JPH0218351B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for dyeing cellulose fibers in orange to dark colors. 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,
It represents a phenyl 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. R ₁ represents hydrogen, a methyl group or an ethyl group.
_R2 has 1-4 carbon atoms, a hydroxy-substituted alkyl group, a cyano-substituted alkyl group, an alkoxy-substituted alkyl group, a halogen-substituted alkyl group,
Represents a carboxy-substituted alkyl group, an alkoxycarbonyl-substituted alkyl group, or a sulfo-substituted alkyl group. Z represents hydrogen or a sulfonic acid group.
A is one phenylene residue or sulfonic acid group which may be substituted with one or two substituents selected from the group of methyl group, ethyl group, methoxy group, ethoxy group, chlorine, bromine, and sulfonic acid group. Represents an optionally substituted naphthylene residue. X is-
_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 can be applied as so-called vinylsulfone type reactive dyes for dyeing textile materials.
However, dyeing with azo-based orange or discoloration 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 dyed with chlorine. Color fastness is low, and discoloration due to chlorine contained in tap water is often a problem, so 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, sodium carbonate, tribasic sodium phosphate, or caustic soda, urea, and a sizing agent, preferably sodium alginate, is printed on the fibers, and after intermediate drying. It is carried out by steaming or dry heating at 100-200℃. 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 solvent 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.) At a temperature of -10°C to 50°C, more preferably at a temperature of 0°C to 20°C, and a pH of 5 to 12, more preferably 6 to 6. Perform cup springing while adjusting the pH to 10, and use the general formula () (In the formula, D, R ₁ and Z have the above-mentioned meanings.) A monoazo compound represented by the following is obtained. Alternatively, after carrying out a similar coupling reaction using the N-acylated product of general formula (), the acyl group is hydrolyzed at a temperature of 50 to 100 °C in the presence of an acid or alkali to form a compound of general formula (). Compounds can also 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 X have the above-mentioned meanings.) The reaction component represented by the formula is heated to a temperature of 0°C to 70°C, more preferably 30°C to 50°C, and a pH of 2 to 9, more preferably 4 to 6. 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 the general formula () can also be obtained by secondarily condensing the monoazo compound of the 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 cyanuric chloride at 20°C while adjusting the pH to PH1 to 8, more preferably PH2 to 5, the diazonium salt of an aromatic amine of general formula () is further preferably heated to -10°C to 50°C. Coupling is carried out at 0°C to 20°C while adjusting the pH to 4 to 10, preferably 5 to 9, and the general formula () (In the formula, D, R ₁ and Z have the above-mentioned meanings.) A monoazo compound represented by the above formula is obtained, and the reaction components of the general formula () are added thereto at a temperature of 0°C to 70°C, more preferably 30°C to 50°C. The dye of the general formula () can also be obtained by condensation while adjusting the pH to PH2 to PH9, more preferably PH4 to PH6. Or general expression () (In the formula, R ₂ and A have the above-mentioned meanings.) Using a compound represented by the formula (2) in place of the reaction component in the general formula (), carrying out the same reaction, and finally esterifying with an acid. or by further treatment with an alkali, the dye of the 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-
Examples include 1,4-disulfonic acid, 2-amino-5-propionylaminobenzene-1,4-disulfonic acid, and the like. Examples of the substituent R ₂ in the reaction component represented by the general formula () include hydroxymethyl group,
2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 4-hydroxybutyl group, 1-methyl-2-hydroxypropyl group, cyanomethyl group, cyanoethyl group, methoxymethyl group, 2-methoxyethyl group, 3-methoxypropyl group, ethoxymethyl group, 2-ethoxyethyl group, chloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 4-chlorobutyl group, carboxymethyl group, 2-carboxyethyl group group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylmethyl group, sulfomethyl group, 2-sulfoethyl group, etc. As the formula residue A,

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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 phosphate ester groups, acetate ester groups, halogen atoms, 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 ordinary households, the 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 solves 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 exhaustion 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 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 not only have lower solubility than the dyes of the present invention and have poor build-up properties, making it impossible to obtain dyed products with high density, but also have the disadvantage of extremely poor wash-off properties. Its practical value 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°C. 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 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-hydroxyethylaminobenzene-3
-β-Hydroxyethylsulfone sulfate 16
pH5-6 with 20% sodium carbonate aqueous solution
The temperature was raised to 40°C while adjusting the temperature, and the mixture was stirred 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 for 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). The compound of formula (1) can also be synthesized as follows. 1-N-hydroxyethylaminobenzene-3
-β-Hydroxyethylsulfone sulfate 16
1-N-hydroxyethylaminobenzene-3-β-hydroxyethylsulfone 11.4
A compound obtained by carrying out exactly the same operation as above except for using
The mixture was added to 500 parts of 100% sulfuric acid over a period of 2 hours, and stirred at the same temperature for 3 hours. Next, the mixture is slowly distilled into 1,200 parts of ice, and the precipitated crystals are separated. The obtained crystals were dispersed in 400 parts of water, and sodium carbonate was added to adjust the pH to 5 to 6. After dissolving, 60 parts of sodium chloride was added to precipitate the crystals again. After washing by suction, the crystals were heated at 60°C. dry. When dyeing was carried out 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. It was done.

