JPS5846185A - Dyeing of cellulosic fiber - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for coloring cellulose fibers in one color from orange to scarlet. More specifically, the present invention provides compounds of the following general formula (I) in the form of free acids: It represents a phenyl group substituted by 1, 2 or 8 substituents from the group of sulfonic acid groups and carboxyl groups.

8ri represents hydrogen, methyl group or ethyl group.

Dog represents a hydroxy-substituted alkyl group, a cyano-substituted alkyl group, an alkoxy-substituted alkyl group, a halogen-substituted alkyl group, a carboxy-substituted alkyl group, an alkoxycarbonyl-substituted alkyl group, or a sulfo-substituted alkyl group having 1-4 carbon atoms. , 2 represents hydrogen or a sulfonic acid group, M is substituted with 1 or 2 substituents selected from the group of methyl group, ethyl group, methoxy group, ethoxy group, chlorine, bromine and sulfonic acid group, represents a phenylene residue which may be substituted with a phenylene residue or a naphthylene residue which may be substituted with one sulfonic acid group, X is -802CH=CH
Represents a bifurcated group -802CH2CH2Y.

Here, Y is a group that is eliminated with an alkali. ) is a method for dyeing cellulose fibers, which is characterized by using the dye shown in the following.

It is known that dyes having l-sulfatoethylsulfonyl g are applied to the dyeing of textile materials as so-called vinylsulfone-type reactive dyes. Dyeing with a scarlet reactive dye does not produce a deep-colored dyed product due to poor build-up properties, and the resulting dyed product generally has a low chlorine susceptibility and often suffers from fading due to the chlorine contained in tap water. Therefore, there has been a strong demand for a reactive dye with good build-up properties and excellent chlorine loading.

Dyes with a monochlorotriazinyl group as a reactive group, which is 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 suitability for stratified dyeing, and furthermore, it has disadvantages such as low acid stability of the dyed product, so it is by no means sufficient for practical use. I could not say it.

For these reasons, the present inventors conducted extensive research in search of an orange to scarlet vinyl sulfone type reactive dye with particularly good build-up properties and excellent chlorine porosity. It has been found that the dye shown gives a highly concentrated dyeing of orange to scarlet color with excellent chlorine susceptibility.

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. Also,
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, a base and a sizing agent, preferably sodium alginate, etc., is printed on the fiber, and after intermediate drying, a color paste of 100 to 200% is used. It is carried out by steaming or dry heating at ℃.

Furthermore, the dyeing of the present invention may be carried out by a continuous method, or cold patch-to-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 (IO D-NH! (39' 1, D has the above meaning) in an aqueous medium at -10°C to 4°C.
A compound which is diazotized at a temperature of 0°C and is represented by the general formula (to) 0 (wherein R1 and Z have the above-mentioned meanings) and a compound that is diazotized at a temperature of -10°C to 60°C, more preferably 0°C to Coupling is carried out at a temperature of 20° C. while adjusting the pH to 5 to 12, more preferably 6 to T; A monoazo compound represented by is obtained.

Alternatively, a similar coupling reaction is carried out using the N-acylated product of the general formula (to), and then the acyl group is hydrolyzed at a temperature of 50 to 100 °C in the presence of an acid or alkali to form the general formula (TV ) can also be obtained.

Then, the compound of general formula (Iv) was heated in an aqueous medium at a temperature of −1
A dichlorotriazinyl compound is obtained by primary condensation with cyanuric chloride at a temperature of 0° C. to 50° C., more preferably 0° C. to 80° C., adjusting the pH to 2 to 10, more preferably 8 to 7, and then the general formula M
2 HN-mu-X(V) In formula 1, R2, mu and X have the above-mentioned meanings. ) are secondarily condensed at a temperature of 0° C. to 70° C., more preferably 80° C. to 50° C., while adjusting the pH to 2 to 9, more preferably 4 to 6 pg, to form a compound of the general formula (I). ) dye can be obtained.

