JPS63211380A - Cold batch-up dyeing method of cellulosic fiber - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for cold patch-up dyeing of cellulosic fiber materials.

<Prior art> Conventionally, monochlorotriazine and vinyl sulfone dyes have been widely used for cold batch-up dyeing of cellulose fiber materials, but these require a long time to dye and it is difficult to obtain a uniform and sufficiently deep color. is difficult, and furthermore,
There is a problem that it is difficult to balance the stability of the dye in an alkaline bath, temperature sensitivity, and fastness, and for some reason, satisfactory dyed products cannot be obtained, and a solution to this problem is strongly desired.

Problems to be Solved> The present invention solves the above-mentioned conventional problems, provides good build-up, good level dyeing properties, and can be used even if the outside air temperature changes or the dyeing temperature fluctuates. To provide an industrially advantageous cold patch-up dyeing that does not change the dyeing rate even if it is damaged, has good fastness to acid hydrolysis, etc., and has excellent dissolution stability in an alkaline bath. It is something.

Means for Solving the Problems> As a result of intensive studies to find a method to solve the above-mentioned problems, the present inventors discovered that the purpose could be achieved by using a specific complex reactive dye, The present invention has now been completed.

That is, the present invention uses a complex reactive dye having the same or different types of vinyl sulfone type reactive groups in the molecule, thereby producing a conventional reactive dye having a plurality of two types of reactive groups and a compound having only one reactive group. Excellent build-up properties, level dyeing properties, and temperature sensitivity in cold patch-up dyeing, which could not be obtained by using conventional reactive dyes.
This was made based on the discovery that good solubility and fastness in alkaline baths can be obtained.

That is, the present invention provides the following general formula [wherein D
is a residue of an organic dye having a sulfonic acid group, Rle R1
and R3 are independently hydrogen or lower alkyl which may have a substituent, Bl and B are independently selected from the group of methyl, ethyl, methoxy, chloro, bromo, nitro, carboxy and sulfo; vinylene optionally substituted with two substituents or naphthylene optionally substituted with sulfo, Zl and Z8 each independently represent vinyl or -GHzCHzL (L is a group that is eliminated by the action of an alkali); , n represents 1-8. ] Provided is a cold patch-up dyeing method for cellulose fibers or textile products containing cellulose fibers, which is characterized by using a reactive dye shown in the following.

According to the method of the present invention, in cold patch-up dyeing, there is almost no difference in density or hue between fixation at low temperatures and fixation at 26° C., and the dye is less susceptible to hydrolysis by alkaline agents.

The dye of the present invention can be produced, for example, as follows.

[In the formula, De R3* n has the above-mentioned meaning. ] and an organic dye having a sulfonic acid group represented by the general formula (III) [wherein, X represents a halogen atom]. ] dictated 2,
4.6-Dolino seconds no 1.8.5-) with riazin,
General formula (IV) R.

[In the formula, 'R1+ Bt + ZI has the above meaning. ] and the general formula (ma) R1 [wherein, Rg * Bz + Zz has the above-mentioned meaning. The difunctional reactive dye represented by formula (I) can be obtained by condensation with two of the same or different amine components shown in the formula (I) in any order.

In the present invention, the lower alkyl group represented by s R1 * Rz + Rs is preferably an alkyl group having 1 to 4 carbon atoms, and examples of the optionally substituted group include a hydroxy group, a cyano group, and an alkoxy group. , halogen, carboxy group, carbamoyl group, alkoxycarbonyl group, alkylcarbonyoxy group, sulfonic acid group, and sulfomoyl group are preferred.

