JP2549583B2 - Method for preventing fading of unfixed dye in reactive dyeing of cellulose fiber - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing unfixed dyes in reactive dyeing of cellulose fibers from fading when they come into contact with combustion exhaust gas such as SO ₂ , NO and NO _2. It is a thing.

[0002]

2. Description of the Related Art Up to now, it has been known that a dye used for dyeing a fiber causes a discoloration or fading when it comes into contact with a certain gas. It is also known that the behavior varies considerably depending on the type of the fibers to be fixed.

For example, when disperse dyes are used for dyeing diacetate fibers or triacetate fibers, remarkable discoloration occurs when contacting with combustion exhaust gas, but in the case of polyester fibers, such discoloration hardly occurs. Absent. Further, in the case of cellulose fibers, generally, discoloration and fading due to contact with combustion waste gas is unlikely to occur, but problems may occur depending on conditions. In this case, the major factors that cause discoloration and fading are light, heat, humidity, the type of dye, the dyeing density, the fixing state of the dye on the fiber, and the like.

A dye which has been widely used until now in dyeing cellulose fibers is a vinyl sulfone type dye, and this type of dye has a clear hue.
In general, it has advantages such as good solubility and good suitability for continuous dyeing, but it tends to cause discoloration and fading at low dyeing concentrations of medium or less, especially 1 to 2% by weight or less, and humidity. It is known that discoloration and fading easily occur even when the value is high.

Further, in the reactive dyeing of cellulose fibers, a factor that greatly affects discoloration and fading is a fixed state of the dye after dyeing. When the dye is not fixed, combustion waste is generated. Discoloration and fading easily occur due to contact with gas. In general, gases known to cause discoloration and fading of dyes for cellulose fibers include Cl ₂ and Br.
There are _{2, SO 2, NO, NO} 2 , etc., what is believed to be the most significant source group in this, SO _2, NO contained in the combustion exhaust gas, a NO _2.

And, such SO ₂ , NO, NO ₂
When unfixed dye in reactive dyeing of cellulose fiber causes discoloration due to contact with combustion waste gas such as
Since the quality and value of dyed products will be significantly reduced due to color deterioration, it is not possible to develop a discoloration and fading prevention method to prevent discoloration even when unfixed dye comes into contact with combustion exhaust gas. This is a very important issue. However, to date, no method has been proposed that can effectively prevent discoloration and fading of unfixed dyes and that the dyeing work is safe and easy.

[0007]

DISCLOSURE OF THE INVENTION The present invention improves the above-mentioned drawbacks and effectively protects unfixed dyes, which are liable to undergo discoloration or fading due to contact with combustion exhaust gas, for safe and easy dyeing work. An object of the present invention is to provide a method of preventing fading of unfixed dye in reactive dyeing of cellulose fiber, which can be performed.

The present inventors have used SO ₂ , NO and NO ₂ gas, which are considered to be the most important cause when the dye for cellulose fiber causes discoloration and fading, as JIS G0655-67 and JIS L0655-67. , AATCO Test Method 23-1962 was used to study the effect of preventing fading.

As a result, it was found that by adding a compound having a specific chemical structure to a dyeing solution or a printing paste, fading of an unfixed dye upon contact with combustion waste gas can be prevented, and the present invention was completed. Let In addition, when confirming that the unfixed dye can be prevented from fading by the method of the present invention, in the method according to JIS L0655-67, NO and NO ₂ gas by phosphoric acid-sodium nitrite are used as the sole gas, and the AATCO test method is used. In the method according to 23-1962, city gas combustion waste gas was used as a mixed gas.

[0010]

The method for preventing discoloration of unfixed dyes according to the present invention comprises the following compounds in a dyeing solution or printing paste when reactive dyeing of cellulose fibers:

[0011]

[Chemical 1]

[0012]

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[0013]

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[0014]

[Chemical 4]

[0015]

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It is characterized in that at least one selected from the above is added. First, the above-mentioned five types of compounds used in the anti-fading method of the present invention will be described.

