KR101175237B1 - Natural green dye extracted from green algae and method for manufacturing thesame - Google Patents

Abstract

The present invention relates to a natural green dye extracted from green algae and a method of manufacturing the green algae stabilizing green algae, green pigment is extracted from the green algae stabilized green algae to form an extract, filtering the solids in the extract, solids The removed extract is concentrated under reduced pressure, quenched, dried, and powdered to provide a method for producing a natural green dye from green algae, whereby a natural green dye can be produced.

Description

Natural green dye extracted from green algae and method for manufacturing thesame}

The present invention relates to a natural green dye extracted from green algae and a method for producing the same, and more particularly, to a method of extracting a natural green dye from green algae, and dyeing the fabric using the natural green dye extracted by the extraction method It's about doing.

In recent years, interest in natural dyes has been increasing due to various adverse effects such as adverse effects on the human body and environmental pollution, skin irritation and allergy.

That is, natural dyes have the advantages of good biodegradability of natural wastes, reduction to soil, prevention of environmental pollution and little toxicity, as well as an elegant color tone and antibacterial, anti-microbial and physical and mental effects. Has the advantage that it does not have.

In addition, natural dyes are increasingly being used because they can meet the needs of more sophisticated consumers who avoid artificiality and prefer natural ones.

Natural dyes are mostly obtained from salt plants growing on land, and marine plants (algae) have rarely been used as natural salts. Algae are a very wide variety and are classified into green algae, brown algae, and red algae from ecological and reproductive methods based on body color. Among them, green algae are green because they contain large amounts of chloroplasts, and contain chlorophyll a and b in similar proportions to higher plants.

The most observed species of marine algae is blue, and its taste and aroma are widely used for food and medicinal purposes. In addition, previous studies have shown that hypertension prevention and anti-cancer and anti-tumor activity, and physiological activity against the immune, nerve and endocrine system.

Seagrass is distributed all over the coast of Korea, especially on the west and south coasts. However, due to the recent changes in algae caused by abnormal temperature and water temperature, the seashore has been invaded by the seashore, damaging the landscape and depositing it.

Therefore, it is easy to obtain materials in the vicinity of Korea, and it is time for research to use green algae, especially green sea, which needs to be disposed of due to excessive inflow in some areas.

The present invention has been made to solve the above-mentioned problems of the prior art, it is a natural green dye with high chlorophyll content and optimizing the pigment stabilization and extraction process of green algae widely distributed on the coast, filtration, concentration under reduced pressure, quenching, dry powdered The purpose is to provide a method for extracting.

Another object of the present invention is to provide a natural green dye extracted from green algae having excellent color and color fastness when dyed to fabric using natural green dye extracted from green algae, and a method of manufacturing the same.

In order to achieve this object, the natural green dye production method according to the present invention is a first step of stabilizing green algae green algae, a second step of extracting the green pigment from the green algae stabilized green algae to form an extract, And a third step of filtering the solids in the extract, a fourth step of concentrating the extract from which the solids have been removed under reduced pressure, and a fifth step of quenching and drying the reduced pressure concentrated extract to prepare a powdered dye. .

In the first step, the green alga may be poured into a stabilizer solution in which a stabilizer is selected from a metal salt, a mixture of the metal salt and an acid, or a mixture of the metal salt and ammonia.

The metal salt may include copper, iron, zinc, and chromium, and the acid may include phosphoric acid or nitric acid.

In the first step, the green algae may be placed in the stabilizer solution having a concentration of 0.025 to 0.5%, and then bathed for 30 to 90 minutes at a temperature of 25 to 100 ° C.

In the second step, an alkali chemicals in which the selected green algae stabilized green algae is selected from potassium hydroxide (KOH), potassium carbonate (K ₂ CO ₃ ), sodium hydroxide (NaOH), and sodium carbonate (Na ₂ CO ₃ ) in water. The extract can be extracted by pouring into an aqueous solution.

In the second step, the green pigment stabilized green algae may be placed in the aqueous alkali solution having a concentration of 0.25 to 1.5%, and then bathed for 30 to 90 minutes at a temperature of 40 to 100 ° C.

The green alga may be one selected from the group including blue, falcon, auditory, and haecam.

In addition, the natural green dye of the present invention, the green algae in the stabilizer solution and the water bath to stabilize the green cattle, and then the green algae stabilized green algae in an aqueous alkali agent solution to form an extract, the solid is filtered through the extract. The remaining extract may be concentrated under reduced pressure, quenched and dried to form a powder.

The green alga may be one selected from the group including blue, falcon, auditory, and haecam.

The natural green dye extracted from the blue may have peak values of visible absorption spectra at 404 nm and 653 nm.

According to the present invention, there is an effect of optimizing the stabilization and extraction process of green algae, which has a high chlorophyll content and is widely distributed along the coast, and extracts natural green dyes which are filtered, concentrated under reduced pressure, quenched and dried.

