JPS6047071A - Monoazo compound and dyeing or printing method using the same - Google Patents

Abstract

NEW MATERIAL:Monoazo compounds of formula I , wherein X is halogen; Y is -SO2CH=CH2, -SO2CH2CH2Z; Z is a group which can be removed by the action of an alkali; A is phenylene, naphthylene; R1, R2 are each H, lower alkyl; R3, R4, R5, R6 are each H, lower alkyl, lower alkoxy, lower alkylcarbonylamino, ureido, sulfo; D is phenyl having 1-3 sulfo groups. USE:Dyes which dye or print fiber materials such as cotton, flax, wool, silk and polyamide 6 with excellent color tone and with excellent fastness to washing, light, rubbing, perspiration and ironing. PREPARATION:An aminoazo compd. of formula II and a compd. of formula IIIare subjected to a condensation reaction with a triazohalogenotriazine of formula IV in any order to obtain the monoazo compd. of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a monoazo compound and a method for dyeing or printing textile materials using the same.

More specifically, the following general formula (I) [wherein, X is a halogen atom, Y is -8020H, (E
H2 Maf: Bar 5O2CH20L12Z,'Z Huff 11. I+ (7) (A group that leaves depending on use, A is a phenylene group or naphthylene group that may have a substituent, ILt.

IL2 each independently represents a hydrogen atom or an optionally substituted lower alkyl group;
4, 'IL5 Oyohi Re Ha, Tsure each independently,
Represents a hydrogen atom, a lower alkyl group, a lower alkokene group, a lower alkylcarbonyl group, a ureido group-sulfo group, and D has 1 to 8 sulfo groups and further has other substituents. represents an optional phenyl group. ] The present invention relates to a monoazo compound or a salt thereof, and a method for dyeing or printing fiber materials using the monoazo compound or a salt thereof.

In the general formula (I), the halokene atom represented by X is particularly preferably chlorine, bromine or fluorine.

Examples of the group represented by 2 which is eliminated by the action of an alkali include a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an if ester group, and a halogen atom.

A is preferably selected from the group of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo groups,
A phenylene group which may be substituted with one or two substituents or a naphthylene group which may be substituted with a hasulfo group 1a, such as H8 (wherein, the bond indicated by an asterisk is a -ryo group) ) In R1 and IL2, the lower alkyl group is:
An alkyl group having 1 to 4 carbon atoms is preferred, and optionally substituted groups include a hydroxy group, a cyano group, an alkoxy group, a halogen group, a carboxy group, and a carbamoyl group.1. Preferred are afrecoxy carbonyl group, alkylcarbonyloxy group, sulfo group, and sulfamoyl group.

Particularly preferred 11. +,' IL2 and -C are, for example, hydrogen, methyl group, ethyl group, n-propyl group, 1
so-propyl group, n-butyl group, 1so-butyl group,
5ea-butyl group, 2-hydroxy group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-
Hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 2.8-dihydroxypropyl group,
3.4-dihydroxybutyl group, anomethyl group, 2-
Cyanoethyl group, 8-anopropyl group, methoxymethyl group, ethquinmethyl group, 2-methoxyethyl group, 2-
Ethquinethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 2-hydroxy-3-methoxypropyl group, chloromethyl group, bromomethyl group, 2-chloroethyl group, 2-bromoethyl group, 3-chloropropyl group,
3-bromopropyl group, 4-chlorobutyl group, 4-bromobutyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 1,2-dicarboxyethyl group, carbamoylmethyl group , 2-carbamoylethyl group, 3-carbamoylpropyl group, 4-carbamoylbutyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 3-methoxycarbonylpropyl group, 3-Work 1
- Base dicarbonylpropyl group, 4-methoxycarbonylbutyl group, 4-ethoxycarbonylbutyl group, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, 2-methylcarbonyloxyethyl group, 2-ethylcarbonyloxymethyl group, 8 -Methylcarbonyloxypropyl group, 81-ethylcarbonyloxypropyl group, 4-methylcarbonyloxyethyl group, 4-ethylcarbonyloxymethyl group, sulfomethyl group, 2-sulfoethyl group, 8-sulfopropyl group! , 4-sulfobutyl group, sulfamoylmethyl group, 2-sulfamoylethyl group, 3-sulfamoylpropyl group, 4-sulfamoylmethyl group, and the like.

几s, IL4. In 几5 and 几6, the term "lower" means 1 to 4 carbon atoms, and Rs is particularly preferred.

Examples of IL4, 1L5, and 6 include hydrogen, methyl group, ethyl group, methoxy group, ethoxy group, acetylamino group, propionyl amino group, ureido group, and sulfo group.

The compounds of the invention are present in the form of the free acid or in the form of its salts, in particular the alkali metal and alkaline earth metal salts, especially the soda, potassium and calcium salts.

The compound of the present invention can be produced, for example, in the following manner.

The following general formula (
II) (In the formula, R2, 'ILa, R4, IL5, 几6OYOHID have the above-mentioned meanings.) An aminoazo compound or a salt thereof represented by the following general formula (III') 1 (In the formula, R1, A, Y have the meanings given above) in an aqueous medium in any order at a temperature of -10°C to 40°C (, FpH2 to pL[9
While adjusting to
The compound of general formula (1) or a salt thereof can be obtained by injecting trihalogeno-lyazine represented by the following general formula (TV) while adjusting the pH to between H2 and 9.

