JPS6381166A - Monoazo compound and dyeing or printing of textile material using said compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [X is H, methyl, ethyl, methoxy, ethoxy or sulfonic acid residue; Z is -SO2CH=CH2 or -SO2CH2CH2Y (Y is group eliminable with alkali); R1 and R2 are H, methyl, ethyl, methoxy, ethoxy, Cl, Br, nitro, sulfonic acid residue or carboxylic acid residue] as a free acid. EXAMPLE:The compound of formula II. USE:Dye for dyeing or printing an OH-containing fiber material such as cellulose or a carbonamide group-containing fiber material such as polyamide in red color. The dyed fiber has excellent various fastnesses. PREPARATION:The compound of formula III as a free acid and the compound of formula IV are condensed with cyanuric chloride in an aqueous medium preferably first at 0-30 deg.C and 2-7pH and then at 10-50 deg.C and 3-6pH and the obtained monoazo compound of formula V is condensed with the compound of formula VI at 70-100 deg.C and 3-7pH.

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 monoazo compound. Example 2 of the conventional Japanese Patent Publication No. 89-18184 discloses a red reactive dye represented by the following formula. Further, Example 1 of Japanese Patent Publication No. 46-824 discloses a red reactive dye represented by the following formula. Problems to be Solved by the Invention Conventionally, various reactive dyes have been widely used for dyeing and printing textile materials. However, at present, the known red dyes are still not at a satisfactory level in terms of dyeing performance, such as build-up properties, and fastness, such as acid hydrolysis fastness, and are still at a level that is not satisfactory. There is a strong desire to provide dyes that The present inventors completed the present invention as a result of intensive studies aimed at improving the drawbacks of known dyes and finding a new compound that can broadly satisfy the requirements required for dyes. Means for Solving the Problems The present invention provides a method for solving the problems in the form of a free acid in the following general formula [wherein X is a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a sulfonic acid group, or an it group] -8o
2CH=CH! In addition, L, Y are groups that are eliminated by the action of an alkali. R1
゜R2 independently represents a hydrogen atom, a methyl group, an ethyl group,
Represents a methoxy group, ethoxy group, chlorine atom, bromine atom, nitro group, sulfonic acid group or carboxylic acid group. ] A monoazo compound represented by the following and a method for dyeing or printing a fiber material using the monoazo compound are provided. In the general formula (I), when Z is CH4C-Y to the group -8, examples of Y include a sulfate ester group, a thiosulfate ester group, a phosphate ester group, and an acetate ester group. Among them, I like Z! 1. shite group
5o2CH=CH, and -8OzCHzCHzO5O
, H. The compounds of the present invention may exist in the form of free acids, but are preferably alkali metal salts or alkaline earth metal salts,
Examples include sodium and potassium salts. Among the monoazo compounds of the present invention represented by the general formula (1), monoazo compounds represented by the following general formula (D (in the formula or having the above meaning)) in the form of a free acid are particularly preferred. The monoazo compound represented by the general formula (1) of the present invention can be produced, for example, in the following manner. A compound represented by the following general formula (N)R1 [wherein R1, R, and 2 have the above-mentioned meanings] are combined in an arbitrary order in an aqueous medium, and then - -10 to 50°C, preferably 0 to 30°C,
While adjusting the pH to 1 to 10, preferably 2 to 7, secondarily at 0 to 70°C, preferably 10 to 50°C,
While adjusting the pH to 2-9, preferably pH 8-6,
By condensation with cyanuric chloride, the following general formula (1) is obtained: [wherein, X, R1, R, and 2 have the above-mentioned meanings. ] A compound represented by the following can be obtained. The monoazo compound represented by the general formula (2) is further mixed with the following compound (Vl) in an aqueous medium at 60 to IOQ°C, preferably 70 to
By condensing at 100° C. while adjusting the pH to 2 to 9, preferably 8 to 7, the general formula (1
) can be obtained. Alternatively, the following compound (■) and compounds represented by general formulas (IV) and (VI) may be used,
in an aqueous medium, in any order - then -10 to 50°
C, preferably at 0-80°C, while adjusting the pH to 1-10, preferably 2-7, and secondarily at 0-70°C.
