JPS60215071A - Fiber-reactive monoazo compound - Google Patents

Abstract

NEW MATERIAL:Dis-azo compounds of formula I (wherein R is H, a 1-4C alkyl; Y is F, Cl; n is 1-3; X is a residue of 1-amino-8-hydroxynaphthalenemono (or di)-sulfonic acid; Z is -SO2CH2CH2Cl, -SO2CH=CH2, -SO2CH2CH2OSO3H, -SO2CH2OPO3H2, -N(R1)SO2CH2CH2OSO3 (wherein R1 is H, methyl, ethyl), a residue of a benzene or naphthalene ring). USE:Reactive dyes which has excellent fastness and good dischargeability and dye cellulosic fibers such as cotton, flax, viscose silk and viscose staple fiber deep blue. PREPARATION:A diazonium compd. obtd. by diazotizing a compd. of formula IIand a diazonium compd. obtd. by diazotizing a naphthylaminesulfonic acid compd. of formula III are coupled with a 1-amino-3-hydroxynaphthalenemono(or di)sulfonic acid in an arbitrary order.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dyeing cellulose fibers deep blue.

More specifically, the present invention can be carried out in the form of a free acid by the following general formula (1) [wherein R is a hydrogen atom or an alkyl group of CX-4, Y
is a fluorine atom or a chlorine atom, n is 112 or 8, or a 1-amino-8-hydroxynaphthalene mono- or disulfonic acid residue. z Ha formula-5O2CH2CH2C
4, -3o2CH=CH2, -8O2CH2CH20S
O3I(, -SO□C玖CH, 0PO3H, or -N
(R1) 5O2CH2CH20SO3H group (where R1 represents a hydrogen atom, methyl group or ethyl group)
This is a patented method for dyeing rose-based fibers, which is characterized by using a dye having the following formula and representing a benzene ring or naphthalene ring residue which may have other substituents.

A water-soluble dye that gives a green to blue hue to textile materials can be obtained by coupling 2 moles of a benzene or naphthalene-based diazonium compound with 1 mole of 1-a-8-sulfonic acids. is already known. Among these dyes, dyes having a monohalogenotriazinyl group are well known as reactive dyes. However, these reactive dyes generally require high dyeing temperatures and lack suitability for exhaust dyeing, so they are only used for textile printing.Furthermore, they have the disadvantage of low acid stability of the dyed products obtained. Therefore, it could never be said to be sufficient for practical use.

On the other hand, it is known that dyes having a β-sulfatoethylsulfonyl group can be applied to dyeing textile materials as so-called vinylsulfone type reactive dyes. However, dyeings made with azo deep blue reactive dyes having a β-sulf-1-toethylsulfonyl group generally have low chlorine fastness (fading due to chlorine contained in tap water is often a problem).

For this reason, the present inventors have conducted intensive studies to develop a deep blue vinyl sulfone-type reactive dye that has particularly excellent chlorine fastness, as well as sufficient light fastness and sweat/sunlight fastness. As a result, it was found that the dye represented by the general formula (1), that is, the disazo dye having a β-sulf-1-toethylsulfonyl group and a monochloro or monofluorotriazinyl group as a reactive group met these conditions. It has been found that it gives a deep blue dyeing.

It has also been found that the dye of the present invention can overcome the drawbacks of reactive dyes having a monochloro or monofluorotriazinyl group as described above.

In the present invention, examples of cellulose fibers include natural or regenerated cellulose fibers such as cotton, linen, viscose human silk, and viscose cotton.

In the case of the exhaust method, the dyeing of the present invention is carried out at relatively low temperatures in a dyebath containing Glauber's salt or common salt in the presence of an acid binder such as soda carbonate, tribasic sodium phosphate or caustic soda.

In the case of printing, pastes such as, for example, sodium alginate, starch ethers or emulsifying pastes, and sodium carbonate, bicarbonate, caustic soda, tribasic sodium phosphate, sodium trichloroacetate or the corresponding potassium or alkaline earth compounds are used. together with alkaline or alkali-releasing agents, optionally with the addition of customary printing aids or dispersants, such as urea, on the fibers, dried and subjected to heat treatment, especially in the presence of water vapor. It can be dyed by

In the case of cold batch dyeing, caustic soda alone or in combination with sodium silicate, soda carbonate, or sodium phosphate is used as an acid binder, and in some cases, mirabilite or common salt is added, and if desired, a solubilizing agent such as urea or a penetrating agent is used. It can be dyed by padding it on a fiber at room temperature under the addition of , rolling it up on a roll, leaving it for 8 hours or overnight, washing with water, and drying.