The five kinds of compounds represented by the above structural formulas are SO which cause discoloration of the dye for cellulose fiber.
_It has an effect of effectively protecting the dye from combustion waste gas such as ₂ , NO, NO _{2 and the} like. Even if these compounds are individually added to the dyeing solution for cellulose fiber or the printing paste, Alternatively, two or more kinds of these compounds may be combined and added.

In the structural formulas of the above-mentioned 5 kinds of compounds used in the present invention, s is an integer of 5 to 20, and p is 0 to 1.
It is limited to an integer of 0 for the following reason. That is, a compound in which s is an integer of 4 or less, or p is an integer of 11 or more is insoluble in water, and even when a solubility improving aid such as urea or methyl alcohol is used in combination,
Since it does not disperse or solubilize in water and cannot be uniformly mixed in the dyeing liquid or the printing paste, the effect of preventing discoloration due to contact with the combustion waste gas cannot be sufficiently exerted.

Further, in the structural formulas of the above-mentioned 5 kinds of compounds to, in the case of a compound in which s + p is an integer of 31 or more, the activity degree of the terminal vinyl group becomes weak, and SO ₂ and NO existing in the air, The binding force with NO ₂ gas or the like is weakened, and as a result, the function of protecting the unfixed dye from such gas is significantly reduced.

Next, the steps for reactive dyeing of cellulose fibers using the method for preventing fading of unfixed dye of the present invention will be described. In the present invention, in order to prevent discoloration of the unfixed dye, it suffices to appropriately select and add the above-mentioned compound to the dyeing solution or printing paste prepared in a usual composition ratio, and thus obtain The dyeing solution or printing paste is applied to the cellulose fibers, and then a fixing process is performed.

The anti-fading method of the present invention can be applied to all reactive dyeing in which absorption and fixation of dye are carried out separately.
The most effective and practical processing method is pad-
The pad method by steam and pad-cure, and the printing method by a print / alkali pad are mentioned. When these methods are carried out, 0.1 to 10% by weight, preferably 0.1 to 10% by weight of the above-mentioned compounds are added to the dyeing solution or the printing paste.
It is preferable to add 5 to 5% by weight.

Further, in the method of the present invention, it is possible to prevent discoloration of the unfixed dye by simply adding the compounds represented by the specific structural formulas to the dyeing solution or the printing paste.
There is an advantage that the dyeing work can be carried out safely and smoothly. Moreover, the dyed cloth treated by the method of the present invention is not only difficult to cause discoloration and discoloration of the dye during the dyeing operation, but also when it is stored in the combustion exhaust gas that causes discoloration after the processing. However, it is difficult to cause discoloration of the dye.

On the other hand, when the reactive dyeing of the cellulose fiber is carried out without adding the above-mentioned compounds (1) to (3), even during the dyeing process, discoloration or fading has already occurred due to the contact with the gas existing in the air during the dry process. In some cases, the discoloration may occur during the transfer to the next step due to non-fixation. Since such discoloration and fading is an irreversible change, the effect remains even after the fixing process.

In the present invention, a compound having a particularly low solubility, such as polyoxyethylene dimethacrylate (a compound in which R is a methyl group, s = 5 and p = 0 in the above chemical formula), polyoxyethylene trimethylolpropane triacrylate ( In the above chemical formula, R is hydrogen, s =
5, a compound of p = 0), polyoxyethylene polyoxypropylene dipentaerythritol hexaacrylate (a compound of the above chemical formula, wherein R is hydrogen, s = 5, p = 10) and the like are added to the dyeing solution or the printing paste. In order to prevent discoloration of the unfixed dye, a dissolution improving aid such as urea or methyl alcohol may be used in combination at an arbitrary ratio. Examples of the method for preventing discoloration of unfixed dye in reactive dyeing of cellulose fibers of the present invention will be shown below, but the present invention is not limited thereto. Incidentally, in each example,
"Part" indicates "part by weight".

[0025]

【Example】

Example 1 Polyoxyethylene dimethacrylate (a compound in which R is a methyl group, s = 14 and p = 0 in the above chemical formula)

[0026]

[Chemical 6]

10 parts of was dissolved in 90 parts of hot water, and the solution prepared in this manner was used as C.I. I. Add 800 parts of a solution containing 2 parts of Reactive Orange 16 (Remazol Orange 3R), 1 part of sodium alginate, 5 parts of sodium metanitrobenzene sulfonate, 20 parts of sodium bicarbonate and 80 parts of urea, and rehydrate the whole. A dye solution of 1000 parts was obtained.

