JP2000355886A - Discharge printing for acrylic fiber material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prozvide a discharge printing method capable of improving discharge printing properties of fiber material especially subjected to fiber dyeing in a high concentration without damaging qualities/feeling of acrylic fiber material and further controlling the amount of a discharge printing used to about half the amount of discharge printing used by a conventional discharge printing method. SOLUTION: In subjecting an acrylic fiber material subjected to fiber dyeing using a cationic dye for discharge printing to discharge printing, a cationic activator is mixed with a textile printing sizing agent for discharging printing and used. Further an accelerating agent of dyeing having performances of swelling the acrylic fiber material or a sizing agent having performances of subjecting the cationic dye for discharge printing to reductive decomposition is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for discharging an acrylic fiber material predyed with a cationic dye for discharge printing.

[0002]

2. Description of the Related Art In general, discharge of an acrylic fiber material is carried out by a cationic dye for discharge (hereinafter referred to as a discharge dye), that is, a cation having at least one azo group (-N = N-) as a chromophore in the dye structure. After pre-dying the fiber material using a dye, in the case of white discharge, a printing paste containing a zinc-based discharge agent such as zinc formaldehyde sulfoxylate is printed on the fiber material, and the dye of the printed portion is subjected to steam heat treatment. There is a method of reducing, decomposing into a colorless form and expressing a white pattern on the dyed part, and in the case of colored discharge, a tin-based discharge agent such as stannous chloride or processed tin and a reduction resistant dye The printing paste containing the printing paste is printed on the fiber material, and the dye of the printing part is reduced by steaming and heat treatment, and it is widely decomposed into a colorless form, and at the same time, the reduction resistant dye is dyed to express a new color pattern. Are known. Dischargeability requires that the discharge dye used for pre-dyeing be easily reduced by the above-mentioned discharge agent and be decomposed into a colorless form. In the case of the acrylic fiber material
Even if a large amount of discharge agent is used, the dye dyed inside the fiber cannot be completely reduced and decomposed. In other words, undissolved dye remains in the discharge area, or tends to be stained with a different color due to recoloring due to oxidation of the decomposed dye, so in the case of white discharge, the discharge area does not become uniform white, or In the case of colored discharge printing, problems such as blurring of the contour of the pattern, and problems such as blurring of the contour of the pattern tend not to occur in the discharge-printed portion of the intended different color.

[0003] The main cause is considered to be insufficient penetration of the discharge agent into the fiber. Further, it is conceivable that the printing paste for discharge printing drips or bleeds due to the long-time steaming heat treatment, that is, the concentration of the discharge agent caused by bleed decreases.

As a measure for improving the above, as a method of infiltrating a discharge agent into the interior of a fiber, a method of mixing a compound which swells or dissolves a fiber into a printing paste for discharge has been disclosed in Japanese Patent Laid-Open No. 55-22.
No. 040, JP-A-53-31885 and JP-A-53-111178. On the other hand, as a method for preventing recoloring of a decomposed dye, a compound which easily binds to a decomposed dye in a printing paste for discharge printing. Alternatively, a method of mixing an ultraviolet absorber, a fluorescent whitening agent and the like has been proposed in Japanese Patent Application Laid-Open No. 54-156885.

Further, a method combining both the methods of infiltration of a discharge agent and prevention of color reversal has been proposed in JP-A-54-120791 and JP-A-55-62279. Use amount (concentration) where effect is most exhibited
This causes problems such as fiber shrinkage and hardening of texture, and some of them are complicated methods, and have problems in terms of price.

As a method of preventing bleeding, a method of using a glue having chemical resistance and heat stability, or a method of performing predrying after printing and before steaming heat treatment is generally performed. However, the bleed of the printing paste for discharge printing containing a high concentration of a discharge agent, a fiber swelling agent, a dissolving agent and the like has not been sufficiently improved.

