

The dyeing method can be selected depending on the nature and physical shape of the fiber, and can be, for example, an exhaust method, a printing method, or a continuous dyeing method including cold, pad, and batch-up methods. Although the dye of the present invention has only one fiber-reactive group in one molecule, C.I. 1. ReactN
Compared to e-sub-ack5, cellulose fibers can be dyed in a deeper color, and the fastness of the dyed product obtained is better.

Furthermore, the dye of the present invention has a higher solubility in water than the dyes described in Tokusekki No. 43-1529 and Jiko No. 45-4337, and has excellent exhaustion rate, fixation rate, and build-up property, and is suitable for cellulose-based dyes. Fibers can be dyed, and the dyed products obtained are excellent in various fastnesses such as light fastness and sunlight fastness, especially fastness to chlorine.

Next, the present invention will be explained in more detail with reference to Examples.

In the text, parts represent parts by weight. Example 1 After diazotizing 15.17 parts of 2-naphthylamine-1,5-disulfonic acid by a conventional method and removing excess head nitric acid with sulfamic acid, 1-amino-2-(3-8-sulfatoethylsulfonyl) A neutral aqueous solution containing 33.85 parts of the trisodium salt of (phenylazo)-18-hydroxynaphthalene-3,6-disulfonic acid is added.

At 10 to 20 qo, a 15% aqueous sodium carbonate solution is added dropwise to maintain the pH at 4 to 7 for 3 hours.

If the diazo compound is no longer detected, the pH is 4 to 6.30.
Salting out at ~4°C and filtering in an oven. Dissolve the obtained wet cake in water and add equimolar amount of monosodium phosphate to pH 5.
~6 and then drying to form the free acid in the form of the following formula '1
A dye represented by 1 was obtained. [Arc (aqueous solution) with a max of 610 ml] Dissolve 0.6 parts of the above dye in 20 ml of water, add 2 parts of ramie, add 1 part of cotton, and raise the temperature to 50°C.

Then, after 3 minutes, add 4 parts of soda carbonate and boil at the same temperature.
Time staining. After dyeing, washing with water and soaping were performed to obtain a dyed product with excellent color fastness, deep build-up, blue to black color, and good texture. Example 2 1-Amino-2-(3-8-sulfatoethylsulfonylphenylazo)-8-hydroxynaphthalene-3,
0-1000 containing 30.55 parts of 6-disulfonic acid
, pHO. A suspension of 5-2 (this is prepared by diazotizing 1-aminobenzene-3-8-sulfatoethyl sulfone by a conventional method to obtain 1-amino-8-hydroxynaphthalene-3
．． Obtained by dropwise coupling with a neutral solution of 6-disulfonic acid.

), 11. of the 2-naphthylamine-1-sulfonic acid group.
After diazotizing 25 parts by a conventional method, a solution in which excess nitrite was removed with sulfamic acid was added, and at 5 to 15 qo, sodium bicarbonate was added over about 1 hour to bring the pH to 6 and no diazo compound was detected. Worship the rope until it stops. The obtained dye solution was adjusted to pH 4.5 to 5.5 and then dried to obtain a dye represented by the following formula [21] in the form of a free acid. [Max 612 Makino (aqueous solution)] Dissolve 0.6 parts of Jogonji dye in 20 parts of water, add 2 parts of sulfur, add 1 part of cotton, and raise the temperature to 5,000.

Then, after 30 minutes, add 4 parts of soda carbonate and boil at the same temperature.
Time staining. After dyeing, washing with water and soaping were performed to obtain a dyed product with excellent color fastness, deep build-up, blue to black color, and good texture. Examples 3 and 4 2 was prepared as a raw material compound by the same method as in Example 1 or 2.
Corresponding dyes were obtained using naphthylamine-3,6-disulfonic acid and 2-naphthylamine-1,6-disulfonic acid.

Cotton was dyed in the same manner as in Example 2 using each of the obtained dyes to obtain a blue to black dyed product with excellent properties and a good texture. Comparative example 1C. 1. Chlorine fastness (ISO method) was measured using a dyed product of each dye whose concentration matched that of a dyed product obtained using 1% owf of ReactNeRlack 5, and expressed in five levels.

(5th grade is the best, 1st grade is the worst) The dyed material used was cotton knit. Each of the dyes described in Examples 1 to 4 of the present invention all gives 4th or 5th class fastness, but in Samuraiko No. 43-15299, Table 1 No.
The dyes described in No. 5 and No. 8 are 1st to 2nd grade, 3rd to 4th grade in order.
All of them were grade 1, except for grade 3 and grade 3.

In addition, in Japanese Patent Publication No. 45-4337, 14 of the dyes described in Examples 1 to 19 of the same publication are 1st class and 5 are 1st class.
It was ~2nd class. Comparative Example 2 Beam described in Example 15 of Japanese Patent Publication No. 45-4337*
Figure 1 shows the results of comparing the dyeing properties of the dye described in Example 2 of the present invention.

In addition, the figure shows the value obtained by dividing the amount of dye used by the amount of cotton used [OWF (%)] on the axis, and the amount of dyeing per unit area of the dyed product [SQ-VALUE = that is, the density of the dyed product] on the vertical axis. ] and show the relationship. As a result, the dye of the present invention can be dyed in an extremely deep color in the entire range from low density dyeing to high density dyeing, and has excellent build-up properties than comparative dye A.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between OWF (%) and SQ-VALUE. In other words, the machine axis is the value [OWF (%)] obtained by dividing the specified amount of dye used by the amount of cotton used, and the vertical axis is the amount of dyeing per unit area of the dyed product [SQ-VALUE = darkness of the dyed product]. This shows the relationship between them. In the figure, A indicates the dye described in Example 15 of Samurai Ko No. 45-14337, and B in the figure indicates the dye of Example 2 of the present invention.

Claims (1)

[Claims] 1 In the form of a free acid, there are the following general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X represents a hydrogen atom or a sulfonic acid group, and The group and the sulfonic acid group are assumed to be in adjacent positions. ] Disazo reactive dye.