The dye of the present invention can be produced, for example, as follows. Meta-phenylenediamine sulfonic acid and an amine represented by the general formula 0 [) % formula % (1) [wherein R and Z have the above-mentioned meaning] are combined into the general formula (to) [wherein Y is the above-mentioned] It is condensed in any order with 2,4.6-)dihalogeno-8-triazine represented by
f) A diazonium compound obtained by diazotizing by a conventional method derived from [in the formula, Z, R, and Y have the above-mentioned meanings];
A diazonium compound obtained by diazotizing a naphthylamine sulfonic acid compound represented by general formula (V) (H03S) Hαα interval (ma) [wherein n has the above-mentioned meaning] by a conventional method, ■) H-X-H(Vl) [In the formula, X has the above-mentioned meaning] Obtained by coupling l-amino-3- represented by It will be done.

Examples of the amine represented by the general formula () that can be used in the present invention include the following compounds.

1-Aminobenzene-2-1-8- or -4-β-sulfoethylsulfone, 1-aminobenzene-8-β
-phosphatoethylsulfone, 1-amino-4-methylbenzene-8-β-sulf-1toethylsulfone, l-aminobenzene-8-β-chloroethylsulfone, 1-amino-4-methoxybenzene-8- β-sulf7toethylsulfone, 1-aminobenzene-4-β-sulfatoethylsulfone-2-sulfonic acid, 1-aminobenzene-5-β-sulf7toethylsulfone-2-sulfonic acid, 1-amino Benzene-5-β-sulf7toethylsulfone-2,4-disulfonic acid, l-aminonaphthalene-
4-β-sulfonyl sulfone, 1-amino-2,
5-dimethoxybenzene-4-β-sulfatoethylsulfone, l-aminobenzene-4-β-sulfatoethylsulfone-2-carboxylic acid, 1-aminobenzene-5
-β-sulf1toethylsulfone-2-carboxylic acid, l
-amino-2-methoxybenzene-4-β-sulfatoethylsulfone, l-amino-2-chlorobenzene-4
-β-sulfatoethylsulfone, 1-amino-2-methoxybenzene-5-β-sulfatoethylsulfone,
2-7 Minonaphthalene-8-β-sulfatoethylsulfone, 2-aminonaphthalene-8-β-sulfatoethylsulfone-6-sulfonic acid, 1-amino-2,5-dimethoxybenzene-4-vinylsulfone, 1 -Amino-
2-Methoxy-5-methylbenzene-4-β-sulfur 7
Toethylsulfone, 1 7 Eno2.5-jethoxybenzene-4-β-sulf 1 Toethylsulfone, l, -
Amino-2-bromobenzene-4-β-sulf7toethylsulfone, 1-amino-2-bromobenzene-4-vinylsulfone, 1-aminobenzene-5-vinylsulfone-2,4-disulfonic acid, l- Aminobenzene-5-
β-phosph 1-toethylsulfone-2,4-disulfonic acid 1-aminobenzene-5-β-chloroethylsulfone-
2,4-disulfonic acid, 2-aminonaphthalene-8-β
-Phosph 1toethylsulfone-6-sulfonic acid, 2-aminonaphthalene-28-vinylsulfone-6-sulfonic acid, 1-amino-2-methoxy-5-methylbenzene-
4-β-chloroethylsulfone, 2-aminophenol-4-β-sulf-1toethylsulfone, 1-aminobenzene-8- or -4-vinylsulfone, 1-amino-2-hydroxybenzene-4-β -sulf-7toethylsulfone, l-aminobenzene-5-vinylsulfone-2
-sulfonic acid, 8-(N-methyl-β-sulfatoethylsulfonylamino)-1-7 minobenzene, 8-(N
-ethyl-β-sulf7toethylsulfonylamino)-
1-7 minobenzene, 8-β-sulf7toethylsulfonylamino-1-aminobenzene 1-(N-methyl or ethylamino)benzene-2,
8 or 4-β-sulfatoethylsulfone, 1-(
N-methylamino)benzene-3-β-phosphate ethyl sulfone, 1-(N-methylamino)-4-methoxybenzene-8-β-sulfatoethyl sulfone, 1
-(N-methylamino)) naphthalene-4-β-sulfatoethylsulfone, 2-(N-methylamino)naphthalene-8-β-sulfatoethylsulfone, 1-(N
-ethylamino)benzene-8-β-phosphateethylsulfone, 1-(N-ethylamino)-4-methoxybenzene-8-β-sulfatoethylsulfone, 1-
(N-ethylamino)naphthalene-4-β-sulfatoethylsulfone, 2-(N-ethylamino)naphthalene-8-β-sulfatoethylsulfone.