The compound of the present invention has fiber reactivity and can be used for dyeing or printing H materials containing hydroxy groups or carbonamide groups. Preferably, the material is used in the form of a fibrous material or in the form of a blend thereof.

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulose fiber materials or their regenerated products and polyvinyl alcohol. Cellulose fiber material 1 is preferably cotton, but also other vegetable fibers such as linden, linen, jute and ramie fibers. Regenerated cellulose fibers are, for example, viscose, staple and hyfilament viscose.

Materials containing carbonamide groups are, for example, metals and natural polyamides and polyurethanes, in the form of fibers such as wool and animal hair, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11 and polyamide-4.

The compounds of the present invention can be dyed or printed on the above-mentioned materials, in particular on the above-mentioned fiber materials, in a manner depending on their physical and chemical properties.

For example, in the case of exhaust dyeing on cellulose fibers - in the presence of an acid binder such as soda carbonate, sodium triphosphate, caustic soda, etc., optionally with the addition of neutral salts, such as mirabilite or common salt, and, if desired, solubilizing aids. , using a penetrant or willow dye together,
It is carried out at relatively low temperatures. Neutral salts which accelerate the exhaustion of the dye can be added only after or before the actual dyeing temperature has been selected, optionally in portions.

When dyeing cellulose fibers according to the padding method, it can be padded at room temperature or at an elevated temperature and, after drying, fixed by steaming or dry heat.

When printing is carried out on cellulose fibers, it can be carried out in one phase, for example by printing with a printing paste containing electroprotective or other acid binders and then steaming at 100-160'C, or in two phases. For example, print with a neutral or weakly acidic printing paste and print with hot 1"fi:f!i'
i! This can be carried out by passing through an alkaline bath containing alkaline crystals, or by overbagging with a passing liquid containing alkaline alkaline crystals, followed by steaming or dry heat treatment.

The printing paste may contain thickening agents or emulsifiers, such as sodium alginate or starch ether, if desired.
For example, it is used in combination with a conventional printing aid (or dispersing agent).

Suitable acid binders for fixing the compounds of the invention on cellulose fibers are, for example, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids or compounds which liberate alkali under heated conditions. Particular mention may be made of hydroxides of alkali metals and alkali metal salts of weak to medium strength inorganic or organic acids, of which soda salts and potassium salts are particularly preferred. Examples of such acid binders include caustic soda, caustic potash, sodium bicarbonate, sodium carbonate, potassium carbonate, primary, secondary, or tertiary sodium phosphate, sodium silicate, sodium trichloroacetate, and the like.

The dyeing of synthetic and natural polyamide and polyurethane fibers involves first exhaustion under pH control from an acidic or slightly acidic dye bath and then conversion to a neutral or even alkaline pIll value for fixation. This can be done by

Dyeing can usually be carried out at a temperature of 60 to 120°C, but in order to achieve level dyeing properties, conventional leveling agents such as cyanuric chloride and 8
It is also possible to use a condensation product of 4 Jl with twice the molar amount of aminobenzenesulfonic acid or haminonaphthalenesulfonic acid, or an addition product of, for example, stearylamine and ethylene oxide.

The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing textile materials. Especially suitable for dyeing cellulose fiber materials, good light fastness and sweat resistance, good moisture resistance, such as washing resistance, peroxidation washing resistance, chlorine water resistance, chlorine bleaching resistance, sweat resistance , has acid hydrolysis resistance and alkali resistance, as well as good abrasion resistance and ironing resistance. In addition, it has excellent build-up properties, level dyeing properties, wash-off properties, good solubility, high exhaustion and fixation properties, and stable quality dyeing that is not affected by fluctuations in dyeing temperature or dye bath ratio. It is characterized by the fact that things can be obtained.

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

Example 1 8.7 parts of cyanuric chloride is added to 50 parts of water at 0 to 10°C and dispersed. To this, 8.0 parts l of 4-(2,5-disphophenylazo)-2-methoxy-5-methylaniline;
eyJ < 10 (The solution was suspended in 1 part and adjusted to pH near ~10 with 10% sodium chloride water dissolved in water.
C and dropwise while adjusting the pH to 4 to 7.

After dropping, add 15% charcoal 0 soda aqueous solution to adjust pI (4
Stir for 2-4 hours while maintaining the temperature at ~7.

Then, 5.6 parts of 1-a2-nobenzene-3-β-sulfatoethylsulfone were completely processed and stirred at 10 to 40°C for 5 hours while adjusting the pLI to 5 to 7 with a 15% aqueous sodium carbonate solution. , a monoazo compound having the following structural formula was obtained in the form of a free acid.

O7' 080alJ (λmax = 896 nm, however, in an aqueous solvent, hereinafter measured under the same conditions) Monoazo compounds of the following general formula obtained by a method similar to the method described in Example 1 are summarized in Table 1.