Then, the desizing-refined No. 60 broad cloth is immersed in the above dyeing solution (squeeze ratio 70%), and then 1
It was dried at 00 ° C. for 3 minutes to obtain a test sample (sample subjected to the anti-fading method of the present invention). At the same time, a sample to which the above compound was not added (non-added sample) was also prepared as a reference by the same method.

Next, the test sample and the additive-free sample were subjected to JI
After treating 3 units in nitric oxide gas according to S L0855-67, heat treatment and fixation were performed at 140 ° C. for 2 minutes. Then, it was washed with water, treated with 2% acetic acid, further washed with water, and then air dried. As a result of measuring the fastness using the gray scale as a scale, the additive-free sample showed discoloration and fading corresponding to gray scale No. 3, while the test sample showed fastness corresponding to No. 5.

Example 2 Polyoxyethylene dipentaerythritol hexaacrylate (in the above chemical formula, R is hydrogen, s = 9,
compound with p = 0)

[0031]

[Chemical 7]

20 parts of C. are moistened with 40 parts of methanol and 100 parts of hot water is added to dissolve them, and the solution thus prepared is used as C.I. I. 20 parts of Reactive Blue 28 (Remazol Blue 3R), 25 parts of sodium alginate
Parts, 50 parts of urea and 5 parts of sodium metanitrobenzene sulfonate were dissolved in 800 parts of the paste, and water was added to obtain 1000 parts of the printing paste.

Then, the above printing paste was printed on a desizing-refined No. 60 broad cloth and dried at 100 ° C. for 5 minutes to obtain a test sample. At the same time, a non-added sample to which the above compound was not added was also prepared as a reference by the same method.

Next, in order to measure the fastness to SO ₂ gas of the test sample and the additive-free sample, JIS was used.
According to L0855-67, instead of sodium sulfite, equimolar anhydrous sodium sulfite was added to generate SO ₂ gas, and both samples were suspended in an SO ₂ gas atmosphere and treated for 30 minutes. After the above treatment, both samples were immersed in a 15% solution of sodium orthosilicate for 20 seconds at 90 to 95 ° C. to fix the dye, and the samples were washed in running water, and then with 2% acetic acid. After soaking, it was washed with water and dried.

As a result of measuring the fastness using a gray scale as a scale, the additive-free sample showed discoloration corresponding to Nos. 3 to 4, while the test sample showed the fastness corresponding to No. 5.

Example 3 Polyoxyethylene polyoxypropylene trimethylolpropane triacrylate (in the above chemical formula,
R is hydrogen, s = 9, p = 5)

[0037]

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After adding 3 parts of polyoxyethylene cetyl ether (30 mol of EO added) to 10 parts of the mixture and making 20 parts of methanol into a uniform solution, 70 parts of hot water at 60 to 70 ° C. was added to disperse. A liquid was prepared. Then, the dispersion liquid thus prepared was used as C.I. I. 2 parts of Reactive Red 22 (Remazol Red B), 1 part of sodium alginate, 5 parts of sodium metanitrobenzene sulfonate
Parts, 20 parts of sodium bicarbonate, and 800 parts of a solution containing 80 parts of urea were added and replenished with water to obtain 1000 parts of the whole dyeing solution.

A No. 60 broad cloth which had been desizing and refined in the same manner as in Example 1 was dipped in the above dyeing solution and then dried to obtain a test sample. At the same time, a non-added sample to which the above compound was not added was also prepared as a reference by the same method.

Next, for the test sample and the additive-free sample, AA was used to measure the fastness to city combustion gas.
In a gas chamber according to TCC Test Method 23-1962, both samples were suspended in a city combustion gas atmosphere and treated at 60 ° C for 1 hour. After the above gas treatment, both samples were taken out, steamed at 100 ° C. for 15 minutes, washed with water to neutralize, washed again with water and air dried. As a result of measuring the fastness using a gray scale as a scale, the additive-free sample showed discoloration and fading corresponding to No. 3, while the test sample showed fastness corresponding to No. 5.

