KR20030012362A - Antifungal natural dye and method of coloring fiber using same - Google Patents

Abstract

PURPOSE: Provided are an antibacterial natural dyes and a dyeing method using it, which has various color tones of yellow according to mordants and extracting solvents, excellent color fastness, wash fastness and light fastness and excellent antibiosis, and prevents various skin diseases. Therefore the antibacterial natural dyes are useful for a diaper, a sanitary towel, clothes and bedclothes. CONSTITUTION: The antibacterial natural dyes contains an extract of sophora root. The dyeing method is as follows: extracting sophora root in water or an organic solvent to get the extract of sophora root having at least 0.1g/ml of dry weight; adding the extract to 20times of water based on weight of fiber to manufacture a dyeing solution having at least 40% o.w.f of concentration and pH 3-6; putting fiber into a dyeing bath at 50-70deg.C for 30-90min to dye; and then treating with the mordant selected from the group containing FeSO4.7H2O, CuSO4.5H2O, K2Cr2O7, SnCl2.2H2O and Al2(SO4)3.

Description

Antimicrobial natural dyes and textile dyeing method using the same {ANTIFUNGAL NATURAL DYE AND METHOD OF COLORING FIBER USING SAME}

[Industrial use]

The present invention relates to an antimicrobial natural dye and a method for dyeing fibers using the same, and more particularly, to a method for dyeing an antimicrobial natural dye having excellent antibacterial effects and a fiber using the same while minimizing skin irritation.

[Prior art]

The skin is contaminated by water vapor, gas, sweat, sebum, and dead skin cells, and as the bacteria grow, clothing, which is in contact with the skin, tends to breed bacteria, mold, and parasites. Increasing people's awareness of cleanliness, the demand for hygienic and comfortable environment, the sanitary processing that can suppress the microorganisms multiplied on the above-mentioned fiber and odorous substances caused by the metabolic activity of the microorganisms is being applied to the clothing material. .

The antimicrobial agent used in the sanitary processing is a substance that mixes or penetrates into the fiber surface by incorporating antimicrobial action into the fiber or by post-treatment. Antimicrobial agents include antimicrobial zeolites, silver, copper, zinc, and ceramics. The organic antimicrobial agent has many quaternary ammonium salts, but recently, safety has been emphasized, such as aminoglucoside and hinokithiol (4-isopropyl-2-hydroxycyclohepta-2,4,6-triene-1-one: Natural materials such as 4-isopropyl-2-hydroxycyclohepta-2,4,6-triene-1-one and chitosan (β-1, polyglucosamine: β-1, polyglucosamine) are used. Less anti-irritant or toxic, antibacterial against gram-positive bacteria and gram-negative bacteria. Guanidine-based antimicrobial agents have a very strong adsorption force on fibers and high washing durability. However, it shows high bactericidal activity against bacteria but its effect is low against fungi.

Textile products that have been sanitized with chemicals generally have good antibacterial effects but are often unsafe to the skin. Elution-type antibacterial and deodorized products can break the balance with existing bacteria by multiplying resistant bacteria when the drug is dissolved in the fiber and transferred directly to the skin. In addition, recently marketed antimicrobial deodorant processed fiber products have excellent antibacterial effect on skin bacteria, but it can cause fungal disease due to imbalance of the skin coexisting bacteria, it is necessary to develop a drug having an antimicrobial effect against fungi. Organic chlorine, phosphonium, and bromine organic compounds are mainly used in wool products for the purpose of preventing damage. Among them, the organic chlorine compound, deldrin, causes central nervous and liver disorders, is scalable to the human body, and bisphosphate compounds. Is known to be carcinogenic. Organic mercury compound sanitizers, which are used for the purpose of preventing the embrittlement of fibers due to fungi, are highly toxic and are rarely used at present because of the risk of causing central nervous system disorders or accumulation in the human body.

In addition, skin damage may also occur due to dyes or post-treatment agents used in clothing. Disorders caused by dyes are most often caused by aniline (aline) and azo (azo) pigments. Products containing amino groups (-NH ₂ ) as basic dyes and pigments containing arsenic, lead, and copper are used. They irritate and irritate the skin, sometimes absorbing it and causing systemic poisoning. Formaldehyde, used as a post-treatment agent, can be released by the sweat or skin heat and released into the skin, causing irritation.

Skin diseases caused by cosmetics include irritant contact dermatitis, allergic contact dermatitis, contact urticaria, pigmentation, change of hair, hair change, acne rash, etc. The fragrance ingredients, preservatives, and pigments included in cosmetics are the most common causes. . Among them, pigment cosmetic dermatitis was highlighted in 1969 when Osmunden reported the relationship between cosmetic pigments and dermatitis, which is the most serious skin disease among cosmetic side effects. The disease often causes pigmentation accompanied by erythematous plaques, papular lesions, and pruritus. The main cause of this problem is pigments in hair cosmetics and hair dyes.

As such, chemicals such as antibacterial agents, sanitary agents, and dyes, which are not secured to human safety, may irritate the skin and harm the human body, and thus, interest in natural dyes that are harmless to the human body has gradually increased.

In addition, the antimicrobial studies on natural staining until now, despite the presence of many kinds of microorganisms on the skin, most of them have antibacterial effect only by considering the antimicrobial effect against Staphylococcus aureus. However, since the difference in the antimicrobial activity is very large according to the types of microorganisms, the study of the antimicrobial activity is not sufficient because only the antimicrobial examination of a specific bacterium is sufficient.

An object of the present invention is to provide an antimicrobial natural dye that can be applied to a functional product that can improve skin by preventing skin diseases while minimizing skin irritation.

Another object of the present invention is to provide a practical antimicrobial natural dye that can replace expensive natural yellow dyes.

Still another object of the present invention is to provide a method for dyeing fibers using the above-described antimicrobial natural dye.

1 is a graph showing the dyeing amount of the cotton cloth dyed according to Examples 1 and 2 of the present invention.

Figure 2 is a graph showing the dyeing amount of silk cloth dyed according to Examples 1 and 2 of the present invention.

Figure 3 is a graph showing the antimicrobial activity of S. aureus of cotton swabs stained according to Examples 1 and 2 of the present invention.

Figure 4 is a graph showing the antimicrobial activity of B. subtilis of cotton woven in accordance with Examples 1 and 2 of the present invention.

Figure 5 is a graph showing the antimicrobial activity of S. epidermidis of cotton woven in accordance with Examples 1 and 2 of the present invention.

Figure 6 is a graph showing the antimicrobial activity of P. acnes of cotton woven in accordance with Examples 1 and 2 of the present invention.

Figure 7 is a graph showing the antimicrobial activity of S. aureus of the silk stained according to Examples 1 and 2 of the present invention.

8 is a graph showing the antimicrobial activity of B. subtilis of silkworms stained according to Examples 1 and 2 of the present invention.

9 is a graph showing the antimicrobial activity of S. epidermidis of silk cloth stained according to Examples 1 and 2 of the present invention.

10 is a graph showing the antimicrobial activity of P. acnes of the silk cloth stained according to Examples 1 and 2 of the present invention.

Figure 11 is a graph showing the antimicrobial activity of C. albicans of cotton woven in accordance with Examples 1 and 2 of the present invention.

12 is a graph showing the antimicrobial activity of A. niger of cotton woven in accordance with Examples 1 and 2 of the present invention.

Figure 13 is a graph showing the antimicrobial activity of T. mentagrophytes of cotton swabs stained according to Examples 1 and 2 of the present invention.

Figure 14 is a graph showing the antimicrobial activity of C. albicans of the silk stained according to Examples 1 and 2 of the present invention.

15 is a graph showing the antimicrobial activity of A. niger of silk cloth stained according to Examples 1 and 2 of the present invention.

16 is a graph showing the antimicrobial activity of T. mentagrophytes of silk cloth stained according to Examples 1 and 2 of the present invention.

17 to 20 are photographs showing bacterial antimicrobial activity against B. subtilis of cotton swabs stained according to Examples 1 and 2 of the present invention.

21 to 24 are photographs showing bacterial antimicrobial activity against P. acnes of cotton swabs stained according to Examples 1 and 2 of the present invention.

25 to 28 are photographs showing bacterial antimicrobial activity against S. epidermidis of silkworms dyed according to Examples 1 and 2 of the present invention.

29 to 32 are photographs showing antifungal properties of T. mentagrophytes of cotton woven in accordance with Examples 1 and 2 of the present invention.

33 to 36 are photographs showing antifungal properties of T. mentagrophytes of silkworms stained according to Examples 1 and 2 of the present invention.