In addition, there is an effect capable of producing a natural green dye with excellent color and color fastness when dyed to the fabric.

1 is a flow chart showing a method for producing a natural green dye in green algae according to an embodiment of the present invention.
Figure 2 is a graph showing the visible absorption spectrum of the salt solution prepared with the natural green dyes 1 to 3 and Comparative dyes 1 and 2 obtained through the comparative example of the present invention.
Figure 3 is a graph showing the absorbance of the salt solution prepared with the natural green dyes 1 to 3 and Comparative dyes 1 and 2 obtained through the comparative example of the present invention.
Figure 4 is a graph showing the change in dyeing amount of the dyed fabric according to the stabilizer concentration of the salt solution prepared with natural green dye 1 obtained through an embodiment of the present invention.
Figure 5 is a graph showing the change in dyeing amount of the dyed fabric according to the concentration of the salt solution prepared with natural green dyes 1, 9 to 11 obtained through an embodiment of the present invention.
6 is a structural diagram showing a structure in which chlorophyllin of green algae is separated.
Figure 7 is a graph showing the visible absorption spectrum of the natural green dye 12 and sodium chlorophyllin obtained through an embodiment of the present invention.
Figure 8 is a graph showing the dyeing amount of the fabric at the dyeing conditions when dyed with the salt solution prepared with natural green dye 12 obtained through an embodiment of the present invention.

Although the terms used in the present invention have been selected as general terms that are widely used at present, there are some terms selected arbitrarily by the applicant in a specific case. In this case, the meaning described or used in the detailed description part of the invention The meaning must be grasped.

Hereinafter, with reference to the preferred drawings and embodiments will be described in detail the technical configuration of the present invention.

However, the present invention is not limited to the embodiments described herein but may be embodied in other forms.

1 is a flow chart showing a method for producing a natural green dye in green algae according to an embodiment of the present invention.

Referring to Figure 1, first, to prepare a green alga to extract the natural dye in step S110. Green algae may be any one selected from the group including blue, falcon, auditory, haecam. In the embodiment of the present invention, the seaweed was used.

Next, the green cattle stabilization process prepared in S120 process. The green pigment stabilization treatment is to stabilize the chlorophyll pigments contained in the green seaweed by placing the dried green alga in a stabilizer solution.

At this time, the temperature of the hot water bath is 25 to 100 ℃, the preferred temperature is 100 ℃, the time for hot water bath may be 30 to 90 minutes, the preferred time may be 60 minutes.

Stabilizers can be used to select one of a metal salt, a mixture of metal salts and acids, a mixture of metal salts and ammonia. Here, the metal salt may include copper (Cu), iron (Fe), zinc (Zn) or chromium (Cr), and the acid mixed with the metal salt may include phosphoric acid (H ₃ PO ₄ ) or nitric acid (H ₂ NO ₃ ). Can be.

Next, the green pigment is first extracted from the green cattle stabilized green in step S130 to form a primary extract. That is, the stabilized green seaweed is placed in an aqueous alkali agent solution, and then bathed at a temperature of 40 to 100 ° C. for 30 to 90 minutes to obtain a primary extract. This process extracts green pigments from the greens. At this time, it is more preferable that the temperature to be heated is 100 ° C, and the time is 60 minutes. And sodium hydroxide aqueous solution is preferably used by 30 times the weight of the green.

At this time, the aqueous alkali solution is prepared by mixing one selected from potassium hydroxide (KOH), potassium carbonate (K ₂ CO ₃ ), sodium hydroxide (NaOH), sodium carbonate (Na ₂ CO ₃ ).

After completion of the first green pigment extraction process, the first extracted green pigment in S140 process in an alkaline aqueous solution solution and the water bath under the same conditions as in S130 to obtain a secondary extract.

In the natural green dye manufacturing method according to an embodiment of the present invention, the green pigment is extracted two times, but may be repeatedly extracted three or four times.

Next, the solids in the respective extracts are removed from the first and second extracts extracted in S150 using a filtration filter.

Next, the solid extract is removed in step S160 and concentrated under reduced pressure.

Next, the extract concentrated in step S170 is quenched and then dried in a freeze dryer in step S180 to form a powdered dye.

Example 1

The dyeing material used was purchased from a market in Gwangju, Jeollanam-do, washed with water, dried at 40 ° C. in an oven dryer, and stored at room temperature. At this time, the green onion is prepared 40g. Put the dried laver 40g to a stabilizer solution of 0.025% copper sulfate _{(cupric sulfate, CuSO 4? 5H} 2 O) solution to 1200ml water bath for 60 minutes in boiling water of 100 ℃ kinda stabilize the pigment chlorophyll contained in the palette. Next, the stabilized green seaweed was put in an aqueous 1% sodium hydroxide solution, and then bathed at a temperature of 100 ° C. for 60 minutes to obtain a primary extract.