C, preferably at 10-50°C, adjusting to pH 2-9, preferably pH 8-6, tertiary at 50-50°C.
At 100°C, preferably 70-100°C, pH 2-
9, preferably with cyanuric chloride while adjusting the pH to 8-7. Subsequently, the following general formula (■) is entered [wherein, X has the above-mentioned meaning]. ] The compound represented by is diazotized by a conventional method, and the pH is adjusted to 1 in an aqueous medium at -10 to 80°C, preferably at 0 to 5°C.
The monoazo compound of general formula (1) can be obtained by carrying out a single-force pulling reaction while adjusting the temperature to 10 to 10, preferably 8 to T. In this method, the order of condensation is not particularly limited, but in consideration of the reaction yield and quality of general formula (I), it is preferable to condense compounds with low reactivity to cyanuric chloride first. is preferred. The compound of the present invention has fiber reactivity and can be used for dyeing or printing hydroxy group-containing or carbonamide group-containing materials. Preferably, the material is used in the form of a fibrous material or 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 is cotton, and other plants m#! , for example linen,
Hemp, jute and ramie Fm fibers are preferred. Regenerated cellulose fibers are, for example, viscose, stable and filament viscose. Materials containing carbonamide groups are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hairs, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11 and polyamide-4. The compound of the present invention can be dyed or printed on the above-mentioned materials, especially on the above-mentioned fiber materials, by a method depending on the 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, tribasic sodium phosphate, caustic soda, etc., optionally with the addition of a neutral salt, such as mirabilite or common salt,
If desired, solubilizers, penetrants or leveling agents are used in combination and the process is carried out at relatively low temperatures. The neutral salts which accelerate the exhaustion of the dyestuff can be added only after the actual dyeing temperature has been reached, or even before then, optionally in portions. When dyeing cellulose fibers according to the padding method, they are padded at room temperature or at an elevated temperature, dried and then

It can be fixed by heating or dry heat. When printing is carried out on cellulose fibers, it can be carried out in one phase, e.g. by printing with a printing paste containing baking soda or other acid binders and then steaming at 100-160°C, or in two phases, e.g. Printing can be carried out by printing with a neutral or weakly acidic printing paste, passing it through a hot electrolyte-containing alkaline washing bath, or overpadding with an alkaline electrolyte-containing padding liquid and steaming or dry heat treatment. In the printing pastes, thickening agents or emulsifiers, such as, for example, sodium alginate or starch ethers, are used, if desired, in combination with customary printing aids and/or dispersants, such as, for example, urea. Ru. 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 alkali metal hydroxides and alkali metal salts of weak to medium strength inorganic or organic acids, of which soda salts and potassium salts are particularly preferred. Such acid binders include, for example, caustic soda, caustic potash, baking soda, soda carbonate, sodium formate, potassium carbonate, and the like. Examples include secondary or tertiary sodium phosphate, sodium silicate, and sodium trichloroacetate. 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 changing to a neutral or even alkaline pH value for fixation. This can be done by Dyeing is usually carried out at a temperature of 60 to 120°C, but in order to achieve leveling properties, conventional leveling agents such as the condensation product of cyanuric chloride and 8 times the molar amount of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid are used. Alternatively, for example addition products of stearylamine and ethylene oxide can be used. The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing textile materials. Particularly suitable for dyeing cellulose fiber materials, with excellent sunlight fastness, sweat sunlight fastness and formalin resistance, excellent wet fastness such as washing fastness, peroxide washing fastness, chlorine fastness, chlorine bleaching fastness It has excellent perspiration fastness, acid hydrolysis fastness and alkali resistance, as well as good rub fastness and iron fastness. In addition, it has excellent build-up properties, level dyeing properties, and wash-off properties, as well as good solubility, high exhaustion, and fixation properties, and is not affected by changes in dyeing temperature, alkaline agent, inorganic salt addition amount, and dye bath ratio. It is characterized by the fact that it is difficult to obtain dyed products of stable quality. In addition, the compound of the present invention exhibits excellent build-up properties and excellent alkali stability in cold patch-up dyeing, and shows almost no difference in density or hue between fixation at low temperatures and fixation at 25°C, and also exhibits excellent alkali stability. It has the ability to be resistant to hydrolysis by agents. The present invention will be explained in detail below with reference to Examples. In the examples, parts and % mean parts and weight %, respectively. Example 1 50.8 parts of the compound represented by the following formula in the form of a free acid was dissolved in 500 parts of water, 18.6 parts of cyanuric chloride was added, and the pH was adjusted to pH 2.5 to 8.0 using a 20% aqueous sodium carbonate solution. While adjusting to 5, adjust to 0.
