KR101285882B1 - Natural dyeing method - Google Patents

Abstract

PURPOSE: The natural dyeing method of cellulosic fiber is provided to have a high degree of exhaustion and excellent wash resistance. CONSTITUTION: The natural dyeing method of cellulosic fiber comprises a step of processing infiltration within the fiber by spraying the processing liquid which includes monomer containing anionic carboxyl group, and redox group initiator in high pressure in the processing machine which wrapped the cellulosic fiber with bobbin; a step of manufacturing the reformed carboxyl group which introduced carboxyl group with the graft polymerization by heating processing machine; and a step of dyeing the fiber manufactured with the reformed cellulose fiber or the fiber in a natural dye after neutralizing, washing and drying it.

Description

Natural Dyeing Method

The present invention relates to a natural dyeing method using a surface-modified cellulose fiber or fabric. More specifically, the present invention relates to a natural dyeing method using cellulose fibers or woven fabrics in which carboxyl groups are introduced into cellulose fibers to induce ionic bonds between fibers and mordant, thereby increasing the dyeing rate of natural dyes and improving laundry durability.

As science and civilization develop and life improves, the desire for nostalgia and natural return is increasing. In addition, as environmental problems arise, the market size of natural dyeing products is gradually increasing due to the appearance of deep and subtle colors as well as additional functions such as antibacterial and deodorizing properties compared to synthetic dyes.

However, in order to improve the fastness of dyeing, dyeing using natural dyes has to increase dyeing rate by repeating dyeing, embedding, washing, and drying process several times, and dyes so difficultly dye are desorbed by repeated washing. This dyeing method requires a lot of labor and time, and many problems occur in the reproducibility of dyeing and the uniformity of dyeing, which is not suitable for industrialization on an industrial scale.

In addition, this method leads to a decrease in color fastness after dyeing. In particular, it significantly lowers the color fastness of the daylight, washes and friction, and thus stabilizes more, improves the fastness of the uniformity, the light fastness, the washing and the friction, and the inherent functions of the natural dyeing. Industrial scale dyeing methods are required.

In the prior art of the dyeing method for increasing the wash durability of natural dyes in Korea Patent Publication No. 10-2004-0061330 (2004.07.07) in order to give an electrostatic function DMSIP (Dimethyl-5-sulfo-isophthalate Na) or SIPEG (5-sulfo-1,3, -bis (2-hydroxy) ester) was added at 0.5-5.0 owf% of the fiber weight and then the reaction was performed at 40-80 ° C for 10-30 minutes.

In addition, Korean Patent Publication No. 10-2004-0035312 (2004.04.29) uses Sodium4- (4,6-dichloro- [1,3,5] triazin-2-ylamino) -benzenesulfonate to form an anionizing agent on cotton fibers. Covalently bonded and dyed with yellow wall dye for 30-50 minutes in the temperature range of 35 ~ 45 ℃ to suggest a method for increasing the durability of the laundry.

In addition, Japanese Patent Application Laid-open No. Hei 4-281079 (1992.10.06) discloses a natural pigment by a mordant method on fibers treated with 40 g / l of 3-chloro-2-hydroxypropyltrimethylammonium chloride (60% purity) and 8 g / l of NaOH. When dyeing, there was a report that the dyeing rate is high and dyeing fastness is excellent.

In Japanese Patent Laid-Open No. 4-184941, there is a report of modifying cotton fiber with methacrylic acid using ferric ions and fruit tree, but the color becomes red as iron ions become trivalent, which contaminates the fiber and dissolves sulfuric acid to dissolve it. This results in embrittlement of cotton fibers and is difficult to apply as a surface modification technique.

The above-mentioned known technology is different from the present invention in the technical configuration.