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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-hydroxyethylaminobenzene-3-β-hydroxyethylsulfone sulfate was added, and the mixture was diluted with a 20% aqueous sodium carbonate solution.
The temperature was raised to 50°C while adjusting the pH to 5-6, and the mixture was stirred 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 (13). When dyeing was carried out using dyes (14) to (18) obtained using the following compounds in the same manner, dyed products with a high density of orange to scarlet and excellent chlorine fastness were obtained.

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[Table] Example 3 Dissolve 0.3 parts of the dye shown in 300 parts of water and add 30 parts of mirabilite.
10 parts of cotton, and raise the temperature to 60℃. After 20 minutes, 5 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.
9.2 parts of cyanuric chloride is added to a solution of 0.1 part of a nonionic surfactant dissolved in 100 parts of water at 0 to 5°C and dispersed. 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 dropping, add 20% sodium carbonate aqueous solution.
Adjust the pH to 3 and stir for an additional 2 hours. Then,
Add 14 parts of sodium bicarbonate. To this, 2-
A solution obtained by diazotizing 9.6 parts of amino-5-methoxybenzenesulfonic acid in a conventional manner was heated to 1°C at 0 to 5°C.
Add in time. After stirring at the same temperature for 4 hours, the pH was adjusted to 5-6 with hydrochloric acid, and then 1-N-hydroxyethylaminobenzene-4-methoxy-3-β
- Add 17 parts of hydroxyethylsulfone sulfate, and while adjusting the pH to 5 to 6 with a 20% aqueous sodium carbonate solution, raise the temperature to 40°C, and stir at the same temperature for 6 hours. Add 40 parts of sodium chloride to precipitate crystals,
After suction filtration, washing, and drying at 60°C, dye (19) was obtained. When dyeing was carried out using dyes (20) to (23) obtained using the following compounds in the same manner as in Example 3, dyed products with high concentration of orange to scarlet with excellent chlorine fastness were obtained. Ta.

[Table] Example 4 Dissolve 0.3 parts of the dye shown in 200 parts of water and add mirabilite.
Add 30 parts, add 10 parts of cotton, and raise the temperature to 50℃.
After 30 minutes, 4 parts of tribasic sodium phosphate was 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. A solution prepared by dissolving 14 parts of 1-N-hydroxymethylaminobenzene-3-β-hydroxyethylsulfone sulfate in 100 parts of water at a pH of 4 to 5 is added dropwise to the mixture 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. Next, add 11.3 parts of J acid and adjust the pH to 5-6 with 20% sodium carbonate aqueous solution.
While adjusting the temperature, raise the temperature to 40°C and stir at the same temperature for 2 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 10 parts of 5-ethoxybenzenesulfonic 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 5~5 with hydrochloric acid.
6, and 60 parts of sodium chloride was added to precipitate crystals, which were filtered under suction, washed, and dried at 60°C to obtain dye (24). When dyeing was carried out using dyes (25) to (28) obtained using the following compounds in the same manner as in Example 4, dyed products with high concentration of orange to scarlet with excellent chlorine fastness were obtained. Ta.

[Table] Example 5 Composition of colored paste 5 parts urea 5 parts Sodium alginate (5%) Paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts Color paste having the above composition The print is printed on mercerized cotton broadcloth, and after intermediate drying, steaming is performed at 100℃ for 5 minutes, followed by washing with hot water, soaping, washing with hot water, and drying. In this way, a scarlet print with excellent chlorine fastness was obtained. Example 6 Composition of colored paste 4 parts dye of the above formula (4) Urea 5 parts Sodium alginate (5%) Base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 14 parts The colored paste having the above composition was mercerized Print on cotton broadcloth, after intermediate drying, steam at 120°C for 5 minutes, wash with hot water, soap, wash with hot water, and dry. In this way, an orange print with excellent chlorine fastness was obtained. Example 7 When dyeing was performed using dyes (29) to (34) produced using the following compounds in the same manner as in Example 1, all dyed with high concentration of orange to scarlet with excellent chlorine fastness. I got something.

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Claims (1)

[Claims] 1 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,
It represents a phenyl 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. R ₁ represents hydrogen, a methyl group or an ethyl group.
_R2 has 1-4 carbon atoms, a hydroxy-substituted alkyl group, a cyano-substituted alkyl group, an alkoxy-substituted alkyl group, a halogen-substituted alkyl group,
Represents a carboxy-substituted alkyl group, an alkoxycarbonyl-substituted alkyl group, or a sulfo-substituted alkyl group. Z represents hydrogen or a sulfonic acid group.
A is a phenylene residue or one sulfonic acid group optionally substituted with one or two substituents selected from the group of methyl group, ethyl group, methoxy group, ethoxy group, chlorine, bromine, and sulfonic acid group represents a naphthylene residue which may be substituted with 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.