JPH0457791B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for dyeing cellulose fibers orange to scarlet. More specifically, the present invention provides the following general formula () in the form of a free acid: (In the formula, D is a methyl group, an ethyl group, a methoxy group,
Phenyl group or sulfonic acid group substituted with 1, 2 or 3 substituents selected from the group of ethoxy group, halogen, acetylamino group, propionylamino group, nitro group, sulfonic acid group and carboxyl group 1, 2 or represents a naphthyl group substituted with three groups. R ₁ represents hydrogen, a methyl group or an ethyl group. _R2 represents a carbamoyl-substituted _C1 - _C3 alkyl group. Z represents hydrogen or a sulfonic acid group. A is a methyl group, an ethyl group, a methoxy group, an ethoxy group,
1 selected from the group of chlorine, bromine and sulfonic acid groups
Alternatively, it represents a phenylene residue which may be substituted with two substituents or a naphthylene residue which may be substituted with one sulfonic acid group. X is a group -
_SO2CH = _CH2 or _{the group -SO2CH2CH2Y} . Here, Y is a group that is eliminated with an alkali. ) This is a method for dyeing cellulose fibers, which is characterized by using the dye shown in the following. It is known that dyes having a β-sulfatoethylsulfonyl group are used as so-called vinylsulfone type reactive dyes for dyeing textile materials. However, dyeing with azo-based orange or scarlet reactive dyes having a β-sulfatoethylsulfonyl group does not produce deep-colored dyed products due to poor build-up properties, and the dyed products obtained are generally chlorine-fast. The color fading phenomenon caused by chlorine contained in tap water is often a problem, and therefore there has been a strong demand for a reactive dye with good build-up properties and excellent chlorine fastness. Dyes with a monochlorotriazinyl group as another typical reactive group different from the β-sulfatoethylsulfonyl group are also known, but these reactive dyes generally require high dyeing temperatures. In addition, it is only used for textile printing because it lacks exhaust dyeing suitability, and furthermore, it has the disadvantage of low acid stability of the dyed product, so it is by no means sufficient for practical use. Ta. For this reason, the present inventors conducted extensive research in search of an orange to scarlet vinyl sulfone type reactive dye that has particularly good build-up properties and excellent chlorine fastness.
It has been found that the dye represented by the general formula (2) gives a dyed product with high density of orange to scarlet color and excellent chlorine fastness. It has also been found that the dye of the present invention can overcome the drawbacks of reactive dyes having a monochlorotriazinyl group as described above. In the present invention, the 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 a relatively low temperature in a dye bath containing Glauber's salt or common salt in the presence of an acid binder such as soda carbonate, tribasic sodium phosphate, or caustic soda. Dyeing can also be done by a textile printing method. For example, a color paste containing an acid binder such as bicarbonate of soda, soda carbonate, tribasic sodium phosphate, or caustic soda, urea, and a sizing agent, preferably sodium alginate, is printed on the fiber, and after intermediate drying, 100% This is done by steaming or dry heating at ~200°C. Furthermore, the dyeing of the present invention may be carried out by a continuous method, or cold patch batch dyeing is also possible. The dye of the present invention can be produced, for example, as follows. An aromatic amine represented by the general formula () D-NH ₂ () (wherein D has the above-mentioned meaning) is diazotized in an aqueous medium at a temperature of -10°C to 40°C to form the general formula () (In the formula, R ₁ and Z have the above-mentioned meanings.) and a PH5 to PH
12 More preferably, coupling is performed while adjusting the pH to 6 to 10, and the general formula () A monoazo compound represented by the formula (wherein D, R ₁ and Z have the meanings given above) is obtained. Alternatively, a similar coupling reaction is performed using an N-acylated compound of general formula (), and then the acyl group is hydrolyzed at a temperature of 50°C to 100°C in the presence of an acid or alkali to form a compound of general formula (). can be obtained. Then, the compound of general formula () is mixed in an aqueous medium at a temperature of -10°C to 50°C, more preferably 0°C to
A dichlorotriazinyl compound is obtained by primary condensation with cyanuric chloride at 30° C. while adjusting the pH to 2 to 10, more preferably 3 to 7.