Alternatively, the reaction components of general formula M can be reacted in an aqueous medium at a temperature of -1O
℃ to 40℃, more preferably 0℃ to 20℃
H1 to pH 8, more preferably pH 2 to pH 6
While adjusting to
Then, at a temperature of 0° C. to 70° C., more preferably 20° C. to 60° C., while adjusting the pH to 2 to 9, more preferably 4 to 6, the general formula (IV) is added.
The dye of general formula (I) can also be obtained by secondary condensation of a monoazo compound.

Alternatively, the compound of the general formula Tai and the reaction components of the general formula M are combined in any order in an aqueous medium at a temperature of -10°C to 4°C.
While adjusting the pH to pH 1 to pH 8 at 0°C, secondarily adjust the temperature to 0°C to 70°C (I) H2 to 1>H9, and condense with cyanuric acid to form a compound of the general formula ('VI').
)OH.

A monochrome oligotriazinyl compound represented by the formula (2 (in the formula, R1, Rg, Z, A, and −
10°C to 50°C, more preferably 0°C to 20°C
The dye of general formula 11) can also be obtained by coupling while adjusting the pH to 4 to 10, more preferably 5 to 9.

Alternatively, the compound of general formula (to) can be prepared in an aqueous medium at a temperature of -10
℃ to 40℃, more preferably 0℃ to 20℃,
pH 1 to Ill 8 more preferably
After primary condensation with cyanuric chloride while adjusting the pH to pH 2 to pH 6, the reaction is performed with a diazonium salt of an aromatic amine of general formula (II) at a temperature of -10°C to 60°C, more preferably at a temperature of -10°C to 20°C, and at a pH of 4 to 20°C. pH
10 More preferably, the compound is coupled while adjusting the pH to 6 to 9 to obtain a monoazo compound represented by the general formula and the reaction components of the general formula M,
Temperature 0°C to 70°C, more preferably 80°C to 6
The dye of general formula (I) can also be obtained by condensation at 0° C. while adjusting the pH to 2 to 9, more preferably 4 to 6 pg.

Or the general formula (to) 2 HN-mu-8O2CH2CH20)I @ (in the formula,
R2,A have the meanings given above. ) is used in place of the reaction component of general formula M to carry out the same reaction, and then the compound represented by general formula (1 ) may be used as a dye.

Examples of the diazo component represented by general formula (6) include 2-7minobenzenesulfonic acid, 2-amino-5-methylbenzenesulfonic acid, 2-amino-6-ethylbenzenesulfonic acid, and 2-amino-15-methoxybenzenesulfonic acid. 2-amino-5-ethoxybenzenesulfonate 2-amino-5-chlorobenzenesulfonic acid 2-amino-5-bromobenzenesulfonic acid 2-amino-b-acetylaminopene 2-amino-6-propionyl sulfonate Aminobenzenesulfonic acid 2-amino-6-nitrobenzenesulfonic acid 2-amino-4-chloro+5-methylbenzenesulfonic acid 2-amino-5-chloro-4-methylbenzenesulfonic acid 2-amino-4-methoxybenzene Sulfo 12-amino-4-ethoxybenzenesulfonate 8-amino-4-methylbenzenesulfonic acid 8-amino-4-ethylbenzenesulfonic acid 3-amino-4-methoxybenzenesulfonate 8-amino-4-ethoxybenzenesulfonate 8-Amino-4-di-tetralobenzenesulfonic acid 8-amino-4-bromobenzenesulfonic acid 4-amino-8-methylbenzenesulfonic acid 4-amino-8-ethylbenzenesulfonic acid 4-amino-8-methoxybenzene Sulfo bottle 4-Amino-8-ethoxybenzene Sulfo 14-amino-8-chlorobenzenesulfonic acid 4-7 i / -8-nitrobenzenesulfonic acid 2-Aminobenzene-1,4-disulfonic acid 2-Aminobenzene-1 ,6-disulfonic acid 2-
7minobenzoic 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-6-sulfobenzoic acid 4-7minor 2.5-dimethylbenzenesulfonic acid 4-amino-2,5-diethylbenzenesulfonic acid 4-amino -2,5-dimethoxybenzenesulfonic acid 4-amino-2,6-diethylbenzenesulfonic acid 4-amino-2,6-dichlorobenzenesulfonic acid 4-amino-2,6-dibromobenzenesulfonic acid 4-amino-2- Methyl-5-methoxybenzenesulfonic acid 4-amino-2-methyl-5-ethokylezenesulfonic acid 2-amino-6-methylbenzene-1,4-disulfonic acid 2-amino-6-ethylbenzene-1,4- Disulfonic acid 2-amino-5-methoxybenzene-1,4-disulfonic acid 2-amino-5-ethoxybenzene-104-disulfonic acid 2-amino-6-acetylaminobenzene-1,4-disulfonic acid 2-amino- 5-propionylaminobenzee 1.4
- Disulfonic acid, etc. can be mentioned.

