JPH07109067B2 - Printing method with microorganisms and microorganisms for decolorizing azo dyes - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for printing with a microorganism and a microorganism for decolorizing an azo dye, more specifically, a substrate dyed with an azo dye or with an azo dye and a non-azo dye, or A base material having a pattern drawn with a paste solution containing at least a specific bacterium and an azo dye,
The present invention relates to a method for printing by treating with a specific bacterium, and a microorganism for decolorizing an azo dye that utilizes an azo dye. Here, "printing" means direct printing (printing a pattern on a white background or ground-dyed fabric), discharge printing [printing a pattern on the ground-dyed fabric (including white discharge printing, colored discharge printing, and semi-discharge printing)].
And anti-staining (those that inhibit dyeing and write patterns).

[0002]

2. Description of the Related Art "Discharge dyeing" is carried out by applying a reducing agent or a sizing solution containing an alkali in a desired pattern to a cloth which has been dyed in advance in a desired pattern and then heat-treating it to reduce the carboxylic acid ester of the disperse dye or the reduction reaction. "White discharge dyeing" that decolorizes by saponification reaction to give a blank pattern, so-called "colored discharge printing" where another color is dyed at the same time as decoloring, white discharge is stopped halfway and the pattern is slightly lighter than the ground color "Semi-discharge printing" is being done. The "direct printing" is a process in which a predetermined pattern is applied (printed or the like) on a base material using a predetermined color paste, then dried, steamed and washed to finish.

[0003]

However, in the above printing method (especially discharge printing method), since a reducing agent or an alkali is used for decolorization, the first plain dye (so-called ground dye) is a dye that is easily decolorized. It is necessary to select a dye, and there are restrictions such that the dye (color dye) to be printed at the time of bleaching is limited to a dye having resistance to reduction reaction and alkali. Further, there are drawbacks such as the fabric being damaged by the reducing agent and halation (bleeding at the color boundary portion) easily occurring.

The present invention overcomes the above-mentioned drawbacks. It has less restrictions on dyes, less pain on the base material, and less bleeding at the color boundary portion, so that it is possible to create fine and complex patterns, and it is vivid. For azo dye decolorization that enables color discharge printing with various colors, and can easily create fading patterns, and uses microbial dyes and azo dyes to utilize the above useful printing methods. The purpose is to provide microorganisms.

[0005]

[Means for Solving the Problems] The present inventors focused on decolorization of azo dyes by microorganisms, and conducted a search to find microorganisms that decolorize azo dyes from dye effluent and other samples (such as soil). As a result, strains belonging to the genus Xanthomonas
It was discovered that Xanthomonas NR25-2 decolorizes azo dyes, and the present invention has been completed.

The method for printing with a microorganism according to the first aspect of the present invention is a method in which an azo dye,
Non-azo dyes and cells of Xanthomonas spp.
Xanthomonas NR25-2 (Accession No.
No. 3119), a liquid or a paste containing at least the fungus body is applied in a desired shape, and then the fungus body is allowed to grow or act in a wet state so that all or part of the azo dye is It is characterized in that it is assimilated and printing is performed by eliminating or reducing the coloring by the azo dye.

The method for printing with a microorganism according to the second aspect of the present invention is a microbial dye belonging to the genus Xanthomonas belonging to the genus Xanthomonas on a composite dyeing substrate dyed with an azo dye and a non-azo dye. Body Xanthomonas NR25-2 (accession number: Microtechnology Research Institute No. 13119) is applied to a desired shape with a liquid or paste containing at least the fungus body, and then the fungus body is grown in a wet state. Alternatively, it is characterized in that all or part of the above azo dye is assimilated and the coloring by the azo dye is eliminated or reduced to perform printing.

The method for printing with a microorganism according to the third aspect of the present invention is an azo dye, a non-azo dye, and a fungus belonging to the genus Xanthomonas on a non-dyed substrate or a dyed substrate dyed with a non-azo dye. Cell of Xanthomonas NR25
-2 (contract number: Microtechnology Research Institute, No. 13119), a liquid or paste containing at least the azo dye and the fungus body is applied in a desired shape, and then the fungus body is moistened. Is allowed to grow or act to assimilate all or part of the azo dye, and the coloring by the azo dye is eliminated or reduced to perform printing. The method for printing with a microorganism according to the fourth aspect of the present invention is the method according to the first to third aspects, wherein the temperature at which the azo dye is assimilated is 30 to 4
This is a method at 2 ° C.

