JPS585367A - Disazo reactive dye - Google Patents

Abstract

NEW MATERIAL:To provide a new disazo compd. for dye represented by formulaIin the form of a free acid (where X and Y are each H or a sulfonic acid group, with adjacent azo and sulfonic acid groups linked to a naphthalene ring to which X and Y are linked). USE:Cellulosic fibre is dyed in blue to black color with excellent fastness to light and chlorine. PREPARATION:A naphthylaminesulfonic acid deriv. of formula II is dissolved or suspended in water and is diazotized with sodium nitrite at below 20 deg.C under an acidic condition given by mineral acid. After removal of excess nitrite with sulfamic acid, the diazotized product is coupled with monoazo dye of formula III.

Description

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

Conventionally, 2 moles of 1-aminobenzene-4-1-sulfatoethylsulfone were diazotized and 1 mole of 1-amino-8-hydroxy was used as a reactive dye for dyeing cellulose fiber materials blue to black to gray. 7 meals - 8.6 -
C0 engineering, R@ obtained by coupling with disulfonic acid
aatima Blaok 5 is known. However, the firmness of dyed products using this dye is not sufficient, and improvements in texture are also desired.

Publication No. 4$1-151!99 discloses a disazo wide-strength dye that dyes cellulose fibers to give a blue to black color with excellent infiltration resistance and light resistance. Improvements are expected in these dyes in particular in terms of sweat, sunlight and chlorine susceptibility, solubility, exhaustion rate, fixation rate, and build-up properties of dyes. For example, the dye represented by the following formula described in Example 1 of the same publication has a salt aggregation degree (XaO method) of 1st to 2nd class, and a solubility in water of 5 otit or less.

By the way, C, I, R@aotive Black 5
g) Solubility in water is greater than Hatake Out/.

Furthermore, a dye represented by the following formula described in Example 6 of the same publication Although the solubility has been improved to some extent,

Compared to R@aati Ma・Blaok 6, a larger amount of dye is required to dye the same density, and the build-up property is still not as good.

Further, similar disazo-reactive dyes are disclosed in 4I-kai No. 114M-431117, but these dyes also have practical problems in terms of fastness other than light fastness and moisture resistance, such as particularly salt bulk fastness. For example, the dye of the formula below described in No. 1 has a chlorine resistance of grade 1, 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 (I) [wherein x and Y each independently represent a hydrogen atom or a sulfonic acid group, %
It is assumed that the azo group and the sulfonic acid group bonded to the 7talene ring to which Y is bonded are in adjacent positions. ] It was discovered that the disazo-reactive dye represented by the following achieves the objective 1ζ, and the present invention was completed.

The disazo-reactive dye represented by the general formula (I) can be combined with the sonoazo dye represented by the general formula (1) to the general formula (to) [in the formula, ! ,!
has the above-mentioned meaning, and the amino group and the sulfonic acid group meet in the production process by coupling a diazo compound of a naphthylaranine sulfonic acid derivative, which is represented by the following characters:

In the following, the Illll method will be explained in more detail.

The naphthylarnesulfonic acid derivative represented by the general formula (2) is dissolved or suspended in water, and diazotized using sodium nitrite at 110° C. or lower under mineral acid acidity. After removing the excess nitrous acid with sulfuric acid, it is coupled with a monoazo dye of the formula (odor).The diazo compound may be added to a solution or suspension of the monoazo dye, or vice versa. The latter may be added to the diazotization solution.

The coupling reaction is pH! ~8. Below 80℃,
Do so 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 the naphthylamine sulfonic acid derivative of general formula (2) that can be used in the present invention.

2-naphthylamine-1-sulfonic acid, g-naphthylamine-1,6-disulfonic acid, g-naphthylamine-8
,6-disulfonic acid,! -Naphthylamine-16,8-
Trisulfonic acid, 2-naphthylamine-1,6-disulfonic acid, l-naphthylamine-2-sulfone II, 1
-7-tylamine-2,7-disulfonic acid The Morobaceae of the present invention includes a wide range of substances having a hydroxyl group,
In particular, textile materials, such as natural or regenerated cellulose, rosewood, eg cotton or viscose yarn materials, can be dyed according to the customary methods carried out using water-soluble reactive mulberry materials.

