JP2810287B2 - Method for producing natural dye and dyeing method using this natural dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a natural blue dye, violacein, and a dyeing method using the dye.

[0002]

2. Description of the Related Art Bioracein, a natural pigment that becomes a blue dye, is contained in the cells of microorganisms belonging to the genus Chromo-bacterium or the genus Janthinobacterium. This dye has a maximum absorption wavelength of 579 nm and a minimum absorption wavelength of 430 nm when dissolved in ethanol, and has a maximum absorption at 700 nm when dissolved in a sulfuric acid / ethanol mixed solution in which the mixing ratio of sulfuric acid to ethanol is 10% by volume. It has the characteristic of showing a green color tone having a wavelength.

As a method for producing this dye, there is known a method in which tryptophan or peptone in which tryptophan is not decomposed is added to a medium and cultured. However, in this method, since expensive reagents such as tryptophan or peptone are used in the culture medium, the production cost of the pigment is naturally high, and even if these media are used, the extraction of the pigment is not easy, and Production volume is also low. For this reason, a more inexpensive and more efficient method has been desired for industrial use. To solve this,
By adding polyurethane foam or cellulose as an adsorption carrier to a medium for culturing microorganisms belonging to the genus Yantinobacterium, by adsorbing the produced dye on the carrier,
A method for producing this type of dye has been disclosed (JP-A-2-39892). According to this method, the dye can be effectively extracted from the adsorbed carrier, and industrial production becomes possible.

[0004]

In this method, the dye is adsorbed on the polyurethane foam or the carrier of the cellulose liquid, and the dye does not appear on the medium itself. Therefore, when dyeing textiles using this dye as a dye, it is necessary to always extract the dye from the adsorption carrier to obtain a powdery dye, and the culture solution itself cannot be used as a dye solution. On the other hand, at present, only a small number of dyes are used as blue-based natural dyes.For example, those derived from indigo, communis, and walnuts are known, but dyes other than indigo are not available because they are not produced in large quantities. Difficult and indigo dyeable conditions are strong alkali,
The range of usable fiber materials was limited. From such a viewpoint, development of an excellent natural blue dye that can be stably supplied has been desired.

An object of the present invention is to provide a method for producing natural dyes which can easily extract bioracene, yield a large amount thereof, can be produced industrially stably, and can be dyed on a wide range of fiber materials. . Another object of the present invention is to provide a dyeing method using a natural dye, which dyes textiles without polluting the environment.

[0006]

According to the method for producing a natural dye of the present invention, a liquid medium is inoculated with a microorganism belonging to the genus Chromobacterium and / or the microorganism belonging to the genus Yantinobacterium. A method of extracting a natural dye consisting of bioracein from one or both of the cells and the liquid medium, by culturing and growing the above microorganisms, separating the culture solution in which the microorganisms proliferated into cells and a liquid medium. . The characteristic configuration is to add animal hair degradation products to a liquid medium inoculated with the microorganism.

In a first dyeing method using the natural dye of the present invention, the microorganism is cultivated and grown in the liquid medium, and a textile is immersed in a culture solution in which the microorganism has grown.
In this method, the temperature of the culture solution is raised to dye the immersed fiber products. The characteristic configuration is to add animal hair degradation products to a liquid medium inoculated with the microorganism. Further, in the second dyeing method using the natural dye of the present invention, a solution (for example, an alcohol solution, an aqueous solution, or the like) of a natural dye composed of bioracein is prepared, and then the solution is dissolved in water. This is a method of dyeing a textile product by immersion, raising the temperature of the aqueous solution, and immersing the textile.

Hereinafter, the present invention will be described in detail. Microorganisms applicable to the present invention belong to either the genus Chromobacterium or the genus Yantinobacterium, produce bioracein, and are strains that excrete bioracein out of the cells by adding animal hair degradation products. Well, not particularly limited. Representative examples of this microorganism include Chromobacterium violaceum ATCC 12472 and Janthinobacterium lividam.
dum ) strains such as ATCC 12473. Further, as a liquid medium for producing the bioracein of the present invention,
It is not particularly limited as long as it is obtained by adding animal hair degradation products to a medium in which bioracein bacteria grow. But,
As a carbon source to this medium, it is better to add an auxiliary carbon source in addition to animal hair degradation products, rather than adding animal hair degradation products alone,
It is preferable because the productivity of bioracein is improved. The auxiliary carbon source is not particularly limited as long as it can utilize these bacteria, and saccharides such as glucose are preferable. However, if animal hair degradation products are not added with only the auxiliary carbon source, little pigment is produced,
Its production is very low.