According to the method for printing with microorganisms of the fifth aspect of the present invention, a pattern heated to a temperature of 50 ° C. or higher is formed on a part of a desired shape formed by applying a liquid containing the above-mentioned bacterial cells or a paste solution. A method of performing at least one of a drawing step, a step of drawing a pattern with an alkaline liquid or sizing agent having a pH of 9 or more, or an acidic solution or sizing agent having a pH of 4 or less, or a step of drawing a pattern with a bactericide. There is so-called "resist prevention". That is, by drawing a pattern using a liquid or a paste that inhibits the growth of bacteria [inhibits assimilation (reaction)], it is possible to prevent decolorization of this part and maintain the coloring by the azo dye, thereby printing. Is to do.

In the above, heating above 50 ° C.
This is because the reaction activity of this bacterium is inhibited. This heating means is not particularly limited. Further, the type of each alkali component and acid component contained in the above-mentioned alkaline liquid or the like and acidic liquid or the like does not matter. As the above-mentioned bactericide (including a sterilizer), various known ones can be used, and examples thereof include reverse soap (trimethyldodecyl ammonium chloride) and heavy metal salts (Ag).
⁺ , Hg ²⁺ ), a 50 to 70% aqueous ethanol solution, a cresol solution, or 20% by weight or more high-concentration saline solution can be used. It should be noted that a predetermined temperature (50 ° C. or higher or lower) and pH (for example, 9 or higher, 4 or lower, or any other value), type of germicide and its concentration, and treatment time. The growth of microorganisms may be almost completely or incompletely selected by variously selecting the above. In the latter,
A blurred pattern (color difference pattern) can be used, and a combination of both patterns can be used to create a more complex and aesthetically pleasing pattern.

The azo dye decolorizing microorganism of the sixth invention is
It consists of Xanthomonas NR25-2 (accession number: Microtechnology Research Institute No. 13119) of a bacterial species belonging to the genus Xanthomonas that utilizes an azo dye to eliminate or reduce the coloring caused by the azo dye. Characterize. Book Seven
The azo dye decolorizing microorganism of the present invention can grow at 5 to 42 ° C.

The "azo dye decolorizing microorganism" of the present invention was isolated by the following method. Collection site Soil at Oizumi Towel Factory Date of collection May 12, 1990 The acclimatization treatment method for this microorganism is as follows. That is, 3 platinum loops of the sample were added to a test tube containing 2 ml of the accumulation medium, and the mixture was cultured at 30 ° C. with shaking, and the fading or decolorized test tube was subcultured at any time. And even after subculture twice, it is still decolorized,
From the fading test tube, pour into the agar medium for general bacteria shown below (adding 0.02% of dye), decolorize the dye pigment with flat plate agar, and isolate the bacteria from which "halo" has been eliminated (this, As shown below, "Xanthomonas NR2 of the genus Xanthomonas
5-2 strain ”. ). As this dye, the azo dye “Brilliant Red 2” manufactured by Sumitomo Chemical Co., Ltd.
B ”was used.

The composition of the above-mentioned accumulation medium is as follows. _{0.1% NaCl K 2 HPO 4 0.1} % MgSO 4 · 7H 2 O 0.05% FeSO 4 · 7H 2 O 0.001
% ZnSO ₄ · 7H ₂ O 0.000
_{1% CuSO 4 · 7H 2 O} 0.000
_{1% MnSO 4 · 7H 2 O} 0.000
1% (NH ₄ ) ₂ SO ₄ 0.5% Dye (“Brilliant Red 2B” above) 0.02% Distilled water is used as dilution water.

The above "Xanthomonas N of the genus Xanthomonas
"R25-2 strain" has been deposited at the Institute of Microbial Science and Technology of the Agency of Industrial Science and Technology, and the deposit number is Micromachine Research Institute No. 13119 (F
ERM P-13119). The scientific properties of this bacterium are as follows. The shape is 0.5 x 0.8 ~
It is a bacterium of 1.5 μm and has mobility. Gram stain is negative. It grows in air and does not grow in anaerobic conditions. Grow at a temperature of 5 ° C to 42 ° C. It grows well at 38 ° C. It grows at a pH of 5-7. Salt grows well below 5%.