Examples of R1, R1, and Rs include methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, 1so-butyl group, 5ec-butyl group, 2-hydroxyethyl group, 2-hydroxy Propyl group, 8-hydroxypropyl group, 2-hydroxybutyl group, 8-hydroxybutyl group, 4-hydroxybutyl &, 2,8-dihydroxypropyl &, 8,4-dihydroxybutyl group, cyanomethyl group, 2-cyanoethyl group , 3-cyanopropyl group, methoxymethyl group, ethoxymethyl group, 2-
Methoxyethyl group, 2-ethoxyethyl group, 8-methoxypropyl group, 8-ethoxypropyl group, 2-hydroxy-3-methoxypropyl group, chloromethyl group, bromomethyl group, 2-chloroethyl group, 2-bromoethyl group,
8-chloropropyl group, 8-bromopropyl group, 4-chlorobutyl group, 4-bromobutyl group, carboxymethyl group, 2-carboxyethyl group, 8-carboxypropyl group, 4-carboxybutyl group, 1,2-dicarboxy Ethyl group, carbamoylmethyl group, 2-carbamoylethyl group, 8-carbamoylpropyl group, 4-carbamoylbutyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxyel group,
2-ethoxycarbonylmethyl group, 8-methoxycarbonylpropyl group, 8-ethoxycarbonylpropyl group,
4-methoxycarbonylbutyl group, 4-methoxycarbonylbutyl group, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, 2-methylcarbonyloxyethyl group, 2-ethylcarbonyloxyethyl group,
8-methylcarbonyloxypropyl group, 8-ethylcarbonyloxypropyl group, 4-methylcarbonyloxybutyl group, 4-ethylcarbonyloxybutyl group, sulfomethyl group, 2-sulfoethyl group, 8-sulfopropyl group, 4-sulfobutyl group group, sulfamoylmethyl group,
Examples include 2-sulfamoylethyl group, 8-sulfamoylpropyl group, 4-sulfamoylbutyl group, and particularly preferred are hydrogen atom, methyl group, and ethyl group.

In the present invention, a group represented by Bl m Bl and *
In the formula Kyo 1, the bond indicated with an asterisk is 5OsZt or Son.
It means a bond leading to Zt. ], etc.

In the present invention, the basic dye having a sulfonic acid group represented by D includes mono- or polyazo-based dyes, metal acid salt-based dyes,
formazan, anthraquinone, phthalocyanine,
Examples include stilbene-based, oxazine-based, dioxazine-based, triphenylmethane-based, nitro-based or azomethine-based dyes having a sulfonic acid group.

Among these, in particular, mono- or polyazo-based, metal salt-based, formazan-based, and phthalocyanine-based dyes can exist in a form having Cu + Cr + CO + Nl or Fe as a compound-forming central atom.

Examples of groups that are eliminated by the action of an alkali (represented by L in the above general formula (I)) include sulfate ester groups, thiosulfate ester groups, phosphate ester groups, acetate ester groups, halogen atoms, etc. do.

In the present invention, cellulose i! Ill/IA includes natural or regenerated cellulose fibers such as cotton, hemp, viscose human silk, and viscose cotton.

The dyeing of the present invention is carried out, for example, in the presence of an acid binder such as caustic soda, soda carbonate, sodium phosphate, sodium silicate, or sodium aluminate, and in some cases, an inorganic salt dispersant such as mirabilite or common salt, a leveling agent, The dyeable material is immersed in a dye solution containing a penetrant, urea, etc., squeezed, wrapped in polyethylene film, etc., and left at room temperature for 8 to 72 hours.

According to the method of the present invention, there is very little temperature sensitivity in cold batch-up dyeing, so even if the temperature of the outside air changes during patching, a uniform dyed product with no difference in density or hue can be obtained. In addition, the dye has good solubility in alkaline baths,
A dyed product with good dyeing reproducibility can be obtained. In addition, it has excellent fastness, and a dyed product with a sufficiently deep color can be obtained with good build-up properties.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In the example,
Parts are by weight unless otherwise specified.

26 parts of the dye shown in Example 1 were dissolved in hot water and cooled to 25°C. This was pre-dissolved in boiling water and cooled to 25°C.
% anhydrous sodium sulfate aqueous solution and 15 parts of a caustic soda aqueous solution of 88 degrees Baume were added, and further water was added to bring the total amount to 25 degrees C.
Immediately after the liquid was made up to 1000 parts, this liquid was used as a padding liquid to pad an unmercerized cotton fabric. The padded unmercerized cotton fabric was rolled up, sealed with polyethylene film and stored indoors at 20°C. Similar method) Unmercerized cotton fabrics, trowel padded, rolled up and sealed with polyethylene film, were stored indoors at 5°C.

Each padding fabric was finished after 5 and 20 hours by washing the dyed material in cold and then hot water, soaping in boiling detergent, washing in cold water and drying.

When we investigated the density and hue differences of dyed items left at 20°C for 5 hours, dyed items left at 20°C for 20 hours, dyed items left at 5°C for 5 hours, and dyed items left at 5°C for 20 hours, we found that:
As shown in Table 1, almost none was observed.