Stir at ~5°C for 8 hours to complete the first condensation. Next, 28.1 parts of 1-aminobenzene-8-βsulfatoethyl sulfone was added, and the temperature was raised to 40°C while adjusting the pH to 4 to 5 using a 20% aqueous sodium carbonate solution. The second condensation is completed by stirring for 10 hours at ambient temperature. Furthermore, 12.8 parts of p-chloroaniline was added, the temperature was raised to 70"C while adjusting the pH to 4-5 using a 20% aqueous sodium carbonate solution, and the mixture was stirred for 6 hours at the same temperature and pH value. After completing the tricondensation, 25 parts of sodium chloride was added to precipitate crystals, which were filtered with suction and dried at 60"C to form a monoazo compound represented by the following formula (1) in the form of free acid. The compound was obtained. 81.9 parts of the compound shown in Example 2 was dissolved in 800 parts of water, 18.6 parts of cyanuric chloride was added, and the pH was adjusted to 2.5 to 3.5 using a 20% aqueous sodium carbonate solution.
Stir at ~6°C for 8 hours to complete the first condensation. Then, 28.1 parts of 1-aminobenzene-4-β-sulfatoethyl sulfone was added, and the pH was adjusted to 4 to 5 using a 20% aqueous sodium carbonate solution, and the temperature was raised to 40°C. The second condensation is completed by stirring for 10 hours at the same pH value. Furthermore, 12.8 parts of 0-chloroaniline was added, the temperature was raised to 70°C while adjusting the pH to 4-5 using a 20% aqueous sodium carbonate solution, and the mixture was stirred for 6 hours at the same temperature and pH value. Finish the tricondensation. Separately, 17.3 parts of 1-aminobenzene-2-sulfonic acid and 81 parts of 85% hydrochloric acid aqueous solution were added to 100 parts of water, and while stirring, θ
20 parts of an 85% aqueous sodium nitrite solution is added dropwise at ~5°C, and after the addition is complete, the mixture is stirred at the same temperature for 2 hours. After the reaction was completed and excess nitrous acid was removed, the above condensation solution was added thereto, the pH was adjusted to 5-6 using a 20% aqueous sodium carbonate solution, and the mixture was stirred at 0-6°C for 10 hours. Terminate the coupling reaction and add 80% sodium chloride.