In order to achieve the above object, the present invention provides an antimicrobial natural dye comprising a ginseng extract.

The present invention extracts ginseng with water or an organic solvent to obtain a ginseng extract with a dry weight of at least 0.1 g / ml, the concentration of the ginseng extract used as a dye of 40% (owf) or more, bath ratio 1: 20, pH 3 to 6 Prepare a salt bath. That is, a red ginseng dye corresponding to 40% or more of the fiber weight is mixed with distilled water corresponding to 20 times the fiber weight to prepare a salt bath having a pH of 3 to 6, and then the fiber is added for 30 to 90 minutes at 50 to 70 ° C. It provides a method for dyeing fibers using an antimicrobial natural dye, including the step of dyeing.

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

According to the present invention, it is easy to obtain a salt material, the price is low, the color is beautiful, the dyeing is good, and the result of the study of selecting natural materials for application to functional products that can improve skin by preventing skin diseases while minimizing skin irritation It was completed by finding out that it satisfies the purpose.

Sophora Radix, used in the present invention, is a root of a plant called Sophora flavescens Aition, a perennial herbaceous plant belonging to the legume, which has been used as an insecticide, analgesic, and insect repellent for long time in Korea. It is a natural substance used externally as an external medicine. Ginseng has been used for jaundice, epilepsy, nausea, fever, diarrhea, hemorrhoids, uterine bleeding, bronchitis, pulmonary tuberculosis, sinusitis, rheumatism, diuresis, analgesic, repellent, and as a medicinal agent as sedative, scabies, eczema, The whole amount has been used externally for the skin disease of dryness and severe itching. In the private sector, the roots, stems and leaves of ginseng are powdered or decocted and used as skin insecticides or crop pesticides.

In addition, since the ginseng obtains a dye from the root, a large amount of pigments are collected, and the pigments of the red ginseng flavonoid compound-based dyes contain yellow pigments, which is a practical substance as a dye for textile products or as a dye for color cosmetics. In addition, domestic and international studies have shown that ginseng has antibacterial and antifungal effects against some bacteria and has immunity enhancing effects. Therefore, unlike chemical hygiene processing agent that has excellent antibacterial effect, but proliferates some resistant bacteria and causes imbalance of superficial bacteria, it prevents skin infectious diseases due to allergic reaction as well as antibacterial effect, and also protects against immune diseases such as skin allergy. As it is effective, it has little side effects even when applied to materials that come into contact with skin for a long time.

The antimicrobial natural dye of the present invention includes such a ginseng extract, and the ginseng extract is obtained by an extraction process of putting ginseng in water or an organic solvent and heating it. The extraction process will be described in more detail by adding ginseng to water when water is used as the extraction solvent and adding this mixture at 70 to 95 ° C. and when using an organic solvent as the extraction solvent. The mixture is obtained by heating at 50-80 ° C. for 4-6 hours. In the heating step, it is possible to use a vessel connected with a cooler to prevent evaporation of the organic solvent and to ensure safety. At this time, the amount of the extraction solvent is used about 7 to 20 times the weight of high ginseng. In the case of repeating the heating process twice, 70 to 95 ° C. (water) or 50 to 80 ° C. (organic solvent) using about 7 to 20 times the extraction solvent of the ginseng weight for 2 to 4 hours. After primary heating, a primary extract was obtained, and a fresh extract solvent was put back into the mixture, followed by extraction at 70 to 95 ° C. (water) or 50 to 80 ° C. (organic solvent) for 1 to 3 hours to obtain a secondary extract. Mix the primary extract and the secondary extract. The extract obtained is filtered and concentrated to produce an extract having a dry weight of at least 0.1 g / ml, preferably 0.1 to 0.5 g / ml. In this case, ethanol, methanol, chloroform, ethyl acetate or hexane may be used as the organic solvent.

It is preferable to use an organic solvent as the extraction solvent because the components of the solvent are easily removed even at a low temperature, and thus it is not necessary to perform a freeze-drying process for powdering, and the process is very simple. In addition, it is possible to obtain a variety of colors than when using water, and the use of an organic solvent is preferable because the antibacterial and antifungal components are dissolved in a large amount to obtain a more excellent antibacterial effect.

The method of dyeing fibers using the antimicrobial and antifungal natural dyes of the present invention obtained by the above-described method is, firstly, ginseng having a dry weight of 0.1 g / ml or more, preferably 0.1 to 0.5 g / ml, used as the natural dye. The extract is added to a bath ratio of 1:20, i.e., 20 times the weight of the fiber, so that the concentration of the natural dye is at least 40%, preferably 40 to 70% (owf: on the weight of fiber) at a pH of 3 to 6. Prepare a dye bath. The fiber is put into this dyeing bath and dyed for 30 to 90 minutes at a temperature of 50 to 70 ° C. This step is carried out while gradually applying heat in order to promote dyeing, and the fiber can be infiltrated evenly by inverting the fibers every predetermined time.

As the fibers, not only natural fibers such as cotton and silk, but also all fibers such as synthetic fibers such as polyester and polypropylene and regenerated cellulose fibers can be used. In addition, the fiber may be in any state such as yarn, woven fabric, knitted fabric or clothing.

Wash and dehydrate the dyed fibers. Subsequently, a mordant treatment may be performed using a mordant. When the mordant treatment is performed, the light fastness and washing fastness may be improved depending on the fiber, and the improvement effect of the antimicrobial and antifungal properties may be promoted depending on the type of microorganism. have. As the mordant, metal mordants such as FeSO ₄ · 7H ₂ O, CuSO ₄ · 5H ₂ O, K ₂ Cr ₂ O ₇ , SnCl ₂ · 2H ₂ O or Al ₂ (SO ₄ ) ₃ are mainly used. Depending on the type and color of the mordant may be used in various ways. When the mordant is used, a solution having a concentration of 2 to 5% (owf) of a bath ratio of 1:20 (weight of fiber: volume of water) is prepared, and then, the fiber is added and heat is maintained at about 50 to 70 ° C. If the cotton is soaked for too long when the temperature exceeds 70 ℃, the dye may be released to the dye bath again, there is a fear that the protein is denatured when traction. When the heat is gradually added to 70 ℃ to cool to maintain the 50 ℃ or more. The mordant may be subjected to a post mortem method in this manner, or may also be subjected to a pre mordant method and a simultaneous mortant method, and may vary depending on the type of fiber and the purpose of dyeing. The time is carried out for 30 to 90 minutes.

Wash it with water, dry it naturally, and repeat the process of dyeing and dyeing at least once. This process is also carried out while the fiber is inverted at regular intervals to allow the dye to penetrate evenly. The embedded fiber is then washed with water and dried.

As described above, the fibers stained with the antimicrobial and antifungal dyes of the present invention are Gram-positive bacteria such as Staphylococcus aureus, Staphylococcus epidermidis, Bacillus subtilis , Acne bacteria Propionibacterium acenes , Aspergillus niger, Candida albicans, Trycophyton mentagrophytes It is antibacterial and antifungal against bacteria.

In addition, the antimicrobial and antifungal raw material of the present invention has an antibacterial and antifungal effect as well as an immunosuppressive effect, so it can be applied to a material for preventing skin diseases, so that there is no side effect even when used in a human body for a long time, such as sanitary napkin, diaper, clothing, bedding, interior It can be applied to various fields such as props.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only one preferred embodiment of the present invention and the present invention is not limited to the following examples.

(Examples 1 and 2)

1. Sample

1) Gosam

1kg of Korean ginseng was purchased from Jegi Jeon-dong, washed with distilled water, and then dried naturally.

2) Test gun

The standard test cloth of the Korea Apparel Testing Laboratory was used.

White cloth: KS K 0905

White dog: KS K 0905

3) reagents

Ferrous sulfate (FeSO ₄ · 7H ₂ O), copper sulfate (CuSO ₄ · 5H ₂ O), potassium dichromate (K ₂ Cr ₂ O ₇ ), tin dichloride (SnCl ₂ · 2H ₂ O), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) and the like were purchased from Deoksan Chemical Industry Co., Ltd. and used.

Glycerol, Re-distilled Ethanol, Distilled Water, Physiological Saline

4) Used strain

(1) bacteria

Gram-positive bacteria

Staphylococcus aureus KCTC1916

Staphylococcus epidermidis KCTC1917

Bacillus subtilis ATCC 1027

* Acen

Propionibacterium acnes ATCC 3314

(2) fungi

Aspergillus niger ATCC9642

Candida albicans KCTC6316

Trycophyton mentagrophytes KCTC6085

5) badge

Mueller Hinton broth (Difco Lab, USA)

Brain Heart Infusion broth (Difco Lab, USA)

Sabouraud Dextrose broth (Japan Isu Pharmaceutical Co., Ltd.)