Then the general formula () (In the formula, R ₂ , A and By controlled secondary condensation, dyes of general formula () can be obtained. Alternatively, the reaction components of the general formula () are reacted in an aqueous medium at a temperature of -10°C to 40°C, more preferably 0°C to 20°C, and PH1 to PH8, more preferably PH2.
Primary condensation with cyanuric chloride while adjusting the pH to 6 to 6, then at a temperature of 0 to 70°C, more preferably 20 to 50°C, and adjusting to PH2 to PH9, more preferably PH4 to 6,
The dye of general formula () can also be obtained by secondarily condensing a monoazo compound of general formula (). Or a compound of general formula () and a compound of general formula ()
of the reaction components in any order in an aqueous medium, firstly at a temperature of -10°C to 40°C to adjust the pH to PH1 to 8, and secondarily at a temperature of 0°C to 70°C to adjust the pH to PH2.
or condensation with cyanuric chloride while adjusting the pH to 9 to form the general formula () (In the formula, R ₁ , R ₂ , Z, A, and X have the above-mentioned meanings.) To obtain a monochlorotriazinyl compound,
Subsequently, a diazonium salt of an aromatic amine of general formula () is added at a temperature of -10°C to 50°C, more preferably 0°C.
PH4 to PH10 at ℃ to 20℃, more preferably
The dye of the general formula () can also be obtained by coupling while adjusting the pH to 5 to 9. Alternatively, the compound of general formula () may be prepared in an aqueous medium at a temperature of -10°C to 40°C, more preferably 0°C to
After primary condensation with sinal chloride while adjusting the pH to PH1 to PH8, more preferably PH2 to 5, at 20°C, a diazonium salt of an aromatic amine of the general formula () and a temperature of -10°C to 50°C, more preferably 0. ℃ to 20℃, adjusting to PH4 to PH10, more preferably PH5 to PH5 to PH9, coupling, general formula () (wherein D, R ₁ and Z have the above-mentioned meanings) is added to the reaction product of the general formula () at a temperature of 0°C to 70°C, more preferably
The dye of the general formula () can also be obtained by condensation at 30°C to 50°C while adjusting the pH to 2 to 9, more preferably 4 to 6. Or general expression () (In the formula, R ₂ and A have the above-mentioned meanings.) By using the compound represented by the formula (2) in place of the reaction component of the general formula (), carrying out the respective similar reactions, and finally oxidizing and esterifying the compound, Alternatively, by further treating with an alkali, a dye of general formula () may be obtained. The diazo component represented by the general formula () is:
For example, 2-aminobenzenesulfonic acid 2-amino-5-methylbenzenesulfonic acid 2-amino-5-ethylbenzenesulfonic acid 2-amino-5-methoxybenzenesulfonic acid 2-amino-5-ethoxybenzenesulfonic acid 2-amino -5-chlorobenzenesulfonic acid 2-amino-5-bromobenzenesulfonic acid 2-amino-5-acetylaminobenzenesulfonic acid 2-amino-5-propionylaminobenzenesulfonic acid 2-amino-5-nitrobenzenesulfonic acid 2-amino -4-chloro-5-methylbenzenesulfonic acid 2-amino-5-chloro-4-methylbenzenesulfonic acid 2-amino-4-methoxybenzenesulfonic acid 2-amino-4-ethoxybenzenesulfonic acid 3-amino-4 -Methylbenzenesulfonic acid 3-amino-4-ethylbenzenesulfonic acid 3-amino-4-methoxybenzenesulfonic acid 3-amino-4-ethoxybenzenesulfonic acid 3-amino-4-chlorobenzenesulfonic acid 3-amino-4-bromo Benzenesulfonic acid 4-amino-3-methylbenzenesulfonic acid 4-amino-3-ethylbenzenesulfonic acid 4-amino-3-methoxybenzenesulfonic acid 4-amino-3-ethoxybenzenesulfonic acid 4-amino-3-chlorobenzenesulfonic acid Acids 4-amino-3-nitrobenzenesulfonic acid 2-aminobenzene-1,4-disulfonic acid 2-aminobenzene-1,5-disulfonic acid 2-aminobenzoic acid 2-amino-4-methoxybenzoic acid 2-amino- 5-methoxybenzoic acid 2-amino-4-acetylaminobenzoic acid 2-amino-5-acetylaminobenzoic acid 2-amino-4-sulfobenzoic acid 2-amino-5-sulfobenzoic acid 4-amino-2,5 -dimethylbenzenesulfonic acid 4-amino-2,5-diethylbenzenesulfonic acid 4-amino-2,5-dimethoxybenzenesulfonic acid 4-amino-2,5-diethoxybenzenesulfonic acid 4-amino-2,5-dimethoxybenzenesulfonic acid Chlorobenzenesulfonic acid 4-Amino-2,5-dibromobenzenesulfonic acid 4-Amino-2-methyl-5-methoxybenzenesulfonic acid 4-Amino-2-methyl-5-ethoxybenzenesulfonic acid 2-Amino-5-methyl Benzene-1,4-disulfonic acid 2-Amino-5-ethylbenzene-1,4-disulfonic acid 2-Amino-5-methoxybenzene-1,4-
