KR100398064B1 - New enzymatic method of natural dyestuffs extraction from plant and its applications - Google Patents

Abstract

The present invention relates to a method for extracting natural pigment using plant cell wall degrading enzyme and its use, and more particularly, to cellulase (plantation of safflower, gardenia, onion skin, joiner, turmeric, turmeric, yellow and white, etc. which are used as natural pigment sources). Natural pigment extraction method for treating the temperature, concentration and pH of plant cell wall degrading enzymes such as cellulase, xylanase or pectinase differently depending on the purpose of treatment and the method of using the pigment extracted therefrom will be. Therefore, according to the present invention, the present invention not only extracts the pigment which is an effective ingredient of the plant more efficiently by decomposing the cell wall using the cell wall degrading enzyme of the plant, but also does not destroy the pigment part and selectively extracts it without impurities. Because it can be used for dyeing and printing, it shows a better effect. Also, the pigment extracted by this method is less destructive and has good binding ability with dyeing cloth, so it can be expensive natural dyeing and color paper, food, toys, etc. There is an effect that can be useful to make it angry.

Description

New enzymatic method of natural dyestuffs extraction from plant and its applications

The present invention relates to a method for extracting natural pigment using plant cell wall degrading enzyme and its use, and more particularly, to cellulase (plantation of safflower, gardenia, onion skin, joiner, turmeric, turmeric, yellow and white, etc. which are used as natural pigment sources). Natural pigment extraction method for treating the temperature, concentration and pH of plant cell wall degrading enzymes such as cellulase, xylanase or pectinase differently depending on the purpose of treatment and the method of using the pigment extracted therefrom will be.

In general, a method of obtaining a natural pigment from a plant has been extracted with water or a solvent from a plant, and the dye has been used for dyeing cloth or paper, and a mordant is used to increase color clarity and color fastness. In the conventional natural dyeing method, the extraction amount of the pigment is low, the sharpness at the time of dyeing and the reproducibility is insufficient, the quality control is difficult, and as a result, it was very difficult to industrialize.

In Korea, dyeing has been carried out on the domestic industrial scale by using salt and natural mordant extracted from natural materials in the natural state centering on functional holders (salts). Master's Thesis, Women's University, 1992]. For example, in the case of side dyeing, which is most commonly used as a blue pigment, the time to obtain the leaf leaves is limited, the extraction process of the pigment component is too complicated, and the dye fermentation time (blooming) takes a long time, making it difficult to put it to practical use. have. Since most other natural dye dyeing methods have been handed down to some salters, it is necessary to quantify and quantify them scientifically to make them practical.

Therefore, natural dyeing technology has recently been studied by some interested scholars (Nam Woo, et al., Modernization of Traditional Natural Dyeing Methods, Final Report of Ministry of Science and Technology, Second Year 1996). For example, in the Nasa insect insect lab, after dyeing using potassium carbonate from safflower, the dyes were changed at different pH, concentration, temperature, etc. and confirmed that they were dyed in various colors according to pH. He is also working to quantify and quantify dyeing. In another example, the Ministry of Science and Technology recognized the necessity of natural dyeing technology, and has already carried out a national project entitled "Experimental Research for Standardization of Pigment Extraction and Dyeing Conditions of Natural Plant Dyes". In this project, pigment extraction, dyeing, and color fastness measurement were performed on 10 representative vegetable salts, and as a result, the researchers who performed the task concluded that natural dye dyeing, although it is very difficult to efficiently dye and standardize and commercialize dyes, The city emphasized that it is the most important core technology. In addition, the Ministry of Commerce, Industry and Energy conducts research on i) color diversification by dyeing and dyeing and ii) daylighting and washing fastness improvement technology through the task of "Color Dyeing of Natural Dyeing and Colorfastness Technology of Dyeing". [Um Sung-il, Korean Traditional Textiles, 1, 19-93, 1998].

However, in order to popularize and secure the competitiveness of natural dye dyes through these prior national projects, there was still a limitation in industrial use due to the lack of reproducibility and insufficient amount of extracted pigments. Since there is a problem that the color fastness to the wash fastness falls, the need for a solution to this situation was very large.

Thus, the inventors of the present invention, as a result of intensive research to solve the above problems, by partially dissolving the cell wall of the natural dye-producing plant with cell wall degrading enzyme of the plant to facilitate the elution of the pigment, thereby increasing the amount of pigment production Of course, by dissolving the homogeneous pigment under a certain extraction conditions to reduce the denaturation to extract a natural pigment with high clarity and fastness at the time of dyeing to complete the present invention.

Therefore, the present invention has a main object to provide a method for extracting natural pigment from plants using plant cell wall degrading enzyme.

In addition, the present invention has another feature to provide a natural dye composition comprising a natural pigment extracted from the above.