6) Machines and Appliances

Spectrophotometer (CM-3700D, Minolta)

Clean bench (MM-80 Manometer, Dwyer instruments, INC)

Autoclave (KMC 1221)

Incubator (D.Y.S. 2935)

Vortex mixer (KMC-1300V)

Rotary evaporator (Sunil Eyela)

Heating mantle (HMG-F100, Hana)

pH Test Strips (SIGMA chemical company, USA)

Platinum

Petridish: 9cm in diameter, 1.5cm in height

2. Dyeing test

1) Extraction of High Ginseng Extract

(1) Water Extract (Example 1)

500 g of red ginseng and 5 L of water were added to an extraction flask connected with a cooler, and the extraction flask was placed on a heating mantle and shaken at 70 ° C. for 2 hours to obtain a primary extract. Subsequently, 4 L of water was further added to the extraction flask and heated at 70 ° C. for 1 hour to obtain a secondary extract. After the obtained primary and secondary extracts were mixed, the resultant was filtered twice with filter paper, and the extract was concentrated using a rotary evaporator to prepare 170 ml of high concentrate. The dry weight of this high concentrate was 0.3 g / ml. The high concentrate was lyophilized using a freeze dryer (Fleezing Dryer ISE, FD5505, Korea) at -50 ° C or lower to obtain a powdered dye.

(2) Ethanol Extract (Example 2)

500 g of red ginseng and 5 l of ethanol re-distilled were placed in an extraction flask connected with a cooler, and the extraction flask was placed on a heating mantle and heated at 50 ° C. for 2 hours to obtain a primary extract. 4 liters of ethanol re-distilled back into the extraction flask was extracted for 1 hour at 50 ℃. After the obtained primary extract and the secondary extract were mixed, the resultant was filtered twice with filter paper and concentrated on a rotary evaporator to obtain 170 ml of a high concentrate having a dry weight of 0.15 g / ml. This high concentrated egg was removed by completely evaporating the ethanol component using a rotary evaporator to prepare a powdered dye containing only pure red ginseng extract component.

2) dyeing and mordant

A dyeing solution having a concentration of 60% (owf), a bath ratio of 1:20, and a pH 4 of the ginseng extract prepared by the above-described method was prepared and transferred to 12 beakers.

Six 24g cotton test cloths and six 8.8g silk test cloths were placed in each of the 12 beakers so as to be completely submerged, and then gradually heated to maintain 60 to 70 ° C. The dye was dyed for 60 minutes, flipping every 5 minutes for even penetration. The dyed test cloth was lightly washed with cold water, dehydrated, and then mordant treated.

Concentration 3% (owf), bath ratio 1: using FeSO ₄ · 7H ₂ O, CuSO ₄ · 5H ₂ O, K ₂ Cr ₂ O ₇ , SnCl ₂ · 2H ₂ O, Al ₂ (SO ₄ ) ₃ as mordant A solution of 20 was prepared.

The test fabric to be mordant was completely immersed in the solution in which the mordant was dissolved, and then slowly heated to maintain 60 ° C. After inverting the test cloths every 5 minutes for 60 minutes, each test cloth was washed with cold water several times and then dehydrated and dried naturally. The above procedure was repeated twice.

3. Results

The dyeing amount, surface color, color fastness and antibacterial and antifungal properties of the test cloth dyed by the above-described method were measured as follows.

1) Desalination Measurement

Using a UV-visible spectrophotometer equipped with an integrating sphere, the surface reflectance of the dyeing material was obtained at 360 nm, the dyeing concentration (K / S) was calculated by Kubelka-Munk equation, and the dyeing amount of the dyeing cloth was evaluated from this value. The results are shown in Tables 1 and 2 below.

K / S value of cotton fabric according to extraction solvent Mordant menstruum Example 1 (water extract) Example 2 (ethanol extract) not used 0.53 1.21 FeSO ₄ 7H ₂ O 0.71 2.12 CuSO ₄ · 5H ₂ O 0.57 1.58 Al ₂ (SO ₄ ) ₃ 0.45 1.53 K ₂ Cr ₂ O ₇ 0.45 4.13 SnCl ₂ 2H ₂ O 0.80 3.25

K / S value of silk fabric according to extraction solvent Mordant menstruum Example 1 (water extract) Example 2 (ethanol extract) not used 4.16 19.76 FeSO ₄ 7H ₂ O 7.08 22.49 CuSO ₄ · 5H ₂ O 6.34 21.53 Al ₂ (SO ₄ ) ₃ 4.84 22.30 K ₂ Cr ₂ O ₇ 5.30 21.14 SnCl ₂ 2H ₂ O 5.30 20.21

In addition, the results are summarized, and the dyeing amounts of the cotton fabric and the silk fabric according to the solvent are shown in Fig. 1 (cotton fabric) and Fig. 2 (cotton fabric), respectively. 1 and 2, □ is Example 1 (water extract), ■ indicates Example 2 (ethanol extract), Fe is FeSO ₄ , Cu is CuSO ₄ , Al is Al ₂ (SO ₄ ) ₃ , K represents K ₂ Cr ₂ O ₇ , and Sn represents SnCl ₂ .

* Cotton fabric

In the test fabric of Example 1, the K / S value of the unstained dyeing cloth was 0.53, whereas the K / S value of the SnCl ₂ · 2H ₂ O-embedded dyeing cloth showed the highest dyeing amount of 0.80, and FeSO ₄ · 7H _The dyeing fabrics treated with ₂ 0 mordant showed a high dyeing amount of 0.71. CuSO ₄ · 5H ₂ O mordant dyeings showed a similar dyeing amount to the unstained dyeings. Al ₂ (SO ₄ ) ₃ mortar dyes and K ₂ Cr ₂ O ₇ mortar dyes showed lower dyeing amounts than unsalted dyes.

In the test fabric of Example 2, the dyeing amount was significantly higher in all the treated dyeing fabrics than in the non-staining dyeing fabrics. In particular, the unstained dyeing cloth had a K / S value of 1.21, while the K ₂ Cr ₂ O ₇ unwashed dyeing cloth had the highest dyeing amount of 4.13.

* Silk fabric

In the test fabric of Example 1, the dye-treated dyeing fabric showed a higher dyeing amount than the dye-free dyeing fabric. In particular, the K / S value of the unstained dyeing cloth was 4.16, while the K / S value of the FeSO ₄ · 7H ₂ O-embedded dyeing cloth was 7.08, showing the highest dyeing amount. In the test fabric of Example 2, the dyeing amount was higher than the dye-free dyeing cloth, but the difference was not so large.

As a result, the amount of dyeing of the test fabric of Example 2 was much higher than that of Example 1 in both the cotton fabric and the silk fabric.

2) Measurement of surface color of dyed fabric

Measure the X, Y, Z and Lab values of the sample at 10 ° field using a spectrophotometer (CM-3700D, Minolta), and use the Munsell colorimetric conversion method according to Equation 1 below to determine the three attribute values HV / C and Hunter The color difference value (Δ) of was obtained and the results are shown in Tables 3 (cotton fabric) and 4 (cotton fabric), respectively. The brightness index is indicated by L, the color coordinate index by a ^* and b ^* values, the color by H (Hue), and the saturation by C (chrome).

[Equation 1]

When both cotton and silk fabrics used the same mordant, the dyed cloth of Example 1 showed a light and high surface color, and the dyed cloth of Example 2 showed a vivid and dark surface color.