The scientific properties and properties of the bacterium are shown below. Gram reaction-type bacteria size 0.5 × 0.8〜
1.5 μm Motility + Growth in air + Growth under anaerobic conditions − Catalase + Oxidase − OF test O Growth at 5 ° C. + Growth at 10 ° C. + Growth at 42 ° C. + Growth at 50 ° C. − Growth at 55 ° C. -Growth at pH 5 and 7 + Growth at 2% NaCl + Growth at 5% NaCl + Growth at MacConky medium + Production of pigment (King B) + Reduction of W nitrate-VP reaction-Production of indole-Production of H ₂ S- PNPG + Urea decomposition + Use of citrate + Use of W gluconate − Use of adipic acid − Use of malic acid + Use of capric acid − Use of phenylacetate − Hydrolysis of arginine dihydrase + starch − Casein Hydrolysis + Gelatin hydrolysis-Exulin hydrolysis + Carbonation : Acid glucose + mannitol - arabinose - xylose - sucrose - the production of mannose + maltose + gas (glucose) -

The present inventors have designated this strain as “Xanthomonas NR
25-2 ”. Azo dyes that are decomposed by this bacterium are usually used as a mixture of various isomers, but this bacterium can utilize all of them.

The above "base material" in the present invention may be any one that can be dyed with an azo dye or the like, and usually,
Although it is woven fabric (any kind of fiber material, weave, etc.) and the like, it is not limited to this, and may be non-woven fabric, paper, resin sheet, or the like.

The "azo dye" is a benzeneazo dye,
It can be applied to all of naphthalene azo dyes and heterocyclic azo dyes. In addition, this azo dye, regardless of the type of direct dye, acid dye, reactive dye, disperse dye, etc.
It can be applied to all azo dyes classified according to target materials and functional groups shown in.

[0019]

[Table 1]

In the present invention, a liquid containing a predetermined bacterium (whether or not a dye is contained is not necessary. When a dye is contained, it is a coloring liquid), a sizing agent containing a predetermined bacterium and a paste component (containing a dye). It does not matter whether it is present or not, and it may be in a liquid form, a paste form, etc. When it contains a dye, it becomes a color sizing agent. The method for applying it on a predetermined substrate is not particularly limited. A desired coating method such as a printing method, an inkjet method, a handwriting method, a roller printing method, or a screen printing method can be used. This sizing agent is usually used for direct printing, and as the sizing component contained therein, starches (wheat starch etc.), modified starch (British gum etc.), modified natural gum (locust bean gum etc.), alginic acid. Sodium, sodium carboxymethyl cellulose, synthetic paste (polyvinyl alcohol, polyvinyl acetate, etc.) and the like can be used.

[0021]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. (1) White discharge printing Example 1 To 200 ml of dry (normal) broth (manufactured by Nissui Pharmaceutical Co., Ltd.) was added 0.02% of an azo dye (“Brilliant Red 2B”, manufactured by Sumitomo Chemical Co., Ltd.), and a 500 ml Sakaguchi flask was added. Strain Xanthomonas NR25-2 was inoculated into
After culturing with shaking for a period of time, the culture solution is centrifuged, the bacterial cells are collected, washed with 0.1N phosphate buffer, and the bacterial cells (bacterial cell dispersion liquid) obtained by centrifugation are directly used as the bacterial solution for discharge. did. Azo direct dye "Kayarus Supra Red 6BL" with a concentration of 3% by weight
When a cloth made of 100% rayon taffeta was dyed by a conventional method using (manufactured by Nippon Kayaku Co., Ltd.), the cloth was dyed red. Place a rubber plate with a star-shaped pattern cut out on this red-dyed cloth, pour the bacterial solution for main discharge into the cut-out pattern, remove the rubber plate, and then moisten the cloth. Then, the product was placed in a constant temperature bath of 30 ° C. for 24 hours to perform white discharge printing. As a result, the azo dye dyeing the cloth was completely assimilated and a white star-shaped pattern was obtained on the red background. Further, there was no bleeding at the color boundary portion, and a clear pattern was shown.

Example 2 In this example, the material of the cloth used was nylon 1
Using 00% taffeta, as a dye for dyeing this fabric, a 3 wt% concentration azo acid dye "Kayanol Milling R
ed BW "(manufactured by Nippon Kayaku Co., Ltd.) (ground color;
(Red) A white discharge treatment was carried out in the same manner as in Example 1 except that a fungus solution-injecting rubber plate with a polka dot pattern cut out was used and the discharge treatment condition was 40 ° C. for 16 hours. As a result, a white polka dot pattern was obtained on the red background.
Also in this case, a clear pattern was shown. The above-mentioned azo acid dye "Kayanol Milling Red BW" is not used for normal discharge printing because it has poor dischargeability with a reducing agent. Therefore, according to this example, even if an azo-based acidic dye, which cannot normally be used for discharge printing, is used, discharge printing can be reliably performed.

