CN114108336B

CN114108336B - Preparation method of color bacterial cellulose mask

Info

Publication number: CN114108336B
Application number: CN202111418969.7A
Authority: CN
Inventors: 李喆; 孙卫华; 徐畅; 姚勇波; 许志; 张葵花; 尹岸林; 李海东
Original assignee: Fujian Changyuan Textile Co ltd; Jiaxing University
Current assignee: Fujian Changyuan Textile Co ltd; Jiaxing University
Priority date: 2021-11-26
Filing date: 2021-11-26
Publication date: 2023-10-20
Anticipated expiration: 2041-11-26
Also published as: CN114108336A

Abstract

The invention relates to a preparation method of a color bacterial cellulose mask, which comprises the steps of inoculating strains into a colored culture solution, performing stationary culture for 3-5 days to obtain a color bacterial cellulose I film with the thickness of 0.1-1 mm, then using the color bacterial cellulose I film as a matrix, performing spray dyeing at different positions on the matrix by adopting spray liquid every 6-12 h, and keeping the color bacterial cellulose I film in the stationary culture state in the colored culture solution during the spray dyeing to obtain color bacterial cellulose II; finally, the colored bacterial cellulose II is soaked in NaOH aqueous solution and uniformly mixed to obtain a mixture, then the curcumin ethanol aqueous solution is mixed with the mixture, and the mixture is heated to 60-100 ℃ and stirred for 30-60 min, and when the temperature is reduced to 30-40 ℃, the pH value is regulated to 4.5-6.0, so that the colored bacterial cellulose III is obtained. The method can endow the bacterial cellulose mask with various colors, can also enable the bacterial cellulose mask to have the function of natural pigment, and has wider application field.

Description

Preparation method of color bacterial cellulose mask

Technical Field

The patent relates to a preparation technology of a bacterial cellulose mask, in particular to a preparation method of a color bacterial cellulose mask.

Background

The facial mask is a product which is used for being coated or applied on the surface of human skin, and is uncovered, scrubbed or reserved after a period of time, thereby playing a role in concentrated nursing or cleaning. The mechanism of the action of the mask is as follows: the facial mask is coated on the surface layer of a human body, the cuticle is softened by covering the skin, and meanwhile, the covering of the facial mask also provides a closed environment for the surface layer of the skin to isolate air or pollution, under the closed environment, the temperature of the skin can be increased, the blood circulation of the skin can be enhanced, capillary vessels and pores can be expanded, the metabolism of the skin can be promoted, the skin can absorb the functional components of the facial mask more easily, or the dirt such as blackheads, aged dander and the like can be removed in the process of sticking and tearing the gel-like film.

The mask base materials commonly used in the market at present mainly comprise various non-woven fabrics masks and biological cellulose masks.

The non-woven fabric type facial mask is the most common on the market at present, and is a material which is formed by bonding or intertwining short fibers, filaments or porous films, so that the non-woven fabric type facial mask is processed into a sheet-shaped or net-shaped material, fiber scraps are not easy to generate, and in the use process, the skin is always in a relatively loose and soft state due to the good moisture retention property of the non-woven fabric, and the skin can not feel tight after essence is lost due to too long dressing time. At present, the dyeing process of the non-woven fabric is mature, and is applied to industrialized production, and products with different colors brought by dyeing the non-woven fabric are widely popular.

The biological cellulose facial mask is a facial mask product which takes biological cellulose as a base material, and the biological cellulose is bacterial cellulose. The bacterial cellulose has a three-dimensional reticular fiber structure, is nano-scale, has a plurality of holes on the fiber, has higher specific surface area, and has a plurality of hydrophilic groups on a molecular chain, thus having good air permeability and water retention. In addition, bacterial cellulose has excellent biocompatibility, tensile strength, tensile property and the like, and has good plasticity, and the dimension of different facial forms can be changed in a cutting mode and the like, so that the skin surface can be highly attached. At present, a plurality of brands at home and abroad also put forward a facial mask taking bacterial cellulose as a base material; however, there is little research on dyeing of bacterial cellulose relative to nonwoven fabric-based masks, and bacterial cellulose produced in laboratory or industrial production is generally white or translucent, single in color and limited in function.

Therefore, the development of a method for imparting various colors to a bacterial cellulose mask is of great significance.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a preparation method of a colorful bacterial cellulose mask. The invention provides new colors of the natural bacterial cellulose mask and functionality brought by the natural pigment by adjusting the proportion of various natural pigments in three processes of fermentation, spray dyeing and post-treatment during fermentation.

In order to achieve the above purpose, the invention adopts the following scheme:

a preparation method of a color bacterial cellulose mask comprises the following steps:

(1) Preparing a colored culture solution containing 0.005-2wt% of natural red pigment; the natural red pigment is one or more of natural black corn pigment, sorghum red pigment, red beet pigment, lac red pigment, cochineal red pigment and safflower red pigment;

(2) Inoculating the strain into the colored culture solution obtained in the step (1), and performing stationary culture for 3-5 d to obtain a colored bacterial cellulose I film with the thickness of 0.1-1 mm;

(3) Spraying the color bacterial cellulose I film obtained in the step (2) on different positions on the substrate by adopting spraying liquid every 6-12 h (the position of each spraying is related to a three-dimensional pattern constructed in advance, the position of each spraying can be different or the same, the positions of each spraying can be single, two or more, and the positions of each spraying are related to the designed pattern in advance), and the color bacterial cellulose I film is kept in a static culture state in the color culture liquid during spraying to obtain color bacterial cellulose II;

the spray liquid is natural blue pigment extracting solution or mixed liquid of natural blue pigment extracting solution and basic culture solution; the natural blue pigment is more than one of purple cabbage pigment, gardenia blue pigment, blueberry pigment and phycocyanin; the content of the natural blue pigment in the spray liquid is 0.003-1.5wt%;

The pigment selected by the spray-drying process is a natural blue pigment, and the natural blue pigment is not stable relative to the natural red pigment, so that the natural blue pigment is used for preparing the colorful bacterial cellulose, and the spray-drying process is adopted to protect the pigment, so that excessive degradation of the pigment is avoided;

when the adopted spray liquid is natural blue pigment extracting solution, the amount of basic culture liquid in the culture medium is sufficient, namely the bacterial cellulose can grow from a film form of 3-5 d culture for every 6-12 h, so that the thickening of bacterial cellulose is realized;

when the spray liquid is the mixed liquid of the natural blue pigment extracting solution and the basic culture solution, the amount of the culture solution in the culture medium only provides a film which grows for 3-5 days, and the mixed liquid sprayed by the spray device contains another part of the culture solution, so that the continuous thickening of the culture solution is realized;

the total amount of the culture solutions used in the two methods is the same;

the dosage of the natural blue pigment in the sprayer is obtained by the proportion of three primary colors according to the set color of the final colored bacterial cellulose;

the spray dyeing adopts a sprayer capable of moving in space positions in three directions of XYZ three-dimensional coordinate axes; the spray dyeing is to uniformly spray the spray liquid;