Disulfonic acid 2-amino-5-ethoxybenzene-1,4-
Disulfonic acid 2-amino-5-acetylaminobenzene-
1,4-disulfonic acid 2-amino-5-propionylaminobenzene-1,4-disulfonic acid 2-aminonaphthalene-1-sulfonic acid 2-aminonaphthalene-1,4-disulfonic acid 2-aminonaphthalene-1,5 -Disulfonic acid 2-aminonaphthalene-1,7-disulfonic acid 2-aminonaphthalene-1,5,7-trisulfonic acid 2-aminonaphthalene-3,6-disulfonic acid 2-aminonaphthalene-3,8-disulfonic acid 2-aminonaphthalene-3,6,8-trisulfonic acid 2-aminonaphthalene-5-sulfonic acid 2-aminonaphthalene-6-sulfonic acid 2-aminonaphthalene-7-sulfonic acid 2-aminonaphthalene-8-sulfonic acid Examples include 2-aminonaphthalene-4,8-disulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, and 2-aminonaphthalene-6,8-disulfonic acid. General formula () In the reaction component represented by, the substituent R ₂ can include carbamoylmethyl group, 2-carbamoylethyl group, and 3-carbamoylpropyl group, and the formula residue A can be, for example,

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【formula】 (In the formula, the bond indicated by an asterisk is

[Formula] means a bond that leads to a group. ), etc. and X is a group -SO ₂ CH=CH ₂ or a group -
represents SO ₂ CH ₂ CH ₂ Y, where Y is a group that is eliminated with an alkali, such as a sulfate ester group,
This includes a thiosulfate group, a phosphate group, an acetate group, a halogen atom, and the like. The dye of the present invention thus obtained has good build-up properties and is excellent in chlorine fastness and sweat/sunlight fastness. Chlorine fastness is 3rd or 4th grade according to ISO method.
In particular, considering that it has recently become a problem that dyed products often fade due to trace amounts of active chlorine contained in tap water during washing in general households, this dye of the present invention has excellent chlorine fastness. is of high value. In addition, the sweat and sunlight fastness, which has become a problem with the expansion of sportswear in recent years, is excellent at 3rd or 4th grade, and from this point of view as well, the dye of the present invention is of high value. Furthermore, with conventional reactive dyes, there was a phenomenon in which the dyed product was affected by acidic gases in the air and its fastness decreased over time, but the dye of the present invention has solved this problem. There is. That is, the acid stability of the dyed product of the dye of the present invention (the test method is to immerse the dyed fabric in 1% acetic acid for 30 minutes,
at a temperature of 37 ± 2 °C using a perspirometer.
(treated at 125 g/cm ² for 6 hours) is good at grade 4-5 or grade 5, and is of high value from this point of view as well. In addition, the dye of the present invention has good alkali stability and shows a high exhaustion rate and fixation rate in exhaust dyeing, and also shows a high fixation rate in textile printing, so it is not only possible to obtain dyed products with high density. At the same time, it has excellent wash-off properties and has the great advantage that unfixed dye can be easily removed. Furthermore, the dye of the present invention has the unique ability to be hardly affected by changes in the dyeing temperature, alkali agent, inorganic salt addition amount, and bath ratio during exhaust dyeing, and allows dyeing to be carried out with extremely high reproducibility. As a dye similar to the present invention, for example,
Publication No. 39-18184 contains the following formula The dyes shown are listed. However, these dyes have lower solubility and poorer build-up properties than the dyes of the present invention, making it impossible to obtain dyed products with high density.They also have the disadvantage of extremely poor wash-off properties, making them impractical for practical use. The value above is small. Furthermore, the latter dyes are particularly poor in light fastness. Next, the method of the present invention will be explained with reference to examples. In the text, parts represent parts by weight. Example 1 Dissolve 0.3 parts of the dye shown in 200 parts of water and add 20 parts of mirabilite.