Korean Patent Publication No. 10-2004-0061330 (2004.07.07) Korean Patent Publication No. 10-2004-0035312 (2004.04.29) Japanese Patent Laid-Open No. 4-281079 (1992.10.06)

The present invention is a general cationic agent (Cation agent) which is a dyeing aid used in conventional textile dyeing in order to solve the problem that the dyeing power decrease, washing fastness, friction fastness, etc., which appear in dyeing the conventional yarn or fabric with natural dyes It is aimed at modifying the surface of cellulose fibers without using dyeing aids or other dyeing aids. It is also an object of the present invention to provide a fabric that is naturally dyed to a woven fabric of modified cellulosic fibers.

In addition, an object of the present invention is to provide a natural dyeing method having a high dyeing rate and excellent washing durability as compared with the conventional natural dyeing method.

It is also an object of the present invention to provide a method capable of modifying the surface of a fiber at a relatively low cost.

It is also an object of the present invention to simplify the manufacturing step of modified cellulose fibers by enabling continuous operation and to provide an economical process.

The present invention for achieving the above object

a) a processing step of injecting a processing liquid containing an anionic carboxyl group-containing monomer and a redox initiator into a fiber by injecting the processing liquid containing the anionic carboxyl group into a bobbin into a fiber;

b) heating the processing machine to prepare modified cellulose fibers into which carboxyl groups are introduced by graft polymerization;

c) after neutralization and washing, dyeing the dried modified cellulose fibers or the fabric made from the fibers with natural dyes;

It relates to a natural dyeing method of cellulose-based fibers comprising a.

The present invention also relates to a natural dyed fiber or fabric produced by the natural dyeing method.

Fibers or fabrics produced by the natural dyeing method of the present invention has a high dyeing rate, has an excellent washing durability.

In addition, the present invention has the advantage that by using a common cheese dyeing apparatus without using an expensive radiation graft apparatus during processing, it is possible to reduce the equipment and production costs.

1 is a FT-IR spectral graph before processing to determine the graft reactivity of the cotton yarn according to Example 1 of the present invention.
2 is a FT-IR spectral graph after processing to determine the graft reactivity of the cotton yarn according to Example 1 of the present invention.
Figure 3 is a photograph of the natural dyed samples of the fabric mixed with bamboo yarn using the grafted reaction cotton yarn and ordinary cotton yarn, respectively.
Figure 4 shows an example of a processing machine for producing a modified cellulose fiber of the present invention.

Hereinafter, the present invention will be described in more detail.

One aspect of the present invention is

a) a processing step of injecting a processing liquid containing an anionic carboxyl group-containing monomer and a redox initiator into a fiber by injecting the processing liquid containing the anionic carboxyl group into a bobbin into a fiber;

b) heating the processing machine to prepare modified cellulose fibers into which carboxyl groups are introduced by graft polymerization;

c) after neutralization and washing, dyeing the dried modified cellulose fibers or the fabric made from the fibers with natural dyes;

It is a natural dyeing method of cellulose-based fibers comprising a.

In one embodiment of the present invention, the processing liquid contains 3 to 10% by weight of anionic carboxyl group-containing monomer, 0.3 to 1.0% by weight of redox-based initiator and water.

In one embodiment of the present invention, the anionic carboxyl group-containing monomer is acrylic acid or methacrylic acid, and the redox-based initiator is an organic peroxide initiator, ammonium peroxodisulfate, sodium pooxodisulfate, potassium peroxodisulfate, Any one or two or more oxidizing agents selected from benzoyl peroxide, hydrogen peroxide, potassium bromate; Perose ammonium sulfate, sodium (meth) bisulfite, thiourea, reducing sugars, or any one or more reducing agents.

In one aspect of the present invention, the density of the cellulose fiber wound on the bobbin in the step a) is 0.1 ~ 0.5g / cc, the temperature at a pressure of 1 to 10 atm from the inside of the bobbin to the outside of the bobbin during the penetration of the processing liquid It is preferable to carry out high pressure injection at 40 to 80 degreeC.