The different positions on the substrate refer to positions of the sprayer for spray dyeing, which are determined according to the pattern of the mask;

the colored bacterial cellulose II is a mixture composed of natural bacterial cellulose, natural red pigment and natural blue pigment, wherein the natural bacterial cellulose, the natural red pigment and the natural blue pigment are generated by fermentation above the colored bacterial cellulose I, which is used as a substrate; and the color of each spray-dyed position on the colored bacterial cellulose II presents a specific color according to the proportion of the natural red pigment in the colored bacterial cellulose I to the natural blue pigment sprayed on the position, and the specific color refers to one of gradual colors (also can be called intermediate colors) from purple red to purple to brilliant purple;

the sprayer can be positioned above the colored culture solution where the colored bacterial cellulose I film is positioned and is connected with the computer output signal end, the sprayer sprays at different positions of each layer on the colored bacterial cellulose I every 6-12 h under the control of the computer end, and finally the space position of the natural blue pigment on each layer is stabilized through the stacking of the layers; the method comprises the steps of converting the pattern of a mask into a digital signal, wherein the position of each layer of the mask is determined by a sprayer connected with a signal output end of a computer, specifically, the position of each layer of the mask is determined by a three-dimensional pattern constructed in advance, finally, each layer of the mask is subjected to spray dyeing through the space movement of the sprayer on the X, Y, Z three axes, and the color of bacterial cellulose is changed finally along with the end of the spray dyeing process, and the color change is influenced by the proportion of the red blue pigment, so that the three-dimensional pattern on the film is constructed;

In each layer of coloured bacterial cellulose II obtained by the spray-dyeing process, the position of the spray-dyeing will vary in colour and the colour of the coloured bacterial cellulose II as a whole will vary slightly, in particular: the color of the spray-dyed position is based on red and blue, different proportions of the two are regulated, the spray-dyed position can show various colors (red and blue are little purplish red, the same amount is purple, and the blue and red are little brilliant purple; namely, various gradual colors from purplish red to purple to brilliant purple can be shown), the color change of the spray-dyed position on each layer is removed after the spray-dyed process is finished, slight diffusion of pigment on the spray-dyed position on each layer (the diffusion of blue pigment on the spatial position point on each layer is smaller relative to the diffusion of the blue pigment on each layer and the range of the pigment on each layer) exists, the slight diffusion of the blue pigment on the spray-dyed position on each layer finally causes the color bacterial cellulose II to show the color change on the whole, and the end of the spray-dyed process is accompanied with the color (the various gradual colors from purplish red to brilliant purple) on the spatial position point on each layer and the whole color (the pink, red and the red) and the intermediate colors of the whole;

(4) Firstly, soaking the colored bacterial cellulose II in the step (3) in NaOH aqueous solution to be uniformly mixed to obtain a mixture, then mixing the curcumin ethanol aqueous solution with the mixture, heating to 60-100 ℃ and stirring for 30-60 min (namely, in a steaming process), regulating the pH value to 4.5-6.0 when the temperature is reduced to 30-40 ℃, regulating the pH value in the temperature range to prevent degradation of three pigments, regulating the pH value to 4.5-6.0, and in the pH value range, enabling natural red pigments to be in stable red, natural blue pigments to be in stable blue and ginger yellow pigments to be in stable yellow, thereby realizing the coloring of various natural pigments on the bacterial cellulose by utilizing a three-primary color matching principle, keeping the color stable, and obtaining the colored bacterial cellulose III;

the color bacterial cellulose III is a mixture of color bacterial cellulose II and curcumin, and corresponds to the color of each spray-dyed position on the color bacterial cellulose II, and the proportion of three pigments at the position presents a specific color after the curcumin is added, wherein the specific color is brown, brilliant green, intermediate color of brilliant green and olive green, intermediate color of brown and deep blue, reddish brown, brilliant orange and deep blue;

As the cooking process proceeds, the color of the position of spray-dyed in the colored bacterial cellulose II is controlled by the ratio of the two pigments of red and blue, and is changed to be controlled by the ratio of the three pigments of red, yellow and blue, so that the color of different positions on each layer of the colored bacterial cellulose III is different along with the ratio of the natural red pigment, the natural blue pigment and the curcumin, and the color is brown, brilliant green, intermediate color of brilliant green and olive green, intermediate color of brown and deep blue, reddish brown, brilliant orange and deep blue. As there is also a trace of blue pigment diffusion during the cooking process, the color bacterial cellulose III produced also has a change in color at the spatial sites of each layer and a slight change in overall color; thus, the colour of the final coloured bacterial cellulose III is the colour at the spatial site of each layer (brown, brilliant green, intermediate colour of brilliant green and olive green, intermediate colour of brown and deep blue, reddish brown, brilliant orange, deep blue), as well as the overall colour (orange, red-orange and their intermediate colours).

The preparation of the natural red pigment extract and the natural blue pigment extract generally adopts a solvent extraction method, and specifically comprises the following steps:

Drying raw materials (typically branches, leaves, roots, stems, etc. of natural plants) containing natural pigment at low temperature to constant weight, and pulverizing and grinding; adding natural pigment powder into a solution containing 30-70wt% of extraction solvent according to the ratio of 1g to 3-30 mL by adopting an ultrasonic auxiliary extraction method, and performing ultrasonic extraction for 5-60 min; and then filtering out residues by suction, and collecting filtrate as natural pigment extracting solution.

The extraction process of the natural black corn pigment comprises the following steps: fully drying black corn grains at low temperature to constant weight, crushing to obtain black corn grain powder, and standing at room temperature for later use; and then adopting an ultrasonic auxiliary extraction method, adding the black corn powder into 30-70% ethanol water solution (preferably 50%) according to the ratio of 1g to 10-30 mL (preferably 1:20 g/mL), carrying out ultrasonic power of 120-200W and ultrasonic time of 15-55 min (preferably 45 min) by an ultrasonic extractor at 15-55 ℃ (preferably 35 ℃) to filter residues, and collecting filtrate as natural black corn pigment extract.

Other pigments in the natural red pigment can also be extracted by the method.

The extraction process of the purple cabbage pigment comprises the following steps: firstly, adopting an ultrasonic auxiliary leaching method, cleaning the purple cabbage, cutting the purple cabbage, grinding the purple cabbage after the purple cabbage is dried, grinding the purple cabbage for 4 to 6 minutes, and then placing the purple cabbage in a closed container for later use; adding the grinded purple cabbage into a hydrochloric acid aqueous solution (preferably 0.3 mol/L) with the concentration of 0.2-0.7 mol/L according to the ratio of 1g to 5-25 mL (preferably 1:10 g/mL), setting the ultrasonic power to be 70-85W, leaching at the temperature of 30-70 ℃ (preferably 40 ℃), leaching for 4-12 min (preferably 8 min), filtering residues after leaching, and collecting filtrate as a purple cabbage pigment extract.

Other pigments in the natural blue pigment can also be extracted by the method.

The amount of the red pigment in the colored culture solution is obtained by the ratio of the three primary colors according to the set color of the final colored bacterial cellulose, and the amount of other components is a prerequisite for preparing the bacterial cellulose in a daily laboratory.

The natural red pigment and the natural blue pigment used in the formulation of the colored broth are determined based on the maximum absorbance that the pigment in the solution can exhibit over a range of wavelengths.

Curcumin is purified on the basis of the crude extract by an acid-base precipitation method, and yellow precipitates are obtained by adjusting the pH value to be 7.3, and the addition proportion of the other two pigments is quantified through the yellow precipitates.

As a preferable technical scheme:

the preparation method of the color bacterial cellulose mask comprises the following specific processes of: removing bacteria from natural red pigment extractive solution with 0.22 μm filter (the natural pigment is unstable at high temperature, and the filter is used for filtering); mixing the natural red pigment extract with the basic culture solution after the sterilization treatment by high-pressure steam (the sterilization treatment process is that the basic culture solution is put into a high-pressure steam sterilization pot for sterilization treatment, the temperature is set to 121 ℃, the pressure is set to 1.1MPa, and the time is set to 30-45 min);

The formula of the colored culture solution is as follows:

1 to 6 weight percent of substance A;

peptone 0.05-1 wt%;

yeast extract 0.05-1 wt%;

0.01 to 0.5 weight percent of citric acid;

disodium hydrogen phosphate 0.04-0.4wt%;

0.02 to 0.2 weight percent of monopotassium phosphate;

0.005-2wt% of natural red pigment;

the balance of water;

the substance A is more than one of glucose, fructose, sucrose and mannitol.