Next, the greens from which the pigment was first extracted were placed in a 1% sodium hydroxide (NaOH) aqueous solution, and the mixture was bathed at a temperature of 100 ° C. for 60 minutes to obtain a secondary extract.

Next, the solids were separated from the extract by filtration of the first and second extracts, and the extracts were separated from the extract, rotated at 50 to 115 to 125 rpm, concentrated under reduced pressure, quenched at -80 ° C. for 24 hours, and then freeze-dried. To dry at -50 ℃ to powder to prepare a natural green dye 1.

Example 2

A natural green dye 2 was prepared in the same manner as in Example 1, except that ferric sulfate (FeSO ₄ ˜7H ₂ O) solution was used as a stabilizer solution instead of the copper sulfate solution to stabilize green color. Was

Example 3

A natural green dye 3 was prepared in the same manner as in Example 1 except for stabilizing the green grass by using a zinc chloride (zinc chloride, ZnCl ₂ ) solution as a stabilizer solution instead of the copper sulfate solution.

Example 4

Except that copper was stabilized using a solution of copper (Cu) and phosphorus (P) in a ratio of 1: 0.5 by mixing phosphoric acid (H ₃ PO ₄ ) in the copper sulfate solution instead of the copper sulfate solution. Natural green dye 4 was prepared by the same process as in Example 1.

Example 5

Except that copper was stabilized using a solution containing copper (Cu) and phosphorus (P) in a 1: 1 ratio by mixing phosphoric acid (H ₃ PO ₄ ) in a copper sulfate solution instead of a copper sulfate solution. Natural green dye 5 was prepared in the same manner as in Example 1.

Example 6

Except that copper was stabilized by mixing a solution of copper sulfate with phosphoric acid (H ₃ PO ₄ ) instead of the copper sulfate solution using a copper (Cu) and phosphorus (P) ratio of 1: 2 as a stabilizer solution. The same process as in Example 1 was performed to prepare natural green dye 6.

Example 7

Except that copper was stabilized using a solution of copper (Cu) and phosphorus (P) in a ratio of 1: 3 by mixing phosphoric acid (H ₃ PO ₄ ) in a copper sulfate solution instead of the copper sulfate solution. The same process as in Example 1 was performed to prepare natural green dye 7.

Example 8

Except that copper was stabilized by mixing a solution of copper sulfate with phosphoric acid (H ₃ PO ₄ ) instead of the copper sulfate solution using a copper (Cu) and phosphorus (P) ratio of 1: 5 as a stabilizer solution. The same process as in Example 1 was performed to prepare natural green dye 8.

Comparative Example 1

Comparative dye 1 was prepared by performing the same procedure as in Example 1 without performing the process of dye stabilization of the green.

Comparative Example 2

Comparative dye 2 was prepared in the same manner as in Example 1, except that methanol was extracted with methanol without performing a dye stabilization process.

Experimental Example 1

The natural green dyes 1 to 3 obtained through Examples 1 to 3 and the comparative dyes 1 and 2 obtained through Comparative Examples 1 and 2 were mixed with a solvent, especially water, in a ratio of 1:50 to adjust the dye concentration, respectively. The visible part spectrum of the prepared saline solution was measured and shown in FIG. 2. In addition, the absorbance of each salt solution prepared by the above method was measured and described in Table 1 and FIG. 3.

Referring to FIG. 2, the salt solutions prepared with the natural green dyes 1 to 3 and the comparative dyes 1 and 2 all exhibit several peaks in the visible part (400-700 nm). The main absorption peak of the salt solution with and without metal pretreatment is largely divided into two, 400 to 420 nm and 630 to 700 nm. Among them, the salt solution prepared with Comparative Dye 2 shows more peaks than the salt solution with and without metal pretreatment. It seems to be influenced by other components extracted in.

Specifically, the salt solution prepared with natural green dye 1 is 404 and 652 nm, the salt solution prepared with natural green dye 2 is 402 and 654 nm, the salt solution made with natural green dye 2 is 413 and 634 nm, and the salt solution prepared with comparative dye 1 The salts prepared with 403 and 454 nm and Comparative Dye 2 showed slight differences between 412 and 664 nm.

On the other hand, Table 1 and Figure 3 shows the results of experiments of the absorbance of the salt solution prepared by Experimental Example 1, respectively. That is, the absorbance is measured for 5 days in order to confirm the effect of stability on the light of the natural green dyes 1 to 3 and the salt solutions prepared with Comparative dyes 1 and 2 prepared by the respective examples.

Exposure time Natural Green Dyes 1 Natural green dyes 2 Natural green dyes 3 Comparative dyes 1 Comparative Dyes 2 Pigmented solution

0 day

3 days

5 days

To determine the effect on the stability of the light of the salt solution prepared with each of the natural green dyes 1 to 3 and Comparative dyes 1 and 2 to about 40 ℃ (at room temperature but the temperature is increased by the light to maintain 40 ℃ The absorbance was measured by storing in Daylight (6500k) + UV for 5 days.