Example 4 Polyoxyethylene polyoxypropylene pentaerythritol tetraacrylate (in the above chemical formula,
R is hydrogen, s = 14, p = 4)

[0042]

[Chemical 9]

20 parts of C. are moistened with 40 parts of methanol and 100 parts of hot water is added to dissolve them, and the solution thus prepared is used as C.I. I. 20 parts of Reactive Yellow 23 (Remazol Yellow GNL), 25 parts of sodium alginate
Parts, 50 parts of urea and 5 parts of sodium metanitrobenzene sulfonate were dissolved in 800 parts of the paste, and water was added to obtain 1000 parts of the printing paste.

Then, the above printing paste was printed on a desizing-refined No. 60 broad cloth and dried at 100 ° C. for 5 minutes to obtain a test sample. At the same time, a non-added sample to which the above compound was not added was also prepared as a reference by the same method.

Next, in order to measure the fastness to SO ₂ gas of the test sample and the additive-free sample, JIS was used.
According to L0855-67, instead of sodium sulfite, equimolar anhydrous sodium sulfite was added to generate SO ₂ gas, and both samples were suspended in an SO ₂ gas atmosphere and treated for 30 minutes. After the above treatment, both samples were immersed in a 15% solution of sodium orthosilicate for 20 seconds at 90 to 95 ° C. to fix the dye, and the samples were washed in running water, and then with 2% acetic acid. After soaking, it was washed with water and dried.

As a result of measuring the fastness using a gray scale as a scale, the additive-free sample showed discoloration and fading corresponding to Nos. 3 to 4, while the test sample showed fastness corresponding to No. 5.

Example 5 Acrylic acid adduct of polyoxyethylene diglycidyl ether (in the above chemical formula, R is hydrogen, s = 4, p
= 0 compound)

[0048]

[Chemical 10]

30 parts of was moistened with 60 parts of methanol and 100 parts of hot water was added to dissolve, and the solution prepared in this manner was added to C.I. I. 20 parts of Reactive Black 5 (Remazol Black B), 25 parts of sodium alginate
Parts, 50 parts of urea and 5 parts of sodium metanitrobenzene sulfonate were dissolved in 800 parts of the paste, and water was added to obtain 1000 parts of the printing paste.

Then, the above printing paste was printed on No. 60 broad cloth which had been desizing and refined, and then dried at 100 ° C. for 5 minutes to obtain a test sample. At the same time, a non-added sample to which the above compound was not added was also prepared as a reference by the same method.

Next, in order to measure the fastness to SO ₂ gas for the test sample and the additive-free sample, JIS was used.
According to L0855-67, instead of sodium sulfite, equimolar anhydrous sodium sulfite was added to generate SO ₂ gas, and both samples were suspended in an SO ₂ gas atmosphere and treated for 30 minutes. After the above treatment, both samples were immersed in a 15% solution of sodium orthosilicate for 20 seconds at 90 to 95 ° C. to fix the dye, and the samples were washed in running water, and then with 2% acetic acid. After soaking, it was washed with water and dried.

As a result of measuring the fastness using a gray scale as a scale, the additive-free sample showed discoloration and fading corresponding to No. 3, while the test sample showed fastness corresponding to No. 5.

[0053]

By using the method for preventing fading of unfixed dye in reactive dyeing of cellulose fiber of the present invention,
SO ₂ which causes discoloration, NO, from combustion exhaust gases, such as NO _2, it is possible to protect the reactive dyes unfixed effectively, deterioration colors of dye product by contact with the combustion exhaust gas Can be prevented. Moreover, when the method of the present invention is used, since it is only necessary to add the compound having a specific chemical structure to the dyeing solution or the printing paste, there is an advantage that the dyeing work can be performed safely and easily.

Claims (1)

(57) [Claims] 1. Non-fixation in reactive dyeing of cellulose fibers, characterized in that, when reactive dyeing of cellulose fibers is performed, at least one selected from the following compounds is added to a dyeing solution or a printing paste. Dye fading prevention method. Embedded image Embedded image Embedded image Embedded image Embedded image