Examples of the naphthylamine sulfonic acid compound represented by the general formula (to) include l-aminonaphthalene-2,8,4
, 5,6 or 7-sulfonic acid, l-aminonaphthalene-2,4-12,5-12°6-12.7-18.5-
18.6-18.7-14.6-14,7- or 5.
7-disulfonic acid, l-aminonaphthalene-2,4,6
-12,4,7- or 8.5.7-) disulfonic acid,
2-aminonaphthalene-1,8,4,5,6,7 or 8-sulfonic acid, 2-aminonaphthalene-1,4-1-
1゜5-1l, 6-1l, 7-18.5-18.6-1
8.7-18.8-14,6-14,7-14,8-1
5.7-15.8- or 6.8-disulfonic acid, 2-
aminonaphthalene-1,4,6-11,4,7-18,
5,7-18°6.8- or 4.6.8-) disulfonic acid.

The l-amino-8-hydroxynaphthalene mono- or disulfonic acid represented by the general formula (VD) is, for example, l-
Examples include amino-8-hydroxynaphthalene-8,4,5- or 6-sulfonic acid and 1-amino-8-hydroxynaphthalene-8,6- or 4,6-disulfonic acid.

The dye of the present invention obtained in this manner has a lower dyeing temperature than the conventional azo deep blue reactive dye having a β-sulfatoethylsulfonyl group.
Alternatively, even at higher dyeing temperatures, dyed products with approximately constant color density can be obtained, regardless of the temperature. That is, the reproducibility of staining is excellent. In addition, the dye of the present invention has excellent level dyeing properties, and in particular, the dye does not bleed or fade when exposed to washing liquids containing oxidizing agents, and it also has excellent chlorine fastness, light fastness, and sweat/sunlight fastness. ing.

Furthermore, since the dye of the present invention exhibits a high exhaustion rate, it is possible not only to obtain dyed products with high density, but also to be advantageous during wastewater treatment since only a small amount of dye remains in the dye bath. has advantages. In addition, the dyed material using the dye of the present invention can be discharged in white, and excellent hot water can be recycled.

Among the dyes of the present invention, those in which the amino group is at the β-position in the general formula (2) are particularly preferred in terms of color density.

As a dye similar to the dye of the present invention, for example, JP-A-52-
Patent No. 98026 describes dyes shown in the following.

However, the acid stability of dyed products obtained using this dye (
The test method is to immerse the dyed fabric in 1% acetic acid for 80 minutes and then soak it at 125f/d for 6 hours at a temperature of 87±2°C using a bar spirometer.
The dyed dyes (time-treated) are inferior to the dyed products of the present invention, require a high dyeing temperature, and lack suitability for exhaust dyeing, and therefore have little practical value.

Next, the method of the present invention will be explained by way of examples.

In the text, parts represent parts by weight.

Example 1 0.3 part of the dye represented by the formula (1) (1) (measured under % formula % conditions) in the form of free acid was dissolved in 200 parts of water and 2 parts of mirabilite was added.
Add 0 parts, add 10 parts of cotton, and raise the temperature to 50°C.

Then, after 80 minutes, add 4 parts of soda carbonate and boil at the same temperature.
Time staining.

After dyeing, wash with water and soap to remove chlorine, secondary light,
A deep blue, highly concentrated dyeing with excellent sweat and sunlight fastness was obtained.