Examples of the substituent R1 in the reaction component represented by general formula (V) include hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 8-hydroxypropyl group, 2-hydroxybutyl group, 4-hydroxy Butyl group% 1-methyl-2-hydroxypropyl group,
Cyanomethyl group, cyanoethyl group, methoxymethyl group,
2-methoxyethyl group, 8-methoxyethyl group, ethoxymethyl group, 2-ethoxyethyl group, chloromethyl group, 2-chloroethyl group, 8-chloropropyl group, 4-chlorobutyl group, carboxymethyl group, 2-carboxyethyl group group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylmethyl group, sulfomethyl group, 2-sulfomethyl group, etc., and examples of formula residues include, for example, 2 (means a bond that leads to the HN- group), etc.

x is a group -802CH:CHI or a group -80
2C) 12CH! Y represents a group that can be eliminated with an alkali, such as a sulfuric ester group, a sulfuric acid ester group, an acetic acid ester 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 resistance and perspiration/sunlight resistance.

Chlorine fastness is grade 8 to grade 4 according to the Iso method, and it has become a problem, especially recently when washing at home, dyed products often fade due to trace amounts of active chlorine contained in tap water1. Considering this, the value of the dye of the present invention, which has excellent chlorine noisiness, is high.Also, it has excellent sweat, sunlight and noisy resistance, which has become a problem with the expansion of sportswear in recent years, at grade 8 to 4. ``From this point of view as well, the value of the dye of the present invention is high.Furthermore, with conventional reactive dyes, a phenomenon has been observed in which the fastness of the dyed product decreases over time when the dyed product is affected by acidic gases in the air, etc. Although it was done.

The dye of the present invention also solves this problem. In other words, the acid stability of the dyed product of the dye of the present invention (the test method is to immerse the dyed fabric in acetic acid for 80 minutes, then use a perspirometer to measure the acid stability of the dye). 2
(processed at 125 f/j for 6 hours at a temperature of c) is good at grade 4 to grade 6 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 that it is possible to obtain dyed products with high density.
It has the great advantage of not only being able to remove water, but also having excellent water-off properties and being able to easily remove unfixed dye.

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, Japanese Patent Publication No. 89-1
No. 8184 describes a dye represented by the following formula.

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 by way of examples.

In the text, parts represent parts by weight.

Example 1 Dye represented by formula (1) 0. Dissolve part a in 200 parts of water and add 2 parts of mirabilite.
Add 0 parts, add 10 parts of cotton, and raise the temperature to 50°C. After 80 minutes, 4 parts of soda carbonate 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 salt-strength properties.

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 11.8 parts of J acid to 100 parts of water, pH 7~
The solution dissolved in step 8 is added dropwise over 1 hour at 0 to 6°C. After the completion of one drop, a 20% aqueous sodium carbonate solution is added to adjust the pH to 8, and the mixture is further stirred for 2 hours. Next, 16 parts of 1-N-hydroxyethylaminobenzene-8-β-hydroxyethylsulfone sulfate was added, and the temperature was raised to 40°C while adjusting the pH to 5 to 6 with a 204 sodium carbonate aqueous solution.
Stir at the same temperature for 6 hours.