Figure 1 shows a photograph (x400) comparing the amount of residual pigment by observing the extraction residue with an optical microscope after extracting the pigment from safflower by the general extraction and enzyme extraction method.

Figure 2 shows the result of dyeing yellow and red pigments using eight different fabrics after extracting the pigment from safflower by the general extraction (a) and enzyme extraction (b) method.

The present invention relates to a method for extracting natural pigment from plants using plant cell wall degrading enzymes.

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

First, the present invention relates to a method for extracting natural pigment from a plant using plant cell wall degrading enzyme, wherein the plants to be extracted include one selected from safflower, gardenia, onion skin, joiner, turmeric, turmeric, and yellow and white use. Since the chemical composition of the cell wall is different for each plant, these dye plants properly control one or more cell wall degrading enzymes selected from cellulase, xylanase and pectinase according to the type of plant selected. Use it. In addition, since the activity of each enzyme is different depending on the type of enzyme treatment, the cell wall on which the pigment is attached is decomposed, so that the glass is easily released. Extract.

In other words, in the case of treating cellulase as a plant cell wall degrading enzyme on a plant, the temperature is 40 to 55 ° C., preferably 40 to 45 ° C. considering the stability of the pigment and the extraction conditions, and the enzyme concentration is applied to the target plant. Although different depending on 8-12 units / g, and pH are 4.0-5.5, Preferably it processes in 4.5-5.4 range. When the plant cell wall degrading enzyme is xylanase, the temperature is 30 to 45 ° C., preferably 40 to 45 ° C., the enzyme concentration is 4 to 8 units / g, preferably 5 to 6 units / g, and the pH is 4.0. -7.0 Preferably, it processes in the range of 4.0-5.0. When the plant cell wall degrading enzyme is pectinase, the temperature is 30 to 45 ° C., preferably 35 to 40 ° C., the enzyme concentration is 10 to 15 units / g, preferably 10 to 12 units / g, and pH. Is treated in the range of 4.8 to 7.5, preferably 5.5 to 6.5.

In addition, the present invention includes a natural dye composition containing a natural pigment extracted by the above extraction method.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples as follows, but the present invention is not limited thereto.

Example: Extraction of Natural Pigment from Plant by Enzyme Extraction Method

Cellulase, pectinase and xylanase were used differently depending on the type of plant using safflower, soybean, seedling, onion skin, yellowish white, gardenia and turmeric as natural plant salts. In terms of the amount used, safflower, turmeric, and gall bladder contain 10 units of cellulase per gram of sample, 5 units of cellulase and 5 units of xylanase for porridge, 5 units of cellulase and 5 units of xylanase for onion, and pectin for onion skin Ten units of AIDS and gardenia used 5 units of cellulase and 5 units of pectinase. In addition, the enzyme extraction temperature was maintained at 50 ℃, pH equal to 5.0. In the enzyme extraction, the dye amount was extracted with the same amount of plant salt and reaction conditions. In addition, the absorbance was measured by using a spectrophotometer to confirm the extraction amount of the pigment, and the results are summarized in Table 1 below.

Comparative Example: Production of Natural Pigments from Plants by a General Extraction Method

As a general extraction, 0.5 g of each plant salt was added to 50 ml of water by using natural plant saline, safflower, soybean, seedling, onion skin, yellow white, gardenia and turmeric, and extracted at 50 ° C. for 30 minutes. The absorbance was measured by the method, and the results are summarized in Table 1 below.

Natural Salt Processing enzyme Absorbance (450nm) Enzyme Extraction (Examples) General extraction (comparative example) Safflower Cellulase 0.53 0.25 Self Cellulase / Xylanase 1.52 0.76 gallnut Cellulase 0.38 0.19 onion Pectinase 0.27 0.22 Yellow white Cellulase / Xylanase 0.57 0.38 curcuma Cellulase 0.93 0.78 Gardenia Cellulase / Pectinase 0.89 0.64 Joiner Cellulase / Xylanase 1.65 0.92

According to the results of Table 1, in the case of safflower, by performing the cellulase enzyme treatment method, it was possible to extract simultaneously without the hassle of extracting the yellow and red pigments in the general extraction method, and the extraction amount was also increased by about 2 times. In case of moth, 1.5 times when extracting with cellulase and xylanase at the same time, 5 times with 5 times with cellulase, small seedlings with 1.8 times when extracting with cellulase and xylanase at the same time, and 1.2 times with extract skin when using pectinase. For example, yellow and white were 1.5 times higher than cellulase and xylanase, and gardenia was 1.4 times higher than cellulase and pectinase, and turmeric was 1.2 times higher than cellulase. Therefore, the extracted pigment showed higher absorbance than enzyme extraction, so it can be seen that a large amount of natural pigments can be extracted, thereby improving the novel method using the enzyme.