For example, in the case of cellulose 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 properties and physical shape of the fiber, such as the 11-layer method, printing, etc. Continuous dyeing methods can be employed, including dyeing methods or cold, pad, and patch-up methods.

Although the dye of the present invention has only one fiber-reactive group in one molecule, it has two fiber-reactive groups;
Compared to R@aOtima@Black 5, cellulose fibers can be dyed in a deeper color, and the resulting dyed product has better durability.

Sara H: Honsha 'I dye N! t41Aws48-15299
It has a higher solubility in water than the dyes described in Publication No. 4I and Publication No. 45-4117, and can dye cellulose fibers with excellent exhaustion rate, fixation rate, and build-up property, and the dyed product obtained is Excellent in various properties such as light and sunlight resistance, especially chlorine resistance.

Next, the present invention will be explained in more detail with reference to examples. In the following, parts represent parts by weight.

Example 1 2-Naphthyl alcohol 1,6-disulfonic acid 15.17
After diazotizing the portion by a conventional method and removing excess nitrous acid with sulfamic acid, 1-amino-2-(11-/-sulfatoethylsulfonylphenylazo)-8- and droxynaphthalene-8,6 -Add a neutral aqueous solution containing 88.85 parts of the trisodium salt of disulfonic acid. At 1G-20°C, keep the pH at 4-7 for 8 hours by dropping an aqueous solution of sodium carbonate. If no diazo compound is detected, I) H4-B, 80-40°C.
After salting out at C, the resulting wet cake was dissolved in water and equimolar sodium phosphate was added to adjust the pH to 5 to 6, followed by drying to form the free acid in the form of the following formula (1). The indicated dyes were obtained.

[Includes wax giOnm (water solvent)] Above dye 0.8
Dissolve 1 part in 20 parts of water, add 20 parts of mirabilite, and add 1 part of cotton.
Add 0 parts and raise the temperature by 5°tic. Then, after 80 minutes had elapsed, 4 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were performed to obtain a black dyed product with excellent tenacity, high build-up properties, and a good texture.

Example 2 1-amino-2-(8-,/-sulfatoethylsulfonylphenylazo)-8-hydroxynaphthalene-3
, 6-disulfonic acid (0-10Cl H0,5-2D suspension containing 80.65 parts of 1-aminobenzene-1
1-1-Sulfate ethyl sulfone was dioridiazotized in a conventional manner to give 1-amino-8-hydroxy sinaftasine-8.
, 6-disulfonic acid by dropwise coupling. ), 2-s7tylamine-1
- After diazotizing 11.25 parts of sulfonic acid by a conventional method,
Sur 77 for excess nitrite? Processing of liquid removed with acid, 6
The pH is brought to 6 by addition of sodium bicarbonate over a period of about 1 hour at ~16° C. and stirred until the diazo compound is no longer detected. The obtained dye solution is PH
A dye represented by the following formula (2) in the form of a free acid was obtained by drying the mixture from 4.5 to 6.6.

Dissolve 0.6 parts of the above dye in 20°C% water, add 20 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 60°C. Then, after 80 minutes had elapsed, 4 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were carried out to obtain a blue to black dyed product with excellent durability, high build-up properties, and a good texture.

Examples 8 to 7 Corresponding dyes were obtained in the same manner as in Example 1 or 2 using the raw material compounds listed in the table below. Using each of the obtained dyes, cotton was dyed in the same manner as in Example 2 to obtain a blue to black dyed product with excellent properties and a good texture.

Procedural amendment April 1980 Commissioner of the Japan Patent Office Shima 1) Haruki Tono1, Indication of the case 1982 Patent Application No. 1087942, Name of the invention Disazo-reactive dye 8, Person making the amendment Case and Relationship Patent applicant address 5-15 Kitahama, Higashi-ku, Osaka Name (20
9) Hijikata, Representative of Sumitomo Chemical Industries, Ltd.
Take 4, Agent Address: 5-16-6 Kitahama, Higashi-ku, Osaka City, Full text of the specification to be amended and drawings 6, Contents of the amendment as attached. Dye 2, Claims In the form of a free acid, the following general formula [wherein, shall be taken as a thing. ] A disazo-reactive dye represented by.