[0007]

DISCLOSURE OF THE INVENTION The present invention improves the dischargeability of a fiber material which is pre-dyed at a high concentration without impairing the quality and texture of the acrylic fiber material. Discharged products having a uniform white or different color pattern can be stably obtained without being contaminated by reductive decomposition dyes or recoloring, and the amount of discharge agent used is about half that of conventional discharge printing. It is intended to provide a discharge printing method which can be suppressed to a minimum.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, the cationic dye dyed on the acrylic fiber easily migrates in the presence of a specific cationic activator. By paying attention to the phenomenon to be caused, it has been found that the dischargeability is improved by releasing the discharge dye, which is dyed inside the fiber where the discharge agent hardly penetrates, from the dyeing seat, and the present invention has been completed.

That is, the present invention provides a method for discharging a pre-dyed acrylic fiber material using a cationic dye for discharge,
This is a method for discharging an acrylic fiber material, characterized by using a cationic activator. In the discharge printing, it is preferable to use a cationic activator mixed with the discharge printing paste, and further to use a propellant and a cationic activator having the ability to swell the acrylic fiber material and the discharge printing paste. Can also be mixed.

In addition, it is preferable to use a sizing agent having a performance of reductively decomposing a cationic dye for discharge printing as the printing paste for discharge printing.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The discharge dyeing cationic dye referred to in the present invention is a reducing discharge dyeing agent,
That is, it is a cationic dye which can be reductively decomposed by a tin-based discharge agent such as stannous chloride and processed tin or a zinc-based discharge agent such as zinc formaldehyde sulfoxylate. Generally, an azo group (-N = N-) as a chromophore. However, although the details are not clear, there is a difference in the types of dyes that can be reductively decomposed between the tin-based discharge agent and the zinc-based discharge agent, so it is necessary to select a dye according to the type and purpose of the discharge agent used in advance. preferable.

The acrylic fiber material referred to in the present invention means a raw cotton, a raw yarn, a filament, a woven fabric, a knitted fabric, a hairy fabric, a non-woven fabric and a nonwoven fabric made of an acrylic fiber dyeable with a cationic dye. This concept includes used clothing, living materials, industrial materials, and the like.

In the present invention, the first dyeing means that the above-mentioned acrylic fiber material is subjected to a conventional dip dyeing method or a continuous dyeing method using a cationic dye for discharge and various dyeing auxiliaries before the discharge treatment. It is to dye using, discharge discharge means white discharge or color discharge, and the dischargeability here means,
In the case of white discharge, it means the whiteness of the white part of the discharge part and the sharpness of the outline of the pattern whitened in the dyed part, and in the case of colored discharge, the discharge dye that dyes simultaneously with the decomposition of the dye in the discharge part (Reduction-resistant dye) It means the original color developing property and the sharpness of the outline of a pattern dyed in a different color in the dyed part.

The cationic activator used in the present invention is usually a quaternary ammonium salt used as a slow-dyeing / leveling agent when dyeing an acrylic fiber with a cationic dye. salts, there are types such as alkyl ammonium salts, quaternary ammonium salts containing an alkyl group of C ₁₂ -C ₁₈ in the molecule. In the method according to the present invention, 0.1 to 2 parts, preferably 0.5 to 1 part, of these cationic activators are mixed and used in the printing paste for discharge printing, whereby excellent discharge property improvement is recognized.

Further, the printing paste for discharge printing used in the present invention has been conventionally used for normal discharge printing, and is generally a discharge agent, a dyeing acid, a sizing agent and, in the case of colored discharge, a paste. It is a viscous aqueous solution containing a color dye and a dye dissolving agent according to the purpose. Specifically, as a discharge agent, in the case of white discharge, it is preferable to use a zinc-based discharge agent such as zinc formaldehyde sulfoxylate, which has a strong reducing property. It is preferable to use inferior tin-based discharge agents such as stannous chloride. The dyeing acid is preferably a non-volatile organic acid, and is generally tartaric acid, malic acid, or the like. Any sizing agent can be used as long as it is used in general printing, for example, carboxymethylcellulose as a cellulose derivative sizing agent, processed sizing agent based on Shiraz, alginic acid from natural seaweeds, polyvinyl alcohol as a synthetic sizing agent, etc. Is mentioned. Further, the achromatic dye is a reduction-resistant cationic dye that is not reductively decomposed by a tin-based discharge agent, and urea is generally used as a dissolving agent for the dye.