Color (H) and color difference (ΔE) of cotton fabric according to solvent and mordant menstruum H (V / S) & ΔE L a b H V / C ΔE Mordant Example 1 (water) Undyed 81.09 -0.16 +0.22 Unsalted 78.73 -1.38 +8.36 7.9Y 7.8 / 1.0 8.56 FeSO ₄ 7H ₂ O 76.26 -0.20 +7.76 4.5Y 7.5 / 1.0 8.96 CuSO ₄ 5H ₂ O 77.28 -1.63 +9.48 8.4Y 7.6 / 1.1 10.12 Al ₂ (SO ₄ ) ₃ 79.16 -2.14 +9.27 9.9Y 7.8 / 1.1 9.46 K ₂ Cr ₂ O ₇ 78.70 -1.05 +7.26 7.3Y 7.7 / 0.9 7.49 SnCl2.2H2O 78.74 -2.88 +15.23 9.2Y 7.8 / 1.9 15.44 Example 2 (ethanol) Undyed 81.09 -0.16 +0.22 Unsalted 78.68 -4.62 +21.71 0.1GY 7.8 / 2.8 22.08 FeSO ₄ 7H ₂ O 62.54 +1.13 +16.41 3.3Y 6.1 / 2.3 24.65 CuSO ₄ · 5H ₂ O 73.67 -1.06 +27.60 5.7 Y 7.3 / 3.7 28.38 Al ₂ (SO ₄ ) ₃ 78.26 -4.23 +31.49 8.6Y 7.8 / 4.2 31.66 K ₂ Cr ₂ O ₇ 71.35 +0.63 +45.02 5.2Y 7.1 / 6.3 45.86 SnCl2, 2H2O 76.90 -1.99 +43.78 6.7 Y 7.7 / 6.0 43.80

Color H (V / S) and color difference (ΔE) of silk fabrics depending on solvent and mordant menstruum H (V / S) & ΔE L a b H V / C ΔE Mordant Example 1 (water) Undyed 71.22 -0.04 -0.08 Unsalted 67.37 -4.17 +19.74 9.9Y 6.6 / 2.6 20.60 FeSO4, 7H ₂ O 57.24 -0.15 +18.82 4.9Y 5.6 / 2.6 23.51 CuSO ₄ · 5H ₂ O 59.44 -2.83 +25.32 7.8Y 5.8 / 3.4 28.13 Al ₂ (SO ₄ ) ₃ 66.37 -4.82 +6.94 9.4 Y 6.5 / 3.6 27.86 K ₂ Cr ₂ O ₇ 62.86 -0.93 +23.96 5.7 Y 6.2 / 3.2 25.46 SnCl ₂ 2H ₂ O 67.58 -5.55 +29.85 9.8Y 6.7 / 4.0 30.64 Example 2 (ethanol) Undyed 71.22 -0.04 -0.08 Unsalted 64.69 -5.70 +45.27 8.8Y 6.4 / 6.0 46.16 FeSO4, 7H ₂ O 33.15 +4.84 +22.09 2.2Y 3.3 / 3.4 44.32 CuSO ₄ · 5H ₂ O 55.00 +4.23 +51.95 4.6Y 5.5 / 7.3 54.66 Al ₂ (SO ₄ ) ₃ 62.28 +0.20 +56.58 6.1Y 6.2 / 2.7 57.36 K ₂ Cr ₂ O ₇ 51.13 +8.80 +51.80 2.8Y 5.1 / 7.6 56.32 SnCl ₂ 2H ₂ O 65.22 -0.87 +57.49 6.6Y 6.5 / 7.8 57.89

* Cotton fabric

Even in the dyeing cloth treated with the same mordant in all the test cloths, the test cloth of Example 2 was darker with lower L value and more saturated than the test cloth of Example 1.

The test cloths of Example 1 all had a value of-and b value of +, indicating the surface color of greenish and yellowish light. Compared to the unstained dyeing cloth, the stained dyeing cloth with SnCl ₂ · 2H ₂ O had the highest saturation and the brightness of FeSO ₄ · 7H ₂ O and CuSO ₄ · 5H ₂ O dyeing was slightly lower. The biggest change of surface color with the unstained test cloth was SnCl ₂ · 2H ₂ O mordant dye.

In the dyeing fabric of Example 2, both the unstained dyeing cloth, CuSO ₄ · 5H ₂ O, Al ₂ (SO ₄ ) ₃ , and the SnCl ₂ · 2H ₂ O dyeing dyeing cloth showed a value of-, b value of +, and The yellowish surface color was shown, and the unbroken dye cloth showed a green color with a strong yellow color. Yellowing tended to have a strong color by embedding it in dyeing cloth. FeSO ₄ · 7H ₂ O mordant dyed cloth showed a slightly reddish yellow color with 3.3Y. Compared to the unstained dyeing cloth, the stained dyeing cloth was generally lower in brightness, and in particular, the brightness of FeSO ₄ · 7H ₂ O-embedded dyeing cloth was the lowest. The surface color change was the highest in K ₂ Cr ₂ O ₇ and SnCl ₂ · 2H ₂ O mordant dyeing cloth, and the color change of the mordant dyeing cloth was larger than that of the unsalted dyeing cloth.

* Silk fabric

Even in the dyeing cloth treated with the same mordant in all the test cloths, the test cloth of Example 2 was darker with a lower L value and the saturation was higher than that of Example 1, so that the dye of Example 2 was darker than the water extract dyeing cloth, but showed a clear surface color.

The test cloths of Example 1 all had a value of-and b value of +, indicating the surface color of greenish and yellowish light. Compared to the unstained dyeing cloth, all of the dyeing dyeing cloths except the FeSO ₄ · 7H ₂ O mordant dyeing cloth were more saturated and the brightness was similar or lower. The change of surface color with the unstained test cloth was the largest in the SnCl ₂ · 2H ₂ O mordant dyeing cloth and the color change of the mordant dyeing cloth was larger than that of the unstained dyeing cloth.

In the test cloth of Example 2, the unstained dyeing cloth and the SnCl ₂ · 2H ₂ O unwashed dyeing cloth showed a value of-, b value of + and green and yellowish surface color. On the other hand, FeSO ₄ · 7H ₂ O and K ₂ Cr ₂ O ₇ , CuSO ₄ · 5H ₂ O mordant dyed fabrics had a value of +, b value-, and H value of FeSO ₄ · 7H ₂ O mordant dye cloth. The Y, K ₂ Cr ₂ O ₇ mordant dyeing was 2.8Y, and the CuSO ₄ · 5H ₂ O mordant dyeing was 4.6Y, showing a yellowish red color.

The brightness of the mortar was generally lower than that of the unstained dye, and in particular, the brightness of FeSO ₄ · 7H ₂ O mortar was decreased. Saturation tended to be generally high, but FeSO ₄ · 7H ₂ O mordant dyed cloth was much lower in saturation. The color change of the surface color was greater in all of the dyeing dyeing cloths except the FeSO ₄ · 7H ₂ O dyeing dyeing cloth compared to the dyeless dyeing fabric.

The surface color of the dyed silk cloth using the ginseng extract was generally yellow in the case of dyeing cloth of Example 1, and changed from yellow representing red to yellow representing green in the case of Example 2 dyeing cloth.

3) color fastness measurement

The fastness of the fibers dyed by the method of Example and Example 1 was measured by the following method and the results are shown in Tables 5 to 6, respectively.

(1) Daylight fastness: KSK 0700 method

(2) washing fastness: KSK 0430 A-1 40'C method

(3) friction fastness: KSK 0650 method

(4) sweat fastness: KSK 0715 method

(5) Dry cleaning fastness: DC KSK 0644 method

Dyeing Fastness of Cotton Fabrics by Extraction Solvents and Mordants Extraction solvent Color fastness Example 1 (water) Daylight fastness Grade 3 when using FeSO ₄ , CuSO ₄ mortar Color fastness Discolored stained cotton cloth Grade 4 without grade 2 without grade 4 Grade 5 with grade 5 without grade Sweat fastness Acid sweat Discoloration stained cotton cloth 4 to 5 grades without salt 4 to 5 grades without salt 4 to 5 grades without salt Alkali sweat Discoloration stained cotton cloth 4 to 5 grades without salt 4 to 5 grades without salt 4 to 5 grades without salt Friction fastness When drying Grade 5 without salt Grade 4 to 5 without salt Dry cleaning fastness Discoloration stained cotton cloth 4 to 5 grades without salt 4 to 5 grades without salt 4 to 5 grades without salt Example 2 (ethanol) Daylight fastness Grades _3-4 when using FeSO ₄ mordant Color fastness Discolored stained cotton cloth When using K ₂ Cr ₂ O ₇ Level 2 without grade 4 to 5 Level without salt Level 4 to 5 Sweat fastness Acid sweat Discoloration stained cotton cloth Unsalted 4-5 grade CuSO ₄ , Al ₂ (SO ₄ ) ₃ , K ₂ Cr ₂ O ₇ , SnCl ₂ -FeSO _{4 When} using 4-5 grade FeSO ₄ , CuSO ₄ , K ₂ Cr ₂ O ₇ 4 ~ Grade 5 Alkali sweat Discoloration stained cotton cloth Non-mordant during 4 to 5 grade FeSO _4, 4 to 5 grade using _{FeSO 4, CuSO 4, Al 2} (SO 4) 3, K 2 Cr 2 O 7, SnCl 2 using 4-5-class Color fastness When drying Grade 4 to 5 without dyes Grade 3 to 4 without salts Dry cleaning Discoloration stained cotton cloth 4 to 5 grades without salt 4 to 5 grades without salt 4 to 5 grades without salt