Example 3 In this example, wool 10 was used as the material of the cloth used.
Using 0% muslin, as a dye for dyeing this cloth, a 1 wt% concentration azo acid dye "Kayanol Milling Y
"ellow 0" (manufactured by Nippon Kayaku Co., Ltd.) and 1 wt% concentration of azo acid dye "Kayanol Milling Red RS 125" (manufactured by Nippon Kayaku Co., Ltd.) (ground color; orange),
A white discharge treatment was carried out in the same manner as in Example 1 except that a rubber plate for injecting a bacterial solution was used in which a triangular pattern was cut out, and the discharge treatment conditions were 30 ° C. and 24 hours. As a result, two kinds of azo dyes that dye the cloth were simultaneously assimilated, and a white triangular pattern was obtained on the orange background.

(2) Color discharge printing Example 4 In this example, the material of the cloth used was 100% cotton.
Using broad, as a dye for dyeing this cloth,
Anthraquinone reactive dye "Mikasion B" with a concentration of 1% by weight
rilliant Blue RS "(manufactured by Nippon Kayaku Co., Ltd.) and 1% by weight concentration of azo reactive dye" Remazol Red B 150 "(manufactured by Mitsubishi Kasei Hoechst Co., Ltd.) were used (ground color: purple) as a dyeing cloth. A pattern was drawn with a brush using the discharge-use bacterium solution used in Example 1, and the discharge-treatment condition was 4
Color discharge treatment was carried out in the same manner as in Example 1 except that the temperature was 0 ° C. for 12 hours. As a result, the treated cotton cloth is
The azo dye that dyes the cloth is assimilated, and the non-azo dye that dyes the cloth remains without being assimilated, and the pattern drawn with the discharge bacteria solution on the purple background is blue (the above anthraquinone dye It was obtained as a dyed color by Further, there was no bleeding at the color boundary portion, and a clear pattern was shown.

Example 5 In this example, wool 10 was used as the material of the cloth used.
Using 0% muslin, as a dye for dyeing this cloth, a 1% by weight concentration of anthraquinone acid dye "Alizar
ine Rubinol 3G 115% "(manufactured by Yamada Chemical Co., Ltd.) and 1% by weight azo acid dye" Kayanol Navy Blue "
R "(manufactured by Nippon Kayaku Co., Ltd.) (ground color: purple), a polka dot pattern cut out, a rubber plate for injecting the bacterial solution was used, and the discharge treatment condition was 40 ° C. for 12 hours. Color discharge printing was performed in the same manner as in Example 1 except for the above. As a result, in the treated 100% wool cloth, the azo dye that dyes the cloth is well assimilated in a short time at 50 ° C. and the non-azo dye that dyes the cloth is not assimilated. A red polka dot pattern was obtained on the purple background. Also in this case, a clear pattern was shown.

Example 6 In this example, the cloth used was diacetate 10
A 0% plain weave cloth was used, and as a dye for dyeing this cloth, a 3% by weight concentration azo disperse dye "Kayalon Fast Yell
ow G "(manufactured by Nippon Kayaku Co., Ltd.), 3% by weight concentration of azo disperse dye" Kayalon Fast Rubine B "(Nippon Kayaku Co., Ltd.) and 3% by weight concentration of anthraquinone disperse dye" Kayalon Fast Blue FN " (Manufactured by Nippon Kayaku Co., Ltd.) (ground color: black), a triangular plate was cut out, a rubber plate for injecting the bacterial solution was used, and the discharge printing treatment condition was 40.
The color discharge printing treatment was carried out in the same manner as in Example 1 except that the temperature was 24 hours. As a result, the two kinds of azo dyes that dye the cloth are simultaneously assimilated, and the non-azo dyes that dye the cloth remain without being assimilated, and a blue triangular pattern is obtained on the black background. Was given. Also in this case, a clear pattern was shown.