Next, an embodiment of the discharge printing method of the present invention will be described. As a general method of the present invention, there is a method of using a fabric woven using acrylic fibers that can be dyed with a cationic dye as the acrylic fiber material. As the discharge dyeing cationic dye, for example, the color index NO. In, CI Basic Yel
It is preferable to perform first dyeing using three primary color dyes of low-15, Red-70 and Blue-65.

Next, as a printing paste for discharge printing, 10 discharge agents were used.
25 to 25 parts, tartaric acid 0.1 to 0.5 part, 30 to 50 parts of the original paste adjusted to 30% by weight of the solid content of the shirasu paste, A discharge printing paste containing 0.5 to 1 part of urea in an arbitrary amount is used, and a quaternary ammonium salt as a cationic activator is used in 0.1 part.
２2 parts are mixed with the printing paste and printed on the fabric.
The viscosity of the printing paste at this time was from 8,000 to 10
It is preferably 000 cp.

Then, for example, by a known method such as continuous or batch type atmospheric steaming, for example, 20 times.
After steaming for 30 minutes to 30 minutes, washing with water and drying are performed by a known method to obtain a desired discharge product.

By carrying out the present invention, for example, by mixing 0.1 to 2 parts by weight of a cationic activator into a printing paste for discharge printing, the amount of the conventionally used discharge agent can be reduced to 20 to 2 parts.
The amount of use can be reduced from 5 parts by weight to 10 to 15 parts by weight.

In the above method, as a means for further improving the efficiency, there is a method in which a dyeing agent having a function of swelling the fiber material is mixed with the cationic activator in the printing paste. By mixing 0.5 to 3 parts of the fiber swelling type dye, the time required for the steaming step can be reduced to 10 to 20 minutes.

As the dyeing agent having the ability to swell the above-mentioned fiber material, a dyeing agent which is generally used as a dyeing agent for deep color dyeing of acrylic fibers or a dyeing agent for disperse dyeing of polyester fibers is used. It is preferably a nonionic or weakly anionic compound which is a carrier, easily forms a finely dispersed emulsion when injected into water, and has no binding ability with a cationic activator or cationic dye. Examples of the fiber swelling type dyeing agent include an alkyl-phthalimide compound and an aromatic ether compound. In the method according to the present invention, 0.5 to 3 parts, and preferably 0.5 to 3 parts, of these dyeing dyes are preferably contained in the printing paste for discharge printing. By mixing and using 1 to 2 parts of the cationic activator simultaneously with the cationic activator, the cationic activator is more easily diffused inside the fiber, so that the discharge process is accelerated and the discharge is considered to be completed efficiently in a shorter time. Can be

Further, at the time of discharging, it is preferable to use a sizing agent having a performance of reductively decomposing the cationic dye for discharge.

The sizing agent having the property of reductively decomposing a cationic dye for discharge printing is a polysaccharide having a primary alcohol in its molecular structure. Examples of the sizing agent include starch-based paste, locust bean-based paste, and galactomannan-based paste. However, it is preferable to cut a part or most of a glucosid bond (—O—) connecting a glucose group in a molecule in order to impart thermal stability and chemical resistance. That is, even when the paste is dissolved at a high concentration, a viscous aqueous solution (print paste) having a relatively low viscosity can be obtained. Specifically, the solid content of the paste in the print paste for discharge printing is 7 to 7%. At 15%, the viscosity of the discharge printing paste becomes B
It is preferably from 5,000 to 10,000 cp (centipoise) as measured by a mold viscometer. A paste (30% of original paste) having a performance of reductively decomposing the discharge dye is used in an amount of 20.
By using ~ 40 parts, the amount of discharge agent can be further increased by 7 ~ 10
Part can be reduced.

According to the method of the present invention, the cationic activator has a function of replacing the dye and the decomposed dye which are dyed on the dyeing seat in the fiber, and forcibly removes a substance which causes a different color contamination from the fiber. Therefore, a uniform white or another color pattern can be developed without recoloring after discharge. Furthermore, according to the method of the present invention, the time for the steam heat treatment can be shortened, so that the problem of bleeding can be solved, and a discharged product without pattern blur can be obtained. Furthermore, since the acrylic fiber material discharged by the method of the present invention can completely reduce and decompose the dyed dye, it is particularly effective when the dye material is dyed at a high concentration of 2.0% owf or more. And has a uniform white or another color pattern without receiving a different color contamination, and has an effect such that the contour of the pattern is not blurred.