For comparison, 25 parts of each of the dyes represented by the following formulas (2) and (8) in the form of free acids were used and external dyeing was carried out by the cold batch-up method in the same manner as in Example 1.
When comparing the density of a dyed product left at C for 5 hours, a dyed product left at 20°C for 20 hours, a dyed product left at 5°C for 6 hours, and a dyed product left at 5°C for 20 hours, formula (2) There was a slight difference in the concentration of dyes left at 20"C for 5 hours, dyed products left at 5°C for 5 hours, and dyed products left at 5°C for 20 hours. ) dye is
The density of dyed products left at 20°C for 5 hours, dyed products left at 5°C for 5 hours, and dyed products left at 5°C for 20 hours was significantly lower. The density of the dyed product left at 20℃ for 20 hours is 100, and the density of the dyed product left at 20℃ for 6 hours is 5℃.
Table 1 shows the densities of the dyed products that were left to stand for hours and those that were left to stand at 5°C for 20 hours.

In addition to Table 1, dyes of formula (1), formula (2), and formula (3) are added at 20°
A comparison of dyed products left for 20 hours at C was found that the dye of formula (1) was able to provide a dyed product with significantly higher density than the dyes of formulas (2) and (3).

Example 2 Using 25 parts of the dye represented by the formula (4) in the form of a free acid, a dyed product was dyed by the cold patch-up method in the same manner as in Example 1 and left at 20°C for 6 hours. Dyed items left for 20 hours, 5
When we examined the density of dyed products left at 5°C for 5 hours and dyed products left at 6°C for 20 hours, almost no difference was observed as shown in Table 2. For comparison, dyeing was carried out by the cold patch-up method in the same manner as in Example 1 using 25 parts each of dyes represented by the following formulas (5) and (6) in the form of free acids.
When we compared the density of a dyed product left at 20°C for 5 hours, a dyed product left at 20°C for 20 hours, a dyed product left at 5°C for 25 hours, and a dyed product left at 5°C for 20 hours, the formula (
The dye in 5) was dyed at 20°C for 6 hours.
The density of dyed products left at 5°C for 5 hours and dyed products left at 5°C for 20 hours was slightly lighter. Moreover, the dye of formula (6) is
The density of the dyed product left at 20°C for 5 hours, the dyed product left at 5°C for 5 hours, and the dyed product left at 5°C for 20 hours was significantly lower. The density of the dyed product left at 20℃ for 20 hours is 1
Table 2 shows the densities of the dyed products left as 00 at 20°C for 5 hours, the dyed products left at 6°C for 5 hours, and the dyed products left at 5°C for 20 hours.

In addition to Table 2, dyes of formula (4), formula (5), and formula (6) are added at 20°
A comparison of dyed products left at C for 20 hours revealed that the dye of formula (4) was able to produce a dyed product that was significantly darker than the dyes of formulas (5) and (6).

Example 8 25 parts of the dye of formula (7) in the form of free acid were dissolved in hot water and cooled to 25°C. Add to this 150 parts of 50 degree Baume water glass and 88
Immediately after adding 15 parts of Baume's aqueous solution of caustic soda and adding water to bring the total amount to 1000 parts at 25° C., this solution is used as a dinging liquid to pad an unmercerized cotton fabric. The padded unmercerized cotton fabric was rolled up and sealed with polyethylene film and stored indoors at 20°C. Unmercerized cotton fabric padded and rolled up in a similar manner and sealed with polyethylene film at 5°C.
It was stored indoors.

Each padding fabric was finished after 5 and 20 hours by washing the dyed material in cold and then hot water, soaping in boiling detergent, washing in cold water and drying.

Dyed items left at 20°C for 5 hours, dyed items left at 20°C for 20 hours, dyed items left at 5°C for 5 hours, dyed items left at 5°C for 2 hours
When the difference in density and hue of the dyed product left for 0 hours was examined, as shown in Table 8, almost no difference was observed.

For comparison, 26 parts of each of the dyes represented by the following formulas (8) and (9) in the form of free acids were used and dyed by the cold patch-up method in the same manner as in Example 8. When we compared the density of dyed products left for a long time, dyed products left at 20°C for 20 hours, dyed products left at 5°C for 6 hours, and dyed products left at 6°C for 20 hours, we found that the dye of formula (8) The density of the dyed product left at 20"C for 5 hours, the dyed product left at 5°C for 5 hours, and the dyed product left at 5°C for 20 hours was low. In addition, the dye of formula (9) was dyed material left at 5M for 5 hours, dyed material left at 5°C for 5 hours, 5°
The density of the dyed product left for 20 hours at C was significantly lower.