The dye stock solution was measured by diluting it with distilled water due to its dark color. When diluted to the same concentration, the amount of absorbance of the remaining pigment was calculated. 3 is shown.

All the saline solution absorbed over time. The salt solution prepared with natural green dye 1 remained about 85% of the pigment at 404 nm. The salt solution prepared with natural green dye 2 was about 80% at 402 nm, the salt solution prepared with natural green dye 3 was about 67% at 413 nm, and the salt solution prepared with comparative dye 1 extracted only with aqueous NaOH solution without substitution with a metal salt at 403 nm. About 83%, the salt solution prepared with Comparative Dye 2 remained about 65% of the pigment. From these results, it was confirmed that the salt solution prepared with the natural green dye 1 has excellent light stability, shows a clear G series when dyed to a fabric, and has the best fastness.

Experimental Example 2

After dyeing the fabric with each of the salt solutions prepared with the natural green dyes 1 to 3 and Comparative dyes 1 and 2 by the method according to Experimental Example 1, the color and color fastness of the fabric was measured to obtain the results shown in Table 2. At this time, the fabric used silk and wool.

Specifically, the dyeing temperature was 100 ℃, dyeing time 60 minutes, pH (pH) was maintained at pH 7, using an infrared high-pressure dye (Ahiba Nuance, Date Color International, USA) was dyed to silk and wool fabrics. At this time, acetic acid (acetic acid) used to adjust the pH was used as the reagent first class.

The dyed fabrics were evaluated for dyeing by measuring the K / S value at the maximum absorption wavelength using a color difference meter (Color-Eye 3100, Macbeth, USA) and the H V / C value of Munsell.

Washing fastness (AATCC Method 61-1989), dry cleaning fastness (AATCC Test Method 132-1989) and friction fastness (AATCC Method 116-1989) were evaluated and daylight fastness (AATCC Method 16-2004) was measured after 20 hours Evaluated by.

textile division K / S value (420 nm) H V / C L ^* a ^* b ^* h ° Color Daylight fastness (20 hours) Silk fabric Natural Green Dyes 1 15.96 6.6GY 4.6 / 4.3 47.61 -14.51 23.56 121.64

2 Natural green dyes 2 15.91 8.5Y 4.7 / 3.6 47.75 -2.71 26.68 95.79

One Natural green dyes 3 18.02 4.9GY 4.3 / 4.7 43.46 -12.80 29.49 113.46

One Comparative dyes 1 18.24 9.1Y 4.4 / 3.7 45.19 -3.22 27.35 96.72

One Comparative Dyes 2 0.81 7.7Y 7.9 / 3.1 79.57 -1.85 23.31 94.54 - One wool Natural Green Dyes 1 28.77 6.9GY 3.1 / 3.7 32.04 -12.27 17.73 124.69

2/3 Natural green dyes 2 27.58 8.3Y 3.3 / 3.1 32.93 -1.46 20.55 94.07

1/2 Natural green dyes 3 28.25 4.6GY 3.1 / 3.8 30.99 -9.73 21.70 114.15

One Comparative dyes 1 29.87 8.8Y 3.0 / 3.0 29.99 -1.62 19.68 94.70

2 Comparative Dyes 2 2.17 1.8GY 6.9 / 4.3 69.88 -6.85 30.19 102.78 - One

Referring to Table 2, fabrics dyed with saline prepared with Comparative Dye 1 and Natural Green Dye 2 exhibited Y-based color, and fabrics dyed with saline prepared with Natural Green Dye 1 and 3 showed GY-based color. .

In particular, the fabrics dyed with saline prepared with natural green dye 1 were GY based colors that are closer to the G series with vivid colors than the fabrics dyed with saline prepared with other dyes. That is, it can be confirmed that the color and the daylight fastness of the fabric dyed with the salt solution prepared with natural green dye 1 is the best.

Experimental Example 3

Using the natural green dyes 1, 4 to 8 obtained in Examples 1, 4 to 8, the dyeability of the fabric dyed with the saline solution prepared by the method of Experimental Examples 1 and 2 was measured and described in Table 3.

textile
division
K / S value HV / C
L ^*
a ^*
b ^*
h °
420nm 640 nm Silk fabric




Natural Green Dyes 1 15.96 3.45 6.6GY 4.6 / 4.3 47.61 -14.51 23.56 121.64 Natural green dyes 4 16.38 4.33 7.8GY 4.6 / 4.4 46.86 -16.80 22.26 127.04 Natural green dyes 5 16.62 4.38 7.7GY 4.5 / 4.4 46.57 -16.68 22.25 126.85 Natural Green Dyes 6 16.38 4.32 7.7GY 4.6 / 4.5 46.92 -16.69 22.47 126.61 Natural Green Dyes 7 16.94 4.26 7.3GY 4.5 / 4.4 46.22 -15.98 22.69 125.16 Natural Green Dye 8 16.14 4.25 8.0GY 4.7 / 4.6 47.80 -17.66 22.81 127.76 wool




