KR101130647B1 - Natural dye, Method for manufacturing the same and Dyeing method using the same - Google Patents

Abstract

According to the present invention, since an anthocyanin is added to the extracted anthocyanin to precipitate an anthocyanin complex compound to prepare a natural dye, the production process is easy, and thus the productivity and economy are excellent. And it is possible to obtain a natural dye with a uniform dyeing, and as the affinity with the fiber is improved, the color is dark and excellent dyeing fastness natural dyes, natural dyes manufacturing method and dyeing method using the same. The method for producing a natural dye of the present invention comprises the steps of preparing an anthocyanin extract from purple plants; Preparing an anthocyanin complex by adding a metal salt to the anthocyanin extract; And preparing a dye by separating the anthocyanin complex.

Description

Natural dyes, Method for manufacturing the same and Dyeing method using the same

The present invention relates to a natural dye, a method for producing a natural dye, and a dyeing method using the same, and more particularly, to a natural dye produced by extracting a pigment containing anthocyanin from a plant, such as Audi, and a dyeing method using the same.

Recently, due to urbanization and industrialization, various modern people suffer from various diseases, especially atopic diseases. These atopy diseases are worse as environmental pollution, water pollution and air pollution become more severe, especially when wearing clothes dyed with synthetic dyes.

To solve this problem, fabrics dyed using natural dyes obtained from nature, such as plants and loess, have been developed. For example, a pigment containing anthocyanin is extracted from a purple plant, such as Audi, to prepare a natural dye, and dyeing natural fibers such as wool using the same.

Such anthocyanins are used in a concentrated state because they are easily soluble in water and are difficult to extract and are complex.

However, since anthocyanin is water soluble, the color is easily changed depending on the pH concentration or temperature, and decomposition occurs easily, and thus, productivity is decreased due to a complex concentration process.

In addition, the concentrate containing anthocyanin has a problem in that reproducibility is difficult because the difference in components and contents varies depending on the material used, that is, dyeing is not uniform.

In addition, when the fabric is dyed using a natural dye containing anthocyanin, the dyed fabric may not have a wide variety of colors and the color fastness is greatly reduced.

In order to solve this problem, a method of treating a mordant during the dyeing process has been proposed, but an anthocyanin dye having a strong water solubility is absolutely insufficient to penetrate into the fiber, and the dye attached to the fiber is also eliminated within a short time. It is difficult to obtain a degree of thick salt and color fastness.

The present invention is derived in order to solve the above problems, and by adding a metal salt to the extracted anthocyanin to precipitate the anthocyanin complex compound to produce a natural dye, the production process is easy and the productivity and economic efficiency is excellent, the metal complex structure The purpose of the present invention is to provide a natural dye having excellent color fastness and dyeing fastness and dyeing method using the same as the stability is improved, the color is varied, the dyeing is uniform, and the affinity with the fiber is improved.

In order to achieve the above object, in one aspect of the present invention, a process for producing an anthocyanin extract from a purple plant; Preparing an anthocyanin complex by adding a metal salt to the anthocyanin extract; And it provides a method for producing a natural dye comprising the step of producing a dye by separating the anthocyanin complex.

In order to achieve the above object, in another aspect of the present invention, there is provided a natural dye prepared from the method for producing a natural dye as described above.

In order to achieve the above object, another aspect of the present invention, the step of preparing a salt solution using the natural dye; Dyeing the fabric using the prepared salt solution; And it provides a dyeing method comprising the step of washing the dyed fabric.

The present invention has the following effects.

First, the method for producing a natural dye according to the present invention, by adding a metal salt to the pigment extract to prepare an anthocyanin complex, there is an effect that is high productivity and economic efficiency as the process is simple and easy.

Second, the natural dye prepared according to the present invention has a complex compound structure, so that various colors can be reproduced easily without decomposition, and uniform dyeing is possible.

Third, the dyeing method according to the present invention has the effect that the salt can be obtained as the affinity between the dye and the fiber is excellent and washing fastness.