In one embodiment of the present invention, the graft reaction in step b) is preferably performed at 40 to 80 ° C. for 30 to 60 minutes.

In one embodiment of the present invention, the washing in step c) is preferably performed for 20 to 40 minutes at 90 ~ 100 ℃.

In one embodiment of the present invention, the dyeing step c) is embedded in 1 ~ 5% owf aluminum mordant at 40 ~ 90 ℃, then dyed for 40 to 60 minutes at 60 ℃ ~ 80 ℃ using natural dyes It is preferable.

In one embodiment of the present invention, the cellulosic fibers may use any one or a mixture of two or more selected from cotton yarn, bamboo yarn, and yarn.

In the dyeing method using the natural dyes of the present invention, it is useful to impart anionic groups to the fiber and increase the binding force according to the ionic bond of the fiber and the mordant to improve the dyeing rate, and at the same time improve the reproducibility of the dyeing and washing durability. In this case, the present invention was completed by discovering that the reproducibility of the dyeing and the durability of the washing were improved by performing a grafting process with the cellulose-based fiber under conditions for permanently providing the anionic group.

It will be described in detail with respect to the specific configuration of the present invention for achieving the above object.

One aspect of the present invention may be made of a processing, bleaching, weaving, printing, dyeing, washing, washing, drying, processing of the refined cellulose fibers.

First of all, the refining process removes contaminants contained in the fiber material and improves permeability and dyeing. The refining agents include alkali activators, organic solvents, enzymes, oxidants, and the like. Use in combination.

Next, in the process of processing for imparting the functionality of the cellulose fiber, in one embodiment of the present invention to prepare a processing liquid. It is preferable that a process liquid contains 3-10 weight% of anionic carboxyl group-containing monomers, 0.3-1.0 weight% of redox-type initiators, and water. When the content of the anionic carboxyl group-containing monomer is less than 3% by weight, the graft reaction hardly occurs, and when the content of the anionic carboxyl group is greater than 10% by weight, the excess monomer is not polymerized and remains in the fabric. It is best to do it. If the redox-based initiator is less than 0.3% by weight, the graft reaction may not be sufficiently initiated. If the redox-based initiator is more than 1.0% by weight, the redox initiator is uneconomical.

Next, in the process of processing the cellulose-based fiber using the prepared processing solution in the present invention, the cellulose-based fiber refined in step a) is sprayed on the processing machine wound on the bobbin to penetrate into the fiber Let's do it. An example of the processing machine is illustrated in FIG. 4, but is not limited thereto. At this time, it is preferable to wind and use the bobbin at the same density, more specifically, 0.1 ~ 0.5g / cc density of the cheese dye so that the processing solution penetrates into the fiber. In addition, it is preferable to allow high pressure injection at a pressure of 1 to 10 atmospheres from the inside of the bobbin to the outside of the bobbin during penetration of the processing liquid. In addition, the temperature is preferably performed at 40 ℃ ~ 80 ℃, the introduction of the carboxy group of the cellulose fibers in the density, pressure and temperature range can be optimized.

Next, in one embodiment of the present invention, the modified cellulose fiber to which the carboxyl group is introduced by graft polymerization is prepared by heating the processing machine in step c). At this time, it is preferable to perform the graft polymerization reaction at 40 ~ 80 ℃ for 30 to 60 minutes. If the reaction temperature is less than 40 ℃ takes a long reaction time, and if the reaction temperature is higher than 80 ℃ due to the polymer of acrylic acid itself may reduce the reaction rate with the fiber.

After the graft reaction is neutralized, the processing liquid is drained, washed with water and dried. At this time, it is preferable to wash | clean, dehydrate, and dry at 90-100 degreeC, after neutralizing to pH 5-6 grade with sodium carbonate.

In the cellulose-based fiber subjected to the treatment of the present invention, the content of the carboxyl group is preferably in the range of 1 to 10% by weight, and when it exceeds 10% by weight, changes in physical properties such as tensile strength and feel of the cellulose fiber may occur. .