Natural Green Dyes 1 28.77 10.13 6.9GY 3.1 / 3.7 32.04 -12.27 17.73 124.69 Natural green dyes 4 25.75 9.51 8.4GY 3.5 / 4.1 36.02 -15.84 18.47 130.62 Natural green dyes 5 25.89 9.68 8.5GY 3.5 / 4.1 36.05 -15.94 18.27 131.10 Natural Green Dyes 6 26.18 9.66 8.2GY 3.5 / 4.1 35.63 -15.55 18.53 130.00 Natural Green Dyes 7 26.94 10.16 8.3GY 3.5 / 4.2 35.35 -15.72 18.58 130.22 Natural Green Dye 8 26.48 10.26 8.3GY 3.4 / 4.1 34.89 -15.55 18.17 130.55

As shown in Table 3, when phosphoric acid is mixed with the copper sulfate solution, green energy is generally used regardless of the mixing ratio of copper and phosphorus as compared with the case of stabilization using copper salt alone as in the case of natural green dye 1. This increased, the saturation also slightly increased, it can be seen that more clear, but the difference in the amount of dyeing can be seen that not large. In addition, it can be seen that the dyeing amount and the color difference are not large depending on the mixing ratio of copper and phosphorus.

Experimental Example 4

When the concentration of the stabilizer in the copper stabilization treatment of the natural green dye 1 obtained through Example 1 is different from the results of experiments on the dyeing amount of the dyed fabric, it is shown in FIG. The dyeing amount, color and color fastness were measured and shown in Tables 4 and 5.

Figure 4 shows the dyeing amount of the dyed fabric according to each concentration when the copper concentration in the stabilization treatment when the natural green dye 1 is prepared. Referring to Figure 4, the lower the concentration of copper increased the amount of dyeing. However, at the concentration below 0.0125%, the color of Y energy increased and saturation was lowered, resulting in a turbid color. Therefore, it can be confirmed that the optimum condition of the copper concentration at the time of stabilization treatment is preferably 0.025%.

On the other hand, when the copper concentration is 0.025%, the dyeing amount of the fabric with respect to the temperature and time during the stabilization treatment was measured to obtain the results shown in Tables 4 and 5.

Table 4 shows the dyeing amount, color and color fastness of the fabric according to the temperature during the stabilization treatment when 0.025% of copper was used as the stabilizer. The lower the temperature at the time of stabilization treatment, the higher the amount of dyeing, but considering the color and the color fastness, it was confirmed that it is preferable to bathe at 100 ° C.

textile Cu pretreatment temperature (℃) K / S value (420 nm) H V / C L ^* a ^* b ^* h˚ ΔE ^* Light resistance (20 hours) Silk fabric



25 16.87 7.3GY 4.4 / 4.7 45.44 -17.08 24.37 125.03 54.66 1/2 40 16.50 7.2GY 4.5 / 4.8 45.84 -17.09 24.95 124.42 54.55 1/2 60 16.56 7.2GY 4.5 / 4.6 45.66 -16.60 24.20 124.45 54.26 2 72 15.79 7.5GY 4.6 / 4.7 46.97 -17.18 23.94 125.67 53.21 2 100 14.99 8.2GY 4.7 / 4.6 48.47 -18.66 22.30 129.91 51.77 2 wool



25 26.79 8.0GY 3.3 / 4.2 33.35 -15.41 18.80 129.33 53.86 2 40 27.26 7.6GY 3.3 / 4.2 33.34 -14.89 19.22 127.76 53.80 2 60 26.33 7.5GY 3.4 / 4.1 34.50 -14.65 19.23 127.31 52.46 2 72 25.89 7.9GY 3.4 / 4.1 37.74 -15.20 18.94 128.76 52.51 2 100 25.05 8.4GY 3.5 / 4.1 34.59 -15.94 18.12 131.34 52.73 2/3

Table 5 shows the dyeing amount, color, and color fastness of the fabric according to the stabilization time with 0.025% copper as the stabilizer. At 30 minutes, 40 and 60 minutes of stabilization treatment, the dyeing amount and color, brightness and saturation showed similar tendency, but the dyeing amount was decreased to 90%, but the dyeing amount decreased, but the color shifted slightly to G series. It was. However, there was little change in daylight fastness with stabilization time.

textile Cu pretreatment time (min) K / S value (420 nm) H V / C L ^* a ^* b ^* h˚ ΔΕ ^* Light resistance (20 hours) Silk fabric