Example 7 In this example, the azo acid dye "Kayanol Milling Yellow 3G" was added to the bacterial solution used in Example 1 as the bacterial solution used.
"W" (manufactured by Nippon Kayaku Co., Ltd.) was used as a coloring discharge liquid, wool was used as a material for the cloth, and an anthraquinone-based acid dye "Alizarine Rubinol 3G 115" was used as a dye for dyeing this cloth. % "(Manufactured by Yamada Chemical Co., Ltd.) and azo acid dye" Kayanol Navy Blue R "
(Manufactured by Nippon Kayaku Co., Ltd.) (ground color: purple), and after discharge printing, steam treatment was carried out at 100 ° C. for 60 minutes under normal pressure, and washing with water and washing with hot water were carried out. Color discharge treatment was carried out in the same manner as in. As a result, both the azo dye on the fungus liquid side and the azo dye that dyes the cloth are substantially assimilated, and the non-azo dye that dyes the cloth remains without being assimilated, resulting in a purple background. A predetermined pattern of substantially red color was obtained.

Example 8 In this example, as the bacterial liquid used, the azo acidic dye "Kayanol Navy Blue R" (manufactured by Nippon Kayaku Co., Ltd.) and the anthraquinone acidic dye were used as the bacterial liquid used in the above-mentioned Example 1. Al
"izarine Rubinol 3G 115%" (manufactured by Yamada Chemical Industry Co., Ltd.) was used for each color discharge liquid, wool was used as the material of the cloth, and azo acid dye was used as the dye for dyeing this cloth. Color discharge printing was performed in the same manner as in Example 7 except that "Kayanol Navy Blue R" (manufactured by Nippon Kayaku Co., Ltd.) was used (ground color: blue). As a result, both the azo dye on the bacterial liquid side and the azo dye dyeing the cloth are almost assimilated, and the non-azo dye on the bacterial liquid side remains without being assimilated, and red to blue background A predetermined pattern of magenta was obtained.

Example 9 In this example, the anthraquinone-based acid dye "Suminol Fast Blu" was added to the bacterial liquid used in Example 1 as the bacterial liquid used.
EG ”(manufactured by Sumitomo Chemical Co., Ltd.) was used to add a coloring discharge liquid, and wool was used as the material for the cloth. The azo acid dye“ Kaya ”was used as the dye for this cloth.
Nol Milling Yellow 0 "(manufactured by Nippon Kayaku Co., Ltd.) 2% by weight and azo acid dye" Kayanol Milling Red RS 125 "
2% by weight (manufactured by Nippon Kayaku Co., Ltd.) was used (ground color;
Color discharge processing was performed in the same manner as in Example 7 except for (orange). As a result, two kinds of azo dyes that dye the cloth are assimilated, and the non-azo dyes on the bacterial solution side remain without being assimilated, and a predetermined blue pattern is obtained on the orange background. Was given.

Example 10 In this example, the anthraquinone-based disperse dye "Diacelliton Fast" was added to the bacterial solution used in Example 1 as the bacterial solution used.
Pink R "(manufactured by Mitsubishi Kasei Hoechst Co., Ltd.) 3% by weight
The added colored discharge liquid was added, the cloth was 100% diacetate plain weave cloth, and the dye for dyeing this cloth was azo disperse dye "Kayalon Fast Yellow".
G "(manufactured by Nippon Kayaku Co., Ltd.) 1% by weight, azo disperse dye" Kayalon Fast Rubine B "(manufactured by Nippon Kayaku Co., Ltd.) 1
% By weight and anthraquinone disperse dye "Kayalon Fast B
lue FN ”(manufactured by Nippon Kayaku Co., Ltd.) (ground color;
(Black color), and the color discharge treatment was performed in the same manner as in Example 7 except that the steam treatment conditions were 100 ° C. and 30 minutes. As a result, two kinds of azo dyes that dye the cloth are assimilated, and two kinds of non-azo dyes on the fungus solution side and the dyed cloth side are not assimilated and remain, and are thin on a black background. A purple predetermined pattern was obtained.