[0009] If necessary, the medium may be supplemented with inorganic salts such as ammonium salt, magnesium salt, potassium salt or calcium salt.
The pH of the medium is adjusted to 5 to 9, preferably 6.5 to 8 in consideration of the growth of the microorganism. The culture temperature is 25 to 35 ° C. when a strain belonging to the genus Chromobacterium is used.
However, when a strain belonging to the genus Yantinobacterium is used, the temperature is preferably from 20 to 30 ° C. As the animal hair source of the animal hair degradation product of the present invention, wool is easily available and suitable,
There is no particular limitation as long as keratin proteins such as angora, cashmere, mohair or chicken wings can be extracted. As a method of obtaining this animal hair degradation product,
A method of purchasing a commercially available hydrolyzed keratin solution and a conventional method (P. Alexander, et al ., Wool, p. 35)
6, Reinhold, New York, 1954). In the case of preparing according to a conventional method, animal hair hydrolyzed with an oxidizing agent such as formic acid, peracetic acid, or hydrogen peroxide is dissolved in 0.3 N aqueous ammonia, and the solution is adjusted to pH 4 or less, and then the pH is adjusted. The solution obtained is filtered or centrifuged. The animal hair degradation product obtained by this method contains a water-soluble portion and a water-insoluble portion, and the dried product is an animal hair degradation product.

The fiber product dyed with the natural dye of the present invention may be a natural fiber, a chemical fiber or a blend of these fibers as long as it is dyed with bioracein. For example, this textile is made of animal hair, hemp, cotton,
Fibers such as silk, vinylon, acrylic, nylon, acetate and rayon; yarns made from these fibers; and fabrics such as woven, knitted and non-woven fabrics. The fabric is a blended fabric,
Includes blended knitted fabrics, mixed nonwoven fabrics, and interwoven or interwoven fabrics.
The first staining method of the present invention comprises, after culturing and growing the above microorganism in a liquid medium to which animal hair degradation products have been added, adding a fiber product to a culture solution in which bioracein is excreted outside the cells by the growth of the microorganism. Is a dip dyeing method in which the temperature of the culture solution is raised to dye the immersed fiber product.

In a second dyeing method of the present invention, a solution (for example, an alcohol solution or an aqueous solution) of a natural dye composed of bioracein is prepared, and the solution is dissolved in water.
In this method, a textile is immersed in the aqueous solution, and the aqueous solution is heated to dye the immersed textile. Here, the alcohol solution may be a solution obtained by concentrating the alcohol solution obtained when bioracein is extracted, or a solution obtained by dissolving a fine bioracein powder obtained by drying the concentrated alcohol solution in alcohol.

In both the first dyeing method and the second dyeing method, a normal dyeing method can be used in which the temperature is raised gradually, for example, and the mixture is boiled for a predetermined time. However, bioracein decomposes gradually under strong acidic and strong alkaline conditions,
The pH of the dyeing liquor is adjusted in the range from weakly acidic to weakly alkaline, preferably around neutrality.

[0013]

When a microorganism belonging to either the genus Chromobacterium or the genus Yantinobacterium is cultured in a liquid medium to which animal hair degradation products have been added, bioracein is excreted outside the cells. The mechanism of excretion of bioracein by the animal hair degradation product out of the cells has not been completely elucidated, but is presumed as follows. That is, animal hair degradation products are used not only as carbon sources and nitrogen sources for microorganisms such as chromobacterium or Yantinobacterium, but also into water-soluble animal hair degradation products using enzymes of microorganisms in the process of use. Decomposed. Since bioracein is easily adsorbed to this water-soluble animal hair degradation product, bioracein is easily transferred from the cells of the culturing microorganism to the water-soluble animal hair degradation product and accumulated in the medium.