30 15.36 8.2GY 4.6 / 4.5 47.47 -17.50 21.86 128.67 52.07 2 40 14.89 8.2GY 4.7 / 4.6 47.99 -17.63 22.09 128.60 51.75 2 60 14.99 8.2GY 4.7 / 4.6 48.44 -17.75 22.29 128.53 51.48 2 90 13.81 8.4GY 4.8 / 4.6 49.71 -18.04 22.08 129.24 50.41 2 wool


30 24.78 8.4GY 3.5 / 4.1 35.51 -15.57 17.92 130.98 51.73 2 40 25.19 8.4GY 3.5 / 4.1 35.97 -15.85 18.36 130.81 51.44 2 60 25.05 8.4GY 3.5 / 4.1 35.65 -15.63 18.03 130.93 51.63 2 90 23.89 8.8GY 3.7 / 4.2 37.60 -16.75 18.52 132.12 50.20 2

Example 9

A natural green dye 9 was prepared in the same manner as in Example 1, except that a green pigment was extracted from the greenery using an aqueous potassium hydroxide (KOH) solution instead of an aqueous sodium hydroxide solution as an aqueous alkali agent.

Example 10

A natural green dye 10 was prepared in the same manner as in Example 1, except that a green pigment was extracted from a greenery using an aqueous potassium carbonate (K ₂ CO ₃ ) solution instead of an aqueous sodium hydroxide solution.

Example 11

A natural green dye 11 was prepared in the same manner as in Example 1, except that a green pigment was extracted from the greenery using an aqueous sodium carbonate (Na ₂ CO ₃ ) solution instead of an aqueous sodium hydroxide solution.

Experimental Example 5

Dyeing the silk or woolen fabric with the salt solution prepared with the natural green dyes 9-11 obtained in Examples 9 to 11 and the salt solution prepared with the natural green dye 1 obtained in Example 1 was used to determine the dyeing amount, color, and light fastness of the fabric. The measured results are shown in Table 5. In addition, when using sodium hydroxide as the alkali agent according to Table 6, it is shown in Figure 5 and Table 7 changes in the dyeing amount of the dyed fabric according to the concentration of sodium hydroxide.

When different kinds of alkaline agents were extracted and the concentration was fixed at 1%, the pigment was well extracted from the saline solution prepared with natural green dyes 1 and 9 obtained by using strong alkali agents such as potassium hydroxide and sodium hydroxide. The K / S value of the fabric was confirmed.

Fabrics dyed with saline prepared with natural green dyes 10 and 11 obtained with weak alkalis such as potassium carbonate and sodium carbonate were greener in color and saturated than fabrics dyed with saline prepared with natural green dyes 1 and 9 It has a high clear color. However, in consideration of dyeing amount, color and light fastness, it was confirmed that it is most preferable to use sodium hydroxide as an alkali agent.

textile division pH K / S value (420 nm) H V / C L ^* a ^* b ^* h ° ΔE ^* Light resistance (20 hours) Silk fabric Natural Green Dyes 1 12.70 15.36 8.2GY 4.6 / 4.5 47.06 -17.47 22.15 128.27 52.53 2 Natural Green Dyes 9 12.82 13.99 8.3GY 4.8 / 4.7 49.76 -18.23 22.52 129.00 50.61 2 Natural green dyes 10 10.34 6.88 9.3GY 5.8 / 4.7 59.82 -19.78 21.71 132.33 42.74 1/2 Natural green dyes 11 10.34
7.62
9.2GY 5.7 / 4.8 58.60
-19.93
22.08
132.07
43.91
1/2
wool


Natural Green Dyes 1 12.70 24.78 8.4GY 3.5 / 4.1 35.69 -15.35 18.49 129.69 51.58 2 Natural Green Dyes 9 12.82 24.14 8.5GY 3.7 / 4.2 37.48 -16.32 18.79 130.98 50.22 2 Natural green dyes 10 10.34 16.38 9.5GY 4.5 / 4.6 46.34 -18.85 19.53 133.99 43.15 1/2 Natural green dyes 11 10.34 17.67 9.2GY 4.4 / 4.6 44.72 -18.38 19.97 132.63 44.49 2

On the other hand, Figure 5 is a graph showing the change in dyeing amount of the dyed fabric according to the concentration of sodium hydroxide used as an alkali agent. That is, it shows the change in the amount of dyeing on the silk and wool of the extraction solution according to the concentration of sodium hydroxide which is an alkali agent used to extract the extract.

Referring to FIG. 5, the higher the concentration of sodium hydroxide, the higher the amount of dyeing was, but not greater than 0.75%.

