KR100387600B1 - Dyeing method using cationizing agents and reactive dyes, and fiber dyed using the same - Google Patents

Abstract

The present invention relates to a dyeing method using a reactive dye, and more particularly, to a method of dyeing using a reactive dye after a cationic agent treatment to a fiber having a hydroxyl group such as cotton, the object of the present invention is a reactive dye By increasing the dyeing efficiency of the dyeing, it is possible to reduce the dyeing processing cost by showing sufficient dyeing effect even with a small amount of dyes, forget-me-not and soda ash, and alleviate the waste water problem caused by dye, forget-me-not, soda ash, etc. It is to provide a dyeing method using a reactive dye that can improve the productivity by reducing the time.

The present invention comprises the steps of pretreatment of a fiber having a hydroxyl group in a conventional manner; A cationization step of putting the pretreated fiber into water and adding a cation agent having an ammonium group and an epoxy group; A dyeing step of putting a cationic fiber in water and adding an anionic water-soluble group and a reactive dye having a functional group capable of reacting with a hydroxyl group of the fiber, a neutral salt and a weak alkali, followed by pickling; A soaping and anionizing step of placing the salted fiber in water and injecting a salt or acid capable of ionically bonding the ammonium group in a conventional soaping agent and a neutral aqueous solution; And post-treating the soaped and anionized fibers in a conventional manner.

Description

Dyeing method using cationizing agents and reactive dyes, and fiber dyed using the same}

The present invention relates to a dyeing method using a reactive dye, and more particularly, to a method of dyeing using a reactive dye after the cationic agent treatment to a fiber having a hydroxyl group such as cotton.

A reactive dye is a dye having a reactive group that can react with a polar group such as hydroxyl group of the fiber to form a covalent bond, and refers to a dye having a strong dyeing ability to the fiber because it forms a covalent bond with the fiber.

Reactive dyes are very important in dyeing cotton or cotton blended fibers. This is because the reactive dye meets all the requirements of the dye, such as color fastness, dye price, color diversity and color reproducibility. Therefore, the dyeing process of cotton or cotton blend fiber is mostly performed using a reactive dye.

In general, in the dyeing of reactive dyes, dyes are adsorbed to fibers in the presence of neutral salts, and covalent bonds are formed between the fibers and dyes in the presence of neutral salts and weak alkalis to complete dyeing.

Conventional cotton fiber dyeing method using such a reactive dye is largely composed of a pre-treatment step, dyeing step, soaping step and post-treatment step.

(1) pretreatment stage

First, put cotton fiber in water, add caustic soda (NaOH), hydrogen peroxide and a refining agent (精練 劑) to raise the temperature to boil. Caustic soda decomposes and removes oily cotton of cotton fibers, hydrogen peroxide acts as a bleaching agent, and as a surfactant, the caustic soda penetrates well into the fiber.

(2) dyeing step

The pretreated fiber is placed in water, and then a reactive dye, forget-me-not (Na ₂ SO ₄ ), and soda ash (Na ₂ CO ₃ ) are sequentially added. This forms and covalently bonds between the reactive dye and the fiber. This is followed by pickling with glacial acetic acid (CH ₃ COOH).

(3) Soaping step

The dyed fibers are placed in water and treated with a soaping agent. The soaping agent serves as a surfactant to remove dye molecules that do not form covalent bonds with the fibers.

(4) post-processing step

Thereafter, dyeing is completed by usual post-treatment such as softening agent treatment.

When dyeing using the reactive dyes described above, there is a problem in that a dye reactor that reacts with a hydroxyl group in the hydrolysis of the dye does not react with the hydroxyl group of cellulose of cotton fibers, thereby reducing the dyeing efficiency.

This low dyeing efficiency requires a large amount of dyes, forages, soda ash, etc. in order to obtain the desired color concentration, so that the dyeing process costly, waste dyes due to undyed dyes, soda ash, soda ash, etc. It is long, causing problems such as low productivity.