In the preparation method of the colorful bacterial cellulose mask, in the step (2), the pH value of the colorful culture solution is 4-6, and the temperature is 30-38 ℃. The natural red pigment is selected to be added into the basic culture solution in the culture stage, because the temperature of the basic culture solution used for fermentation is 30-38 ℃ and the pH value is 4-6, under the condition, the natural red pigment is relatively stable, the degradation of the natural red pigment can be avoided, and more pigment can be reserved.

The preparation of the culture solution and the culture are two different processes, wherein the temperature of the colored culture solution is 30-38 ℃, the state of the finally obtained culture solution is described after the process of preparing the culture solution is finished, and the culture temperature of the culture process is 28-37 ℃ so as to ensure the normal growth of bacterial films, and the current temperature difference of the two processes is irrelevant.

In the preparation method of the colorful bacterial cellulose mask, in the step (2), the conditions of static culture are as follows: the culture temperature is 28-37 ℃. Too high or too low a culture temperature, both of which affect the activity of the bacterial species and thus the bacterial cellulose yield; the temperature of 28-37 ℃ is a proper condition for bacterial fermentation to produce bacterial cellulose, and the bacterial cellulose yield can be increased along with the increase of the culture days when the bacterial cellulose is cultured at any temperature in the temperature range.

In the preparation method of the color bacterial cellulose mask, in the step (3), the spray liquid is a mixed liquid of a natural blue pigment extracting solution and a basic culture solution. When the spray liquid is the mixed liquid of the natural blue pigment extracting solution and the basic culture solution, conditions can be created for thickening each layer of the colorful bacterial fiber I, and dyeing can be performed at different space positions of each layer.

In the preparation method of the colorful bacterial cellulose mask, in the step (3), the formula of the mixed solution of the natural blue pigment extracting solution and the basic culture solution is as follows:

1-6wt% of a substance B;

peptone 0.05-1 wt%;

yeast extract 0.05-1 wt%;

0.01 to 0.5 weight percent of citric acid;

disodium hydrogen phosphate 0.04-0.4wt%;

0.02 to 0.2 weight percent of monopotassium phosphate;

0.003 to 1.5 weight percent of natural blue pigment;

the balance of water;

the substance B is more than one of glucose, fructose, sucrose and mannitol.

The preparation method of the colorful bacterial cellulose mask comprises the following steps: x-axis is 0-30 cm, Y-axis is 0-30 cm, Z-axis is 0-34 cm.

In the preparation method of the color bacterial cellulose mask, in the step (3), the spray dyeing speed is 1-15 mL/min, and the diameter of liquid drops sprayed by a sprayer is 0.5-6 mu m.

According to the preparation method of the colorful bacterial cellulose mask, the static culture conditions in the step (3) are consistent with those in the step (2).

According to the preparation method of the color bacterial cellulose mask, the mass ratio of the color bacterial cellulose II to the NaOH aqueous solution in the mixture in the step (4) is 1-10:100; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 70-95 wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1-10:1000, and the mass percentage of the final curcumin in the system is 0.001-0.1 wt%; the system consists of an aqueous NaOH solution and an aqueous ethanol solution of curcumin.

The mass ratio of the colored bacterial cellulose II to the NaOH aqueous solution is 1-10:100, at which the colored bacterial cellulose II is ensured to be fully immersed into the NaOH aqueous solution, and the fully immersed ensures that the bacterial cellulose reaches the medical grade through final cooking.

The volume ratio of the ethanol aqueous solution to the NaOH aqueous solution of the curcumin is 1-10:1000, which is obtained from the dyeing performance of bacterial cellulose of the curcumin, and the dyeing performance of the curcumin on the bacterial cellulose is good in the range.

The concentration of ethanol in the aqueous ethanol solution is 70 to 95wt% in the range where the maximum dissolution of curcumin is ensured in view of the solubility of curcumin.

The mechanism of the invention is as follows:

firstly, preparing a red pigment culture solution, obtaining a color bacterial cellulose I film substrate through a culture stage, then preparing color bacterial cellulose II through a spray dyeing process, finally adding curcumin in the alkaline solution dipping process, and regulating the pH value to obtain color bacterial cellulose III.

The spray dyeing process comprises the steps of dyeing relatively unstable blue pigment in a relatively mild manner, enabling the relatively unstable blue pigment not to be damaged to the greatest extent through spraying and reserving the relatively unstable blue pigment, spraying and dyeing natural blue pigment at different positions of each layer through a spray dyeing technology, fixing the blue pigment by stacking the final layers, and finally constructing bacterial cellulose with different patterns and colors by using pigments at different spatial positions; the blue pigment sprayed on the bacterial cellulose can not obviously move at pigment sites, on one hand, because the adsorption effect of hydroxyl groups or hydrogen bonds of the bacterial cellulose on pigment molecules is realized, on the other hand, the next spraying is realized through a certain time interval, so that more pigment molecules are adsorbed on the bacterial cellulose, and most importantly, after a period of time, the next layer of bacterial cellulose film grows out, the fixation effect of the superimposed pigment is realized between layers, and the blue pigment is ensured not to obviously move when the blue pigment is sprayed on the bacterial cellulose through the implementation. Layered spray dyeing is to finally construct a three-dimensional pattern as a whole by stacking layers by layer-to-layer using spray dyeing sites for each layer.

The alkaline solution dipping process can better diffuse curcumin on one hand, so that the coloring of curcumin on the color bacterial cellulose II is improved, the final alkaline solution dipping process is also the final adjustment of color, the red and blue pigments can generate color change due to the improvement of pH value in the alkaline solution dipping process, and three pigments of red, blue and yellow are adjusted to the three primary colors through the callback of the final pH value, so that the pre-designed color is achieved; the end of the alkali liquor dipping process can not generate the movement of the position of the pigment sprayed in the colored bacterial cellulose II, the position fixing of the pigment sprayed in the colored bacterial cellulose II is mainly realized through the following two aspects, firstly, the pigment molecules are firmly adsorbed through hydroxyl groups or hydrogen bonds of the bacterial cellulose, secondly, the colored bacterial cellulose I film is taken as a matrix, the spraying is performed every 6-12 hours, the spraying equipment is controlled by the digital signal output end of a computer, the spraying is performed at different positions of each layer, the final layer is overlapped with the layers, the colored bacterial cellulose II is generated, and the superposition between the layers also has a fixing effect on the position of the pigment, so that the position of the pigment sprayed after the alkali liquor is steamed does not have obvious change compared with the position before;

The nature of natural pigments is unstable, which also leads to a change in their color. In the prior art, a natural pigment is generally added into bacterial cellulose to prepare colorful bacterial cellulose, the color of the colorful bacterial cellulose is single, the single natural pigment is easy to display the expected color through the control of temperature and pH value, and a plurality of natural pigments are added, and as the respective color changes are affected by the pH value and the temperature, the plurality of natural pigments are mixed, and under the same condition, the expected color is not easy to display, which also limits the plurality of natural pigments to a great extent and dyes certain substances.

The invention adopts a plurality of natural pigments to carry out color matching, and controls the proportion of the added natural pigments based on the principle of three primary colors, thereby leading the color of the finally obtained colored bacterial cellulose to be close to the target color designed by color matching and avoiding the generation of larger deviation with the target color caused by the unstable structure of the natural pigments in the process of preparing the colored bacterial cellulose.