Table 7 shows the dyeing amount and color according to the concentration of sodium hydroxide. The silky green color increased with increasing sodium hydroxide concentration, but the yellow color increased above 1%. As it increased, yellow increased. Therefore, the preferred concentration of sodium hydroxide was set to 0.75% in consideration of dyeing amount and color.

textile NaOH concentration (%) K / S value (420 nm) H V / C L ^* a ^* b ^* h˚ Silk fabric



0.25 10.68 8.3GY 5.2 / 4.6 50.33 -17.96 22.23 128.95 0.50 12.83 8.4GY 5.0 / 4.7 50.89 -18.37 22.38 129.37 0.75 14.89 8.5GY 4.7 / 4.7 48.47 -18.66 22.30 129.91 1.00 14.69 8.5GY 4.8 / 4.7 48.96 -18.63 22.27 129.90 1.50 15.52 8.2GY 4.7 / 4.7 48.09 -18.53 22.24 129.81 wool



0.25 21.53 8.9GY 3.8 / 4.2 39.11 -16.83 18.32 132.56 0.50 23.89 8.8GY 3.5 / 4.2 36.32 -16.51 17.98 132.56 0.75 25.19 8.5GY 3.4 / 4.2 34.59 -15.94 18.12 131.34 1.00 25.89 8.3GY 3.3 / 4.1 34.13 -15.45 18.02 130.61 1.50 26.94 7.7GY 3.2 / 4.1 33.00 -14.61 18.60 128.16

Example 12

A natural green dye 12 was prepared in the same manner as in Example 1, except that 0.75% aqueous sodium hydroxide solution instead of 1% aqueous sodium hydroxide solution was used as an alkaline aqueous solution to extract green pigment from the greenery.

Seaweed contains a chlorophyll component, which is a porphyrin pigment. Chlorophyll has magnesium in the center of the molecule, and four pyrroles are bonded to a methine group to form a porphyrin ring. One pyrrole and an alcohol, phytyl, are bound by esters. Due to the long carbon chain of phytyl, chlorophyll is fat-soluble.

Chlorophyll is unstable in light, temperature, metal ions, acids, alkalis, enzymes, etc. Magnesium in the center of the molecule is replaced by a hydrogen atom and is easily eliminated by extraction or processing. Change. The pheophytin is bright green when mixed with metal ions such as cobalt, copper, iron and zinc, which is called chlorophyllin.

Chlorophyllin containing metal ions hydrolyzes the pytyl group by alkali and replaces it with a carboxyl group so that it becomes water-soluble and soluble in water. Soluble chlorophyllin is called cobalt chlorophyllin sodium, copper chlorophyllin sodium, iron chlorophyllin sodium according to the metal ion of the center of the molecule.

Depending on the nature of the metal ion, its use varies. Sodium chlorophyllin is used in food additives, dyes, oral deodorants, natural wound healing agents, artificial photosynthesis and antimutagenic activity. Sodium copper chlorophyllin is a mixture of numerous chlorin forms extracted from natural chlorophyll, which is light green, and is separated into Cu (II) chlorin e ₄ and Cu (II) chlorin e ₆ , the structure of which is shown in FIG. 6. .

Experimental Example 6

The visible absorption spectrum of natural green dye 12 and sodium chlorophyllin sodium was measured and shown in FIG. 7. Referring to FIG. 7, the visible absorption spectra of the natural green dye 7 were shown at 404 nm and 653 nm, and sodium chlorophyllin showed two peaks at 405 nm and 630 nm, respectively. This means that natural green dye 12 had a structure very similar to that of chlorophyllin.

Experimental Example 7

When the fabric is dyed with the dye solution prepared with natural green dye 12, the dyeing amount according to the dyeing conditions is measured and shown in FIG. In addition, the dyeing fastness of the fabric according to the light and shade of the color was measured and shown in Table 8.

(A) is a dyeing temperature, (b) is a dyeing time, (c) is a pH, and (d) is a graph which shows the amount of dyeing according to a blue pigment concentration.

Referring to (a) of FIG. 8, as a result of dyeing the fabric with a salt solution having a ratio of 1:30 of natural green dye 12 and a solvent, the silk fabrics were dye-equilibrium at 80 ° C., and the wool fabrics were dyed as the temperature increased. It was. However, at 100 ° C., the color becomes turbid and the Y energy increases, so that the most preferable temperature conditions are 80 ° C. for the silk and 90 ° C. for the wool. At this time, the dyeing time was adjusted to 60 minutes, acidity pH7.

In addition, referring to Figure 8 (b), in the case of dyeing the fabric with a salt solution of 1:30 ratio of the natural green dye 12 and the solvent, the dyeing temperature of the silk and wool as shown in Figure 8 (a) After setting the 80 ℃ and 90 ℃ can be confirmed the amount of dyeing according to the dyeing time.

In the first 30 minutes of the dyeing start time, the dyeing amount rapidly increased, and the dyeing equilibrium was achieved at 60 minutes for the silk and 90 minutes for the wool, but all dyeing was performed at 60 minutes. At this time, the acidity was adjusted to pH7.