The purpose of the present invention is to increase the dyeing efficiency of the reactive dyes, to achieve a sufficient dyeing effect even with a small amount of dyes, forget-me-not, soda ash, etc. to reduce the dyeing processing cost, waste water by the dye, forget-me-not, soda ash, etc. in the remaining bath To alleviate the problem, it is to provide a dyeing method using a reactive dye that can improve the productivity by reducing the total dyeing time.

In order to achieve the above object, the first dyeing method using the cationic agent and the reactive dye according to the present invention comprises the steps of pretreatment of a fiber having a hydroxyl group by a conventional method; A cationization step of putting the pretreated fiber into water and adding a cation agent having an ammonium group and an epoxy group; A dyeing step of putting a cationic fiber in water and adding an anionic water-soluble group and a reactive dye having a functional group capable of reacting with a hydroxyl group of the fiber, a neutral salt and a weak alkali, followed by pickling; A soaping and anionizing step of placing the salted fiber in water and injecting a salt or acid capable of ionically bonding the ammonium group in a conventional soaping agent and a neutral aqueous solution; And post-treating the soaped and anionized fibers in a conventional manner.

The second dyeing method using a cationic agent and a reactive dye according to the present invention is a dyeing machine having a means for mechanically abrasion of the iron surface of the fiber has water, hydroxyl groups and fibers having irregularities on the surface, and ammonium and epoxy groups A cationization step of introducing a cationic agent; The dye was introduced with new water, cationized fiber, anionic water-soluble group and reactive dye having a functional group capable of reacting with a hydroxyl group of the fiber, an enzyme capable of breaking down a fiber having a hydroxyl group, a neutral salt and a weak alkali. Pickling step after pickling; A soaping and anionizing step of introducing new water, dyed fiber, conventional soaping agent, and a salt or acid capable of ionically bonding the ammonium group to the dyeing machine in the dyeing machine; And post-treating the soaped and anionized fiber in a conventional manner,

By using the dyeing machine to mechanically wear the iron surface of the fiber.

Hereinafter, the present invention will be described in detail.

As described above, the first dyeing method using the cationizing agent and the reactive dye according to the present invention includes a pretreatment step, a cationization step, a dyeing step, a soaping and anionization step, and a post-treatment step. Each step will be described in detail below.

(1) pretreatment stage

In the present invention, first, the fiber having a hydroxyl group is pretreated by a conventional method. As the fiber having a hydroxyl group, cotton fiber or cotton blend fiber is preferable, and cotton fiber is more preferable. There are numerous hydroxyl groups in the cellulose of cotton fibers. The pretreatment method used in the above-described prior art is applied as it is.

(2) cationization step

The pretreated fiber is placed in water, and a cationic agent having an ammonium group and an epoxy group is added thereto. At this time, a hydroxyl group of the fiber and an epoxy group of the cationic agent react to form a covalent bond (ether bond) between the fiber and the cationic agent. As the cationic agent, polyamine polyamide epichlorohydrin resin is preferable.

When the fiber is cationized, the dye can be easily accessed by the ion affinity of the water-soluble group (anion) of the dye and the ammonium group (cation) of the cationic agent covalently bonded to the fiber when dye is introduced in the subsequent dyeing step. . Due to this effect, the dyeing efficiency is increased compared to the reactive dye dyeing method (prior art) which is not cationic.

(3) dyeing step

A reactive dye having a cationized fiber in water and having an anionic water-soluble group and a functional group capable of reacting with a hydroxyl group of the fiber; Neutral salts; And weak alkali. By the addition of the reactive dye and the neutral salt, the anionic water-soluble group of the reactive dye and the ammonium group of the cationic agent covalently bonded to the fiber are ion-bonded. Neutral salts are more soluble in water than dyes, so they push the dye out of the water, allowing the dye to adsorb to the fiber. In this state, the weak alkali reacts the hydroxyl group of the fiber with the functional group of the reactive dye to form a covalent bond between the reactive dye and the fiber. In other words, the reactive dye is ionic bonded to the cationic agent covalently bonded to the fibers and covalently bonded to the fibers.