The bleaching process uses bleach to decompose and discolor the remaining color material in the finished dough after refining and refining to obtain whiteness for the purpose of the final product and to remove other impurities. Bleaches include oxidizing bleaches and reducing bleaches. This process is essential for cotton and hemp with contaminants.

Next, the fibers can be woven and used as necessary, followed by a mordant process.

In the dyeing process, the color fastness and the desired color can be obtained according to the choice of the amount and type of mordant used in dyeing the natural dyes. The mordant acts as a link between the dye and the low dye rate. In addition, since natural dyes have low fastness, the color is not light unless they are buried, and the color is gradually changed or disappeared when exposed to sunlight or washed for a long time. When it is buried, a deep and deep color is obtained, and dyeing fastness is also very high. In addition, dyes extracted from plants have a lot of multi-colored dyes containing various kinds of pigments can be obtained a variety of colors by different mordants. The method of embedding is preemption, co- embedding and post embedding. Presalt is a method in which a mordant is adsorbed onto the fiber in advance and then dyed. Simultaneous dyeing is dyeing by mixing dye and mordant, and post-moring dyeing is a method of treating mordant after dyeing dye on fabric.

The method of embedding is selected according to the characteristics of the fiber, dye and mordant. Copper mordant makes it green and increases the color fastness. Dissolve in hot water and use. Ferrous mordants include ferric sulfate (FeSO ₄ · 7H ₂ O) and iron chloride (FeCl ₂ · 6H ₂ O). Ferric acetate (iron oxide) is more stable. Iron sulfate should be washed with water sufficiently if acid remains after dyeing or it will discolor or damage fibers. Iron-dyeing darkens colors such as dark tea, gray, and black. Alumescent agent, alum, aluminum acetate, aluminum chloride and the like can be used. The amount and type of mordant used depends on the dye and the color to be dyed, but the concentration is preferably 1-5% owf, and the mordant treatment temperature is preferably 40 ° C. to 90 ° C. When the mordant is treated using the mordant, it is possible to increase the dyeing rate of the natural dye by the strong ionic bond between the carboxyl group and the mordant introduced into the modified cellulose fiber.

In the dyeing process, the fiber, yarn, fabric, etc., which have undergone the above process, are adjusted in a dyeing machine, and the liquid ratio of the fiber weight is adjusted to 10-20 (dye 10-20: fiber 1), and then the temperature is well maintained at 20 ° C to 40 ° C. After adding the dissolved dye, dye for 20 to 40 minutes. Then slowly raise the temperature and dyeing sufficiently for 40 to 60 minutes at 60 ℃ ~ 80 ℃. If the temperature is raised rapidly, it may cause disproportionation of dyeing, so if possible, it is good to raise the temperature to 1 ℃ / min, so that the most uniform dyeing is possible. In addition, it is possible to improve the reproducibility and fastness of the dyeing by sufficiently dyeing time.

The washing process is washed with water to remove undyed dyes and remaining mordants during dyeing and embedding. Insufficient water washing causes unevenness after dyeing, and it is important to be very careful because all fastnesses such as washing fastness and daylight fastness are remarkably decreased.

In the drying process, it is preferable to set the drying temperature in consideration of thermochromic properties of natural dyes, and to set the drying temperature so as not to change the original primary color after dyeing, and to dry for a short time between 140 ° C and 180 ° C.

Machining process is a process that gives different performance according to the purpose of the final product. Flameproof, water-repellent, hydrophilic, flexible, hardening, antistatic processing, etc. It is desirable to give.

EXAMPLES Hereinafter, the present invention will be described in detail, but the scope of the present invention is not limited to the examples.

Hereinafter, physical properties were measured by the following method.

1) Color yield (K / S)

It measured by the following formula 1 using CCM (DATA COLOR company).