% to precipitate crystals, suction-filter and dry at 60°C to obtain a monoazo compound represented by the following formula (2) in the form of a free acid. Examples 8 to 20 In Example 2, instead of 1-aminobenzene-2-sulfonic acid, the compound (■) in the second column of the table below was used, and in place of the compound (■) in the eighth column, 1 -Aminobenzene-4-β-sulfatoethylsulfone was replaced with the compound (■) in the fourth column, and 0-chloroaniline was replaced with the compound (W) in the fifth column. Example 2 The monoazo compounds of Example Nos. 8 to 20 were synthesized in the same manner as above, and the sixth column shows the color tones on cotton. Dyeing Example 1 0.8 parts of the monoazo compound (1) obtained in Example 1 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,
After washing with water and soaping, a highly concentrated dyed product with excellent build-up properties was obtained in various fastnesses, especially chlorine fastness, sunlight fastness and perspiration/sunlight fastness. Dyeing Example 2 0.8 part of the monoazo compound obtained in Example 10 was added to 150
of water, add 80 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 60"C. After 20 minutes, add 4 parts of soda carbonate and add 1 part of sodium chloride at the same temperature.
Time staining. After dyeing, washing with water and soaping were carried out to obtain a highly concentrated dyed product with good build-up properties and excellent fastness properties, particularly chlorine fastness, sunlight fastness, and sweat/sunlight fastness. Dyeing Example 8 Each of the monoazo compounds obtained in Examples 1 to 11 was 0.8
Dissolve one part in 800 parts of water, add 80 parts of mirabilite, and dissolve 10 parts of cotton.
of water and raise the temperature to 60″C. Then, after 20 minutes,
Add 5 parts of soda carbonate and dye at the same temperature for 1 hour. After dyeing, washing with water and soaping are performed to determine the color fastness,
In particular, a highly concentrated dyeing with good build-up properties and excellent chlorine fastness, sunlight fastness and perspiration/sunlight fastness was obtained. Dyeing Example 4 Each of the monoazo compounds obtained in Examples 12 to 20 was 0.
Dissolve 8 parts in 200 parts of water, add 80 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 50''C.After 80 minutes, add 4 parts of tribasic sodium phosphate and dissolve at the same temperature. Time dyeing. 'After dyeing, washing with water and soaping were performed to obtain a highly concentrated dyed product with excellent build-up properties, especially in various fastnesses, especially chlorine fastness, sunlight fastness, and sweat/sunlight fastness. Dyeing example 5 Color paste composition Urea 5 parts Sodium alginate (5%) Base paste 50 parts Hot water 25 parts Baking soda
2 part balance
18 parts A colored paste having the above composition is printed on mercerized cotton broadcloth, and after intermediate drying, steaming is performed at 100°C for 5 minutes, followed by hot water washing, soaping, hot water washing, and drying to finish. In this way, a printed product was obtained which had a high fixation rate, was excellent in various fastnesses, especially chlorine fastness, sunlight fastness and perspiration/sunlight fastness, and had good build-up properties. Dyeing example 6 Color paste composition Urea 5 parts Sodium alginate (5%) Base paste 50 parts Hot water
25 parts baking soda
2 part balance
14 parts A colored paste having the above composition is printed on mercerized cotton broadcloth, and after intermediate drying, steaming is performed at 120°C for 5 minutes, followed by hot water washing, soaping, hot water washing, and drying to finish. In this way, a printed product was obtained which had a high fixation rate, was excellent in various fastnesses, especially chlorine fastness, sunlight fastness and perspiration/sunlight fastness, and had good build-up properties. Dyeing Example 7 25 parts of each of the monoazo compounds obtained in Examples 1 to 11 are dissolved in hot water and cooled to 25°C. 82.5 to this
Add 5.6 parts of % caustic soda aqueous solution and 150 parts of 50° Baume water glass, and then add water to bring the total volume to 25%.