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

Conventionally, 2 moles of 1-aminobenzene-4-β-sulfatoethylsulfone were diazotized and 1 mole of 1-amino-8-hydroxy was used as a reactive dye for dyeing cellulose fiber materials blue to black to gray. Naphthalene-8,6-
C obtained by coupling with disulfonic acid, 1. Re
activeBlack 5 is known. However, the fastness of dyed products using this dye is not sufficient, and improvements in texture are also desired.

Japanese Patent Publication No. 4B-15299 discloses disazo-reactive dyes that dye cellulose fibers to give blue or black dyeings with good moisture resistance and light resistance. Improvements are expected in terms of fastness to chlorine, dissolution chamber, exhaustion rate, fixation rate, and build-up properties. 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 water solubility of 80 f/ or less. Incidentally, the solubility of C, I, and Reactive Black 5 in water is 800 y/ or more.

Furthermore, a dye represented by the following formula described in Example 5 of the same publication Although the solubility of C and I has been improved to some extent.

Compared to Reactive Black 5, a larger amount of dye is required for dyeing to the same density, and the build-up performance is still inferior to that of Reactive Black 5.

Further, similar disazo reactive dyes are disclosed in Japanese Patent Publication No. 46-4887, but these dyes also have practical problems in terms of fastness other than light fastness and moisture fastness, such as fastness to chlorine in particular. It is something.

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, the following general formula CI) was obtained in the form of a free acid (wherein, X represents a hydrogen atom or a sulfonic acid group, and X is bonded to the naphthalene ring). The azo group and sulfonic acid group to be bonded are assumed to be in adjacent positions. ] It was discovered that the disazo-reactive dye represented by the following is suitable for the purpose, and the present invention was completed.

The disazo-reactive dye represented by the general formula (I) is a disazo-reactive dye represented by the formula (II).
) The monoazo dye represented by the general formula (2) [wherein, X has the above-mentioned meaning, and the amino group and the sulfonic acid group are in adjacent positions. It can be produced by coupling a diazo compound of a naphthylamine sulfonic acid derivative shown in ].

The manufacturing method will be explained in more detail below.

The naphthylamine sulfonic acid derivative represented by the general formula (2) is dissolved or suspended in water, heated under mineral acid acidity at 20° C. or below, and diazotized using sodium nitrite. After removing excess nitrous acid with sulfamic acid, it is coupled with a monoazo dye of formula (II). 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 a pH of 2 to 80° C. or below 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 (2) that can be used in the present invention.

2-naphthylamine-1-sulfonic acid, 2-s7tylamine-1,5-disulfonic acid, 2-naphthylamine-8
, 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 rayon materials, can be dyed according to customary methods carried out with water-soluble reactive dyes, e.g. in the case of cellulosic fibers, the dyes of the invention and acid bonds Dyeing is carried out using agents such as caustic soda and 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 patch-up methods.

Although the dye of the present invention has only one fiber-reactive group in one molecule, C, which has two fiber-reactive groups, 1. R
Compared to Active Black 5, cellulose fibers can be dyed in a deeper color, and the obtained dyed product has better viscosity.

Furthermore, the dye of the present invention has higher solubility in water than the dyes described in JP-A-44B-15299 and JP-B-45-4887, and has excellent exhaustion rate, fixation rate, and build-up property, making it suitable for dyeing cellulose-based delicates. I can do it,
Moreover, the obtained dyed products have various fastness properties such as secondary light and sunlight resistance.
It is particularly excellent in terms of chlorine hardness.

Next, the present invention will be explained in more detail with reference to Examples. In the text, parts represent parts by weight.

Example 1 2-naphthylamine-1,5-disulfonic acid 15.17
was diazotized by a conventional method, excess nitrous acid was removed with sulfamic acid, and 1-amino-2-(8-β-sulfatoethylsulfonylphenylazo)-8-hydroxynaphthalene-8,6- A neutral aqueous solution containing 88.85 parts of the trisodium salt of disulfonic acid is added. 10-20
℃, the pH is kept at 4-7 for 8 hours by dropwise addition of 15% aqueous sodium carbonate solution. When the diazo compound is no longer detected, salting out occurs at pH 4-6.80-40°C,
The wet cake obtained by filtration is dissolved in water, added with an equimolar amount of monobasic sodium phosphate to adjust the pH to 5 to 6, and then dried. As a result, a dye represented by the following formula (1) was obtained in the form of a free acid.