Then, after cooling again to 0-5° C., 12.6 parts of sodium hydrogen carbonate are added. To C, add a solution prepared by diazotizing 6 m of 2-amino-5-methoxybenzenesulfonic acid IJ in a conventional manner at 0 to 5°C for 1 hour. After stirring at the same temperature for 2 hours, add hydrochloric acid. pl ( was adjusted to 5 to 6, and 40 parts of sodium chloride was added to precipitate crystals, which were suctioned, filtered, washed, and dried at 60°C to obtain dye (1).

The compound of formula (1) can also be synthesized as follows.

1-N'-hydroxyethylaminobenzene-8-β-
In place of 16 parts of hydroxyethylsulfone sulfate, 1-N-hydroxyethylaminobenzene-8-β-
A compound obtained by carrying out exactly the same operation as above except for using 11.4 parts of hydroxyethyl sulfone was added over 2 hours to 500 parts of 1004 sulfuric acid at 6 to 20°C on wet charcoal, and at the same temperature. Stir for 8 hours.

Next, the mixture was slowly discharged into 1200 parts of ice, and the precipitated crystals were separated by furnace.

The obtained crystals were dispersed in 400 parts of water, and sodium carbonate was added to adjust the pH to 5 to 6 and dissolved, and then 60 parts of sodium chloride was added to precipitate the crystals again. 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 susceptibility were obtained. It was done.

Example 2 0.8 parts of the dye represented by formula (18) is dissolved in 160 parts of water, 80 parts of Glauber's salt is added, 10 parts of cotton are added, and the temperature is raised to 60°C.

Then, after 20 minutes, add 4 parts of soda carbonate and boil at the same temperature.
Time staining.

After dyeing, washing and soaping were performed to obtain a highly concentrated scarlet dyed product with excellent chlorine susceptibility.

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 6°C.

To this, 7-aino-4-hydroxy-8-(2-sulfo-4-
A solution of ethoxyphenyl azo)naphthalene-2-sulfonic acid was added dropwise over 1 hour while maintaining pH 4 to 5 with a 204 sodium carbonate aqueous solution, and stirred for 2 hours at a temperature of θ to 10°C.

Subsequently, 1-N-hydroxyethylaminobenzene-8
- Add 16 parts of β-hydroxyethylsulfone sulfate, raise the temperature to 50°C while adjusting the pH to 5 to 6 with a 204 sodium carbonate aqueous solution, and stir at the same temperature for 6 hours.
Next, 40 parts of sodium chloride was added to precipitate crystals, which were suction-filtered, washed, and dried at 60°C to dissolve the dye (1
8) was obtained.

Dye (14) obtained in the same manner using the following compound
When one color was dyed using (18), dyed products with high concentration of orange to scarlet with excellent chlorine resistance were obtained.

Example 8 0.8 part of the dye represented by formula (19) was dissolved in 800 parts of water and 8 parts of sodium sulfate was added.
Add 0 parts, add 10 parts of cotton, and raise the temperature to 60°C. After 20 minutes, 6 parts of soda carbonate 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 resistance.

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 (0 to 5 c) is added and dispersed. To this, add 11.3 parts of J acid to 200 parts of water, pH 7-8.
The solution was added dropwise at 0 to 6° C. over 1 hour. After 0 dropwise addition, 20% aqueous sodium carbonate solution was added to adjust the pH to 8, and the mixture was further stirred for 2 hours. Then, 14 parts of sodium bicarbonate are added. A solution obtained by diazotizing 9.6 parts of 2-amino-6-medoxybenzenesulfonic acid in a conventional manner is added to this at 0 to b°C over 1 hour. After stirring at the same time for 4 hours, the pH was adjusted to 6-6 with hydrochloric acid, and then #1-
N-hydroxyethylaminobenzene-4-methoxy-
Add 17 parts of 8-β-hydroxyethylsulfone sulfate, and add 17 parts of 8-β-hydroxyethylsulfone sulfate to 1)) Ilt6 with 20% aqueous sodium carbonate solution.
The temperature was raised to 40° C. while adjusting the temperature to 60° C., and the mixture was stirred at the same temperature for 6 hours.