Dyeing fastness of silk by extractant and mordant Extraction solvent Color fastness Example 1 (water) Daylight fastness Grade 4 at no salt Color fastness Discolored stained cotton cloth K ₂ Cr ₂ O _{7 In} case of 3rd grade without bleeding In case of 4-5 grade Sweat fastness Acid sweat Discolored stained cotton cloth 4 to 5 grades without salt 4 to 5 grades without salt 4 to 5 grades without salt Alkali sweat Discolored stained cotton cloth 4 to 5 grades without salt 4 to 5 grades without salt 4 to 5 grades without salt Color fastness When drying Grade 5 without salt Grade 4 to 5 without salt Dry cleaning fastness Discolored stained cotton cloth 4 to 5 grades without salt 4 to 5 grades without salt 4 to 5 grades without salt Example 2 (ethanol) Daylight fastness Class 4 when using K ₂ Cr ₂ O ₇ Color fastness Discolored stained cotton cloth When using SnCl2 mortar, 3 ~ 4 unsalted, 4 ~ 5 unsalted, 4-5 Sweat fastness Acid sweat Discolored stained cotton cloth Class 4 without printing Class 4 without printingFeSO ₄ , K ₂ Cr ₂ O ₇ Level 4 with printing Alkali sweat Discolored stained cotton cloth Grade 4 to 5 without salt FeSO ₄ , CuSO ₄ , Al ₂ (SO ₄ ) ₃ , grade _{4 if} using K ₂ Cr ₂ O ₇ FeSO ₄ , grade 3 to 4 with K ₂ Cr ₂ O ₇ Color fastness When drying Grade 3 to 4 without mortality Grade 4 with no mortality Dry cleaning fastness Grade 4 without grade 4 Grade 5 without grade 4 Grade 4 without grade

* Cotton fabric

Example 1 The color fastness of FeSO ₄ · 7H ₂ O and CuSO ₄ · 5H ₂ O mordant dyeing fabrics in dyeing cloth showed a moderate level. In washing fastness, the fastness of washing to discoloration was low as 2nd grade, but the degree of washing fastness of contaminated cloth when using cotton cloth and woolen cloth showed excellent fastness to all 4-5 grades. The sweat fastness against acid and alkaline sweat showed excellent fastnesses in both unstained and unwashed dyed cloths, 4 to 5 grades. The friction fastness of all the test cloths showed the fastness of the 4-5 grade. In particular, the friction fastness of unstained dyed cloth was the highest in class 5. Dry cleaning fastness showed good fastnesses of 4 to 5 in all test cloths.

The fastness of daylight in the test cloth of Example 2 was relatively good fastness of FeSO ₄ · 7H ₂ O mordant dyed cloth 3 to 4 grade.

The wash fastness against fading in washing fastness was low, but the stain fastening of the contaminated cloth showed excellent fastness of all test cloths in the case of the attached white cloth and the woolen cloth, respectively. The sweat fastness showed excellent fastness in the case of acidic sweat with the grade of fading fading 4-5 grades. When the contaminated cotton cloth and the contaminated blanket were used, the sweat fastness was excellent with grades 4 to 5 when the mordant was used. In the case of alkali sweat, most of the test cloths had a grade of discoloration, which was good at level 4 or higher. When the contaminated cotton cloth and the contaminated blanket were used, the sweat fastness was excellent in most of the test cloths, grades 4-5. When wet, the fastness to friction was solid-free with grade 4, better than mordant dyed cloth, and when dry, the fastness to dry dye-free and CuSO ₄ · 5H ₂ O mordant dyed fabric was good at grades 3 to 4. Dry cleaning fastness was excellent in most test cloths 4 to 5 grade or more.

* Silk fabric

The fastness of daylight in the test cloth of Example 2 was relatively good in FeSO ₄ · 7H ₂ O and K ₂ Cr ₂ O ₇ mordant dyed cloth. The degree of discoloration in washing fastness was good in the SnCl ₂ .2H ₂ O mordant dyeing cloth 3 to 4 grade. Washing fastness when the contaminated cotton cloth and silk cloth were used, all of the test cloths showed excellent fastness to the fourth to fifth class. In case of acidic sweat, the discoloration of all the test cloths was good in grades 4 to 5, and the sweat fastness when using the contaminated cotton cloth was good in all the test cloths.

When the contaminated silk cloth was used, Fe ₂ SO ₄ · H ₇ O and K ₂ Cr ₂ O ₇ mordant dye cloths were excellent in the fourth grade. In the case of alkaline sweat, the fading sweat fastness was relatively good in all the test cloths above grade 4, and in the case of contaminated cotton cloth, the mordant dye cloth was relatively good in the fourth grade. In the case of contaminated silk cloth, mordant dye cloth was about 3 to 4 grades. The friction fastness at drying was 3 to 4 grades of unstained dyeing cloth and SnCl ₂ · 2H ₂ O showed 3rd grade. The friction fastness at the time of wetting was good in the non-stained dyeing cloth and SnCl ₂ .2H ₂ O mordant dyeing cloth of 4th grade.

The dry cleaning fastness against discoloration was shown to be good with no-dye dye and SnCl ₂ · 2H ₂ O dye-dyed cloth. It was favorable to grape grade 4 or more. The dry cleaning fastness by contaminated silk cloth showed that all test cloths were good at level 4.

4) Antibacterial

(1) antimicrobial activity against bacteria

① Antimicrobial activity in Mueller Hinton liquid medium (MH medium)

The test fabric was cut into 1 cm x 5 cm and placed in a test tube containing 1 ml of MH medium. However, in case of transplanting P. acnes , GAM liquid medium was used. The medium containing the test piece was autoclaved at 120 ° C for 20 minutes. After transplanting each bacteria into the test tube containing the test specimen once with platinum teeth, and incubated in the incubator at 37 ℃ for 24 to 48 hours and then visually observe the growth of the bacteria as follows: It is shown in Tables 7-8, respectively.

-: Bacteria do not grow at all

+: Germs grow at least

Antimicrobial Activity against Bacteria in Dyed Cotton Cloth Extraction solvent Mordant S. aureus B. subtilis S. epidermis P. acnes Undyed + + + + Example 1 (water) Unsalted + + + + FeSO ₄ - + - + CuSO ₄ - - - - Al ₂ (SO ₄ ) ₃ - - - + K ₂ Cr ₂ O ₇ - - - + SnCl ₂ - - - + Example 2 (ethanol) Unsalted - - - - FeSO ₄ - - - - CuSO ₄ - - - - Al ₂ (SO ₄ ) ₃ - - - - K ₂ Cr ₂ O ₇ - - - - SnCl ₂ - - - -

Antibacterial against Bacteria in Dyeing Canine Extraction solvent Mordant S. aureus B. subtilis S. epidermis P. acnes Undyed + + + + Example 1 (water) Unsalted + + + + FeSO ₄ + + + + CuSO ₄ - - - - Al ₂ (SO ₄ ) ₃ - + - - K ₂ Cr ₂ O ₇ - + - + SnCl ₂ - - - + Example 2 (ethanol) Unsalted - - - - FeSO ₄ - - - - CuSO ₄ - - - - Al ₂ (SO ₄ ) ₃ - - - - K ₂ Cr ₂ O ₇ - - - - SnCl ₂ - - - -

* Cotton fabric

Among the test cloths of Example 1, the unstained dyeing cloth had no inhibitory effect on all bacteria, and there was a difference between the mordants and the types of bacteria in the buried dyeing cloth.

In other words, S. aureus and S. epidermidis had no inhibitory effect on unstained dyeing cloth, but staining agent treated with mordant showed the inhibitory effect regardless of the type. P. acnes was found to be antimicrobial activity only in CuSO ₄ · 5H ₂ O mordant dyed cloth.

Example 2 In the test cloth stained with the extract, unbroken dye cloth had antimicrobial effects against Gram-positive bacteria such as S. aureus, B. subtilis, and S. epidermids and P. acnes . Antibacterial activity was recognized in Gram-positive bacteria and P. acnes in all dye samples treated with mordant.

* Silk fabric

In the test cloth of Example 1, no inhibitory effect was observed in all the bacteria in the unstained dyeing cloth, and in the stained dyeing cloth, there was a difference according to the type of mordant and bacteria.

S. aureus and S. epidermidis had inhibitory effects on CuSO ₄ · 5H ₂ O, K ₂ Cr ₂ O ₇ , SnCl ₂ · 2H ₂ O, and Al ₂ (SO ₄ ) ₃ mortars. For P. acnes , antimicrobial activity was recognized only in dyed fabrics treated with CuSO ₄ · 5H ₂ O, Al ₂ (SO ₄ ) ₃ .