The extracellular medium, that is, bioracein discharged into the culture solution, is obtained by adding a solvent which is immiscible with the medium to the liquid medium, extracting the bioracein with a solvent, dehydrating the extract, and concentrating the extract. It is obtained in the form of fine powder by further drying. Bioracein retained in the cells is obtained in the form of a fine powder by drying the cells, immersing the dried product in alcohol to extract bioracein, and drying and solidifying the extract. When the fiber product is immersed in the above culture solution in which bioracene has not yet been extracted or in a solution obtained by dissolving an alcohol solution of bioracein or the like in water, and the temperature of the culture solution or aqueous solution is increased, the bioracein in the solution is converted into the fiber product. Dyes and dyes textiles blue.

[0015]

Next, embodiments of the present invention will be described in detail, but the embodiments described here are merely examples, and the present invention is not limited to these embodiments.

<Example 1> Chromobacterium violaceum ATCC 1247 belonging to the genus Chromobacterium
2 was used to produce a natural blue dye, bioracein. First, a loopful of Chromobacterium bioraceum was inoculated into a nutrient broth containing 3 g of Bacto-beef extract and 5 g of Bacto-peptone per liter of medium and uniformly mixed, and pre-cultured at 30 ° C. for 18 hours. did. Then, 1 g of dipotassium phosphate, 0.5 g of magnesium sulfate, 1 g of ammonium sulfate and 5 g of glucose
And 10 g of wool degradation product, uniformly mixed and adjusted to pH 7 to 1 liter of wool medium, and
The cells were inoculated and cultivated by rotary shaking at 30 ° C. and 120 rpm for 5 days.

The obtained culture solution was separated into bacterial cells and medium by centrifugation, and bioracein was extracted therefrom. That is, from the cells, the cells were dried and then immersed in ethanol to extract bioracein into ethanol. Ethanol was removed from the extract by an evaporator, and the retained matter was evaporated to dryness. The extract was extracted again with ethanol. The extract was filtered, concentrated and dried to obtain a black-purple fine powder pigment. From the medium, 2 parts by volume of ethylene acetate and 1 part by volume of ethanol were added to 9 parts by volume of the medium, and then the ethylene acetate-ethanol layer was separated. The solvent extract was dehydrated with anhydrous sodium sulfate, concentrated, and the retained product was dried to dryness, extracted again with ethanol, and the extract was filtered, concentrated and dried to obtain the same black-purple fine powder pigment. I got 0.5 g of the pigment was obtained from the cells, and 0.6 g of the pigment was obtained from the medium.

Example 2 Janthinobacterium lividum ATCC 12473 belonging to the genus Yantinobacterium
Produced a natural blue dye, Bioracein. First, 1% of wool degradation product was added to the same nutrient pros as in Example 1. One platinum loop of Yantinobacterium lividum was inoculated into this medium and precultured at 25 ° C. for 18 hours. Next, the same wool medium as in Example 1 was inoculated with 1% of this culture solution, and cultured with rotation and shaking at 25 ° C. and 120 rpm for 5 days.

For comparison, 1% of each of the above culture solutions was inoculated into a peptone medium (Comparative Example 1) and a glucose medium (Comparative Example 2) instead of the above-mentioned wool medium, and cultivated by rotary shaking under the same conditions as above. . Here, the peptone medium is medium 1
Per liter, 1 g of dipotassium phosphate, 0.5 g of magnesium sulfate, 1 g of ammonium sulfate, 5 g of glucose, and 10 g of peptone were added and uniformly mixed to adjust the pH to 7. In addition, glucose medium per liter of medium,
It was prepared by adding 1 g of dipotassium phosphate, 0.5 g of magnesium sulfate, 1 g of ammonium sulfate and 10 g of glucose and adjusting the pH to 7 by uniform mixing.

A pigment was extracted from the culture solution cultured in the wool medium, the culture solution cultured in the peptone medium, and the culture solution cultured in the glucose medium in the same manner as in Example 1. Table 1 shows the results. As is clear from Table 1, the amount of the pigment produced in the wool medium was about 7.5 times that of the peptone medium. In the glucose medium, the growth of the bacteria was observed, but no pigment was produced.