[Formula 1]

K / S = (1-R) ² / 2R (Kubelka-Munk equation)

        K: extinction coefficient, S: scattering coefficient,

R: reflectance at a given wavelength

2) washing fastness

Wash fastnesses were measured according to ISO 105-C03.

It measures the degree of discoloration after washing, and if a lot of color falls out, it becomes blurred and the grade becomes 1st grade (defective in case of 1st grade; the higher the grade, the better)

3) wet friction fastness

Wet friction fastnesses were measured according to ISO 105-X12.

Rub the stained sample with a rubbing cloth attached to a white cotton cloth, and measure the degree of contamination of the rubbed fibers (standard cotton cloth).

4) touch

The texture was judged by hand.

○: Excellent (same texture as cotton yarn before treatment)

△: normal (slightly thick texture)

×: bad (hard and rough texture)

Example 1

15 kg of acrylic acid as the anionic monomer and 1 kg of sodium peroxodisulfate as a polymerization initiator and 0.5 kg of sodium bisulfite were mixed in 500 kg of water to prepare a processing solution.

The refined 100 kg cotton yarn was wound and used in bobbins at the same 0.3 g / cc density as the cheese dyeing process so that the processing liquid can fully penetrate the inside of the fiber by pressure injection.

The processing liquid prepared in the 100kg scale machine was sprayed for 5 hours at a pressure of 5 atm from the inside of the bobbin through the spindle to infiltrate evenly from the outside to the inside of the fiber, and the grafting reaction was performed at 50 ° C. for 40 minutes. After neutralizing to pH 5 with sodium carbonate, the mixture was washed at 90 DEG C for 30 minutes, dehydrated and dried.

After bleaching 200 g of cellulose-based fabric woven with anionic group-introduced yarn, and using aluminium mordant, 5% owf (on the weight of fiber) based on the weight of the fiber, the liquid ratio is 1:10 (fiber 1: water). 10: 0.05 weight ratio of mordant) and the initial temperature were stirred at 40 degreeC for 20 minutes, and then heated up at 80 degreeC and embedded in 30 minutes. The washed fabric was washed twice with water and dehydrated, and the onion solution (the filtered solution after adding 2 g of onion skin and 500 g of water and cutting for 2 hours) was dyed at 80 ° C. for 10 minutes at 10% o.w.f. based on the weight of the fiber. After dyeing and washing with water, it was dehydrated and dried, and the dyeing properties such as color yield, washing fastness and friction fastness were measured and shown in Table 1.

1 and 2 are FT-IR as a spectrum graph in order to determine the reactivity of the sample processed before being neutralized according to Example 1 of the present invention, Figure 1 is the FT-IR spectrum before processing, Figure 2 It is the FT-IR spectrum after processing. 1 and 2, the carbonyl (C = O) peak of the acrylate did not appear prior to the processing, but after the processing, acrylic reacted with cotton and the carbonyl (C = O) of the acrylate at 1720 cm ^-1 . A peak appeared to be observed.

[Example 2]

The polymerization initiator was used in the same manner as in Example 1, except that 1 kg of ammonium peroxodisulfate and 0.5 kg of sodium metabisulfite were used, and chopped as a natural dye.

The Maddera (Naju Natural Dye Foundation) powder was completely dissolved using 2% owf and dyed, and the dyeing properties such as color yield, washing fastness and friction fastness were measured and shown in Table 1.

[Example 3]

A natural dye was dyed in the same manner as in Example 1 except that the animal dye Lac (Naju Natural Dye Foundation) was used 2% owf, and the dyeing properties such as color yield, wash fastness and friction fastness were measured. It was shown in Table 1.

Example 4

A natural dye was used in the same manner as in Example 1, except that the vegetable dye, yellowish white (Naju Natural Dye Foundation product), was used to measure dyeing properties such as color yield, washing fastness, and friction fastness. It was shown in 1.