Example 11 In this Example, the non-azo reactive dye (anthraquinone reactive dye) "Mikacion Brilliant Blue RS" (manufactured by Nippon Kayaku Co., Ltd.) was used as the bacterial fluid used in the bacterial fluid used in Example 1 above. 3% by weight of A) and B of 0.1% by weight of the same dye were used, cotton was used as the material of the cloth, and the azo reactive dye " Re
mazol Red B150 "(manufactured by Mitsubishi Kasei Hoechst Co., Ltd.) 2% by weight was used for dyeing on a red background, and the prescribed pattern was drawn using each of the above two kinds of solutions A or B. Is 40 ° C for 12 hours, and the post-treatment conditions are as follows: dipping in alkaline solution (90 ° C) for 15 seconds, washing with water, dipping in 5% by weight acetic acid aqueous solution for 15 seconds to neutralize, and then washing with water and washing with water. Color discharge was performed in the same manner as in Example 7 except that the above was performed. As a result, the non-azo dyes on the bacterial liquid side having different concentrations remained as they were, and a predetermined pattern of two colors of dark blue and light blue was obtained on the red background. The composition of the alkaline liquid (“%” below represents% by weight) is as follows. Anhydrous sodium sulfate: 10%, sodium carbonate:
15%, potassium carbonate: 5%, sodium hydroxide: 2
%, Sodium silicate: 1%, water: 67% (total 100
%).

Comparative Example 3% by Weight Concentration Azo Reactive Dye "Remazol / Diamira Bril
"R. Red 5B" (manufactured by Mitsubishi Kasei Hoechst Co., Ltd.) was used to place a rubber plate cut out in a polka dot pattern on a cloth made of 100% cotton dyed by a conventional method. Then, the following colored discharge paste is printed on the cut-out pattern portion. After drying, steam heat treatment at 100 ° C for 10 minutes, then superheated steam treatment at 170 ° C for 7 minutes, washing with water, sodium perborate 5g / l, bath ratio 1:40, oxidation treatment at 50 ° C for 10 minutes. After that, it was washed and dried. [Composition of colored discharge paste] (The following "%" represents% by weight.) Slene dye "Mikethren Brilliant Blue R" (manufactured by Mitsui Toatsu Dye Co., Ltd.): 3%, Rongalit C: 12%, potassium carbonate: 7%, naphtha crystal gum 35% aqueous solution: 60%, glycerin: 3%, water: 15% (total 10
0%). As a result, a blue polka dot pattern was obtained on a red background. In this case, equipment for steam treatment is required, it is necessary to prepare many kinds of chemicals, and the process is complicated.

(3) Direct printing Example 12 In this Example, 4% by weight of an azo direct dye "Kayarus SupraYellow RL" (manufactured by Nippon Kayaku Co., Ltd.) and a copper phthalocyanine series were added to the bacterial solution used in the above Example 1. Direct dye "Sumili
ght Supra Turquoise Blue G conc. "(manufactured by Sumitomo Chemical Co., Ltd.) and 10% by weight of British gum (the balance is water), and the kneaded paste is used as a color discharge paste. On the other hand, 3% by weight concentration of azo direct dye "Kaya
"Rus Supra Red 6BL" (manufactured by Nippon Kayaku Co., Ltd.) was used to dye a cloth of rayon 100% Habutae by a conventional method, and the cloth was dyed red. This 100% rayon that has been dyed red is colored with a double-colored discharge dye paste, which is squeezed out of the tube to draw a pattern. Keep this cloth wet 3
Put it in a constant temperature bath of 0 ° C for 18 hours, take it out from the constant temperature bath, steam at 100 ° C for 40 minutes under normal pressure, wash with water,
I washed with hot water. As a result, the two kinds of azo dyes on the paste solution side and the dyed cloth side are substantially assimilated (these two kinds of azo dyes remain to some extent), and the non-azo dyes on the paste solution side are assimilated. Without being left, a dull green-blue pattern was obtained on the red background.

(4) Concerning Extent of Discharge Dyeing Example 13 In this Example, the bacterial solution used in Example 1 was used, and two kinds of cloth, rayon or cotton, were used. Azo direct dye "Kayarus Supr" on cloth
a Yellow RL "(manufactured by Nippon Kayaku Co., Ltd.) (ground color: yellow), discharge printing conditions: 40 ° C., 36
The test was conducted in the same manner as in Example 1 except that the time was used. As a result, in the case of cotton, the coloring by the azo dye was completely decolorized, but in the case of rayon, it was not completely decolorized although the color became light. When this rayon was treated in the same manner for 72 hours at the same temperature, it was possible to almost completely decolorize it. Therefore, it can be seen that the coloring by the azo dye is decolored or reduced depending on the conditions, and the degree of decolorization varies depending on the type of cloth and the assimilation temperature.