40 parts of sodium chloride was added to precipitate crystals, which were suction filtered, washed, and dried at 60°C to obtain dye (19).

When dyeing was carried out using dyes (20) to (28) obtained using the following compounds in the same manner as in Example 8, dyed products with high concentration of orange to scarlet with excellent chlorine resistance were obtained. It was done.

Example 4 0.8 parts of the dye represented by formula (24) was dissolved in 200 parts of water, 80 parts of Glauber's salt was added, 10 parts of cotton were added, and the temperature was raised to 60°C. After 80 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 scarlet dyed product with high LN density and excellent chlorine staining.

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 I is added and dispersed at O-6°C. To this was added a solution prepared by dissolving 14 parts of 1-N-hydroxymethylaminobenzene-Jl-/-hydroxyethylsulfone sulfate in 100 parts of water at a pH of 4 to 5.
After the completion of 0 dropwise addition in 1 hour, 20-sodium carbonate aqueous solution was added to adjust the pH to m, and the mixture was further stirred for 2 hours. Then, 11.8 parts of J acid was added, and the temperature was raised to 40° C. while adjusting the pH to 6 to 6 with a 20% aqueous sodium carbonate solution, and the mixture was stirred at the same temperature for 2 hours.゛Then again O~
After cooling to 5° C., 12.6 parts of sodium bicarbonate are added. To this, 0 to 6 parts of a diazotized solution of 10 parts of 2-amino-6-nitokylebenzenesulfonic acid was added in a conventional manner.
Add for 1 hour at °C. After stirring at the same temperature for 2 hours, the pH was adjusted to 6-6 with hydrochloric acid, 60 parts of sodium chloride was added to precipitate crystals, filtered by suction, washed, and dried at 60°C to obtain dye (24). When dyeing was performed using dyes (25) to (28) obtained using the following compounds in the same manner as in Example 4, all of them were dyed with high concentration of orange to scarlet color with excellent chloride resistance. I got something.

Example 6 Color paste composition Dye of formula (1) 5 parts Urea 5 parts yzW4 Soy (54) Original paste 50 parts Hot water
26 parts baking soda
2 parts balance 18 parts A colored paste having the above composition is printed on mercerized cotton broadcloth, and after intermediate drying, steaming is performed at too much degree Celsius for 6 minutes, followed by hot water washing, soaking, hot water washing, and drying to finish.

In this way, a scarlet print with excellent chlorine fastness was obtained.

Example 6 Color paste composition Dye of the above formula (4) 4 parts Urea 6 parts Alze-like Shun Soda (64) Gens 50 parts Heat
Hot water 25 parts Baking soda
2 Part Balance Item 1 Color paste with the above composition is printed on mercerized cotton broadcloth, and after intermediate drying, it is soaked for 5 minutes at 1.120℃, washed with hot water, soaked, washed with hot water, dried, and finished. Geru.

In this way, an orange print with excellent chlorine fastness was obtained.

Claims (1)

[Scope of Claims] In the following general formula C in the form of a free acid, D is a methyl group, an ethyl group, a methoxy group, an ethoxy group, a halogen, an acetylamino group, a peropionylamino group, a nitro group, or a sulfonic acid group. and carboxyl group! , represents a phenyl group substituted with 2 or 8 substituents. R1 represents hydrogen, a methyl group or an ethyl group. R2 is a 6, hydroxy-substituted alkyl group, cyano-substituted alkyl group, alkoxy-substituted alkyl group, halogen-substituted alkyl group, carboxy-substituted alkyl group, alkoxycarbonyl-substituted alkyl group, or sulfo-substituted alkyl group having 1-4 carbon atoms; 2 represents hydrogen or a sulfonic acid group, M is 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 phenylene residue which may be substituted with one sulfonic acid group or a naphthylene residue which may be substituted with one sulfonic acid group. I is the group -802CH==CH2 or the group -802CH2C
This represents H2Y! is a group that leaves with alkali. ) A dyeing method for cellulose fibers characterized by using the dye shown in .