The method comprises the following steps: the invention selects three specific natural pigments, namely natural red pigment (natural black corn pigment, sorghum red pigment, red leaf beet pigment, lac red pigment, cochineal red pigment, carthamus red pigment), natural blue pigment (purple cabbage pigment, gardenia blue pigment, blueberry pigment and phycocyanin) and curcumin, which can meet the color requirement of three primary colors; in addition, the invention also divides the color matching process into three steps, namely: the method is characterized in that natural red pigment is added in a bacterial cellulose fermentation culture stage to prepare colored bacterial cellulose I, the natural red pigment is in a basic culture solution in the fermentation stage, namely, the temperature is 30-38 ℃, the pH value is 4-6, the stability is relatively good, the second step is a spray-dyeing process, the relationship between the first step and the second step is tight, the spray-dyeing is carried out by taking a colored bacterial cellulose I film fermented for 3-5 days as a matrix, the colored bacterial cellulose I is spray-dyed every 6-12 hours, each layer of the colored bacterial cellulose I grows gradually along with the increase of time, corresponding three-dimensional patterns are finally stacked through spray-dyeing at different positions on each layer, the control time is 6-12 hours, the thin layer cannot grow out after the time is too short, the next layer of spray-dyed is needed to be thickened, the construction of the three-dimensional patterns is unfavorable, and a certain time interval exists, and the method is favorable for fixing the natural blue pigment;

The natural red and blue pigments contain anthocyanin, and the anthocyanin has different structures under different pH values, and the anthocyanin has different colors under different pH values due to different existence modes of the anthocyanin structures caused by the pH values, but the existence mode of the anthocyanin structure can be changed reversibly due to the different pH values, which is also the basis of the color callback caused by the subsequent alkali liquor treatment of the callback of the pH values (namely, three pigments can show color change along with the pH values, and the color tone of the three pigments is in a three-primary color state through the adjustment of the pH values in the post treatment); and then the prepared colored bacterial cellulose II and curcumin are subjected to color matching in alkali liquor, and the color matching temperature, time and pH value of the alkali liquor are controlled according to the color change conditions of the three natural pigments in different environments, so that the unstable structure formed by the natural pigments in the process of preparing the colored bacterial cellulose is overcome.

When the temperature, time and pH value of alkali liquor are controlled, the determination method of the invention comprises the following steps:

the pH value is regulated to 4.5-6.0, and within the range of the pH value, the natural red pigment is stable red, the natural blue pigment is stable blue, and the curcumin is stable yellow, so that the coloring of various natural pigments on bacterial cellulose can be realized by utilizing the principle of three primary colors, and the color stability is maintained. The dyeing of the third pigment is treated by heating and stirring for 30-60 min at 60-100deg.C before the pH adjustment, wherein the pH is reduced to 30-40deg.C, and the pH is adjusted to 4.5-6.0 at relatively low temperature, and the color and self-properties of the pigment are relatively stable.

In addition, the three natural pigments selected by the invention have the functions, so that the color bacterial cellulose II prepared by the invention has the functions of resisting tumor, delaying aging, resisting oxidation, fading spots and the like due to the addition of the two pigments; the color bacterial cellulose III has antibacterial function on the basis of the function of the color bacterial cellulose II due to the addition of curcumin.

Advantageous effects

(1) According to the preparation method of the colored bacterial cellulose, the first step is to endow the colored bacterial cellulose I film substrate obtained by culture and fermentation with new colors at different sites on the colored bacterial cellulose I through a spray dyeing process of the second step, so that colored bacterial cellulose II with different colors is obtained, and the third step is to add a third pigment in post-treatment to change the colors at the spray dyeing sites, so that colored bacterial cellulose III is obtained, and finally, the colored bacterial cellulose III is added into the bacterial cellulose along with the colors with different proportions, so that the purpose of generating the new colors is achieved;

(2) The addition of the spray dyeing process in the invention utilizes the growth process of the bacterial cellulose, and provides a method for realizing three-dimensional patterning of the bacterial cellulose on the basis of generating new colors of the bacterial cellulose;

(3) The color bacterial cellulose can achieve the purpose of controllable color, can enable the bacterial cellulose to have the function of natural pigment, has controllable color and functionalization, and can be widely applied.

Drawings

FIG. 1 is a schematic diagram of a spray-dyeing process and corresponding region positions of a sprayer according to the present application;

FIG. 2 is a schematic representation of the positions of different colors on colored bacterial cellulose II according to the present application.

Detailed Description

The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.

The extraction process of curcumin comprises the following steps: firstly slicing the cleaned turmeric medicinal material, drying the turmeric medicinal material to constant weight in a vacuum drying oven at 45 ℃, sieving the turmeric medicinal material by a 50-mesh sieve, wrapping a certain amount of turmeric powder by filter paper, placing the turmeric powder in a Soxhlet extractor (boiling range 60 ℃) filled with 350ml of petroleum ether until the solution is colorless, opening the filter paper to dry the turmeric powder in the shade in a fume hood to obtain defatted turmeric powder, adding the defatted turmeric powder into 50% ethanol water solution according to the solid-to-liquid ratio of 1g to 10mL, extracting at the temperature of 60 ℃ for 2.5h, wherein the pH value is 4.0, the yield of curcumin is 5.78%, and finally further purifying the extract by an acid-base precipitation method, wherein the purification process is as follows: adjusting pH of the extractive solution to 7.3 to form yellow precipitate of curcumin.

The spray dyeing of the invention adopts a sprayer capable of moving in space positions in three directions of XYZ three-dimensional coordinate axes; and the range of movement is: x-axis is 0-30 cm, Y-axis is 0-30 cm, Z-axis is 0-34 cm. If a CREALITY3D printer is adopted, the model adopts an end-3 max, the printing size is 300mm, 300mm is 340mm, a spray head which is originally used for melting by an instrument is changed into a spray head for spraying solution through modification, the spray head is connected with a small metering pump, and the metering pump controls the quantity of the solution sprayed by the spray head.

The invention relates to a natural red pigment-containing colored culture solution: firstly, removing bacteria from the natural red pigment extracting solution by using a 0.22 mu m filter; mixing the natural red pigment extract with bacteria removed with the basic culture solution after high-pressure steam sterilization treatment; the formulations of the respective colored culture solutions containing the natural red pigments are shown in tables 1 to 3, respectively.

TABLE 1

TABLE 2

TABLE 3 Table 3

The invention adopts a spray liquid prepared by mixing natural blue pigment extract and basic culture liquid, and the formula is shown in the following table 4:

TABLE 4 Table 4

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The term name of the color in the present invention refers to the 37 color zones in GB 3899.2.