In the test cloth of Example 2, there was an antimicrobial effect against S. aureus , B. subtilis , S. epidermidis and P. acens . The mordant dyes were mordant and bacteria different.

That is, in Example 2 dyeing cloth treated with CuSO ₄ · 5H ₂ O, SnCl ₂ · 2H ₂ O, Al ₂ (SO ₄ ) ₃ , the antibacterial activity was recognized for all bacteria.

② Determination of antimicrobial activity in Mueller Hinton agar

The test specimens were cut into 1 cm x 2.5 cm size, and S. aureus , B. subtilis , and S. epidermidis were attached on MH flat media, and P. acnes on GAM agar flat media.

Sterile platinum was used to transfer the bacteria to the intermediate region of the test piece once.

-: Bacteria did not grow at all

+: Less than 30% of bacterial growth inside the test cloth

++: 30-90% or more bacterial growth inside the test cell

+++: Bacterial growth is recognized above 90% of test cells or outside of test cells.

The results were repeated until the same result was repeated twice, and the statistical method used the X ² test (two-by-two table). The results are shown in Tables 9 to 10, respectively.

Antimicrobial Activity of Bacteria on Cotton Fabrics Extraction solvent Mordant S. aureus * B.subtilis ** S. epidermidis P. acnes Undyed ++ +++ + + Example 1 (water) Unsalted ++ ++ + ++ FeSO ₄ + +++ - + CuSO ₄ + +++ - - Al ₂ (SO ₄ ) ₃ + ++ - - K ₂ Cr ₂ O ₇ + ++ - - SnCl ₂ ++ ++ + - Example 2 (ethanol) Unsalted - - - - FeSO ₄ - - + - CuSO ₄ - - - - Al ₂ (SO ₄ ) ₃ + - - - K ₂ Cr ₂ O ₇ - - - - SnCl ₂ - - - -

Antimicrobial Activity of Silk Fabrics Extraction solvent Mordant S. aureus ** B. subtilis ** S .epidermidis * P. acnes Undyed +++ +++ +++ + Example 1 (water) Unsalted ++ +++ + - FeSO ₄ ++ +++ + - CuSO ₄ ++ +++ + - Al ₂ (SO ₄ ) ₃ + +++ + + K ₂ Cr ₂ O ₇ + +++ ++ + SnCl ₂ ++ +++ + - Example 2 (ethanol) Unsalted - - - - FeSO ₄ - - + - CuSO ₄ - - - - Al ₂ (SO ₄ ) ₃ - - - - K ₂ Cr ₂ O ₇ + + + - SnCl ₂ - - - -

* P <0.05 ** P <0.005

* Cotton fabric

In S. epidermidis in Example 1 staining, no bacterial growth was observed in FeSO ₄ H ₂ O, CuSO ₄ H ₂ O, K ₂ Cr ₂ O ₇ , and Al ₂ (SO ₄ ) ₃ mortar. P. acnes showed no inhibitory effect, and no bacterial growth was observed in P. acnes in CuSO ₄ · H ₂ O, K ₂ Cr ₂ O ₇ , Al ₂ (SO ₄ ) ₃ , and SnCl ₂ · H ₂ O mortars. There was a great inhibitory effect.

Example 2 The dyeing fabric of S. aureus, B. subtilis, and gram-positive for P. acnes, such as S. epidermidis non-mordant dye ethanol Po _{CuSO 4 · H 2 O, K} 2 Cr 2 O 7, SnCl 2 · In H ₂ O mordant dye cloth, the growth of bacteria was not recognized at all, indicating a very high inhibitory effect.

The results of Table 9 are collectively shown in FIGS. 3 to 6. Figure 3 is a S. aureus , FIG. 4 is B. subtilis , FIG. 5 is S. epidermidis , FIG. 6 is the result of P. acnes , and in FIGS. 3 to 6, □ is Example 1 (water extract), and ■ is Example 2 (ethanol Extract), Fe represents FeSO ₄ , Cu represents CuSO ₄ , Al represents Al ₂ (SO ₄ ) ₃ , K represents K ₂ Cr ₂ O ₇ , Sn represents SnCl ₂ .

In addition, photos showing the growth of bacteria are shown in FIGS. 17 to 20 ( B. subtilis ) and 21 to 24 ( P. acnes ), respectively. 17 to 24, R is colorless, E is Example 2 (ethanol extract), W is Example 1 (water extract), N is no salt, Fe is FeSO ₄ , Cu is CuSO ₄ , Al is Al ₂ (SO ₄ ) ₃ , K represents K ₂ Cr ₂ O ₇ , and Sn represents SnCl ₂ .

In Example 1 and Example 2, both of the antimicrobial properties were recognized, but the antimicrobial activity of Example 2 was better than that of Example 1. That is, looking at the results shown in Tables 9 to 10, and FIGS. 3 to 6 and 17 to 24, the staining fabric of Example 2 and the staining fabric of Example 1 were significantly different in antimicrobial activity against S. aureus and B. subtilis . It was recognized ( S. aureus : P = 0.006, B. subtilis : P = 0.002), the antibacterial effect of the dyeing cloth Example 2 tended to be greater when the same mordant treatment.

P. acnes was the antimicrobial effect only when treated with mordant in the case of the dyeing of Example 1, the dyeing of Example 2 was excellent in antimicrobial effect because the bacteria do not grow in all the dyeing.

Antimicrobial activity according to mordant was improved for S. aureus , S. epidermidis and P. acnes in the dyeing cloth of Example 1. In the dyeing cloth of Example 2, there was little increase in the inhibitory effect due to the mordant treatment, indicating that no use of mordant was necessary.

* Silk fabric

The results of Table 10 are summarized and shown in FIGS. 7 to 10. 7 is a S. aureus , FIG. 8 is B. subtilis , FIG. 9 is S. epidermidis , FIG. 10 is the result of P. acnes , and in FIGS. 7 to 10, □ is Example 1 (water extract), and ■ is Example 2 (ethanol Extract), Fe represents FeSO ₄ , Cu represents CuSO ₄ , Al represents Al ₂ (SO ₄ ) ₃ , K represents K ₂ Cr ₂ O ₇ , Sn represents SnCl ₂ .

In addition, photos showing the growth of bacteria are shown in Figures 25 to 28 ( S. epidermidis ), respectively. 25 to 28, R is unstained, E is Example 2 (ethanol extract), W is Example 1 (water extract), N is no salt, Fe is FeSO ₄ , Cu is CuSO ₄ , Al is Al ₂ (SO ₄ ) ₃ , K represents K ₂ Cr ₂ O ₇ , and Sn represents SnCl ₂ .

In other words, in Example 1 dye-free dye-free dyeing was S. aureus , S. epidermidis , P. acnes was inhibitory effect. In mordant dyes, there were differences between bacteria and mordants, but they had antimicrobial effects against S. aureus , S. epidermidis and P. acnes . In particular, P. acnes showed inhibitory effect because no growth of bacteria was observed in FeSO ₄ · H ₂ O, CuSO ₄ · H ₂ O, SnCl ₂ · H ₂ O mordant dyeings.

In Example 2, the antibacterial effect was excellent for all bacteria when treated with mordant and unsalted dyeing. In particular, the use of mordant did not necessarily require the use of mordant, even though it did not use mordant.

In Example 1 and Example 2, the antibacterial effect was recognized, but the antimicrobial effect of Example 2 was found to be more excellent. That is, when Example 1 and Example 2 are compared, it is as follows.

For Gram-positive bacteria, Example 2 staining and Example 1 staining were significantly different in antimicrobial activity ( S. aureus : P = 0.004, B. subtilis : P = 0.001, S. epidermidis : P = 0.018). The antimicrobial effect of dyeing cloth showed a higher tendency than that of Example 1 dyeing cloth. In the case of P. acnes , there was a difference in the type of test cloth in Example 1 dyeing, and in Example 2 dyeing cloth, bacteria did not grow in all the dyeing cloths.

The antimicrobial activity of mordant treatment was improved for S. aureus in Example 1. However, in Example 2 dyeing cloth, it was shown that even without using mordant, the mortar is not necessary because the antibacterial effect is very good.

(2) antifungal activity against fungi

C. albicans and A. niger were incubated for 72 hours in Sabrod Dextrose Flat Medium, and T. mentagrophytes were incubated in Sabrod Dextrose Slope Medium for 100 hours, and then diluted in physiological saline. .

