JPS6253487A - Method for dyeing or printing 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 The present invention relates to a method for dyeing or printing cellulose fibers. Conventionally, dyeing or printing of cellulose fibers using reactive dyes has been carried out using exhaust dyeing, one-bath or two-bath dyeing. continuous staining method,
Cold-fix methods and one- or two-phase printing methods are known and practiced, but dyeing power, processing efficiency,
In terms of workability and dye versatility, the 1-bath pad steam dyeing method is often used for dyeing, and the 1-phase steam printing method is often used for textile printing.
When using a dye solution containing IHt% sodium bicarbonate and steaming for 1 to 3 minutes at 100 to 105°C, maximum dyeing was reached in about 1 minute of steaming time.
Equilibrium is maintained for up to about 3 minutes, but after about 8 minutes, a decrease in density or a change in hue may occur due to hydrolysis of the dye, and this tendency is especially noticeable in light colors, so steam However, time management was considered important.
Even if you control the steam time, the steam temperature, humidity,
If there is a slight variation in the steam flow rate, this will replace the lack of reproducibility depending on the lot of steam processing of dyed products.On the other hand, the same conditions are adopted for steam printing of 1 bill. However, similar phenomena occur in the behavior and reproducibility during dyeing.In addition, vinyl sulfone-based reactive dyes are used as background dyes, and low-reactivity substitution type reactive dyes (such as monochlorotriazine) are used as accent color dyes. In the one-phase resist dyeing method using ff1f reactive dye), the optimum steam time for the former C is 1 to 8 UJ, and the optimum steam time for the latter C
Since the optimum steam time is different from 8 to 12 minutes, there is a drawback that the common optimum time l$jJ cannot be adopted for both.

For this reason, it is recommended to change the alkaline agent used in ground dyeing to an alkaline substance other than sodium monocarbonate, such as sodium trichloroacetate or soter acetate, or use either the former or the latter when treating sodium bicarbonate. Alternatively, there are cases where methods are used that sacrifice the maximum dyeing strength of both products.0 In addition, in conventional methods, when dye liquids or printing pastes containing sodium bicarbonate are stored, dyes may be damaged over time due to hydrolysis of the dyes. There are problems such as a decrease in concentration and the occurrence of specks due to a decrease in the solubility of the dye, and this phenomenon accelerates especially in the summer when the temperature is high, so the printing paste must be controlled very strictly when using the dye solution. The present inventors have developed an industrially advantageous dyeing or printing method for cellulose fibers using reactive dyes, including the density of dyed and printed products, reproducibility of hue, compatibility with low-reactivity substitution type reactive dyes, and As a result of extensive research into methods that could significantly improve the stability over time of dyes in dye solutions or printing pastes containing We have discovered that these problems can be solved, and have completed the present invention. The present invention involves padding or printing cellulose fibers with a dye solution or printing paste containing a reactive dye and less than 1 weight part of sodium bicarbonate. The present invention is particularly useful for dyeing or printing cellulosic fibers in medium or light colors, which is characterized by fixation treatment. The dye has the following general formula (1), Dl-80,-Y (1) (where Dl is a residue of an organic dye having a sulfonic acid group,
Y is -CH-C) (represents a group - or -CH, CH, Z group, where 2 represents a group that is eliminated by the action of an alkali), and a reactive dye represented by the following general formula (2
) (wherein, D is a residue of an organic dye having a sulfonic acid group,
IJ and n are each independently a hydrogen atom or C1~
C, ayki/l/ group or hydroxy group, cyano group, alkoxy group, halogen, capoxy group, carpamoy/L
' group, alkoxycarbonyl group, 7μ carbonyloxy group, sulfo group, C1-C4 alkyl optionally substituted with sulfamoy/L' group A/J%, A is methyl group, ethyl group, methoxy group, chlorine, A phenylene group optionally substituted with one or two substituents of bromine or a sulfo group, or a naphthylene group optionally substituted with one sulfo group, X is a halogen atom, and Y is a group -80, CH
-CH.