Although the reason why the method of the present invention is superior to the conventional method is not clear, it is considered as follows.
That is, in the conventional method, a method is used in which a compound which swells or dissolves the fiber is mixed with a printing paste for discharge printing and used in a fiber material dyed (yarn-dyed) at a high concentration, thereby allowing a discharge agent to penetrate inside the fiber. Although it was general, the amount of use of the compound exhibited the most effect, causing problems such as fiber shrinkage and texture hardening, and it was insufficient to improve the dischargeability while maintaining the fiber quality. Conceivable.

On the other hand, in the method of the present invention, by using a discharge printing paste mixed with a cationic activator, the cationic activator is diffused inside the fiber, and at the same time, replaced with the cationic dye stained on the dyeing seat. Therefore, it is presumed that the dye is liberated and the reductive decomposition of the dye diffused to the vicinity of the fiber surface is promoted, and an extremely excellent discharge effect can be obtained.

[0027]

EXAMPLES Hereinafter, the effects of the present invention will be described with reference to examples. In this example, the discharge of pile fabric, which is difficult to obtain the most stable discharge product, will be specifically described. In the examples, parts and% represent parts by weight and% by weight, respectively, unless otherwise specified.

Example 1 Commercially available acrylic synthetic fiber:
Using an overmeyer dyeing machine, a dye measured in the following dye formulation into a dyebath adjusted to pH 4 with RCL7 denier raw cotton of Kanecaron (manufactured by Kanegafuchi Chemical Co., Ltd.),
Dyed at 100 ° C. for 60 minutes. In addition, the discharge dye used for the first dyeing can be easily reduced and decomposed with a zinc-based discharge agent and a tin-based discharge agent, Astrazon Yellow 3R manufactured by Dystar Japan and Catilon Red CD-FGLH, manufactured by Hodogaya Chemical Co., Ltd. Blue
GLH was used. [Dye formulation] Astrazon Yellow 3R: 2.1% owf Cathilon Red CD-FGLH: 0.7% owf Cathion Blue GHL: 1.7% owf In order to use the obtained dyed cotton as a raw material for the pile portion of the pile fabric, dyed cotton is used as a fair note machine. Then, slivers were formed by a carding machine, and a high pile material was produced by a sliver knitting method.

Next, a printing paste for discharge printing was prepared in accordance with the formulation shown in Table 1 in order to discharge the high pile material white. As a discharge agent, Decr manufactured by BASF, which has the strongest reducing power
olin was used. A quaternary ammonium salt, Astra, manufactured by Bayer, which is commonly used as a cationic dye slowing agent as a cationic activator mixed with a printing paste for discharge printing
Using gal PAN, 1 part was added to the amount of the printing paste for discharge printing. As the sizing agent, Gluenau Lamegum, a Shiraz-based paste having no property of reductively decomposing the discharge dye, is used, and the viscosity of the discharged discharge print paste after adjustment is 8,000 to 8,000 in a B-type viscometer.
Adjusted to 10,000cp. Using a roller printing machine, the adjusted printing paste for discharge printing is printed on the pile surface of the high pile raw material at a printing amount of 200 to 300 g / m ² , and 98 to 10
After performing steaming heat treatment in a steaming machine at 3 ° C for 20 minutes, washing and drying were performed. Next, in order to improve the pile disorder and feeling of the high pile material, a polishing-shearing treatment was performed to prepare the high pile fabric into a final product form.
The high pile fabric obtained by the above operation is discharged uniformly at a depth of 3 to 4 mm from the pile hair tip, and the whiteness of the discharged portion and the boundary between the pre-dyed portion and the discharged portion (pattern outline). Was clearly expressed, and the texture of the pile portion was a good discharge.