Immediately after reaching t, ooo parts at 0.degree. C., the cotton fabric is rolled up using this solution as a padding solution, sealed with a polyethylene film, and stored in a room at 20.degree. Cotton fabrics padded in a similar manner and sealed with rolled up polyethylene film are stored indoors at 5°C. After each padding cloth has been left for 20 hours, the dyeing is finished by washing in cold and then hot water, soaping in boiling detergent, washing in cold water and drying. When we investigated the difference in density and hue between dyed products left at 20'C for 20 hours and dyed products left at 5"C for 20 hours, almost no differences were observed. Also, there was no build-up property during cold patch-up dyeing. A dyed product with good color was obtained. Dyeing Example 8 25% of each of the monoazo compounds obtained in Examples 12 to 20
A dyed product with good build-up properties was obtained by performing the cold patch-up method in the same manner as in dyeing example 7. When the difference and hue difference were examined, almost no difference was observed. Dyeing Example 9 26 parts of each of the monoazo compounds obtained in Examples 1 to 11 are dissolved in hot water and cooled to 25°C. 82.5 to this
% caustic soda aqueous solution and 80 parts of anhydrous sodium sulfate, and further water was added to bring the total volume to 1% at 25°C.
．． Immediately after making 000 parts, this liquid is used as a padding liquid to pad a viscose rayon fabric. The padded viscose rayon fabric is rolled up, sealed with polyethylene film and stored indoors at 20°C. In a similar manner, viscose rayon fabrics sealed with a padded rolled polyethylene film are stored indoors at 6°C. After each padding cloth has been left for 20 hours, the dyeing is washed in cold and then hot water, soaped in boiling detergent,
Finish by washing with cold water and drying. When the differences in density hue and density were examined between a dyed product left at 20°C for 20 hours and a dyed product left at 5°C for 20 hours, almost no differences were observed. Dyeing Example 10 20% of each of the monoazo compounds obtained in Examples 12 to 20
A dyed product with good build-up properties was obtained by performing the cold patch-up method in the same manner as in Dyeing Example 9. When examining the difference in density and hue, almost no difference was observed. Dyeing Example 11 In Dyeing Example 8Iζ, 5 to 8 parts of sodium carbonate was used.
Dyeing was carried out in exactly the same manner except that the dye was changed, and a dyed product having the same quality as the dyed product obtained in Dyeing Example 8 was obtained for each of the monoazo compounds 1 to 11 used. Dyeing Example 12 Dyeing was carried out in exactly the same manner as in Dyeing Example 8 except that the temperature was changed from 60'C to 50°C, and the dyed product was equivalent to that obtained in Dyeing Example 3 for each of the monoazo compounds 1 to 11 used. A dyed product with a quality of . temperature to 70°C
The same was true in the case of Dyeing Example 18 Dyeing was carried out in exactly the same manner as in Dyeing Example 3, except that the amount of Glauber's salt used was changed from 30 parts to 15 parts, and the dyed products obtained in Dyeing Example 8 were obtained for each of the monoazo compounds 1 to 11 used. A dyed product with the same quality as that of the first half was obtained. Dyeing Example 14 In Dyeing Example 4, the amount of water used was changed from 200 parts to 150 parts, and the amount of Glauber's salt used was changed from 30 parts to 28 parts. A dyed product having the same quality as the dyed product obtained in Dyeing Example 4 was obtained for each of No. 20.

Claims (1)

[Claims] 1) In the form of a free acid, the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X is a hydrogen atom, a methyl group, an ethyl group, a methoxy group, Ethoxy group or sulfonic acid group, Z is group -SO_2C
H=CH_2 or a group -SO_2CH_2CH_2Y, where Y is a group that is eliminated by the action of an alkali. R_1
, R_2 each independently represent a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a chlorine atom, a bromine atom, a nitro group, a sulfonic acid group, or a carboxylic acid group. ] A monoazo compound represented by 2) In the form of a free acid, the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, Z has the meaning described in claim 1. ] The monoazo compound according to claim 1, which is represented by: 3) In the form of free acid, the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X is a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a sulfonic acid group. , Z is a group -SO_2C
H=CH_2 or a group -SO_2CH_2CH_2Y, where Y is a group that is eliminated by the action of an alkali. R_1
, R_2 each independently represent a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a chlorine atom, a bromine atom, a nitro group, a sulfonic acid group, or a carboxylic acid group. ] A method for dyeing or printing textile materials, characterized by using a monoazo compound represented by the following.