or represents a group -8o, CH, CH, Z, where 2 represents a group that is eliminated by the action of an alkali O) Reactive dyes represented by O) are preferred; all of these reactive dyes are known; One or more types selected from the general formulas (1) and (2) can be used. The amount of sodium bicarbonate used in the dye solution or printing paste containing these reactive dyes is determined by of! ! Less than 1% by weight based on the amount, but usually in the range of 0.1% or more, preferably determined as appropriate depending on the amount of the reactive dye used as shown in the table below 0 0.8 or less 0.2 ~ 0.80.8~0.5
0.8-0.5 0.6 or more 0.
5-0.7 In steam treatment as a fixing treatment performed after padding or printing with a dye liquid or printing paste containing less than 1% by weight of bicarbonate of soda, the steam time showing the best dyeing is 8 to 16 minutes. . This is the conventional 1
This means that the steam time that gives the best dyeing has been significantly extended compared to ~8 minutes. Therefore, according to the present invention, slight fluctuations in temperature, humidity, steam flow rate, and time can be avoided in steam processing. In addition, in the reaction-reactive resist dyeing method, which is carried out in combination with the reactive dye of general formula (1) and a low-reactivity substitution type reactive dye, it is possible to obtain reproducible dyed and printed products even if Since the process can be performed within the optimum steam time for substituted reactive dyes (e.g. monochlorotriazine reactive dyes), i.e. 8 to 12 minutes, the best dyeing is obtained for both;
Processing with reproducibility is possible.

Furthermore, the storage stability of alkali-containing dye solutions and printing pastes can be greatly improved by the method of the present invention, which can be advantageously developed in terms of work management. Examples of the fibers include cotton, vinyloseneuf, visco, cotton silk, and copper acetate fiber, and these fibers may be used alone or in combination of two or more types.

Specifically, the present invention can be carried out, for example, as follows.
] in boiling water, then add an equivalent amount of less than 1 weight (preferably adjusted according to the amount of reactive dye used as described above) of sodium bicarbonate and the reactive dye, and if necessary, a pad liquid of the reactive dye or Agents commonly used in printing pastes, such as urea as a dye dissolving agent, sodium metanitrobenzesis μphonate as a reduction inhibitor, metal ion sequestering agents, disodium salt of sodium ethylenediaminetetophacetate, and anti-migration agents. Alternatively, sodium alginate penetrating agent, leveling agent, etc. can be optionally added as a printing sizing agent. After applying to the cellulose fiber, dry or undried, steam treatment at 100 to 110°C for 8 to 15 minutes is applied. After the reactive dye is fixed, it is washed with water, subjected to soaping treatment at 90 to 98°C, washed with water, and dried to finish.The dyed or printed fabric obtained by this method has a high density It has the advantage of stable hue and excellent reproducibility.It also has the advantage of improving the storage stability of reactive dye pad liquid or printing paste.The industrial value of the present invention is extremely high. Next, a concrete explanation will be given using an example.0 In the text, parts indicate parts by weight.Example 1 5 parts of a golden yellow reactive dye having the following structure in the form of a free acid was dissolved in 329 parts of boiling water, and the mixture was cooled. After that, 50 parts of urea, 10 parts of sodium metanitrobenzenesulfonate,
Add 2 parts m salt of ethylenediaminetetraacetic acid, 8 parts, 3 parts of sodium bicarbonate, and 600 parts of Duck Algin NSPM (sodium alginate: a product of Kibun Food Co., Ltd.) 5% paste to make a total of 1000 parts of uniform printing paste. This printing paste was printed on a cotton satin fabric, and then dried for 8 minutes, 5 minutes, 7 minutes, 10 minutes, and 15 minutes at 100°C under saturated steam.
The printed fabrics obtained in this way had a constant dyeing strength and were reproducible.On the other hand, the printed fabrics were steam-treated for 20 minutes, washed with water, soaped, and finished with water. The maximum dyeing strength of the former was 90% lower than that of the former, and the dyeing strength gradually decreased when steaming was applied for a long time.Example 0 2 A black reactive dye that also has the following structure in the free acid form 2
0 part was dissolved in about 300 parts of boiling water, cooled, and then mixed with 10 parts of sodium metanitrobenzenesulfonate, 3 parts of 2Na salt of ethylenetetraacetic acid, 8 parts of sodium dihydrogenate, and Tamano! J.S.A.
-25 (MyBrain anti-covering agent: Arayo Kagakusha product) 8
Add all parts to prepare a total of 1,000 parts of padding liquid. This padding liquid is covered with a cotton boblin cloth/'IsK pad and dried intermediately.

Next, steam treatment is performed for 5, 7, and 10 minutes at 100C under saturated steam, followed by washing, soaping, and washing with water.The dyed fabric thus obtained has a constant dyeing power. The results were reproducible.