As the anionic water-soluble group, a sulfonate group is preferable, and a monochlorotriazine group and / or vinylsulfon sulfate group is preferable as a functional group capable of reacting with a hydroxyl group of the fiber. If the reactive dye has such a functional group, an ether bond will be formed between the fiber and the reactive dye. Specifically, when the hydroxyl group of the fiber reacts with the monochlorotriazine group, chlorine ion (Cl ⁻ ) is dropped, and when the hydroxyl group of the fiber reacts with the vinyl sulfonic acid sulfate group, the sulfate group (SO ₄ ^2- ) is dropped, and the ether bond between the fiber and the reactive dye is lost. Is formed.

Manganese (Na ₂ SO ₄ ) is preferable as the neutral salt, and soda ash (Na ₂ CO ₃ ) is preferable as a weak alkali.

After pickling, the weak alkali is neutralized and the dyeing reaction is terminated. The pickling is preferably glacial acetic acid (CH ₃ COOH).

(4) Soaping and Anionization Steps

The dyed fiber is placed in water, and a conventional soaping agent and an anionizing agent are added thereto. The softening agent serves as described in the above-mentioned prior art.

As anionic agents, salts or acids capable of ionically bonding ammonium groups in neutral aqueous solutions are used. Anionic surfactant or citric acid is preferable as the salt or acid, and sodium alkylsulfonate is more preferable. As described above, when the dyeing step is completed, the reactive dye is covalently bonded to the fiber and is ionically bound to the cationic agent covalently bonded to the fiber. For example, sulfonate groups) and ammonium groups of the cationic agent form an ionic bond.

By adding the anionizing agent in this way, it is possible to solve the problem of reducing the light fastness of the cationic agent when not added. The problem of decreasing the light fastness of the cationic agent is that the ammonium group of the cationic agent is denatured and the chemical structure of the periphery is changed during the daylight exposure of the fiber to which the cationic agent is bound. Say) problem. This problem is solved by the addition of the anionizing agent, and as described above, an ionic bond is formed in the water-soluble period of the ammonium group and the anionizing agent of the cationic agent, thereby blocking the solar denaturation of the ammonium group.

(5) post-processing step

Thereafter, dyeing is completed by usual post-treatment such as softening agent treatment.

In the second dyeing method using the cationic agent and the reactive dye according to the present invention is to dye a fiber having a hydroxyl group and irregularities on the surface. The fiber refers to clothes made of cloth or cloth having hydroxyl groups on the fiber itself, such as cotton fiber or cotton blend fiber. This method is a dyeing method used to produce a so-called two-tone effect that is dyed darkly on the concave surface and lightly dyed on the iron surface according to the irregularities on the fiber surface.

For the two-tone effect, it is necessary to mechanically wear the iron surface of the fiber during the dyeing process of the fiber. This operation consists of a dyeing machine having a means for mechanically wearing the iron side of the fiber. As such a dyeing machine, a rotary washer including a drum having a protrusion on its inner surface may be exemplified. If this is used, the iron surface of the fiber may be worn by the protrusion of the rotating drum inner surface.

The application of this dyeing method does not require a pretreatment step when dyeing fibers made of pretreated fabrics such as clothing.

In the dyeing step of this dyeing method, an enzyme capable of breaking down a fiber having a hydroxyl group is used. This enzyme is used to break off the hairs generated by abrasion on the iron surface of hydroxyl-containing fibers. In the dyeing step, the dye adsorbed on the filament of the iron side of the fiber falls with the fuzz due to the action of this enzyme, and eventually the iron side of the fiber is dyed lighter than the concave surface. If the fibers are cotton or cotton blend fibers, cellulase, a cellulosease, is used as such an enzyme. Cellulase is active in acidity and neutral in activity. The former is called acidic bio and the latter is called neutral bio. Neutral bio is used in the present invention.

In addition, the basic configuration of the above-described first dyeing method is applied to the second dyeing method as it is.

Hereinafter, preferred embodiments of the present invention will be described.

Example 1 (General dyeing method)

Put a cotton cloth into the first bath containing water and boil it, then add 4g / l caustic soda, 2g / l hydrogen peroxide, and 0.5g / l of Rukowet-RDA (trade name; sold by Jeongam Trading Co.) as a refining agent. Inject, boil for another hour, and drain.