1 part, add 10 parts of cotton, and raise the temperature to 50℃. After 30 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing and soaping were carried out to obtain a highly concentrated scarlet dyed product with excellent chlorine fastness. The above dye is synthesized, for example, as follows. To a solution in which 0.1 part of a nonionic surfactant is dissolved in 100 parts of water, 9.2 parts of cyanuric chloride is added and dispersed at 0 to 5°C. To this, add 11.3 parts of J acid to 100 parts of water, pH 7.
The solution dissolved in step 8 is added dropwise at 0 to 5°C over 1 hour. After dropping, add 20% sodium aqueous solution.
Adjust the pH to 3 and stir for an additional 2 hours. Then 1
-N-carbamoylethylaminobenzene-3-
Add 16 parts of β-hydroxyethylsulfone sulfate, and raise the temperature to 40° C. while adjusting the pH to 5 to 6 with a 20% aqueous sodium carbonate solution, and stir at the same temperature for 6 hours. Then, after cooling again to 0-5°C, 12.6 parts of sodium bicarbonate are added. To this, 2-amino-
A solution obtained by diazotizing 9.6 parts of 5-methoxybenzenesulfonic acid in a conventional manner is added at 0 to 5°C over 1 hour. After stirring at the same temperature for 2 hours, adjust the pH to 5 with hydrochloric acid.
6, 40 parts of sodium chloride was added to precipitate crystals, which were filtered under suction, washed, and dried at 60°C to obtain dye (1). When dyeing was performed using dyes (2) to (12) produced using the following compounds in the same manner as in Example 1, dyed products with high concentration of orange to scarlet with excellent chlorine fastness were obtained. Ta.

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[Table] Example 2 Dissolve 0.3 parts of the dye shown in 150 parts of water and add mirabilite.
Add 30 parts, add 10 parts of cotton, and raise the temperature to 60℃.
Then, after 20 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing and soaping were carried out to obtain a highly concentrated scarlet dyed product with excellent chlorine fastness. The above dye is synthesized, for example, as follows.
To a solution in which 0.1 part of a nonionic surfactant is dissolved in 200 parts of water, 9.2 parts of cyanuric chloride is added and dispersed at 0 to 5°C. To this, 7-amino-4-hydroxy-3-(2
A solution of -sulfo-4-ethoxyphenylazo)naphthalene-2-sulfonic acid was added dropwise over 1 hour while maintaining pH 4-5 with a 20% aqueous sodium carbonate solution, and the mixture was stirred at a temperature of 0-10°C for 2 hours. Subsequently, 16 parts of 1-N-carbamoylethylaminobenzene-3-β-hydroxyethylsulfone sulfate was added, and the temperature was raised to 50°C while adjusting the pH to 5 to 6 hours with a 12% aqueous sodium carbonate solution.
Stir at the same temperature for 6 hours. Then, 40 parts of sodium chloride was added to precipitate crystals, which were filtered under suction, washed, and dried at 60°C to obtain dye (18). When dyes (14) to (18) obtained using the following compounds were dyed in the same manner, dyed products with excellent chlorine fastness and high orange to scarlet color density were obtained.

[Table] Example 3 Dissolve 0.3 parts of the dye shown in 200 parts of water and add 20 parts of mirabilite.
1 part, add 10 parts of cotton, and raise the temperature to 50℃. After 30 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing and soaping were performed to obtain an orange dyed product with excellent chlorine fastness. The above dye is synthesized, for example, as follows. To a solution in which 0.1 part of a nonionic surfactant is dissolved in 100 parts of water, 9.2 parts of cyanuric chloride is added and dispersed at 0 to 5°C. To this, add 11.3 parts of J acid to 200 parts of water, pH 7.