Example 14 In this example, as the bacterial solution used, the azo direct dye "Kayarus Supra Yellow RL" was added to the bacterial solution used in Example 1 above.
(Nippon Kayaku Co., Ltd.) was used with a colored discharge liquid containing 3% by weight, rayon was used as the material of the cloth,
3% by weight of anthraquinone-based reactive dye "Mikacion Brilliant Blue RS" (manufactured by Nippon Kayaku Co., Ltd.) was used as a dye for dyeing this cloth (ground color: blue), discharge condition was 40 ° C, 12 hours. A semi-colored discharge printing process was performed in the same manner as in Example 1 except for the above. As a result, all of this azo direct dye was not assimilated and a part of it remained, resulting in a greenish blue pattern on a blue background. As described above, since the rayon base material is used and under this discharge-printing condition, the half-discharge printing is performed, it becomes possible to carry out grading dyeing.

Example 15 In this example, as a colored discharge paste solution, a copper phthalocyanine direct dye "Sumilight" was added to the bacterial solution used in Example 1 above.
Supra Turquoise Blue G conc. "(Sumitomo Chemical Co., Ltd.) 4% by weight, azo direct dye" Kayarus Supra Yellow "
RL "(manufactured by Nippon Kayaku Co., Ltd.) and 10% by weight of British gum (the balance is water) and kneaded into paste A (green), and this azo direct dye" Kayaru "
s Supra Yellow RL "(manufactured by Nippon Kayaku Co., Ltd.) is used, and 100% rayon habutae is used as the material for the cloth, and the cloth is not dyed. A direct printing process was performed in the same manner as in Example 12 except that a predetermined pattern was drawn using each of the two types of sizing agents (A agent and B agent). As a result, under this discharging condition, part of the azo dye on the side of the paste A is assimilated, while the side of the paste B does not contain the azo dye to be assimilated, Two types of patterns, greenish blue (partially assimilated portion) and blue, were formed on a white background.

Example 16 In this example, a 2% by weight concentration azo direct dye "Kayarus Supra Red 6BL" (manufactured by Nippon Kayaku Co., Ltd.) was used as a dye for dyeing cloth (ground color: red). The discharge-printing treatment was performed in the same manner as in Example 1 except that the discharge-printing conditions were 40 ° C., 6 hours, 12 hours, and 24 hours. The result is shown in FIG. This figure is a black and white copy of a color photograph. The gray parts of ducks and bears are the pattern parts, and the black parts are the ground color (actually red) part.
And, in this figure, (A) is for a discharge time of 24 hours, (B) is for a discharge time of 12 hours,
(C) is the case where the discharge time is 6 hours. According to this result, white discharge is performed after 24 hours,
As the reaction time was shortened to 12 hours and 6 hours, the degree of discharge printing became smaller and the reddishness became darker in order, and semi-discharge printing (that is, creation of a blurred pattern) could be performed. In addition, this (A)
1 is slightly gray in FIG. 1 because it indicates the color (not white) of the light yellow fabric that has been decolorized and emerged, and the dyed color red is almost completely. It has disappeared. From the above, the degree of "blurring" can be freely changed by selecting the reaction condition.

(5) Effects of the Examples In addition to being assimilated by any of the various azo dyes (reactive dyes, direct dyes, acid dyes and disperse dyes) used in the above-mentioned examples, non-azo dyes are also used. (Anthraquinone-based reactive dye, anthraquinone-based acid dye, anthraquinone-based disperse dye and copper phthalocyanine-based direct dye)
As can be seen from the fact that the azo dye is not assimilated, the bacterium shows excellent selectivity and wide application of the azo dye capable of assimilation.

Further, various azo dyes contained in the bacterial solution and various azo dyes dyed on the cloth are also utilized, and various azo dyes dyed on the various base materials can be obtained. , But the degree of assimilation may vary, but was assimilated. Therefore, the types of dyes contained in the bacterial liquid (whether or not azo dyes and non-azo dyes are used) and the types of dyes dyed on the fabric (whether azo dyes and non-azo dyes are used or not) Various combinations with (.)) Or by performing a plurality of each combination at the same time, it is possible to freely create a coloring and / or blurring pattern suitable for the purpose.

Further, the discharge degree can be changed by changing the type of the base material, the assimilation temperature, the assimilation time, etc. (half discharge can be made freely), so that the pattern such as "shading" can be freely made. You can Moreover, since discharge can be carried out even at a relatively high temperature of 30 to 40 ° C., most of the bacteria are killed, which is preferable for health and hygiene.