After washing with water and draining 40 degreeC water and the said pre-treated cloth in a 2nd bathtub, it receives a new water and indexes INDEX-C (trade name; the product made by the Centigrade Chemical International Inc. of United States) or pinecket as a cationic agent. (Finecat) -CD (trade name: manufactured and sold by Jeongam Trading Co., Ltd.) 3% by weight (relative to the fabric) was added, and after about 5 minutes, the temperature was raised to 70 ° C., and the temperature was maintained for 15 minutes.

In the third bath, a cloth treated with water and the above cationic agent is added. The third bath after dissolving 14% by weight of Synozol Black-RW (liq.) (Trade name; sold by Kyungin Corporation) as a dye in water heated to 30 ° C in water. Split into Thereafter, while gradually increasing the temperature, 60 g / l of manganese (Na ₂ SO ₄ ) was divided into 60 g / l at 60 ° C., and 20 g / l of soda ash (Na ₂ CO ₃ ) was separately added after 30 minutes. After 1 hour, glacial acetic acid (CH ₃ COOH) is added and pickled.

After receiving water in the fourth bath and adding the dyed cloth, the temperature is increased to 85 to 95 ° C. Then, 1.5g / ℓ of FINESOAP-R (trade name; sold by Jeongam Trading Co., Ltd.) and FINESOAP-CC (trade name; sold by Jeongam Trading Co., Ltd.), respectively, was added thereto. Leave for at least 30 minutes.

After washing with an overflow (flow-flow) method, the usual post-treatment, such as a softening agent treatment, and then dried and normalized according to the usual method.

The dyeing method described above describes a laboratory method, and in the actual dyeing plant, one dyeing machine is used instead of the first to fourth baths, and the same method is otherwise applied.

Example 2 (dyeing method for producing two-tone effect)

Add 40 ° C water and cotton garments to a rotary washer and use INDEX-C (trade name; manufactured by Centigrade Chemical International, Inc.) or Pinecat- as a cationic agent. Add 3 to 5% by weight of CD (trade name: manufactured and sold by Jeongam Trading Co., Ltd.), drain about 20 minutes, and cool. The cationization is performed at a lower temperature than in Example 1. If the temperature is high, the cationic agent can penetrate into the inside of the thread of the clothes, but in the dyeing of clothes, only the surface is sufficient.

Water heated to 40 ° C and 30 g / l of Nachos (Na ₂ SO ₄ ) were added, and after 10 minutes, Synozol Red HF-3B (trade name; sold by Kyungin Corporation) 2.0% by weight (above) After dissolving in water, disperse separately. After 10 minutes, the temperature was gradually raised to 55 ° C, and 2 g / l of Finase-MR (trade name: sold by Jeongam Trading Co., Ltd.), an active cellulase, was added in a neutral aqueous solution, and drained after 30 minutes. It is cold. After receiving fresh water, 10 g / l of soda ash (Na ₂ CO ₃ ) is added, the temperature is raised to 60 ° C. and maintained for 20 minutes, followed by cooling after draining. After receiving fresh water, add glacial acetic acid (CH ₃ COOH) to pickle and cool. In Example 1, the additives were added in order of dye, forget-me-not and soda ash, but in this case, it was added in order of forget-me-not, dye, enzyme, and soda ash. If the forget-me-not is added before the dye, the effect of pushing out the dye of the neutral salt described above is easier to adsorb the dye onto the fiber than the case where the feeding order is reversed. This is to improve the dyeing, because the two-tone dyeing uses a rotary washer, so the speed of water flow should be faster, so the dyeing effect needs to be stronger. After the enzymatic action, soda ash is added, so that the dyeing is completed by soda ash injection.

Receive fresh water and raise the temperature to 80-95 ℃. Then, 1.5g / ℓ of FINESOAP-R (trade name; sold by Jeongam Trading Co., Ltd.) and FINESOAP-CC (trade name; sold by Jeongam Trading Co., Ltd.), respectively, was added thereto. Leave for at least 15 minutes. After washing with an overflow (flow-flow) method, the usual post-treatment, such as a softening agent treatment, and then dried and normalized according to the usual method.