The solution dissolved in step 8 is added dropwise at 0 to 5°C over 1 hour. After the addition is complete, 20% aqueous sodium carbonate solution is added to adjust the pH to 3, and the mixture is further stirred for 2 hours. Then 1-N-carbamoylethylaminobenzene-
Add 16 parts of 3-β-hydroxylethyl sulfone sulfate and raise the temperature to 40°C while adjusting the pH to 5 to 6 with a 20% aqueous sodium carbonate solution.
Stir for an hour. Then, after cooling again to 0-5°C, 12.6 parts of sodium bicarbonate are added. A solution obtained by diazotizing 15 parts of 2-aminonaphthalene-1,5-disulfonic acid in a conventional manner is added to this at 0 to 5°C for 1 hour. After stirring at the same temperature for 2 hours, adjust the pH to 5~5 with hydrochloric acid.
6, and 40 parts of sodium chloride was added to precipitate crystals, which were filtered under suction, washed, and dried at 60°C to obtain dye (19). In the same manner as in Example 3, the following dyes (20) -
(24), dyed products with high concentration of orange to scarlet color with excellent chlorine fastness were obtained in all cases.

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[Table] Example 4 Dissolve 0.3 parts of the dye shown in 150 parts of water and add mirabilite.
Add 20 parts, add 10 parts of cotton, and raise the temperature to 60℃.
Then, after 20 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing and soaping were performed to obtain a highly concentrated orange dyed product with excellent chlorine fastness. The above dye is synthesized, for example, as follows. To a solution in which 0.1 part of a nonionic surfactant is dissolved in 200 parts of water, 9.2 parts of cyanuric chloride is added and dispersed at 0 to 5°C. To this, 2-aminonaphthalene 1-1
-2-amino-5-hydroxy-6-(1-sulfo-2-naphthylazo)-1 synthesized from 11 parts of diazonium salt of sulfonic acid and 16 parts of 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid. ，
A solution of 7-sidulfonic acid was added dropwise over 1 hour while maintaining the pH between 4 and 5 with 20% sodium carbonate, and the mixture was stirred for 2 hours at a temperature of 0 to 10°C. Subsequently, 16 parts of 1-N-carbamoylethylaminobenzene-3-β-hydroxyethylsulfone sulfate was added, and the temperature was raised to 50°C while adjusting the pH to 5 to 6 with a 20% aqueous sodium carbonate solution. Stir for 6 hours. Next, 40 parts of sodium chloride was added to precipitate crystals, which were filtered under suction, washed, and dried at 60°C to obtain dye (25). When the following dyes (26) to (29) were dyed in the same manner, dyed products with high chlorine fastness and orange to scarlet color were obtained.

[Table] Example 5 Color paste composition Dye of formula (1) 4 parts Urea 5 parts Sodium alginate (5%) Base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 14 parts Color paste with the above composition is printed on mercerized cotton broadcloth, and after intermediate drying, it is steamed at 120℃ for 5 minutes, washed with hot water, soaped, washed with hot water, and dried to finish. In this way, a scarlet print with excellent chlorine fastness was obtained.

Claims (1)

[Claims] 1 The following general formula in the form of a free acid: (In the formula, D is a methyl group, an ethylene group, a methoxy group,
Phenyl group or sulfonic acid group substituted with 1, 2 or 3 substituents selected from the group of ethoxy group, halogen, acetylamino group, propionylamino group, nitro group, sulfonic acid group and carboxyl group 1, 2 or represents a naphthyl group substituted with three groups. R ₁ represents hydrogen, a methyl group or an ethyl group. _R2 represents a carbamoyl-substituted _C1 - _C3 alkyl group. Z represents hydrogen or a sulfonic acid group. A is a methyl group, an ethyl group, a methoxy group, an ethoxy group,
It represents a phenylene residue optionally substituted with one or two substituents or a naphthylene residue optionally substituted with one sulfonic acid group obtained from the group of chlorine, bromine and sulfonic acid groups. X represents _a group _-SO2CH = _CH2 or _a group _-SO2CH2CH2Y . Here, Y is a group that is eliminated with an alkali. ) A dyeing method for cellulose fibers characterized by using the dye shown in the following.