The present invention is not limited to the specific examples described above, and various modifications may be made within the scope of the present invention depending on the purpose and application. That is,
The combination of the dye contained in the bacterial solution and the dye to be dyed on the substrate and the type of this substrate can be other than the above-mentioned examples, and the number of dyes used at the same time is not particularly limited. It is also possible to use a number other than the above-mentioned embodiment. Furthermore,
If the assimilation (reaction) conditions are within the temperature range where the bacteria grow,
Various selections can be made. Further, since the fixing of the dye is carried out in an alkaline solution, it can be fixed not only by immersing in the alkaline solution but also by microcapsulating the alkaline solution and destroying it by temperature or shearing force.

[0042]

EFFECTS OF THE INVENTION According to the method for printing with microorganisms of the present invention, since no reducing agent or alkali is used, there are few restrictions on the dye, less pain on the base material, and less bleeding at the color boundary portion. Therefore, fine and complicated patterns can be created. In addition, according to this printing method, it is possible to carry out discharge printing having a bright color, and a gradation (half discharge printing) pattern is also possible.
It can be created freely and easily by selecting discharge conditions. Furthermore, by selecting various combinations of the types of dyes contained in the bacterial solution and the types of dyes dyed on the cloth, it is possible to create a coloring and / or blurring pattern suitable for the purpose. In addition, since the activity of microorganisms can be easily suppressed by heating or treating with an alkaline solution having a pH of 9 or more, it is possible to easily and surely carry out stain-proofing. In addition, by using the azo dye decolorizing microorganism of the present invention, the coloring due to the azo dye can be reliably and easily eliminated or reduced.

[Brief description of drawings]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D06P 5/12 101 // (C12N 1/20 C12R 1:64) (C12S 11/00 C12R 1: 64)

Claims (7)

[Claims] 1. An azo dye, a non-azo dye, and a fungus body Xanthomonas NR25-2 of a bacterium belonging to the genus Xanthomonas (accession number; No. 13119), a liquid or a paste containing at least the fungus body is applied in a desired shape, and then the fungus body is allowed to grow or act in a wet state so that all or part of the azo dye is A method for printing with a microorganism, which comprises assimilating and performing printing by eliminating or reducing coloring by the azo dye. 2. A composite dye substrate dyed with an azo dye and a non-azo dye, and a bacterium of an azo dye, a non-azo dye and a bacterium belonging to the genus Xanthomonas Xanthomonas N.
A solution or paste containing at least the fungus body of R25-2 (contract number: Microtechnology Research Institute No. 13119) is applied in a desired shape, and then the fungus body is grown or acted in a wet state. A method for printing with a microorganism, which comprises assimilating all or part of the above azo dye to eliminate or reduce the coloring caused by the azo dye, and perform printing. 3. An azo dye, a non-azo dye, and a fungus body Xant of a bacterium belonging to the genus Xanthomonas on a non-dyed base material or a dyed base material dyed with a non-azo dye.
homonas NR25-2 (accession number: Microtechnology Research Institute, Contribution No. 131
No. 19), a liquid or a paste containing at least the azo dye and the fungus body is applied in a desired shape, and then the fungus body is grown or acted in a wet state so that all of the azo dye Alternatively, a method for printing with a microorganism, which comprises assimilating a part of the dye to eliminate or reduce the coloration by the azo dye, and perform printing. 4. The temperature at which the azo dye is assimilated is 30.
The method for printing with a microorganism according to claim 1, wherein the temperature is from about 42 ° C. 5. A step of drawing a pattern heated to a temperature of 50 ° C. or higher on a part of a desired shape formed by applying the liquid containing the bacterial cells or a paste solution, an alkaline liquid having a pH of 9 or higher. Alternatively, at least one of the step of drawing a pattern with a sizing agent, an acidic liquid having a pH of 4 or less or a sizing agent, or the step of drawing a pattern with a bactericidal agent is carried out. . 6. A fungus body of an Xanthomonas NR25-2 strain, belonging to the genus Xanthomonas, which utilizes an azo dye to eliminate or reduce the coloring caused by the azo dye (Accession No. ) A microorganism for decolorizing azo dyes, which comprises: 7. A method capable of growing at 5 to 42 ° C. 6.
The azo dye decolorizing microorganism described.