Example 2 7.1 parts of 4-(4-sulfophenylazo)-2-sulfoaniline was added to 100 parts of water, and pl(5
Adjust to ~6 and dissolve.

Cool to 0°C, 2, 4. Rotrifluoro-1,8
, 2.7 parts of 5-1-riazine were added dropwise, and at the same time p Tl was maintained at 5 to 6 days with a 15% aqueous sodium carbonate solution. After condensation, ■−
Add 5.6 parts of aε-nobenzene-3-β-sulfatoethyl sulfone, and add 15% aqueous sodium carbonate solution to pH 5~
The mixture was stirred at 10 to 40° C. for 5 hours while adjusting the temperature to 7, to obtain a monoazo compound having the following structural formula in the form of a free acid.

(λruax = 359 nm) Monoazo compounds of the following general formula obtained by a method similar to that described in Example 2 are summarized in Table 2. Example 8 1-Aminobenzene-4- was added to 150 parts of water. Add 28.1 ml of β-sulfatoethyl sulfone, add 28.1 ml of β-sulfatoethyl sulfone, and add 28.1 ml of β-sulfatoethyl sulfone.
1 (adjusted to 4 to 7. Cool to 0 to 20°C, add 18.4 parts of cyanuric chloride, and stir for 4 hours while adjusting the pH to 3 to 6 with a 15% aqueous sodium carbonate solution.

4-(4-sulfophenylazo)-2-methoxy-5-methylanine82. IN was suspended in 100 parts of water, and the pH was adjusted to 7 to 9 with caustic soda.
Add at 0°C while adjusting pH to 5 to 7, then add 1
The mixture was stirred for 5 hours while adjusting the pH to 5-7 with a 5% aqueous sodium carbonate solution to obtain a monoazo compound having the following structural formula in the form of a free acid.

(λmax 896 nln) The obtained monoazo compounds of the following general formula are summarized in Table 3. Dissolve in 200 parts, add 10 parts of Glauber's salt and 10 parts of cotton, raise the temperature to 60°C, add 4 parts of soda carbonate, and dye for 1 hour.

After washing with water, soaping, rinsing with water and drying, a bright yellow dyed product having excellent fastness, extremely good build-up properties, and good discharge properties was obtained.

This compound also has excellent solubility, and has good level dyeing and dyeing reproducibility.

Example 5 The same performance is exhibited by dyeing according to the method described in Example 4 using the monoazo compounds described in Example 3 and Tables 1 to 3.

Example 6 0.1 + 'o, 8 and 0.6 parts of each of the monoazo compounds described in Examples 5 and 6 were dissolved in 200 parts of water, and 10 parts of Glauber's salt and 10 parts of cotton were added.
Raise the temperature to 0°C, add 4 parts of soda carbonate, and dye at the same temperature for 1 hour. Next, by washing with water, soaping, washing with water and drying, a bright yellow dyed product with high build-up and fastness is obtained, and has excellent dischargeability, and furthermore,
It is also excellent in that it is not affected by dyeing temperature fluctuations and provides products with stable quality.

Continued from page 1 0 Inventor Akira Takeshita Osaka Company 3-11-98 Kasugade-naka, Konohana-ku, I-shi Jumin Kagaku Kogyo Co., Ltd.:

Claims (1)

[Claims] 1) The following general formula [wherein, X is a halogen atom, and Y is -8020H-OB2]
Mf = Bar 802CII20U2Z, Z Huff
Luka'l (7) Group that leaves due to action, A is substituted!
A phenylene group or a naphthylene group, R+, which may be replaced by & and L). R2 each independently represents a hydrogen atom or an optionally @-substituted lower alkyl group, R8, H,, i,
R5 and +11+ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylcarbonylamino group-ureido group, or a sulfo group, and D is 1
Represents a Fe, Nyl group having 1 to 3 sulfo groups and optionally having other substituents. ] A monoazo compound or a salt thereof. 21) The compound or salt thereof according to claim 1, wherein D is a phenyl group having 1 to 3 sulfo groups. 8) D has 1 to 8 sulfo groups, and further includes a lower alkyl group, a lower alkoxy group, a halogen group, a lower alkylcarbonylamino group, a pencyylamino group,
0 group, and at least one selected from carboxyl group
The compound or salt thereof according to claim @1, which is a phenyl group having various substituents 94) R8, R4
, 11,5 and R6 represent a lower alkyl group, a lower alkoxy group, a lower alkylcarbonylamino group, a ureido group, or a sulfo group, and the group is a hydrogen atom. A compound or a salt thereof according to Items 1' to 3. - 5) The following general formula λ [In the formula,
0H = OH2 years old f: Bar 502CH20112Z
+Z Haf A group that leaves once due to the action of l.
represents a phenylene group or a naphthylene group which may have a substituent, Rt and 几2 each independently represent a hydrogen atom or a lower alkyl group which may be substituted or substituted, R
s, 几4. R5 and R6 each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a g-class alkylcarbonyl group, a ureido group, or a sulfo group, and D has 1 to 3 to 14 sulfo groups; 1. represents a phenyl group which may further have other substituents. ] A method of dyeing or printing a fiber material using a monoazo compound or a salt thereof.