① Smearing of C. albicans & A. niger of dyed fabric

After attaching the specimen cut to 1 cm × 6 cm to the Sabrod dextrose plate medium, 3.5 × 10 ³ diluted fungi were transplanted into the upper two parts of the specimen one by one side by side, and 3.5 × 10 ⁴ diluted fungi were added to the lower specimen. Both sites were implanted in the same manner.

After incubation in a 30 ℃ incubator 24 and 48 hours after the growth of each was measured and the results are shown in Tables 11 and 12, respectively, and after 48 hours to summarize the results of Figure 11 (C. albicans) and Figure 12 (A. niger) , respectively.

② T. Mentagrophytes smear of dyed fabric

4.2 × 10 ⁵ diluted fungi and 4.2 × 10 ⁶ diluted fungi were plated in the same manner as C. albicans and A. niger . After incubation in a 30 ℃ incubator, the growth of fungi after 48 hours and 72 hours was measured and the results are shown in Tables 11 and 12, respectively, and the results after 72 hours are summarized in FIG. In addition, the growth of fungi after 72 hours was shown in Figs. 29 to 32 (cotton fabric) and 33 to 36 (cotton fabric), respectively.

C. albicans

-: No spore growth was recognized at the site of inoculation

+: Spores with a density of 20% or less are formed in 1 cm width around the inoculation.

++: Spores of 20-50% density are formed in 1 cm width around the inoculation.

+++: Spores of 50-70% density are formed in 1 cm width around the inoculation.

++++: 70-90% density spores are formed in 1cm width around the inoculation

+++++: Spores of more than 90% density are formed within 1 cm width around the inoculation.

A. niger

-: No spore growth was recognized at the site of inoculation

+: Spreading the growth of spores less than 0.3 cm in diameter at the site of inoculation

++: Spreading of spores with a diameter of 0.5 cm ± 0.2 cm at the site of inoculation

+++: Spreading of spores with a diameter of 1.0 cm ± 0.2 cm at the site of inoculation

++++: Spreading of spores with a diameter of 1.5 cm ± 0.2 cm at the site of inoculation

+++++: Spore growth of 1.8 cm or more in the inoculation site.

T. Mentagrophytes

-: No spore growth was recognized at the site of inoculation

+: Spreading the growth of spores less than 0.2 cm in diameter at the site of inoculation

++: Spreading of spores with a diameter of 0.3cm ± 0.1cm at the site of inoculation

+++: Spreading the growth of spores with a diameter of 0.6cm ± 0.1cm at the inoculation site

++++: Spread of spores with a diameter of 0.8cm ± 0.1cm at the site of inoculation

+++++: Spreading the growth of spores of 1 cm or more in diameter at the site of inoculation

The results were repeated until the same result was repeated twice, and the statistical method used X ² test (two-by-two table).

Antifungal properties of cotton fabrics against fungi menstruum Mordant C. albicans A. niger T. metagrophytes 24 hours 48 hours 24 hours 48 hours 24 hours 48 hours Undyed ++ ++++ ++ ++++ + +++ Example 1 (water) Unsalted +++ ++++ - +++ - ++ FeSO ₄ ++ ++++ - +++ + ++ CuSO ₄ ++ ++++ - ++ + ++ Al ₂ (SO ₄ ) ₃ ++ ++++ - +++ + ++ K ₂ Cr ₂ O ₇ ++ ++++ - +++ + ++ SnCl ₂ + +++ - +++ + ++ Example 2 (ethanol) Unsalted ++ +++ - +++ - + FeSO ₄ ++ ++++ + +++ + + CuSO ₄ ++ ++++ + +++ + ++ Al ₂ (SO ₄ ) ₃ ++ ++++ + ++++ - + K ₂ Cr ₂ O ₇ ++ +++ - +++ ++ ++ SnCl ₂ + ++ - +++ - -

* P <0.05 ** P <0.005

Number of fungi: C. albicans & A. niger -3.5 x 10 ⁴ pcs

: T. mentagrophys -4.2 x 10 ⁶ pcs

C. albicans

The degree of fungus growth after 24 hours

The antimicrobial properties of the mordant treatment showed that the staining treatment of Example 1 and the staining fabric of Example 2 had the strongest inhibitory effect in the treatment of SnCl ₂ · H ₂ O staining.

That is, spores of about ++ were observed around the inoculation of the test cloth which was not dyed, but the staining fabric of Example 1 had an inhibitory effect of + in the fabric treated with SnCl ₂ · H ₂ O.

Example 2 Dyeing Stain In the stained cloth treated with SnCl ₂ · H ₂ O mortar, the degree of + spores was formed, and there was an inhibitory effect.

Fungal growth after 48 hours

The antimicrobial effect of mordant treatment in Example 1 dyeing cloth or Example 2 dyeing cloth was strong in the inhibitory effect in the SnCl ₂ · H ₂ O mordant dyeing cloth was improved antibacterial effect during mordant treatment.

That is, the test cloth was not stained ++++, but in Example 1 dyeing cloth, only the stained cloth treated with SnCl ₂ · H ₂ O was +++ to inhibit the fungus.

In the fabric dyed by the method of Example 2, the diffusion sites of the spores from the inoculation site were generally similar, but the formation density of the spores was different according to the test cloth.

Stained cloth with SnCl ₂ · H ₂ O mordant was similar in spore spreading rate compared to the test unstained with ++, but only 50% or less spores were formed within 1cm width. It became. The unstained dyeing and K ₂ Cr ₂ O ₇ mordant dyeing + + was inhibited by fungi.

A. niger

The degree of fungus growth after 24 hours

Example 1 No fungal growth was observed in all test cells, so the fungal inhibitory effect was very high up to 24 hours. In Example 2 test samples, all test cells had an inhibitory effect, but no salt-free test cloth, K ₂ Cr ₂ O ₇ , SnCl ₂ · In the dyeing cloth treated with H ₂ O mortar, no fungi were grown, and the inhibitory effect was great. In Example 1, both the dyeing cloth and Example 2 do not have a difference in antimicrobial effect even without using a mordant, it was found that the use of mordant is not necessary.

Fungal growth after 48 hours

Example 1 In the case of dyeing cloth, the inhibition effect was most improved when CuSO ₄ · H ₂ O.

Example 2 It was shown that the use of a mordant does not need to be used since the dyeing cloth does not have a difference in antimicrobial effect even without using a mordant.

In other words, the unstained test cloth was ++++, but the dyeing cloth of Example 1 was mostly +++ and had a slight inhibitory effect, and the CuSO ₄ · H ₂ O mordant Example 1 dyeing cloth had the greatest inhibitory effect to ++. .

Example 2 Dyeing cloth Al ₂ (SO ₄ ) ₃ Most of the test cloth was + +, a slight inhibitory effect.

T. mentagrophys

Fungal growth after 48 hours

In other words, the test cloth that was not dyed at 4.2 X 10 ⁶ was +. In Example 1, only dye-free dye was inhibited by-. In ethanol extract dyeing, dye-free dye and SnCl ₂ · H ₂ O, Al There was an inhibitory effect of-in ₂ (SO ₄ ) ₃ mortar.

The treatment of mortar showed little difference between the antibacterial effect on T. metagrophytes and the absence of mortar treatment.

Extent of fungus growth after 72 hours

The unstained test cloth was formed with spores of 0.6 cm in diameter around the inoculation with +++, but in the dyeing cloth of Example 1, all the dye cloths had a slight inhibitory effect with ++.

Among the dyeing cloths of Example 2, the unstained dyeing cloth, Al ₂ (SO ₄ ) ₃ and FeSO ₄ · H ₂ O dyeing dyeing cloth was formed with fine spores at the inoculation site of + by 0.1 cm.

In the stained cloth treated with SnCl ₂ · H ₂ O, the growth of fungi was 100% inhibited and the antibacterial effect was great. In K ₂ Cr ₂ O ₇ mordant dyed fabric was found to inhibit the fungus with ++. The antimicrobial effect of the mordant treatment at the time of dyeing was ineffective in the case of Example 1 dyeing cloth, and in ethanol dyeing cloth, it was improved in the treatment of SnCl ₂ · H ₂ O.

In the case of 4.2 X 10 ⁶ , the significant difference in the antimicrobial effect of Example 2 staining cloth and Example 1 dyeing cloth was recognized (P = 0.02). That is, the antimicrobial effect in the dyeing cloth of Example 2 was much greater than that of the dyeing cloth of Example 1.