Example 1A

Raw material preparation:

a1# colored culture solution, wherein the pH value of the colored culture solution is adjusted to 6, and the temperature is 38 ℃;

preparing a spray liquid: a natural blue pigment extract having a natural blue pigment content of 0.0075 wt%; the natural blue pigment is purple cabbage pigment;

(1) Preparation of a colored bacterial cellulose I film: inoculating strain into A1# colored culture solution, wherein the cell density of strain is 10 ⁵ Performing stationary culture for 3d at a volume per ml;

(2) Uniformly spraying liquid (spray dyeing) on different positions on a substrate by adopting a sprayer at intervals of 6 hours by adopting spraying liquid, wherein the spray dyeing speed is 15mL/min, the diameter of liquid drops sprayed by the sprayer is 6 mu m, and the color bacterial cellulose I film is positioned in a color culture solution and kept in a static fermentation state during spray dyeing (the condition of static culture is that the culture temperature is 37 ℃ and the culture days are 11 d) to obtain color bacterial cellulose II;

the different positions on the substrate refer to the positions of the sprayer for spray dyeing, namely the region 1, the region 2 and the region 3, which are determined according to the pattern (shown in figure 1) of the mask; the spray dyeing process of the color bacterial cellulose I film is divided into three layers, and the corresponding spray dyeing positions of the 1 st layer, the 2 nd layer and the 3 rd layer are respectively areas 1, 2 and 3;

The colored bacterial cellulose II is a mixture composed of natural bacterial cellulose, natural red pigment and natural blue pigment, wherein the natural bacterial cellulose, the natural red pigment and the natural blue pigment are generated by fermentation above the colored bacterial cellulose I, which is used as a substrate; and each spray-dyed location (location number referring to fig. 2) and its corresponding color (table below) on the colored bacterial cellulose II is:

position numbering	Color of
		5	Peach red color
1、2、3、4	Intermediate colors of mauve and purple

FIG. 2 is a schematic representation of the whole of a coloured bacterial cellulose II, wherein 1, 4 correspond to the two positions of region 1 in FIG. 1, 2 correspond to regions 2,3 in FIG. 1 and regions 3,5 in FIG. 1 correspond to the colour of the bacterial cellulose whole body;

(3) Firstly, soaking the colored bacterial cellulose II in a 3wt% NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing an ethanol aqueous solution of curcumin with the mixture, heating to 60 ℃, stirring for 30min, and adjusting the pH value to 5 when the temperature is reduced to 32 ℃ to obtain the colored bacterial cellulose III;

in the mixture, the mass ratio of the colored bacterial cellulose II to the NaOH aqueous solution is 1:10; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 95wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1:10, and the mass percentage of the final curcumin in the system is 0.001wt%; the system consists of an aqueous NaOH solution and an aqueous ethanol solution of curcumin.

The color bacterial cellulose III is a mixture of color bacterial cellulose II and curcumin, and the color of each spray-dyed position on the color bacterial cellulose II is corresponding to the specific color of the three pigments at the position after the curcumin is added, and the specific color is shown in the following table:

position numbering	Color of
		5	Orange-red and orange intermediate color
1、2、3、4	Brown color

Example 2A

raw material preparation:

a2# colored culture solution, wherein the pH value of the colored culture solution is adjusted to be 4, and the temperature is 30 ℃;

preparing a spray liquid: a natural blue pigment extract having a natural blue pigment content of 0.600 wt%; the natural blue pigment is a mixture of purple cabbage pigment and blueberry pigment with the mass ratio of 1:1;

(1) Preparation of a colored bacterial cellulose I film: inoculating strain into A2# colored culture solution, wherein the cell density of strain is 10 ³ Performing stationary culture for 5d at a volume per ml;

(2) The color bacterial cellulose I film is used as a matrix, a sprayer is used for uniformly spraying liquid (spray dyeing) at different positions on the matrix at intervals of 12 hours by adopting the spraying liquid, and the spray dyeing process is the same as that of the embodiment 1A, and the difference is that: the spray dyeing speed is 10mL/min, the diameter of liquid drops sprayed by a sprayer is 3 mu m, and the color bacterial cellulose I film is positioned in the colored culture solution and kept in a static fermentation state during the spray dyeing (the condition of static culture is that the culture temperature is 28 ℃ and the culture days are 7 d), so that the color bacterial cellulose II is obtained;

The color bacterial cellulose II is a mixture which is formed by taking color bacterial cellulose I as a substrate and fermenting natural bacterial cellulose, natural red pigment and natural blue pigment which are generated above the color bacterial cellulose I; and each spray-dyed location (location number reference fig. 2) and its corresponding color (table below) on the colored bacterial cellulose II is:

(3) Firstly, soaking the colored bacterial cellulose II in a 5wt% NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing the curcumin ethanol aqueous solution with the mixture, heating to 65 ℃, stirring for 60min, and adjusting the pH value to 4.5 when the temperature is reduced to 30 ℃ to obtain the colored bacterial cellulose III;

in the mixture, the mass ratio of the colored bacterial cellulose II to the NaOH aqueous solution is 1:20; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 90wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1:50, and the mass percentage of the final curcumin in the system is 0.08wt%; the system consists of an aqueous NaOH solution and an aqueous ethanol solution of curcumin.

Position numbering	Color of
		5	Orange red
1、2、3、4	Bright green

Example 3A

raw material preparation:

a3# colored culture solution, wherein the pH value of the colored culture solution is adjusted to be 5, and the temperature is 35 ℃;

preparing a spray liquid: a natural blue pigment extract having a natural blue pigment content of 0.12 wt%; the natural blue pigment is prepared from the following components in percentage by mass: 3. a mixture of gardenia blue pigment and phycocyanin pigment;

(1) Preparation of a colored bacterial cellulose I film: inoculating strain into A3# colored culture solution, wherein the cell density of strain is 10 ⁶ Performing stationary culture for 4d at a volume per ml;

(2) The color bacterial cellulose I film is used as a matrix, a sprayer is used for uniformly spraying liquid (spray dyeing) at different positions on the matrix at intervals of 7h by adopting the spraying liquid, and the spray dyeing process is the same as that of the embodiment 1A, and the difference is that: the spray dyeing speed is 6mL/min, the diameter of liquid drops sprayed by a sprayer is 0.5 mu m, and the color bacterial cellulose I film is positioned in a colored culture solution and kept in a static fermentation state during the spray dyeing (the static culture condition is that the culture temperature is 32 ℃ and the culture days are 7d; the color bacterial cellulose II is obtained);

(3) Firstly, soaking the colored bacterial cellulose II in an NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing an ethanol aqueous solution of curcumin with the mixture, heating to 70 ℃, stirring for 40min, and adjusting the pH value to 6.0 when the temperature is reduced to 35 ℃ to obtain colored bacterial cellulose III;

in the mixture, the mass ratio of the colored bacterial cellulose II to the NaOH aqueous solution is 1:30; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 85wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1:100, and the mass percentage of the final curcumin in the system is 0.01wt%; the system consists of an aqueous NaOH solution and an aqueous ethanol solution of curcumin.

position numbering	Color of
		5	Orange-red and orange intermediate color
1、2、3、4	Intermediate colors of brilliant green and olive green

Example 4A

raw material preparation:

a4# colored culture solution, wherein the pH value of the colored culture solution is adjusted to 4.5, and the temperature is 34 ℃;

preparing a spray liquid: a natural blue pigment extract having a natural blue pigment content of 0.600 wt%; the natural blue pigment is a mixture of purple cabbage pigment, gardenia blue pigment and phycocyanin with the mass ratio of 1:1:1;

(1) Preparation of a colored bacterial cellulose I film: inoculating strain into A4# colored culture solution, wherein the cell density of strain is 10 ⁷ Performing stationary culture for 5d at a volume per ml;

(2) The color bacterial cellulose I film is used as a matrix, a sprayer is used for uniformly spraying liquid (spray dyeing) at different positions on the matrix at intervals of 8 hours by adopting the spraying liquid, and the spray dyeing process is the same as that of the embodiment 1A, and the difference is that: the spray dyeing speed is 1mL/min, the diameter of liquid drops sprayed by a sprayer is 0.5 mu m, and the color bacterial cellulose I film is positioned in a colored culture solution and kept in a static fermentation state during the spray dyeing (the static culture condition is that the culture temperature is 31 ℃ and the culture days are 8d; the color bacterial cellulose II is obtained);