The density of the dyed material left at 20°C for 20 hours is taken as 100, and the density of the dyed material left at 20°C for 5 hours, the dyed material left at 5°C for 5 hours, and the density of the dyed material left at 5°C for 20 hours are calculated as follows. It is shown in Table 8.

In addition to Table 8, dyes of formula (7), formula (8), and formula (9) are added at 20°
When comparing dyed products left for 20 hours at C, the formula (
Using the dye 7), it was possible to obtain a dyed product with significantly higher density than the dyes of formulas (8) and (9).

Example 4 25 parts of a dye of the formula at3 in the free acid form are dissolved in hot water and cooled to 25°C. This was pre-dissolved in boiling water and cooled to 26°C.
150 parts of an aqueous solution of unscented salt and 16 parts of an aqueous solution of caustic soda at 88 degrees Baume, and further water was added to bring the total volume to 25 degrees Celsius.
Immediately after making up to 1000 parts, this liquid is used as a padding liquid to pad a viscose rayon fabric.

The padded viscose rayon fabric was rolled up, sealed with polyethylene film and stored indoors at 20°C. The viscose rayon fabric, padded and rolled up in a similar manner and sealed with polyethylene film, was stored indoors at 5°C. Each padding fabric was dyed after 5 and 20 hours, washed with cold water, then hot water, soaped in boiling detergent, and washed again with cold water.
Dry and finish.

When we investigated the density and hue differences of dyed items left at 20°C for 5 hours, dyed items left at 20''C for 20 hours, dyed items left at 5°C for 5 hours, and dyed items left at 5°C for 20 hours, we found that:
As shown in Table 4, it was hardly observed.

For comparison, using 25 parts each of the dyes represented by the following formulas (11) and (12) in the form of free acids, dyeing was carried out by the cold patch-up method in the same manner as in Example 4.
Dyed items left at 5°C for 5 hours, dyed items left at 20°C for 20 hours, dyed items left at 5°C for 6 hours, dyed items left at 5°C for 20 hours
When we compared the density of dyed products left for a long time, we found that the formula (11
) dyes are dyed at 20°C for 5 hours, dyed at 5°C for 5 hours.
The density of the dyed product left for an hour and the dyed product left to stand at 5°C for 20 hours was low. Moreover, the dye of formula (12) is
The density of dyed products left at 5°C for 5 hours, dyed products left at 5°C for 5 hours, and dyed products left at 5°C for 20 hours was significantly lower. The density of the dyed product left at 20°C for 20 hours is 10
Dyeings left at 20°C for 5 hours as 0, 5 at 5°C
Table 4 shows the densities of the dyed products left to stand for hours and the dyed products left to stand at 5° C. for 20 hours.

Table 4 In addition, when the dyes of formula (10), formula (11), and formula (12) were compared with each other by dyeing products that had been left at 20°C for 20 hours, it was found that the dye of formula (10) had the formula ( 11), it was possible to obtain a dyed product with significantly higher density than the dye of formula (12).

Examples 5 to 24 Using dyes represented by formulas (18) to (82) in the form of free acids, dyeing was performed by the cold batch γ-tube method in the same manner as in Example 1, and left at 20°C for 5 hours. dyed material, 2
When we investigated the density difference between dyed products left at 0°C for 20 hours, dyed products left at 5°C for 5 hours, and dyed products left at 5°C for 20 hours, almost no difference was observed.

The mrti of the dyed product left at 20°C for 20 hours is 100.
Dyed items left at 20°C for 5 hours, dyed items left at 5°C for 6 hours, 20 hours at 5°C Table 5 Side 0 -w

Claims (1)

[Claims] In the form of a free acid, the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, D is a residue of an organic dye having a sulfonic acid group, R
_1, R_2 and R_3 are independently hydrogen or lower alkyl which may have a substituent; B_1 and B_2 are independently from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, carboxy and sulfo; phenylene optionally substituted with one or two selected substituents or naphthylene optionally substituted with sulfo, Z_1 and Z_2 each independently represent vinyl or -C
H_2CH_2L (L is a group that is eliminated by the action of an alkali)
, n represents 1-3. ] A cold batch-up dyeing method for cellulose fibers or textile products containing cellulose fibers, characterized by using a reactive dye shown in the following.