On the other hand, a recipe prepared in the same manner using 20 parts of bicarbonate of soda had a low dyeing power, and as the steaming time increased, the dyeing power gradually decreased and a stable dyed fabric could not be obtained.

Example 8 5 parts of a golden yellow reactive dye having the following structure in the form of a free acid were dissolved in 829 parts of boiling water, cooled, and mixed with 50 parts of urea, 10 parts of sodium metanitrobenzenesulfonate, and 2 parts of ethylenediaminetetraacetic acid. 8 parts of salt, 8 parts of bicarbonate of soda, and 600 parts of Duck Algin NSPM (sodium alginate: a product of Kibun Food Co., Ltd., 5% base) were added to prepare a total of 1000 parts of uniform printing paste.

This printing paste is placed in a sealed container and stored in a constant temperature bath at a temperature of 40° C. for 5 and 10 days. This printing paste and the printing paste immediately after preparation are simultaneously printed on a rayon fabric and dried intermediately.

Next, steam treatment is performed at 100° C. for 7 minutes under saturated steam, followed by washing, soaping, and washing with water to finish.

All of the printed fabrics thus obtained were stable with constant dyeing strength.

On the other hand, when 20 parts of bicarbonate of soda was used and the other conditions were the same, the printing paste stored for 5 days had a dyeing strength of 89g (69g), and the printing paste stored for 10 days had a dyeing strength of 52% compared to the printing paste immediately after preparation. , a printed fabric with stable dyeing strength could not be obtained Example 4 Orange reactive dye X having the following structure in the form of a free acid
1 part of urine was dissolved in 200 parts of boiling water, and after cooling, 150 parts of urine,
Add 15 parts of meta-nitrobenzene sodium sulfonate, 2 parts of ethylenediaminetetophacetic acid, 43 parts of N carbonate soda, Y parts of N carbonate soda, 550 parts of duck algin NSPM (sodium alginate: a product of Kibun Food Co., Ltd.) 5 g 6 paste, and the remaining amount of water. , a total of 1000 parts of uniform printing paste is prepared.

In this case, the dye X part refers to 5 parts, 10 parts, and 20 parts.
Part Y of sodium bicarbonate is 3 parts and 5 parts for each dye concentration.
Part, 7 part, 9 part, 18 part, 17 part, 20 part, 25 part, 5
Indicates that 0 parts were combined.

This printing paste is printed on a cotton broadcloth for intermediate printing.

Next, steam treatment is performed at 100° C. for 5, 7, and 10 minutes under saturated steam, followed by washing, soaping, and washing with water to finish.

The optical density of the printed fabric thus obtained was measured and expressed as relative dye strength (b).

Here, the relationship between the amount of dye used and the optimum amount of sodium bicarbonate used was as follows: Reactive dye Sodium bicarbonate 5 parts → 8 parts 10 parts → 5 parts 20 parts → 7 parts Under these conditions, the steam treatment time was 5 parts. It was observed that stable maximum dyeing strength was exhibited even when the time was changed from 10 minutes to 10 minutes.

H

Claims (3)

[Claims] (1) A method for dyeing or printing cellulose fibers, which comprises padding or printing cellulose fibers with a dye liquid or printing paste containing a reactive dye and less than 1% by weight of sodium bicarbonate, and fixing the cellulose fibers. (2) As a reactive dye, the following general formula D_1-SO_2-Y (in the formula, D_1 is a residue of an organic dye having a sulfonic acid group, Y is a -CH=CH_2 group or -CH_2CH_2Z
2. The dyeing or printing method according to claim 1, characterized in that a reactive dye represented by the following formula is used. (3) As a reactive dye, there are the following general formulas ▲ mathematical formulas, chemical formulas, tables, etc. C_1 to C_4 alkyl group optionally substituted with alkyl group or hydroxy group, cyano group, alkoxy group, halogen, carboxy group, carbamoyl group, alkoxycarbonyl group, alkylcarbonyloxy group, sulfo group, sulfamoyl group, A is methyl group , an ethyl group, a methoxy group, a phenylene group optionally substituted with one or two substituents of chlorine, bromine or a sulfo group, or a naphthylene group optionally substituted with one sulfo group, X is a halogen atom , and Y is a group -SO_2CH
=CH_2 or the group -SO_2CH_2CH_2Z, where Z represents a group that is eliminated by the action of an alkali. ) The dyeing or printing method according to claim 1, characterized in that a reactive dye represented by the following formula is used.