Figure 1 shows the ultraviolet-visible absorbance results of the anthocyanin extract according to an embodiment of the present invention.
Figure 2 shows the results of thermogravimetric analysis of natural dyes according to an embodiment of the present invention.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. Therefore, the present invention encompasses all changes and modifications that come within the scope of the invention as defined in the appended claims and equivalents thereof.

Hereinafter, a method of preparing natural dyes according to an embodiment of the present invention will be described in detail.

First, anthocyanin is extracted from purple plants to prepare anthocyanin extract.

As the purple plant, all purple plants including anthocyanins, such as audi, blueberries, grapes, branches, purple sweet potatoes, purple lettuce, morning glory can be used. In particular, Audi contains an anthocyanin in a large amount and is composed of soft tissues, so that it can be easily crushed and thus there is an advantage in that the pigment can be easily extracted.

When the purple plant is composed of soft tissues such as audi and blueberries, a special grinding process may not be necessary. However, when a plant having a hard skin layer such as purple sweet potato is used, the purple plant may be extracted to more easily extract pigments. A crushing process can be carried out to reduce the size.

The crushing process may be performed using conventional means, for example, cutting using a knife or the like, or a high-speed hammer such as a compression crusher such as a jaw crusher, or a hammer crusher that rotates and cuts a cutter or a hammer at high speed. Rotary mills can be used.

Subsequently, a process of solvent immersing the purple plant may be performed. That is, a small size of the pulverized purple plants are immersed in a solvent and treated at a suitable temperature for a predetermined time to extract a pigment.

The solvent may include at least one of water, an alcohol solvent, a ketone solvent, an amine solvent, a hydrocarbon solvent, a carboxyl solvent, and a benzene solvent. In addition, catalysts such as inorganic salts may be added to facilitate extraction.

Subsequently, a process of separating an insoluble solid material from the dye extract is performed. That is, a process of separating a solution in which a pigment containing anthocyanin is dissolved from a solid substance that is insoluble in the solvent may be performed. This is because when the insoluble solid material is included in the natural dye, it is difficult to maintain a constant salt concentration and cause stains on the fabric.

Separation of the solid material may be performed using a filter paper, a hollow fiber membrane filter, or using a centrifuge.

After preparing an anthocyanin extract as described above, an anthocyanin complex is prepared by adding a metal salt to the anthocyanin extract.

The anthocyanin has a property of being easily soluble in water as it has a plurality of water-soluble groups in the structure. Accordingly, there is a problem that it is not easy to separate anthocyanin from the extract. Therefore, conventionally, a natural dye containing anthocyanin was prepared by concentrating such anthocyanin extract or removing the solvent to powder.

However, when producing a natural dye containing anthocyanin by such a conventional method, the process is complicated, productivity is low, and uniform dyeing is difficult because it does not control the exact dye concentration as well as other components, including the pigment, In other words, there is a problem of poor reinflammation. In addition, since anthocyanin is water-soluble, affinity with water is stronger than that of fiber, and thus, it is difficult to obtain a dark color.

Therefore, to solve the above problems, the present invention adds a metal salt to the anthocyanin extract to produce an anthocyanin complex. Thus, only anthocyanins can be selectively extracted to obtain a uniform color as the pigment component is uniform, and the anthocyanin complex can be easily precipitated as it is easily precipitated, thereby improving productivity and economy.

The metal salt is not particularly limited, and may include at least one of an aluminum metal salt, a copper metal salt, an iron metal salt, a tin metal salt, and a chromium metal salt as follows. In particular, when the copper salt is used as the metal salt, a black pigment can be obtained, and the affinity with the fiber is good, so that there is an advantage of obtaining excellent dyeing fastness.

The precipitated anthocyanin complex can then be easily separated from the solvent through a separation process. The separation process may be carried out through a method such as conventional filtering.

Then, the separated anthocyanin complex is dried. The drying step is carried out by appropriately adjusting the drying temperature and drying time according to the solvent used. That is, it may be desirable not to dry for a long time at a high temperature so that the anthocyanin complex does not decompose.

Subsequently, the dried anthocyanin complex compound may be powdered to a predetermined size to obtain a dye. The powdering process may be carried out through conventional methods.