Example 2 In the same manner as in Example 1, a discharge printing treatment was carried out using the discharge printing paste of the discharge printing paste formulation shown in Table 1. Here, Levegal PEW manufactured by Bayer Co., which is a dyeing dye having an action of swelling the fibers, was used. The steaming heat treatment after printing was shortened to 10 minutes. The high pile fabric obtained by the above operation is the same as in Example 1.
Almost in the same manner as in the discharge-printed product, the whiteness of the discharge-printed portion and the boundary between the pre-dyed portion and the discharge-printed portion (the contour of the pattern) were clearly expressed, and the texture of the pile portion was also good.

(Example 3) The printing paste for discharge printing of Example 3 shown in Table 1 was used. Here, Meyh is a sizing agent having the property of reductively decomposing the discharge dye used for the first dyeing.
Locust bean paste Meypro Gum NP-25 manufactured by All Corporation was used. In order to easily confirm whether or not Meypro Gum NP-25 has the property of reductively decomposing the discharge dye, Mypro Gum
An aqueous solution in which NP-25 was dissolved at a solid content of 10% was prepared, and a small amount of a dye solution in which a dye for discharge was dissolved was added and stirred. After steaming heat treatment was performed for 10 minutes, the dye in the aqueous solution became colorless. Decolorized. Using the above-described printing paste for discharge printing, a discharge treatment was performed in the same manner as in Example 2, and the obtained high pile fabric was superior in whiteness of the discharged portion to that of Examples 1 and 2, and The boundary (the contour of the pattern) between the first dyed portion and the discharged portion was more clearly expressed, and the texture of the pile portion was a good discharged product.

(Comparative Example 1) The high pile material prepared in Example 1 was prepared using the conventional printing paste formulation for discharge printing shown in Table 1.
Discharge treatment was performed in the same manner as in Example 1. In addition, the steaming process after printing was changed to 30 minutes. The obtained high pile fabric was incompletely discharged at the discharge portion, that is, the discharge portion was purple-contaminated with a different color and was not a discharge product. The reason why the discharge discharge part caused a discharge failure in purple was
This is presumably because the discharge agent could not penetrate into the fiber and could not discharge the red dye and blue dye for discharge, which were dyed inside the fiber.

(Comparative Example 2) As shown in Table 1, the high pile material prepared in Example 1 was mixed with a conventional discharge printing paste and a discharge dyeing agent having an action of swelling the fibers was discharged. The paste was adjusted and subjected to discharge printing in the same manner as in Example 1. In addition, the steaming process after printing was changed to 30 minutes. Since the fibers were swollen to make the discharge agent easily penetrate into the fibers, the obtained discharge-printed product had improved whiteness compared to that of Comparative Example 1, but the boundary between the pre-dyed portion and the discharge-printed portion (pattern outline) ) Has a pattern blur due to the bleed of the printing paste for discharge printing,
The texture of the pile portion was hardened under the influence of an excessive amount of the swelling agent, and was not a discharge-printed product.

As described above, the discharged products obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated as follows. When the quality of other discharge-printed products was determined, the results were as shown in Table 1.

In the quality judgment, five experts in high pile processing were evaluated, and the average evaluation of the five persons was used as the judgment result. The symbols in the table indicate ◎: best, 最 良: good, Δ: inferior, ×: worst.

[0036]

[Table 1] (Example 4) In order to color-discharge the high pile material produced in Example 1, a printing paste for discharge printing was prepared according to the formulation shown in Table 2. In addition, Astrazon Gold. Yellow GL-E, Astrazon Brill. Red manufactured by Dystar, Inc.
Using 4G, three primary colors of Astrazon Blue F2RL, it was blended so that another color of the discharged part dyed the skin color. When the discharge printing was performed in the same manner as in Example 1 using the printing paste for discharge printing, the obtained high pile fabric was 3 to 4
Discharged uniformly at a depth of mm, the other part of the discharged part is dyed in flesh color, the boundary between the first dyed part and the discharged part (pattern outline) is clearly expressed, and the texture of the pile part is also good It was a discharge product.