[Comparative Examples 1 to 4]

Fabrics woven using unprocessed cellulosic fibers were naturally dyed in the same manner as in Examples 1 to 4 to measure and evaluate color yield and wash fastness. The results are shown in Table 1 below.

[Table 1]

As shown in Table 1, it was found that the color yield and wash fastness increased compared to the comparative example, which is due to the ionic bond of the fiber and mordant. When the mordant and the dye are dyed by coordination bond, most of them are desorbed after washing with water, and the color is blurred.

[Example 5]

As a result of measuring reactivity according to the concentration of the redox polymerization initiator, in Example 1, the amount of polymerization initiator added in the 3% anionic monomer composition was adjusted to vary the diluted concentrations and observed whether the reaction proceeded accordingly. As shown in Table 2, when the concentration of the neutralization initiator is 0.3% or more, the graft neutralization reaction occurs.

[Formula 1]

Yield = (increased working weight after processing / actual weight before processing) × 100

[Table 2]

[Example 6]

As a result of measuring the reactivity according to the concentration of the processing liquid, the reaction degree was observed while changing the diluted concentration by adjusting the amount of monomer added in the processing agent composition in Example 1, the concentration of the monomer was not less than 3% It can be seen that the graft reaction occurred with the carbonyl (C═O) peak.

[Table 3]

[Example 7]

As a result of reactivity measurement according to the reaction temperature, processing treatment steps other than the change in reaction temperature were performed under the same conditions as in Example 1. In addition, after processing the processing liquid, the reaction was performed at the reaction temperature for 30 minutes, and the reaction degree was observed after washing the water treatment. have.

[Table 4]

Claims (9)

a) a processing step of injecting a processing liquid containing an anionic carboxyl group-containing monomer and a redox initiator into a fiber by injecting the processing liquid containing the anionic carboxyl group into a bobbin into a fiber;
b) heating the processing machine to prepare modified cellulose fibers into which carboxyl groups are introduced by graft polymerization;
c) after neutralization and washing, dyeing the dried modified cellulose fibers or the fabric made from the fibers with natural dyes;
Natural dyeing method of cellulose fibers comprising a. The method of claim 1,
The processing solution is a natural dyeing method comprising 3 to 10% by weight of anionic carboxyl group-containing monomer, 0.3 to 1.0% by weight redox-based initiator and water. 3. The method according to claim 1 or 2,
The anionic carboxyl group-containing monomer is acrylic acid or methacrylic acid,
The redox-based initiator is any one or two or more selected from organic peroxide initiators, ammonium peroxodisulfate, sodium pooxodisulfate, potassium peroxodisulfate, benzoyl peroxide, hydrogen peroxide, potassium bromate Oxidizing agents; A natural dyeing method selected from any one or two or more reducing agents selected from ferros ammonium sulfate, sodium (meth) bisulfite, thiourea, reducing sugars. The method of claim 1,
The density of the cellulose fiber wound on the bobbin in step a) is 0.1 ~ 0.5g / cc, the natural dyeing method of high pressure spraying at a pressure of 1 to 10 atm from the inside of the bobbin to the outside of the bobbin when the processing liquid penetrates . The method of claim 1,
The graft reaction in step b) is to perform a natural dyeing method for 30 to 60 minutes at 40 ~ 80 ℃. The method of claim 1,
Washing in step c) is a natural dyeing method that is performed for 20 to 40 minutes at 90 ~ 100 ℃. The method of claim 1,
In the step c), the dyeing method is a natural dyeing method of dyeing at 40 ~ 90 ℃ using 1-5% owf aluminum mordant, and then dyed at 60 ℃ ~ 80 ℃ using a natural dye. The method of claim 1,
The cellulosic fibers are natural dyeing method of any one or two or more selected from cotton yarn, bamboo yarn, yarn. Natural dyed fiber or fabric produced by the manufacturing method according to claim 1.

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