Position numbering	Color of
		5	Red color
1、2、3、4	Purple color

(3) Firstly, soaking the colored bacterial cellulose II in an NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing an ethanol aqueous solution of curcumin with the mixture, heating to 68 ℃, stirring for 50min, and adjusting the pH value to 5.5 when the temperature is reduced to 36 ℃ to obtain colored bacterial cellulose III;

in the mixture, the mass ratio of the colored bacterial cellulose II to the 3.5 weight percent NaOH aqueous solution is 1:40; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 80wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1:200, and the mass percentage of the final curcumin in the system is 0.02wt%; the system consists of an aqueous NaOH solution and an aqueous ethanol solution of curcumin.

position numbering	Color of
		5	Orange red
1、2、3、4	Intermediate brown and deep blue

Example 1B

raw material preparation:

the pH value of the colored culture solution is adjusted to 6, and the temperature is 30 ℃;

b1# spray liquid;

(1) Preparation of a colored bacterial cellulose I film: inoculating strain into B1# colored culture solution, wherein the cell density of strain is 10 ¹³ Performing stationary culture for 5d at a volume per ml;

(2) The color bacterial cellulose I film is used as a matrix, a sprayer is adopted to uniformly spray the spraying liquid (spray dyeing) at different positions on the matrix by adopting the b1# spraying liquid every 11h, and the spray dyeing process is the same as that of the embodiment 1A, and the difference is that: the spray dyeing speed is 12mL/min, the diameter of liquid drops sprayed by a sprayer is 2 mu m, and the color bacterial cellulose I film is positioned in the colored culture solution and kept in a static fermentation state during the spray dyeing (the static culture condition is that the culture temperature is 28 ℃ and the culture days are 11d; the color bacterial cellulose II is obtained);

Position numbering	Color of
		5	Bright red
1、2、3、4	Mauve color

(3) Firstly, soaking the colored bacterial cellulose II in a 3wt% NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing an ethanol aqueous solution of curcumin with the mixture, heating to 60 ℃, stirring for 55min, and adjusting the pH value to 5 when the temperature is reduced to 32 ℃ to obtain the colored bacterial cellulose III;

in the mixture, the mass ratio of the colored bacterial cellulose II to the NaOH aqueous solution is 1:60; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 70wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1:600, and the mass percentage of the final curcumin in the system is 0.06 wt%; the system consists of NaOH aqueous solution and curcumin ethanol aqueous solution.

position numbering	Color of
		5	Orange red
1、2、3、4	Reddish brown

Example 2B

raw material preparation:

b2# colored culture solution, wherein the pH value of the colored culture solution is 5, and the temperature is 33 ℃;

b2# spray liquid;

(1) Preparation of a colored bacterial cellulose I film: inoculating strain into B2# colored culture solution, wherein the cell density of strain is 10 ⁸ Standing and culturing for 4d to obtain the final product;

(2) The color bacterial cellulose I film is used as a matrix, a sprayer is adopted to uniformly spray the spraying liquid (spray dyeing) at different positions on the matrix by adopting the b2# spraying liquid every 6h, and the spray dyeing process is the same as that of the embodiment 1A, and the difference is that: the jet dyeing speed is 9mL/min, the diameter of liquid drops sprayed by a jet sprayer is 2 mu m, and the color bacterial cellulose I film is positioned in a colored culture solution and kept in a static fermentation state during the jet dyeing (the static culture condition is that the culture temperature is 30 ℃ and the culture days are 7d; the color bacterial cellulose II is obtained);

Position numbering	Color of
		5	Peach red
1、2、3、4	Intermediate colors of mauve and purple

(3) Firstly, soaking the colored bacterial cellulose II in a 4wt% NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing an ethanol aqueous solution of curcumin with the mixture, heating to 100 ℃, stirring for 30min, and adjusting the pH value to 6.0 when the temperature is reduced to 40 ℃ to obtain the colored bacterial cellulose III;

in the mixture, the mass ratio of the colored bacterial cellulose II to the NaOH aqueous solution is 1:80; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 80wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1:1000, and the mass percentage of the final curcumin in the system is 0.08wt%; the system consists of an aqueous NaOH solution and an aqueous ethanol solution of curcumin.

Position numbering	Color of
		5	Orange yellow
1、2、3、4	Bright orange

Example 3B

raw material preparation:

b3# colored culture solution, wherein the pH value of the colored culture solution is 4, and the temperature is 38 ℃;

b3# spray liquid;

(1) Preparation of a colored bacterial cellulose I film: inoculating strain into B3# colored culture solution, wherein the cell density of strain is 10 ⁸ Standing and culturing for 3d to obtain the final product;

(2) The color bacterial cellulose I film is used as a matrix, a sprayer is adopted to uniformly spray the spraying liquid (spray dyeing) at different positions on the matrix by adopting the b3# spraying liquid every 9h, and the spray dyeing process is the same as that of the embodiment 1A, and the difference is that: the spray dyeing speed is 10mL/min, the diameter of liquid drops sprayed by a sprayer is 0.8 mu m, and the color bacterial cellulose I film is positioned in a colored culture solution and kept in a static fermentation state during the spray dyeing (the static culture condition is that the culture temperature is 37 ℃ and the culture days are 9d; the color bacterial cellulose II is obtained);

Position numbering	Color of
		5	Peach red and red intermediate color
1、2、3、4	Brilliant purple

(3) Firstly, soaking the colored bacterial cellulose II in a 3.5wt% NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing an ethanol aqueous solution of curcumin with the mixture, heating to 66 ℃, stirring for 35min, and adjusting the pH value to 5.0 when the temperature is reduced to 32 ℃ to obtain the colored bacterial cellulose III;

in the mixture, the mass ratio of the colored bacterial cellulose II to the NaOH aqueous solution is 1:90; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 95wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1:1000, and the mass percentage of the final curcumin in the system is 0.1wt%; the system consists of an aqueous NaOH solution and an aqueous ethanol solution of curcumin.

Position numbering	Color of
		5	Orange red
1、2、3、4	Deep blue color

Example 4B

raw material preparation:

the pH value of the colored culture solution is 4, and the temperature is 33 ℃;

b4# spray;

(1) Preparation of a colored bacterial cellulose I film: inoculating strain into B4# colored culture solution, wherein the cell density of strain is 10 ⁹ Standing and culturing for 5d per ml to obtain the final product;

(2) The color bacterial cellulose I film is used as a matrix, a sprayer is adopted to uniformly spray the spraying liquid (spray dyeing) at different positions on the matrix by adopting the b4# spraying liquid every 8 hours, and the spray dyeing process is the same as that of the embodiment 1A, and the difference is that: the jet dyeing speed is 7mL/min, the diameter of liquid drops sprayed by a jet sprayer is 4.5 mu m, and the color bacterial cellulose I film is positioned in a colored culture solution and kept in a static fermentation state during the jet dyeing (the static culture condition is that the culture temperature is 35 ℃ and the culture days are 8d; the color bacterial cellulose II is obtained);

Position numbering	Color of
		5	Intermediate colors of red and bright red
1、2、3、4	Intermediate colors of mauve and purple

(3) Firstly, soaking the colored bacterial cellulose II in an NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing an ethanol aqueous solution of curcumin with the mixture, heating to 63 ℃, stirring for 40min, and adjusting the pH value to 4.5 when the temperature is reduced to 31 ℃ to obtain colored bacterial cellulose III;

in the mixture, the mass ratio of the colored bacterial cellulose II to the 4.5wt% NaOH aqueous solution is 1:100; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 95wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1:1000, and the mass percentage of the final curcumin in the system is 0.009wt%; the system consists of an aqueous NaOH solution and an aqueous ethanol solution of curcumin.