Example 5 A printing paste for discharge printing shown in Table 2 was prepared. Using the printing paste for discharge printing, a discharge treatment was performed in the same manner as in Example 1. The steaming heat treatment after printing is 10
Minutes. The high-pile fabric obtained by the above-mentioned operation is similar to the discharge-printed product of Example 4, and the other color of the discharge-printed portion is dyed in flesh color, and the boundary between the first-dyed portion and the discharge-printed portion (pattern outline) is clearly expressed, In addition, the texture of the pile portion was a good discharged product.

Example 6 A printing paste for discharge printing was prepared according to the formulation shown in Table 2. Here, a locust bean-based glue Meypro Gum NP-25, which is a sizing agent having the property of reductively decomposing the discharge dye used in the first dyeing, was used.

Using the above-described printing paste for discharge printing, discharge printing was carried out in the same manner as in Example 5, and the obtained high pile fabric had a different skin color in the discharged portion than the discharged products of Examples 4 and 5. Discharged products were developed more vividly, the boundary (pattern outline) between the pre-dyed part and the discharged part was more clearly expressed, and the texture of the pile part was also good.

(Comparative Example 3) The high pile material produced in Example 1 was subjected to discharge treatment in the same manner as in Example 1 by using the conventional discharge paste formula for discharge printing shown in Table 2 (Comparative Example 3). .
In addition, the steaming process after printing was changed to 30 minutes. In the obtained high pile fabric, discharge of the discharge part is incomplete,
That is, the discharge-printed part was contaminated with purple and was not a discharge-printed product. It is considered that the reason why the discharge discharge portion was purple and the discharge discharge failure occurred was that the discharge discharge agent could not penetrate into the interior of the fiber and the discharge red dye and the blue dye dyed inside the fiber could not be discharged.

(Comparative Example 4) The high pile material prepared in Example 1 was discharged by mixing a conventional discharge printing paste shown in Table 2 (Comparative Example 4) with a propellant having an action of swelling the fiber. The printing paste for printing was adjusted, and discharge printing was performed in the same manner as in Example 1. In addition, the steaming process after printing was changed to 30 minutes. Since the fibers were swollen to make the discharge agent easily penetrate into the fibers, the obtained high pile fabric had a different color of the discharge part from that of Comparative Example 3 to a flesh color, but it did The borders (outline of the pattern) of the part had a pattern fall due to the bleed of the printing paste for discharge printing, and the texture of the pile part was hardened under the influence of an excessive amount of swelling agent, so it could not be said that it was a discharge product .

As described above, the discharged products obtained in Examples 4 to 5 and Comparative Examples 3 and 4 were subjected to the JIS staining gray scale by discharging the discharged product of Example 6 in which the skin color of the discharged region was the most vivid. In the case of class 5, the quality of the other discharge-printed products was determined as shown in Table 2 below.

[0043]

[Table 2] In the quality judgment, a high pile processing expert 5
And the average evaluation of five persons was used as the judgment result.
The symbols in the table indicate ◎: best, ：: good, Δ: poor, ×: worst.

[0044]

According to the method for discharging synthetic fiber material of the present invention, it is possible to obtain an extremely excellent discharge product, to reduce the amount of discharge agent used in comparison with the conventional discharge method, and to obtain the steaming after printing. It is extremely high in industrial value, for example, the process time can be shortened.

Continued on the front page F term (reference) 4H057 AA02 BA03 BA24 CA03 CA06 CA08 CA33 CA90 CB08 CB15 CB18 CB21 CC03 DA01 DA19 DA33 DA34 GA90

Claims (4)

[Claims] 1. A method for discharging an acrylic fiber material, comprising using a cationic activator when discharging an acrylic fiber material pre-dyed with a cationic dye for discharge printing. 2. The acrylic material according to claim 1, wherein a cationic activator is mixed with the printing paste for discharge when discharging an acrylic fiber material pre-dyed with a cationic dye for discharge. Discharge method for fiber based materials. 3. The discharge printing of an acrylic fiber material according to claim 2, further comprising mixing a dyeing agent having a performance of swelling the acrylic fiber material and a cationic activator into a printing paste for discharge printing. Method. 4. The method for discharging an acrylic fiber material according to claim 1, wherein a sizing agent having a performance of reductively decomposing a cationic dye for discharging is used as the printing paste for discharging. .