In addition, referring to FIG. 8 (c), when the silk fabric is dyed at 80 ° C. and the wool fabric is at 90 ° C. in a salt solution having a ratio of 1:30 of natural green dye 12 and a solvent, the silk fabric has a maximum at a weak acidic condition of pH 6. The amount of dyeing was shown, but the color was a yellow-colored GY-based color. Woolen dyes increase with increasing pH, and dyeing tends to decrease under strong acidic conditions. Considering the amount of dyeing and color, it was confirmed that the most preferable acidity is pH 8.

Finally, referring to (d) of FIG. 8, when dyeing the silk fabric at 80 ° C. and the wool fabric at 90 ° C. with a salt solution having a ratio of 1:30 of natural green dye 12 and a solvent and an acidity of pH 8, the concentration of the blue pigment is increased. The increase in dyeing tends to be similar to that of Freundlich type isotherm. As a result of the experiment for checking the pH effect, it was confirmed that the most preferable acidity was pH 8 in consideration of the amount of dyeing and color, but the difference in the amount of dyeing and color did not appear significantly due to the difference in pH of pH 7 and 8.

Finally, Table 8 shows the dyeing fastnesses of the fabrics according to the shades of color.

textile A joke of color Dye concentration K / S valve (420nm) H V / C Washing Dry cleaning Rubbing Color change Stain Color change Stain First Second First Second Dry Wet Silk fabric Low 0.50 3.86 7.2GY 6.6 / 3.9 4 5 5 4/5 5 5 5 4/5 Medium 2.00 13.26 8.3GY 5.2 / 4.9 4 5 5 4/5 5 5 4/5 4 High 5.00 19.19 8.8GY 4.3 / 4.9 4 5 5 4 5 5 4/5 3/4 wool Low 0.25 4.60 6.6GY 6.0 / 3.6 4 5 5 4/5 5 5 5 4/5 Medium 1.00 16.20 7.6GY 4.5 / 4.2 4/5 5 5 4/5 5 5 4/5 4/5 High 3.00 27.26 8.3GY 3.4 / 4.3 4/5 5 5 4/5 5 5 4/5 4/5

Referring to Table 8, the silk fabrics had 4 grades of wash fastness, 4-4 / 5 dry dryness, and no bleeding regardless of color shade. The color fastness was 5 grades in pale color, 4/5 grades in neutral and deep color, and 4/5 grades in pale color when dried. Daylight fastness was low, with a half rating. Washing fastness of wool was 4-4 / 5, dry cleaning fastness was 4/5 and there was no otitis. The friction fastness was excellent with the grade of 4 / 5-5.

On the other hand, in the case of daylight fastness, up to 2-2 / 3 grades can be obtained according to the test results, the stabilizer type shown in Table 1, the copper pretreatment temperature and time shown in Tables 4 and 5, the type of extracted alkali shown in Table 6, and the like. .

As a result, the natural green dye extracted from the green algae of the present invention and its manufacturing method suggest an optimized method of extracting the natural green dye from green algae, especially green seaweed, and dyeing with excellent color and color fastness when dyeing the fabric using the extracted natural green dye The effect is to get a fabric. In addition, although the specific example was not presented, the same result was obtained in other green algae.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, Various changes and modifications will be possible.

Claims (10)

A first step of stabilizing green algae;
A second step of extracting a green pigment from the green cow stabilized green algae to form an extract;
A third step of filtering solids in the extract;
A fourth step of concentrating the extract from which the solids have been removed under reduced pressure; And
And quenching and drying the extract under reduced pressure, thereby preparing a powdered dye.
The second step is an alkaline aqueous solution in which a green algae stabilized green algae is selected from potassium hydroxide (KOH), potassium carbonate (K ₂ CO ₃ ), sodium hydroxide (NaOH), and sodium carbonate (Na ₂ CO ₃ ) in water. Method of producing a natural green dye, characterized in that is carried out including the step of extracting the extract by hot water.
The method of claim 1, wherein the first step is
The green algae manufacturing method characterized in that the green algae in a stabilizer solution in which a stabilizer is selected from a metal salt, a mixture of the metal salt and acid or a mixture of the metal salt and ammonia dissolved. The method of claim 2,
The metal salt comprises copper, iron, zinc, chromium,
The acid is a natural green dye production method characterized in that it comprises phosphoric acid or nitric acid. The method of claim 3, wherein the first step,
The green algae is placed in the stabilizer solution having a concentration of 0.025 to 0.5%, and a natural green dye production method for 30 to 90 minutes at a temperature of 25 to 100 ℃. delete The method of claim 1, wherein the second step,
The green pigment stabilized green algae is placed in the aqueous alkali agent having a concentration of 0.25 to 1.5% and a natural green dye production method characterized in that the water bath for 30 to 90 minutes at a temperature of 40 to 100 ℃.
The method of claim 1,
The green alga is a green green dye production method, characterized in that the one selected from the group including the blue, the hearing, haecam. delete delete delete

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