Position numbering	Color of
		5	Orange yellow
1、2、3、4	Intermediate brown and deep blue

The dimensions of the colored bacterial cellulose III in the present invention are shown in tables 5 and 6 below:

TABLE 5

Parameters (parameters)	Example 1A	Example 2A	Example 3A	Example 4A
					Average diameter (nm) of nanofibers	29	50	47	45
Average distance between nanofibers (nm)	860	900	820	780

TABLE 6

Parameters (parameters)	Example 1B	Example 2B	Example 3B	Example 4B
					Average diameter (nm) of nanofibers	25	37	30	32
Average distance between nanofibers (nm)	300	640	510	500

For the colored bacterial cellulose II obtained by the end of the spray dyeing process and the colored bacterial cellulose III obtained by the steaming process in examples 1A-4A and examples 1B-4B, the colors of the spray dyeing sites of the layers are consistent, and based on the method of the above examples, colored bacterial cellulose with different colors of each layer can be obtained, for example, for examples 2A and 3A, the overall color of the colored bacterial cellulose II obtained by the end of the spray dyeing process is the intermediate color of pink and red, and the color of the spray dyeing sites of the colored bacterial cellulose II is the intermediate color of brilliant violet, purple and brilliant violet, respectively. The overall color of the colored bacterial cellulose III obtained after the steaming process is orange red and intermediate colors of orange red and orange, and the site color of the colored bacterial cellulose III is brilliant green, intermediate colors of brilliant green and olive green.

The invention can also adopt the spray-dyeing mode of the embodiment 2A for the first layer and the spray-dyeing mode of the embodiment 3A for the second layer, namely, the spray-dyeing of different levels with different blue pigment concentrations is carried out under the environment of similar matrix colors, so that the color difference of spray-dyeing sites among different layers of the colored bacterial cellulose II is achieved, and the color difference of spray-dyeing sites among different levels is also obtained through the colored bacterial cellulose III obtained in the final post-treatment stage. In practice this difference in color of the spray-dyed sites between the layers is a combination of spray-dyed patterns between the various embodiments.

Example 1C

raw material preparation:

a colored culture solution of C1# with pH value adjusted to 5 and temperature of 32 ℃;

preparing a spray liquid: the spraying liquid adopts the spraying liquid in 2A and 3A in the embodiment;

(1) Preparation of a colored bacterial cellulose I film: inoculating strain into C1#In the color culture solution, the cell density of the strain is 10 ⁷ Standing and culturing for 4d to obtain the final product;

(2) Uniformly spraying spray liquid (spray dyeing) on different positions on a substrate by using a sprayer, wherein the spray dyeing speed is 12mL/min, the diameter of liquid drops sprayed by the sprayer is 5 mu m, and the different positions on the substrate are positions, namely a region 1, a region 2 and a region 3, of the spray dyeing of the sprayer according to the pattern (shown in figure 1) of the mask; the spray dyeing process of the color bacterial cellulose I film is divided into three layers, and the corresponding spray dyeing positions of the 1 st layer, the 2 nd layer and the 3 rd layer are respectively areas 1, 2 and 3; the first layer was spray-dyed with the spray liquor of example 2A every 8 hours, the spray-dyed with the spray liquor of example 3A for 3d, the spray-dyed with the spray liquor of example 3A every 8 hours for 4d, the third layer with the spray liquor of example 2A for 3d, and the spray-dyed with the spray liquor of example 2A every 8 h. The color bacterial cellulose I film is positioned in a color culture solution during spray dyeing and kept in a static fermentation state (the static culture condition is that the culture temperature is 36 ℃), so as to obtain color bacterial cellulose II;

position numbering	Color of
		5	Peach and red intermediate color
1、2、4	Brilliant purple
		3	Intermediate colors of purple and brilliant purple

(3) Firstly, soaking the colored bacterial cellulose II in a 4wt% NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing an ethanol aqueous solution of curcumin with the mixture, heating to 65 ℃, stirring for 50min, and adjusting the pH value to 5 when the temperature is reduced to 33 ℃ to obtain the colored bacterial cellulose III;

in the mixture, the mass ratio of the colored bacterial cellulose II to the NaOH aqueous solution is 1:30; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 90wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1:100, and the mass percentage of the final curcumin in the system is 0.03wt%; the system consists of an aqueous NaOH solution and an aqueous ethanol solution of curcumin.

position numbering	Color of
		5	Orange-red and orange intermediate color
1、2、、4	Olive green
		3	Intermediate brown and deep blue

Example 2C

raw material preparation:

a C2# colored culture solution, wherein the pH value of the colored culture solution is adjusted to be 4, and the temperature is 34 ℃;

preparing a spray liquid: the spray liquid in 3A and 3B in the above embodiments is adopted;

(1) Preparation of a colored bacterial cellulose I film: inoculating strain into C2# colored culture solution, wherein the cell density of strain is 10 ⁸ Standing and culturing for 5d per ml to obtain the final product;

(2) The color bacterial cellulose I film is used as a matrix, the spray liquid is uniformly sprayed (spray-dyed) at different positions on the matrix by adopting a sprayer, the spray-dyeing speed is 9mL/min, the diameter of liquid drops sprayed by the sprayer is 3 mu m, and the different positions and the spray-dyeing process on the matrix are basically the same as those of the embodiment 1C, and the difference is that: the first layer was spray-dyed with the spray liquor of example 3A every 6 hours for 2d, the second layer was spray-dyed with the spray liquor of example 3B every 6h for 3d, and the third layer was spray-dyed with the spray liquor of example 3A every 6h for 3d. The color bacterial cellulose I film is positioned in a color culture solution to keep a static fermentation state (the condition of static culture is that the culture temperature is 31 ℃) during spray dyeing, so as to obtain color bacterial cellulose II;

(3) Firstly, soaking the colored bacterial cellulose II in a 5wt% NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing an ethanol aqueous solution of curcumin with the mixture, heating to 74 ℃, stirring for 35min, and adjusting the pH value to 4.5 when the temperature is reduced to 30 ℃ to obtain the colored bacterial cellulose III;

in the mixture, the mass ratio of the colored bacterial cellulose II to the NaOH aqueous solution is 1:50; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 85wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1:200, and the mass percentage of the final curcumin in the system is 0.02wt%; the system consists of an aqueous NaOH solution and an aqueous ethanol solution of curcumin.

Position numbering	Color of
		5	Orange yellow
1、2、4	Intermediate brown and deep blue
		3	Brown and reddish brown intermediate colors

Example 3C

raw material preparation:

a C3# colored culture solution, wherein the pH value of the colored culture solution is adjusted to 6, and the temperature is 32 ℃;

preparing a spray liquid: the spraying liquid adopts the spraying liquid in 1B and 2B in the embodiment;

(1) Preparation of a colored bacterial cellulose I film: inoculating strain into C3# colored culture solution, wherein the cell density of strain is 10 ⁵ Standing and culturing for 4d to obtain the final product;

(2) The color bacterial cellulose I film is used as a matrix, the spray liquid is uniformly sprayed (spray-dyed) at different positions on the matrix by adopting a sprayer, the spray-dyeing speed is 7mL/min, the diameter of liquid drops sprayed by the sprayer is 6 mu m, and the different positions and the spray-dyeing process on the matrix are basically the same as those of the embodiment 1C, and the difference is that: the first layer was spray-dyed with the spray liquor of example 1B every 10 hours, the spray-dyed with the spray liquor of example 2B for 3d, the spray-dyed with the spray liquor of example 2B every 10 hours for 3d, and the third layer was spray-dyed with the spray liquor of example 1B every 10h for 2d. The color bacterial cellulose II is obtained by keeping the color bacterial cellulose I film in a static fermentation state in a colored culture solution during spray dyeing (the condition of static culture is that the culture temperature is 31 ℃);

position numbering	Color of
		5	Peach red color
1、2、4	Intermediate colors of mauve and red
		3	Mauve color