In the prior art (reactive dye dyeing method using no cationizing agent), the dyeing ratio was about 60%, but the method of the present invention was about 80%.

Since the dyeing rate is good, the same level of dyeing effect can be achieved even with a small amount of dye, forage and soda ash compared to the prior art. Specifically, compared to the prior art, the amount of dye is reduced by 20-50%, the amount of forget-me-not and soda ash is 30-50%. These savings also reduced the contamination of the waste water (residual bath).

The daylight fastness and the fastness to washing were maintained in the state of the art.

In the present invention, it is one of the important features to treat the anionizing agent, if the same method as the present invention, but without anionizing treatment, daylight fastness is 2 to 3 grade, whereas the present invention 4 ~ 5 (Daylight fastness is indicated by grades 1-7, the higher the value, the better).

The method of the present invention can be applied to a dyeing method for producing a so-called two-tone effect, and when applied, it can produce a two-tone effect while still exhibiting the advantages described above.

The dyeing method using the cationic agent and the reactive dye according to the present invention increases the dyeing efficiency of the reactive dye, thereby exhibiting a sufficient dyeing effect even with a small amount of dyes, forget-me-not, soda ash, etc. to reduce the dyeing processing cost, remaining in the bath Wastewater problems caused by dyes, forget-me-not, soda ash, etc. are alleviated, and the overall dyeing time is shortened to improve productivity. In addition, the method also has the effect of solving the problem of reducing the light fastness of the cationic agent that is involved in dyeing the reactive dye after the cationic agent treatment by the anionic agent treatment.

The dyeing method using the cationic agent and the reactive dye according to the present invention is also applied to the dyeing method for producing a so-called two-tone effect to have a two-tone effect with the aforementioned advantages.

Claims (12)

delete delete delete A cationization step of adding a water and hydroxyl group having a concave-convex fiber on the surface and a cationic agent having an ammonium group and an epoxy group to a dyeing machine having a means for mechanically wearing the iron surface of the fiber; The dye was introduced with new water, cationized fiber, anionic water-soluble group and reactive dye having a functional group capable of reacting with a hydroxyl group of the fiber, an enzyme capable of breaking down a fiber having a hydroxyl group, a neutral salt and a weak alkali. Pickling step after pickling; A soaping and anionizing step of introducing the salt or acid capable of ionically bonding the ammonium group to the dyeing machine again in fresh water, dyed fiber, conventional soaping agent and neutral aqueous solution; And post-treating the soaped and anionized fiber in a conventional manner. The dyeing method using a cationic agent and a reactive dye that mechanically wears the iron surface of the fiber using the dyeing machine. 5. The dyeing method according to claim 4, wherein the dyeing machine having a means for mechanically wearing the iron surface of the fiber is a rotary type dyeing machine including a drum having a protrusion on an inner surface thereof. The dyeing method using a cationic agent and a reactive dye according to claim 4, wherein the fiber having hydroxyl groups and irregularities on its surface is a cloth made of cotton. The dyeing method according to claim 6, wherein the enzyme capable of decomposing the fiber having a hydroxyl group is a cellulase. The method of claim 4, wherein The cationic agent is a polyamine polyamide epichlorochlorohydrin resin, characterized in that the dyeing method using a cationic agent and a reactive dye. The method of claim 4, wherein The anionic water-soluble group is a sulfonate group, and the functional group capable of reacting with the hydroxyl group of the fiber is selected from the group consisting of a monochlorotriazine group, vinylsulfon sulfate group or a mixture thereof. Dyeing method. The dyeing method according to claim 4, wherein the additive is added in the order of the neutral salt, the reactive dye, the enzyme, and the weak alkali in the dyeing step. The method of claim 4, wherein The salt or acid capable of ionically bonding the ammonium group in the neutral aqueous solution is a dyeing method using a cationic agent and a reactive dye, characterized in that an anionic surfactant or citric acid. Fibers dyed by the method of any one of claims 4-11.