[0021]

[Table 1]

<Example 3> In the same manner as in Example 1, cotton yarn, nylon filament yarn, and the like were obtained by using a dark purple culture solution obtained by culturing Chromobacterium bioraceum ATCC12472 from which bioracene had not yet been extracted. A vinylon spun yarn, an acetate filament yarn, a worsted yarn, a rayon filament yarn, an acrylic spun yarn, a raw yarn, and a polyester spun yarn were dyed. That is, the nine kinds of yarns are immersed in the almost neutral culture solution without pH adjustment,
Occasionally, with stirring, the temperature was gradually raised over about 20 minutes, and the mixture was left in a boiling state for about 20 minutes. After the standing, the temperature was lowered to around 30 ° C., and the above nine kinds of yarns were taken out of the culture solution, washed with tap water, and subsequently washed with a 50 ° C. warm bath for 10 minutes. As a result, under these dyeing conditions, the yarns other than polyester spun yarn are dyed well, especially nylon filament yarn,
The vinylon spun yarn and raw yarn could be dyed in deep purple.

Example 4 In the same manner as in Example 1, a culture solution of Chromobacterium violaceum ATCC12472 was prepared, separated by centrifugation, and the cells were taken out.
After drying the cells, the cells were immersed in ethanol to extract bioracein into ethanol. After concentrating the ethanol solution, 1 part by volume of the concentrated solution was added to 9 parts by volume of water and uniformly mixed. A nylon cloth was immersed in the mixed solution, and the temperature was gradually raised over about 20 minutes with occasional stirring, and the mixture was left in a boiling state for about 20 minutes. Thereafter, a nylon cloth dyed purple was obtained in the same manner as in Example 3.

[0024]

As described above, according to the method for producing a natural dye of the present invention, an animal hair degradation product obtained at low cost from waste wool, waste wool, etc. can be used, and biolacein can be inexpensively and efficiently obtained. Can be produced. Thereby, natural dyes can be supplied industrially stably. In addition, the obtained pigment of bioracein can be dyed on a wide range of fiber materials, and the excellent purpleness of the pigment is extremely valuable as a natural blue-based dye which is rare.

According to the first dyeing method of the present invention, a solution obtained by culturing microorganisms in a medium to which animal hair decomposition products have been added is used as a dye liquor, so that dyeing is performed in the same bath as fermentation production of microorganisms. be able to. For this reason, the conventional steps of extracting and purifying the dye from the culture solution during staining can be omitted, and the time and cost required for the step can be saved.
Further, according to the second dyeing method of the present invention, a solution obtained by diluting an alcohol solution or the like containing bioracein at a high concentration with water is used as a dyeing solution, and by dyeing textiles with the dyeing solution, the biolacein can be satisfactorily liquored. It can be dispersed in the inside and dyed uniformly without impurities.

In particular, the dyeing method of the present invention is safe and environmentally friendly, and according to this method, a fiber dyed product having more stable quality can be obtained as compared with the conventional dyeing process using natural dyes.

Claims (6)

(57) [Claims] 1. A microorganism belonging to the genus Chromobacterium and / or a microorganism belonging to the genus Yantinobacterium is inoculated into a liquid medium, and the microorganism is cultured and grown in the liquid medium, and the microorganism is grown. A method for producing a natural dye comprising extracting a natural dye consisting of bioracein from one or both of the cells and the liquid medium, wherein the liquid culture medium is inoculated with the microorganism. A method for producing a natural dye, comprising adding an animal hair decomposition product. 2. The method for producing a natural dye according to claim 1, wherein auxiliary carbons are added to the liquid medium together with the animal hair decomposition product. 3. Inoculating a liquid medium with one or both of a microorganism belonging to the genus Chromobacterium and a microorganism belonging to the genus Yantinobacterium, culturing and growing the microorganism in the liquid medium, and growing the microorganism. A dyeing method using a natural dye for immersing a fiber product in a cultured medium, and heating the culture solution and dyeing the immersed fiber product, wherein an animal hair degradation product is added to a liquid medium inoculated with the microorganism. A dyeing method using a natural dye. 4. A natural dye for preparing a solution of a natural dye comprising bioracein, dissolving the solution in water, immersing the textile in the aqueous solution, and heating the aqueous solution to dye the immersed textile. Staining method using 5. A textile product dyed by the dyeing method according to claim 3. 6. A textile product dyed by the dyeing method according to claim 4.