Natural dyes containing an anthocyanin complex compound prepared by the above-described method can obtain a uniform dyeing according to a constant dye concentration, and have a good affinity with fibers to produce a fabric having a dark color and excellent color fastness. There is an advantage to this.

The natural dye includes at least 80% of a metal and a compound represented by Formula 1 and Formula 2 below.

[Formula 1]

[Formula 2]

The natural dye, when measured by a thermogravimetric analyzer (TGA, Perkin Elmer, nitrogen gas filling, heating rate 10 ℃ / min), the weight loss starts at a temperature in the range of 55 to 80 ℃.

The metal includes at least one of copper, aluminum, iron, tin and chromium.

In particular, the anthocyanin complex containing copper is characterized by having a black color.

Next, a dyeing method using a natural dye containing an anthocyanin complex compound obtained as described above will be described in detail.

First, a salt solution is prepared using the natural dyes described above.

The salt solution is preferably to disperse the natural dye evenly in water as the natural dye consisting of the anthocyanin complex is not soluble in water.

Subsequently, a predetermined amount of the prepared saline solution is added to the dyeing machine according to the weight of the fabric to be dyed, that is, the bath ratio.

The dyeing machine is not particularly limited, and since the dyeing is performed at normal pressure, no special apparatus is required, but it may be preferable that a means capable of controlling the temperature is installed.

The fabric is not particularly limited, and any fabric made of a fiber having a hydrophilic group may be used. For example, it is possible to use a fabric made of natural fibers, including cotton fibers, hemp fibers, wool fibers, or silk fibers. Alternatively, a fabric made of regenerated fiber including rayon fiber, acetate fiber, or tencel fiber may be used.

Subsequently, the fabric is dyed using a dyeing machine including a saline solution. The dyeing process may be carried out step by step. That is, after slowly warming up to the temperature at which the anthocyanin complex is decomposed at room temperature, maintaining the separation temperature for a predetermined time, then slowly increasing the temperature to the dyeing temperature, maintaining the dyeing temperature for a predetermined time, and then cooling the same. Through the dyeing process can be made.

The anthocyanin complex has a stable structure at room temperature, but the anthocyanin and the metal are separated at a temperature of about 60 ℃, thereby changing the color of the salt solution. On the other hand, as the anthocyanin and the separated metal penetrated into the fiber at the dyeing temperature again, the original color is converted.

The separation temperature, which is a temperature at which the anthocyanin and the metal are separated, may range from 55 to 65 ° C. If the separation temperature is less than 55 ° C, the anthocyanin complex may not be smoothly separated because the anthocyanin complex is not well separated. On the other hand, if the separation temperature exceeds 65 ° C, the anthocyanin complex is rapidly separated, resulting in uneven dyeing. Can be.

The dyeing temperature, which is the temperature at which the separated dye penetrates smoothly into the fiber and adheres to the fiber, may range from 75 to 85 ° C. If the dyeing temperature is less than 75 ℃ sufficient dyeing can be achieved as the anthocyanin does not sufficiently penetrate into the fiber, while if the dyeing temperature exceeds 85 ℃ anthocyanin is decomposed to obtain a desired color Can't.

For example, in the case of dyes containing copper metals, the initial dyeing solution is turbid green, but gradually increases in temperature and turns to red as the anthocyanin complex is separated when the temperature reaches the separation temperature. As the anthocyanin migrates into the fiber, it turns blue.

Thus, the separation time and the dyeing time can be appropriately adjusted by measuring the color or transparency of the salt solution.

The separated metal serves as a mordant. That is, the separated metal penetrates into the fiber, binds to the reactor present in the fiber, and recombines with the separated anthocyanin to serve to strongly fix the anthocyanin inside the fiber.

Meanwhile, after dyeing the fabric, anthocyanins may remain in the salt solution remaining in the dyeing machine, and a recovery process may be further performed to recover and reuse the anthocyanins remaining in the salt solution.

The recovery process is to cool the salt solution so that the precipitate is produced by recombining the anthocyanin and the metal ion, and the cooled salt solution to allow the anthocyanin and the metal ion sufficiently combined for a predetermined time and filtered to separate the precipitate from the salt solution And then drying the separated precipitate.