Mix 610 parts m (water solvent) 0.6 part of the above dye is dissolved in 200 parts of water, 20 parts of Glauber's salt is added, 10 parts of cotton are added, and the temperature is raised to 50°C. Then, after 80 minutes had elapsed, 4 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were carried out to obtain a blue to black dyed product with excellent color fastness, rich build-up property, and good texture.

Example 2 1-amino-2-(8-β-sulfatoethylsulfonylphenylazo)-8·-hydroxynaphthalene-8
, 6-disulfonic acid, 0 to 10°C, p
A suspension of H0,5-2 (this is l-aminobenzene-
8-β-Sulfatoethyl sulfone was diazotized by a conventional method to obtain 1-amino-8-hydroxynaphthalene-8,
Obtained by dropwise coupling with a neutral solution of 6-disulfonic acid. ), 2-naphthylamine-1-
After diazotizing 11.25 parts of sulfonic acid by a conventional method, a solution in which excess nitrous acid had been removed with sulfamic acid was added, and 5 to
The pH is brought to 6 at 15° C. by addition of sodium bicarbonate over a period of about 1 hour, and the mixture is stirred until the diazo compound is no longer detected. The obtained dye solution was adjusted to pH
4.5 to 5.6 and then drying to obtain a dye represented by the following formula (2) in the form of a free acid.

(max 612 nm (water solvent)) above dye 0.6
Dissolve 1 part in 200 parts of water, add 20 parts of mirabilite, and add 1 part of cotton.
Add 0 parts and raise the temperature to 60°C. Then, after 80 minutes,
Add 4 parts of soda carbonate and dye at the same temperature for 1 hour. Examples 8 and 4 In which dyed products with excellent color fastness, rich build-up properties, blue to black color and good texture were obtained by washing with water and soaping after dyeing. 2 as a compound
Using -naphthylamine-8,6-disulfonic acid and 2-naphthylamine-1°6-disulfonic acid, corresponding dyes were obtained. - Using each of the obtained dyes, cotton was dyed in the same manner as in Example 2 to obtain a blue to black dyed product with excellent performance and a good texture.Comparative Example 1 C, 1, Reactive Rlack 5 1%ow
Chlorine fastness (ISO method) was measured using a dyed product of each dye whose concentration matched that of the dyed product obtained using f, and was expressed in five levels. (6th 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 gave 4th to 5th class fastness, but
In No. 99, the dyes listed in Tables 1, -5 and 8 of the publication were all 1st class, except for 1st to 2nd class, 8th to 4th class, and 8th class.

In addition, in Japanese Patent Publication No. 46-4887, 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 FIG. 1 shows the results of a comparison of the dyeing properties of the dye described in Example 15 of Publication No. 45-4887 and the dye described in Example 2 of the present invention. In addition, in the figure, the horizontal axis shows the value obtained by dividing the amount of dye used by the amount of cotton used (OWF (%)), and the vertical axis shows the amount of dyeing per unit area of dyed material C5Q-VAL.
UE--that is, the darkness of the dyed material] and show the relationship therebetween.

As a result, the dye of the present invention was dyed at a lower concentration than the comparative dyes.
It can be dyed in extremely deep colors in all areas of high concentration dyeing, and has the characteristics of excellent build-up properties.

4. Brief Description of the Drawings FIG. 1 is a diagram showing the relationship between OWF (%) and SQ-VALUE. In other words, the horizontal axis is the value obtained by dividing the specified amount of dye used by the amount of cotton used [OWF (%)], and the vertical axis is the amount of dyeing per unit area of the dyed product C3Q-VALUE-Darkness of the dyed product] This shows the relationship between them.

In the figure, A indicates the dye described in Example 15 of Japanese Patent Publication No. 45-4887. B in the figure indicates the dye of Example 2 of the present invention.

Claims (1)

[Scope of Claims] In the form of a free acid, the following general formula [wherein X and Y each independently represent a hydrogen atom or a sulfonic acid group; The groups are assumed to be in adjacent positions. ] A disazo-reactive dye represented by.