Experimental Example 1: Comparison of dyeing properties of cloth using general extraction and enzyme extraction dye

After dyeing the natural pigment extracted by the method of the above example and the natural pigment extracted by the method of Comparative Example for 1 hour at a bath ratio 1:50, a temperature of 50 ℃, pH 7.0 for each cotton and silk (silk) for 1 hour After washing the dyeing cloth with distilled water, and dried, spectrophotometer [computer color matching system; JS555, Tokyo, JAPAN] using the Hunter method (K / S), color difference (ΔE), brightness index (L ^* ), perceptual color index (yellow-blue) (a ^* ), The surface color difference was investigated by determining the color values of perceptual color index (green-ruler) (b ^* ) and saturation index (c ^* ).

(One) Comparison of dyeability of safflower dyes

Dyeing results of safflower dyes are summarized in Table 2 below.

Extraction Method Surface color difference ΔE L ^* a ^* b ^* c ^* Cotton Enzyme extraction 98.57 71.86 64.19 20.78 84.97 General extraction 70.22 39.92 65.30 85.10 150.42 Silk Enzyme extraction 47.47 0.69 17.55 8.97 26.52 General extraction 17.83 57.34 43.49 99.68 143.17

According to the results of Table 2, the staining of the enzyme extraction pigments compared to the general extraction pigments are clear enough to see with the visible staining, the use of dyes by enzyme extraction can be seen that the dyeability is superior.

(2) Comparison of Dyeing Properties of Self-dye

Dyeing comparative results of the self-dye dye are summarized in Table 3 below.

Extraction Method Surface color difference ΔE L ^* a ^* b ^* c ^* Cotton Enzyme extraction 1.64 68.96 12.73 -0.93 11.80 General extraction 0 67.41 12.37 -1.35 11.02 Silk Enzyme extraction 3.74 64.68 13.25 -1.04 13.26 General extraction 4.17 63.47 11.03 -1.67 9.36

According to the results of Table 3, the dyeing pattern of the enzyme extract pigments compared to the general extraction pigments in the case of cotton does not have a significant difference in the degree of staining, but in the case of the dog using a dye by enzyme extraction the difference in the dyeability It can be seen that.

(3) Dyeing Comparison of Onion Dye

Dyeing results of onion dyes are summarized in Table 4 below.

Extraction Method Surface color difference ΔE L ^* a ^* b ^* c ^* Cotton Enzyme extraction 47.36 92.87 -7.41 33.87 26.73 General extraction 36.55 89.38 -4.63 22.40 17.77 Silk Enzyme extraction 62.94 75.77 -7.77 57.69 49.92 General extraction 73.46 82.53 -9.72 67.06 57.34

According to the results of Table 4, compared to the general extraction pigment, the staining pattern of the enzyme extraction pigment is more deeply dyed in the case of cotton, the case of the dog using a pigment by enzyme extraction shows a vivid brown color of the enzyme It can be seen that the effect of the pigment by extraction is more excellent.

(4) Comparison of dyeability of sulfur white dyes

The dyeability comparison results of sulfur white dye are summarized in Table 5 below.

Extraction Method Surface color difference ΔE L ^* a ^* b ^* c ^* Cotton Enzyme extraction 20.76 77.31 9.17 16.61 25.78 General extraction 28.94 84.14 5.7 21.3 27.00 Silk Enzyme extraction 32.12 61.99 16.60 30.03 46.63 General extraction 28.69 68.24 11.41 27.31 38.72

According to the results of Table 5, the dyeing pattern of the enzyme extraction pigment compared to the general extraction dyes in the case of cotton, the degree of visible dyeing was slightly pale off, and in the case of the dog using the dye by enzyme extraction It was shown that the color of the dark yellow system has a better effect of the pigment by enzyme extraction.

(5) Comparison of Dyeability of Turmeric Dye

Dyeing results of turmeric dyes are summarized in Table 6 below.

Extraction Method Surface color difference ΔE L ^* a ^* b ^* c ^* Cotton Enzyme extraction 96.05 89.99 -7.16 89.94 82.78 General extraction 92.53 89.04 -4.63 87.02 82.50 Silk Enzyme extraction 3.28 84.35 -8.64 98.34 89.70 General extraction 2.81 84.76 -9.12 97.06 88.56

According to the results of Table 6, compared to the general extraction pigments, the stained aspect of the enzyme extract pigments were both bright and dark yellow staining was found that the dye by enzyme extraction is more effective in dyeing.

(6) Comparison of Dyeing Properties of Gardenia Dyes

The staining results of the gardenia dyes are summarized in Table 7 below.