Antifungal Activity of Silk Fabrics against Fungi menstruum Mordant C. albicans A. niger T. metagrophytes 24 hours 48 hours 24 hours 48 hours 24 hours 48 hours Undyed +++ +++++ ++ +++++ +++ +++++ Example 1 (water) Unsalted +++ +++++ + ++++ +++ ++++ FeSO ₄ ++ +++ + ++++ ++ +++ CuSO ₄ +++ +++ - ++++ +++ +++++ Al ₂ (SO ₄ ) ₃ ++ ++++ ++ +++++ ++ +++ K ₂ Cr ₂ O ₇ ++ +++ - +++ +++ ++++++ SnCl ₂ ++ +++ - +++ +++ ++++ Example 2 (ethanol) Unsalted ++ +++ + +++ - + FeSO ₄ ++ +++ + ++++ - - CuSO ₄ +++ +++ ++ ++++ - + Al ₂ (SO ₄ ) ₃ ++ +++ ++ +++++ - - K ₂ Cr ₂ O ₇ ++ ++ + +++ + +++ SnCl ₂ ++ ++ - ++ - -

* P <0.05 ** P <0.05

C. albicans

-: No spore growth was recognized at the site of inoculation

+: Spores with a density of 20% or less are formed in 1 cm width around the inoculation

++: Spores of 20-50% density are formed in 1 cm width around the inoculation.

+++: 50 ~ 70% density spores are formed within 1cm width around the inoculation

++++: 70-90% density spores formed in 1 cm width around inoculation

+++++: Spores of more than 90% density are formed in 1 cm width around the inoculation

A. niger

-: No spore growth was recognized at the site of inoculation

+: Spreading the growth of spores less than 0.3 cm in diameter at the site of inoculation

++: 0.5 cm × 0.2 cm in diameter at the site of inoculation

Spread

+++: Spreading of spores with a diameter of 1.0 cm × 0.2 cm at the site of inoculation

++++: Spreading of spores with a diameter of 1.5 cm × 0.2 cm at the site of inoculation

+++++: Spore growth of 1.8 cm or more in the inoculation site.

T. Mentagrophytes

-: No spore growth was recognized at the site of inoculation

+: Spreading the growth of spores with a diameter of 0.2 or less at the site of inoculation

++: Spreading of spores with a diameter of 0.3cm × 0.1cm at the site of inoculation

+++: Spreading the growth of spores with a diameter of 0.6cm × 0.1cm at the inoculation site

++++: Spread of spores with a diameter of 0.8cm × 0.1cm at the site of inoculation

+++++: Spreading the growth of spores of 1 cm or more in diameter at the site of inoculation

C. albicans

The degree of fungus growth after 24 hours

In the unstained test cloth, +++, but in Example 1 stained cloth FeSO ₄ · H ₂ O, K ₂ Cr ₂ O ₇ , Al ₂ (SO4) ₃ , SnCl ₂ · H ₂ O mordant dyed cloth suppressed with ++ In Example 2, the dye-free, FeSO ₄ · H ₂ O, K ₂ Cr ₂ O ₇ , Al ₂ (SO 4) ₃ , SnCl ₂ · H ₂ O mordant dyeing was inhibited by ++.

Fungal growth after 48 hours

In the unstained test cloth was +++++, but Example 1 was dyed fabric FeFe ₄ · H ₂ O, K ₂ Cr ₂ O ₇ , SnCl ₂ · H ₂ O, CuSO ₄ · H ₂ O +++ had an inhibitory effect.

Example 2 In the dyeing cloth, the spreading areas of the spores were generally similar from the inoculation site, but the formation density of the spores was different according to the type of test cloth. Unstained test cloth was +++++ to form spores of more than 90% density within 1 cm width around the inoculation, whereas SnCl ₂ · H ₂ O-embedded dyeing cloth and K ₂ Cr ₂ O _7- embedded dyeing cloth were ++. The degree of spore diffusion was similar, but the spore density was less than 50%. The unstained dyeing, FeSO ₄ · H ₂ O, Al ₂ (SO ₄ ) ₃ , CuSO ₄ · H ₂ O unwashed dyeing was +++ to inhibit the fungus.

A. niger

The degree of fungus growth after 24 hours

Example 1 In the dyed fabric was unstained test ++ but unbroken and FeSO ₄ · H ₂ O mordant dyed fabric +, K ₂ Cr ₂ O ₇ , SnCl ₂ · H ₂ O, CuSO ₄ · H ₂ O Dyeing was found to be inhibitory effect with-. Example 2 Dyed fabric in the SnCl ₂ · H ₂ O mordant treatment dyed fabric in was fungi did not grow non-mordant siheompo and _{FeSO 4 · H 2 O, K} 2 Cr 2 O 7 mordant inoculated with the dyed fabric treatment + Only spores with a diameter of 0.3 cm or less were observed at the site, and the inhibitory effect was recognized.

Fungal growth after 48 hours

The unstained test specimens were +++++ at 3.5 X 10 ^4, but in Example 1 staining samples, all samples except Al ₂ (SO ₄ ) ₃ mordant dyes had inhibitory effect and K ₂ Cr ₂ O ₇ , SnCl _{In the 2} · H ₂ O mordant dye cloth, the inhibitory effect was large as +++. Example 2 In the dyeing cloth, all the test cloths except Al ₂ (SO ₄ ) ₃ dyeing cloth had the inhibitory effect, and especially the SnCl ₂ · H ₂ O dyeing cloth was the largest inhibitory effect to ++.

T. mentagrophys

Fungal growth after 48 hours

Antimicrobial activity according to mordant was improved in FeSO ₄ · H ₂ O and Al ₂ (SO ₄ ) ₃ mortar treatment in Example 1 dyeing cloth, and Example 2 dyeing cloth is superior to mordant dyeing cloth without the mordant treatment As a result, it was found that mordant treatment was not necessary. That is, in Example 2 dyeing cloth, no spores are formed in the unstained dyeing cloth, FeSO ₄ · H ₂ O and Al ₂ (SO ₄ ) ₃ , SnCl ₂ · H ₂ O, CuSO ₄ · H ₂ O dyeing dye cloth The antibacterial effect was very large.

The antimicrobial effect of Example 2 staining cloth and Example 1 dyeing cloth was statistically significant difference (P = 0.002).

Extent of fungus growth after 72 hours

The unstained test cloth was highly promoted to +++++, but in Example 1 dyeing cloth, there was an inhibitory effect on ++++ in unsalted dyeing cloth and SnCl ₂ · H ₂ O mordant dyeing cloth and Al ₂ (SO ₄ ) ₃ and FeSO ₄ · H ₂ O mordant dyed fabric was great inhibitory effect as +++.

Example 2 In the dyeing cloth, the inhibitory effect was large in all the test cloths. In particular, FeSO ₄ · H ₂ O, Al ₂ (SO ₄ ) ₃ , SnCl ₂ · H ₂ O mordant dyeing was found to have a very high inhibitory effect because no spores formed.

In the case of 4.2 X 10 ^{6, in the} dyeing cloth of Example 1, there was a dyeing cloth having an inhibitory effect depending on the type of mordant, but the inhibitory effect of the dyeing cloth was higher in Example 2. (P = 0.006).

As described above, the antimicrobial natural dyes of the present invention are yellow dyes with various color applications depending on the type of mordant and the extraction solvent. Since it is possible to mass production and practicality, it is possible to prevent various skin diseases of skin because it has excellent antibacterial effect to fungi, fungi such as fungus such as athlete's foot, as well as skin bacteria and cadmium, which cause various inflammations.

In addition, the dyeing fastness, sweat fastness, dry cleaning fastness, stain cleaning fastness, etc. are excellent without any fixing agent when dyeing. Daylight fastness and fading wash fastness are also good by using mordant, so it can be applied to clothing products and bedding.

Claims (4)

Antimicrobial natural dyes comprising Gosam extract. Extracting ginseng with water or an organic solvent to obtain a ginseng extract having a dry weight of at least 0.1 g / ml; Adding the red ginseng extract to water corresponding to 20 times the fiber weight to prepare a dyeing bath having a pH of 3 to 6 having a concentration of red ginseng extract of 40% o.w.f or more; Put the fiber in the dyeing bath to dye for 30 to 90 minutes at 50 to 70 ℃ A method of dyeing fibers using an antimicrobial natural dye comprising a step. The dyeing method according to claim 2, further comprising a step of treating the obtained fiber with a mordant after the dyeing step. According to claim 3, wherein the mordant is selected from the group consisting of FeSO ₄ · 7H ₂ O, CuSO ₄ · 5H ₂ O, K ₂ Cr ₂ O ₇ , SnCl ₂ · 2H ₂ O and Al ₂ (SO ₄ ) ₃ Dyeing method.