(3) Firstly, soaking the colored bacterial cellulose II in a 4wt% NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing an ethanol aqueous solution of curcumin with the mixture, heating to 82 ℃, stirring for 30min, and adjusting the pH value to 6 when the temperature is reduced to 28 ℃ to obtain colored bacterial cellulose III;

in the mixture, the mass ratio of the colored bacterial cellulose II to the NaOH aqueous solution is 1:200; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 92wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1:500, and the mass percentage of the final curcumin in the system is 0.01wt%; the system consists of an aqueous NaOH solution and an aqueous ethanol solution of curcumin.

position numbering	Color of
		5	Orange and orange intermediate colors
1、2、4	Brown color
		3	Intermediate color of bright orange and brown

Example 4C

raw material preparation:

a C4# colored culture solution, wherein the pH value of the colored culture solution is adjusted to 4, and the temperature is 29 ℃;

preparing a spray liquid: the spraying liquid adopts the spraying liquid in 1B and 4B in the embodiment;

(1) Preparation of a colored bacterial cellulose I film: inoculating strain into C3# colored culture solution, wherein the cell density of strain is 10 ⁷ Standing and culturing for 3d to obtain the final product;

(2) The color bacterial cellulose I film is used as a matrix, the spray liquid is uniformly sprayed (spray-dyed) at different positions on the matrix by adopting a sprayer, the spray-dyeing speed is 9mL/min, the diameter of liquid drops sprayed by the sprayer is 10 mu m, and the different positions and the spray-dyeing process on the matrix are basically the same as those of the embodiment 1C, and the difference is that: the first layer was spray-dyed with the spray liquor of example 1B every 12h for 3d, the second layer was spray-dyed with the spray liquor of example 4B every 12h for 2d, and the third layer was spray-dyed with the spray liquor of example 1B every 12h for 2d. The color bacterial cellulose I film is positioned in a color culture solution to keep a static fermentation state (the condition of static culture is that the culture temperature is 35 ℃) during spray dyeing, so as to obtain color bacterial cellulose II;

position numbering	Color of
		5	Intermediate colors of red and bright red
1、2、4	Mauve color
		3	Intermediate colors of mauve and purple

(3) Firstly, soaking the colored bacterial cellulose II in a 5wt% NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing an ethanol aqueous solution of curcumin with the mixture, heating to 85 ℃, stirring for 32min, and adjusting the pH value to 5 when the temperature is reduced to 29 ℃ to obtain colored bacterial cellulose III;

in the mixture, the mass ratio of the colored bacterial cellulose II to the NaOH aqueous solution is 1:150; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 88wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1:600, and the mass percentage of the final curcumin in the system is 0.03wt%; the system consists of an aqueous NaOH solution and an aqueous ethanol solution of curcumin.

position numbering	Color of
		5	Orange red
1、2、4	Brown and reddish brown intermediate colors
		3	Intermediate colors of deep blue and brown

Claims

1. The preparation method of the color bacterial cellulose mask is characterized by comprising the following steps:

(3) Taking the colored bacterial cellulose I film obtained in the step (2) as a matrix, adopting spraying liquid to spray-dye at different positions on the matrix every 6-12 h, and keeping the colored bacterial cellulose I film in a static culture state in a colored culture liquid during spraying to obtain colored bacterial cellulose II;

the colored bacterial cellulose II is a mixture composed of natural bacterial cellulose, natural red pigment and natural blue pigment, wherein the natural bacterial cellulose, the natural red pigment and the natural blue pigment are generated by fermentation above the colored bacterial cellulose I, which is used as a substrate; and the color of each spray-dyed position on the colored bacterial cellulose II presents a specific color along with the proportion of the natural red pigment in the colored bacterial cellulose I to the natural blue pigment sprayed on the position, and the specific color refers to one of gradual colors from purple red to purple to brilliant purple;

(4) Firstly, soaking the colored bacterial cellulose II in the step (3) in NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing the curcumin ethanol aqueous solution with the mixture, heating to 60-100 ℃, stirring for 30-60 min, and adjusting the pH value to 4.5-6.0 when the temperature is reduced to 30-40 ℃ to obtain the colored bacterial cellulose III;

the color bacterial cellulose III is a mixture of color bacterial cellulose II and curcumin, and the color of each spray-dyed position on the color bacterial cellulose II corresponds to the ratio of three pigments at the position to each other, and the three pigments at the position show specific colors after the curcumin is added, wherein the specific colors are brown, brilliant green, intermediate colors of brilliant green and olive green, intermediate colors of brown and deep blue, reddish brown, brilliant orange and deep blue.

2. The method for preparing a color bacterial cellulose mask according to claim 1, wherein the specific process of step (1) is as follows: firstly, removing bacteria from the natural red pigment extracting solution by using a 0.22 mu m filter; mixing the natural red pigment extract with bacteria removed with the basic culture solution after high-pressure steam sterilization treatment;

the formula of the colored culture solution is as follows:

1 to 6 weight percent of substance A;

peptone 0.05-1 wt%;

yeast extract 0.05-1 wt%;

0.01 to 0.5 weight percent of citric acid;

disodium hydrogen phosphate 0.04-0.4wt%;

0.02 to 0.2 weight percent of monopotassium phosphate;

0.005-2wt% of natural red pigment;

the balance of water;

the substance A is more than one of glucose, fructose, sucrose and mannitol.

3. The method for preparing a color bacterial cellulose mask according to claim 1, wherein in the step (2), the pH value of the color culture solution is 4-6, and the temperature is 30-38 ℃.

4. The method for preparing a color bacterial cellulose mask according to claim 1, wherein in the step (3), the conditions of the stationary culture are: the culture temperature is 28-37 ℃.

5. The method for preparing a color bacterial cellulose mask according to claim 1, wherein in the step (3), the spray liquid is a mixed liquid of a natural blue pigment extract and a basic culture liquid.

6. The method for preparing a color bacterial cellulose mask according to claim 1, wherein in the step (3), the formula of the mixed solution of the natural blue pigment extract and the basic culture solution is as follows:

1-6wt% of a substance B;

Peptone 0.05-1 wt%;

yeast extract 0.05-1 wt%;

0.01 to 0.5 weight percent of citric acid;

disodium hydrogen phosphate 0.04-0.4wt%;

0.02 to 0.2 weight percent of monopotassium phosphate;

0.003 to 1.5 weight percent of natural blue pigment;

the balance of water;

the substance B is more than one of glucose, fructose, sucrose and mannitol.

7. The method of claim 1, wherein the range of movement in step (3) is: x-axis is 0-30 cm, Y-axis is 0-30 cm, Z-axis is 0-34 cm.

8. The method for preparing a color bacterial cellulose mask according to claim 1, wherein in the step (3), the spray dyeing speed is 1-15 mL/min, and the diameter of the liquid drops sprayed by the sprayer is 0.5-6 μm.

9. The method for preparing a color bacterial cellulose mask according to claim 1, wherein the stationary culture conditions in the step (3) are identical to those in the step (2).

10. The method for preparing a color bacterial cellulose mask according to claim 1, wherein the mass ratio of the color bacterial cellulose II to the NaOH aqueous solution in the mixture of the step (4) is 1-10:100; in the ethanol aqueous solution of curcumin, the concentration of ethanol in the ethanol aqueous solution is 70-95 wt%, when the ethanol aqueous solution of curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of curcumin to the NaOH aqueous solution is 1-10:1000, and the mass percentage of the final curcumin in the system is 0.001-0.1 wt%; the system consists of an aqueous NaOH solution and an aqueous ethanol solution of curcumin.