Reference Example 1 [Synthesis example of dye (1) of Example 1] 2-aminonaphthalene-1,5-disulfonic acid 7.58
and 160 parts of water, 40 parts of ice and 8.7 parts of concentrated hydrochloric acid, and
Diazotization is carried out at ~5° C. by injecting 5.1 parts of 85% sodium nitrite solution. After eliminating excess nitrous acid, a neutral solution of 7.78 parts of 1-amino-8- and droxynaphthalene-3,6-disulfonic acid was injected over about 1 hour at 0 to 10°C until the pH was 1. , 0 to 2.0. After stirring this mixture for several hours, it is neutralized with a caustic soda solution to pH 7, and salted out with sodium chloride at 80-85°C to obtain a monoazo dye.

On the other hand, 4.61 parts of cyanuric chloride and 4.70 parts of m-phenylenediaminesulfonic acid were adjusted to pH 1.5-8.0 in 50 parts of a surfactant aqueous solution and kept at 0-5°C for 1-2 hours. one condensation and then 1-aminobenzene-8-
β-sulfatoethyl sulfone 6.95'll added, t
The second condensation is carried out by stirring overnight at 25-80° C. while maintaining the pH at 5-5.5 with 20% sodium carbonate solution.

Then, after adding 5-0 parts of ice and 7.1 parts of concentrated hydrochloric acid,
Diazotization is carried out by adding 5.8 parts of % sodium nitrite solution. The diazotized solution from which excess nitrous acid has been removed is poured into a monoazo dye suspension made alkaline with sodium bicarbonate at 5 to 10°C, and the mixture is stirred for 1 to 2 hours to effect coupling. Adjust the pH to 5.5-6.0 with dilute sulfuric acid and lower the temperature to 50-55°C.
After that, add sodium chloride to this solution for salting out, filter, wash, and dry at 60°C. 88.5 parts of dye (1) were obtained.

Examples 2 to 18 In Example 1, instead of dye (1), the following (2) to (
Dyeing was carried out in the same manner except that dye No. 18) was used.

A deep blue, intense dyeing with excellent fastness properties was obtained.

The following dyes are as follows: Column A: 1-amino-8-hydroxynaphthalene mono- or disulfonic acid [compound of general formula (VI) above] Column B: diazo component of monoazo dye [compound of general formula α)] Column C: Diazo component of disazo dye [the above general formula (IV)
Amine constituting the compound [compound of the above general formula [)] Column D: 2,4.6-)dihalogeno-8-triazine [compound of the above general formula (1)] Column E: By λmax of the disazo dye solution characterized.

＼ Example 19 0.8 part of the dye represented by the formula (19) (% formula %) in the form of free acid was dissolved in 200 parts of water and 2
Add 0 parts, 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 performed to obtain a dyed product with high concentration of deep blue color and excellent fastness to chlorine, side light, sweat and sunlight.

Reference Example 2 [Synthesis example of dye (19) of Example 19] Other than reversing the coupling order of two types of diazonium compounds to 1-amino-8-naphthalene-8,6-disulfonic acid in Reference Example 1 was synthesized in the same manner.

Examples 20 to 85 In Example 19, the following (20
) to (85) were used in the same manner. A deep blue-intensity IE dyeing with excellent fastness properties was obtained.

The dyes listed below are characterized by:

A column: 1-amino-8-hydroxy mono- or disulfonic acid B column: Diazo component of monoazo dye [the above general formula (IV)
Amine constituting the compound of formula (1) above [compound of general formula (1)] Column C: 2.4.6-)rehalogeno-5-) riazine [compound of general formula (1)] Column D: Diazo component of disazo dye [ Compound of the above general formula (V)] Column E: λmax of disazo dye solution

Claims (1)

[Claims] In the form of a free acid, the following general formula [wherein R is a hydrogen atom or an alkyl group of 01 to 4, Y
represents a fluorine atom or a chlorine atom, n represents 112 or 8, and X represents a 1-amino-8-hydroxynaphthalene mono- or disulfonic acid residue. Z is the formula -8O□CH2CH2C
11-8O, CH=CH2, -8O2CH2CH20S
O3H1-502CH2CH20PO3) (2 or -
N(R1) Represents a benzene ring or naphthalene ring residue that has a 5O2CH2C pigeon 0803H group (where R1 represents a hydrogen atom, methyl group, or ethyl group) and may have other substituents. . : A disazo compound represented by.