Extraction Method Surface color difference ΔE L ^* a ^* b ^* c ^* Cotton Enzyme extraction 87.80 81.09 13.49 85.37 98.86 General extraction 84.51 80.91 11.18 82.06 93.24 Silk Enzyme extraction 1.59 71.87 5.92 99.93 105.8 General extraction 88.81 74.69 63.91 86.99 150.9

According to the results of Table 7, the stained aspect of the enzyme extract pigments compared to the general extract pigments did not have a big difference in the case of cotton, but in the case of the dog is dyed bright yellow, the pigment by enzyme extraction is more effective in dyeing Could know.

(7) Dyeing Comparison of Dyeing Dye

Dyeing results of the Dyeing Dyes are summarized in Table 8 below.

Extraction Method Surface color difference ΔE L ^* a ^* b ^* c ^* Cotton Enzyme extraction 35.16 74.58 8.91 32.90 41.81 General extraction 34.41 74.46 8.85 32.15 41.00 Silk Enzyme extraction 59.71 57.62 16.82 57.38 74.20 General extraction 58.99 59.20 15.69 56.97 72.66

According to the results of Table 8, the dyes of the enzyme extract pigments were colored in a brown brown color for both cotton and silk compared to the general extract pigments, indicating that the pigments obtained by enzyme extraction were more effective in dyeing. .

Experimental Example 2 Extraction Pattern of Safflower and Dyeing Properties of Multi-Smith Fabrics during General Extraction and Enzyme Extraction

After safflower enzyme and general extraction, respectively, by the method of Examples and Comparative Examples, the residues of safflower were observed with a 400-fold optical microscope, and the results are shown in FIG. 1. As a result, the safflower residue by the general extraction method (Comparative Example) was not perfect in the extraction of pigments, whereas the residual amount was large, whereas the safflower residue by the enzyme extraction method (Example) confirmed that there was almost no pigment remaining. In addition, the superiority of the enzyme extraction method according to the present invention could be objectiveized.

In addition, in order to compare the dyeability according to the type of fabric was dyed using a test fabric multi-fiber fabric No. 49 (Multifiber Style # 49) recognized by the internationally recognized institution for dyeing, the results are shown in Figure 2 below. In other words, in the case of yellow and red, acetate fiber (Spun diacetate), polyester fiber (Spun polyester (dacron)), polyacrylic fiber (Spun polyacrylic (orlon 75)) was not dyed, cotton fiber (cotton), poly Amide fibers (Spun polyamide (nylon 6.6)), silk (Spun silk), viscose fibers (Spun viscose) and wool fibers (Worsted wool) was found that the degree of dyeing is much clearer.

Experimental Example 3: Comparison of Wash Fastness after Staining with General Extraction and Enzyme Extracting Safflower Pigment

To the recommended concentration of the manufacturer using water, neutral detergent, water-drying detergent (home dry, SK Chemicals) and dry cleaning agent to the dog dyed with safflower dye by the method (1) of Experimental Example 1 After washing with stirring for 30 minutes, the wash solution was analyzed with a spectrophotometer. As a result, 0.08 and 0.03 for water-washing fabrics stained with safflower dye extracted by the general extraction method (comparative example) and enzyme extraction method (example), and 0.10 and 0.03 for neutral detergent, 0.06 and In the case of 0.02 and dry cleaning, 0.03 and 0.01 were shown.

Therefore, compared to the case of dyeing with safflower extract, the dye was significantly less elution in the dyed cloth than in the case of dyeing by general extraction, and the color fastness was excellent. When dyeing with the pigment extracted enzyme was found to significantly improve the dyeing quality.

As described above, the present invention relates to a natural pigment extraction method using plant cell wall degrading enzyme and its use. Therefore, according to the present invention, the present invention not only extracts the pigment which is an effective ingredient of the plant more efficiently by decomposing the cell wall using the cell wall degrading enzyme of the plant, but also does not destroy the pigment part and selectively extracts it without impurities. Because it can be used for dyeing and printing, it shows a better effect. Also, the pigment extracted by this method is less destructive and has good binding ability with dyeing cloth, so it can be expensive natural dyeing and color paper, food, toys, etc. There is an effect that can be useful to make it angry.

Claims (4)

In the method of extracting pigments from plants using plant cell wall degrading enzyme, Extraction of natural pigments from plants, characterized by extracting natural pigments from plants at a temperature of 30-55 ° C. and pH 4.0-7.5 using plant cell wall degrading enzyme per unit of 1 g of plants. Way. The method of extracting natural pigment from a plant according to claim 1, wherein the plant is safflower, gardenia, gall bladder, onion skin, joiner, turmeric, turmeric, yellow white. The method of claim 1, wherein the plant cell wall degrading enzyme is at least one selected from cellulase, xylanase and pectinase. Natural dye composition, characterized in that it contains a natural pigment extracted by the enzyme extraction method of claim 1.