At this time, a metal salt may be added to the salt solution to further promote the generation of the precipitate.

Next, the dyed fabric is washed with water. That is, the dye remaining on the surface of the fabric is removed through the washing process.

The washing process may be performed in an acid state such as acetic acid is added. Thereby, there is an advantage to obtain a fabric having a more vivid color.

Hereinafter, the effects of the present invention will be described in more detail through Examples and Comparative Examples. These examples are merely to aid the understanding of the present invention and do not limit the scope of the present invention.

Example  1: Preparation of Anthocyanin Extract

1000 g of Audi was pulverized using a blender, and then it was put in a countercurrent condenser contained in 1000 g of solvent, water, and treated at 80 ° C. for 4 hours to prepare a pigment extract. On the other hand, the Audi was used to buy the produced in South Korea, Gyeongsangbuk-do, Sangju.

Subsequently, the anthocyanin extract was prepared by removing the insoluble solid and the like using the filter membrane having a molecular weight exclusion size of 10,000 Daltons.

The anthocyanin extract thus obtained was diluted 100-fold, and the absorbance was measured using an ultraviolet-visible spectrophotometer (UV-Visible Spectrophotometer, Sinco, Korea). The results are shown in FIG. 1.

Example  2: preparation of anthocyanin complex and natural dye

500 g of the anthocyanin extract obtained as described above was kept at 40 ° C., stirred, and 10 g of copper acetate was added thereto to react until the red color was changed to green, and then left until a precipitate was sufficiently produced.

Subsequently, a precipitate was obtained and the precipitate was filtered using a filtration device to obtain an anthocyanin complex.

Subsequently, the filtered anthocyanin complex was dried in a hot air dryer at 70 ° C., and then ground to obtain a powdered natural dye having a diameter of 100 to 200 μm.

The temperature at which the weight loss of the natural dye thus obtained starts is measured using a pyrolysis thermogravimetric analyzer (TGA, Perkin Elmer, nitrogen gas filling, temperature increase rate 10 ℃ / min), the results are shown in FIG.

As shown in Figure 2, the natural dyes can be seen that the weight loss starts at a temperature in the range of 55 to 80 ℃.

Example  3: using natural dyes Silk  Dyeing method

Using a natural dye obtained as described above in a dyeing machine (INTEC CO. LTD, model sec. 36 no. SP-15, Japan) containing a salt solution having a pH of 3, 50% owf, and a bath ratio of 1:10. After immersing the silk dough, after raising the temperature at a rate of 2 ℃ / min from room temperature to 60 ℃ and maintained for 20 minutes, after raising the temperature at a rate of 1 ℃ / minute from 60 ℃ to 80 ℃ Staining is carried out at this temperature for 30 minutes, and then the temperature of the dyeing machine is cooled down to 40 ° C. at a rate of 2 ° C./min. At this time, the stirring speed of the dyeing machine was 50 times / min.

Subsequently, after discharging the saline solution from the dyeing machine, the washing solution to which acetic acid was added was added to the dyeing machine and washed twice, followed by drying to prepare silk dyed paper.

Comparative example  One

In the above-described embodiment, a silk dyed paper was prepared by the same method as in the embodiment except for dyeing silk dough using a natural dye containing anthocyanin prepared by the following process.

At this time, the natural dye containing the anthocyanin was obtained through the following process. First, 100 g of Audi was pulverized using a blender, and then it was placed in a countercurrent condenser containing 500 ml of water, which was treated at 30 ° C. for 24 hours to prepare a pigment extract. Subsequently, the anthocyanin extract was prepared by removing the insoluble solid and the like using the filter membrane having a molecular weight exclusion size of 10,000 Daltons. Subsequently, a solvent was removed from the anthocyanin extract using an ultrafiltration membrane to obtain a separated pigment concentrate, which was dried and ground to obtain a natural dye.

Comparative example  2

In Comparative Example 1, silk dyed paper was obtained in the same manner as in Comparative Example 1 except that the obtained silk dyed paper was treated with a mordant, washed with water, and dried. At this time, the mordant was copper acetate and the concentration was 20% o.w.f.

Comparative example  3

In Comparative Example 1, silk dyed paper was obtained by the same method as Comparative Example 1, except that silk dough treated with a mordant was used.

The silk dough treated with the mordant was obtained by treating the silk dough with a mordant, washing with water and drying before dyeing the silk dough. At this time, the mordant was copper acetate and the concentration was 20% owf.

The dyeing amount and wash fastness of the silk dyed paper obtained by the above Examples and Comparative Examples were measured by the following method, the results are shown in Table 1.

Dyeing amount (K / S) measurement

In order to indirectly confirm the degree of adhesion of the dye on the silk dyed paper, the K / S value was measured using the following method. The reflectance (R, Reflectance) was measured using a spectrophotometer (Color-Eye 7000A, Machbeth, USA), and then substituted into the equation K / S = (1-R) ² / 2R to obtain a K / S value.

Color fastness  Measure

In order to confirm the degree of dye drop after washing of silk dyed paper, the degree of washing dog was measured according to the KS K 0430 A-1 method.

division Dyeing amount (K / S) Color fastness Exterior Example 7.2 5 Great Comparative Example 1 1.5 3 Good Comparative Example 2 3.1 3 usually Comparative Example 3 3.3 3 usually

Claims (18)

Preparing anthocyanin extract from purple plants;
Preparing an anthocyanin complex by adding a metal salt to the anthocyanin extract; And
Separation of the anthocyanin complex compound to produce a dye. The method of claim 1,
The purple plant is a manufacturing method of natural dyes, characterized in that the Audi. The method of claim 1,
The process for producing the anthocyanin extract,
Preparing a dye extract by immersing the purple plant in a solvent; And
Method of producing a natural dye comprising the step of separating the insoluble solid object from the dye extract. The method of claim 3,
The process of preparing the anthocyanin extract further comprises the step of grinding the purple plant. The method of claim 3,
The solvent is a method for producing a natural dye comprising at least one of water, alcohol solvent, ketone solvent, amine solvent, hydrocarbon solvent, carboxyl solvent, benzene solvent. The method of claim 1,
The metal salt is a method of producing a natural dye comprising at least one of aluminum metal salt, copper metal salt, iron metal salt, tin metal salt, chromium metal salt. The method of claim 1,
The process of manufacturing the dye,
Separating the anthocyanin complex;
Drying the separated anthocyanin complex; And
Method of producing a natural dye comprising the step of grinding the dried anthocyanin complex. metal; And
Natural dyes containing 80% or more of the compounds represented by the following formula (1) and (2).
[Formula 1]

(2)

The method of claim 8,
The natural dyes, natural dyes, characterized in that the weight loss starts at a temperature in the range of 55 to 80 ℃ measured by a thermogravimetric analyzer (TGA, Perkin Elmer, nitrogen gas filling, temperature increase rate 10 ℃ / min). The method of claim 8,
The metal is a natural dye, characterized in that it comprises at least one of copper, aluminum, iron, tin, chromium. Preparing a salt solution using the natural dye according to claim 8 or 10;
Dyeing the fabric using the prepared salt solution; And
Dyeing method comprising the step of washing the dyed fabric. The method of claim 11,
The dyeing process of the fabric dyeing method comprising the step of maintaining for a predetermined time at a temperature of 55 to 65 ℃. The method of claim 11,
The dyeing process of the fabric dyeing method comprising the step of maintaining for a predetermined time at a temperature of 75 to 85 ℃. The method of claim 11,
The dyeing process of the fabric dyeing method characterized in that to adjust the dyeing time by measuring the transparency of the salt solution. The method of claim 11,
The dyeing process further comprises the step of recovering the anthocyanin complex compound remaining in the salt solution. The method of claim 11,
The process of washing the dyed fabric is a dyeing method, characterized in that performed using an aqueous solution in an acidic state. The method of claim 11,
The fabric is a dyeing method, characterized in that the natural fibers, including cotton fibers, hemp fibers, wool fibers, or silk fibers. The method of claim 11,
The fabric is a dyeing method, characterized in that the regenerated fiber, including rayon fibers, acetate fibers, or tencel fibers.

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