CN114108336A

CN114108336A - Preparation method of colorful bacterial cellulose facial mask

Info

Publication number: CN114108336A
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: 2022-03-01
Anticipated expiration: 2041-11-26
Also published as: CN114108336B

Abstract

The invention relates to a preparation method of a colorful bacterial cellulose facial mask, which comprises the steps of inoculating a strain into a colored culture solution, carrying out static culture for 3-5 days to obtain a colorful bacterial cellulose I film with the thickness of 0.1-1 mm, then taking the colorful bacterial cellulose I film as a substrate, carrying out spray-painting at different positions on the substrate by adopting a spray liquid every 6-12 hours, and during the spray-painting, keeping the colorful bacterial cellulose I film in the colored culture solution in a static culture state to obtain colorful bacterial cellulose II; and finally, soaking the colorful bacterial cellulose II in NaOH aqueous solution, uniformly mixing to obtain a mixture, mixing the ethanol aqueous solution of curcumin 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 colorful bacterial cellulose III. The method can endow the bacterial cellulose facial mask with diversified colors, and also can enable the bacterial cellulose facial mask to have the function of natural pigment, so that the application field is wider.

Description

Preparation method of colorful bacterial cellulose facial mask

Technical Field

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

Background

The facial mask is a product which is applied or coated on the surface of human skin and is uncovered, scrubbed or kept after a period of time, so that certain centralized nursing or cleaning effects are achieved. The mechanism of action of the mask is as follows: the facial mask is applied to the surface layer of a human body, the cuticle is softened by covering the skin, meanwhile, the covering of the facial mask also provides a closed environment for the surface layer of the skin, air or pollution is isolated, and under the closed environment, the temperature of the skin is increased, the blood circulation of the skin is enhanced, capillaries and pores are expanded, the metabolism of the skin is promoted, the skin can absorb the effective components of the facial mask more easily, or a colloidal film is formed to remove dirt such as blackheads, aged dandruff and the like in the sticking and tearing process.

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

The non-woven fabric facial mask is the most common one in the market at present, short fibers, filaments or a porous membrane are bonded or intertwined to be processed into a sheet-shaped or net-shaped material, fiber fragments are not easy to generate, and the skin is always in a relatively relaxed and soft state due to good moisture retention of the non-woven fabric in the using process and cannot be tense due to essence loss caused by long-time application. At present, the dyeing process of the non-woven fabric is mature, and is applied to industrial production, and products with different colors brought by the dyeing of the non-woven fabric are widely popular.

The biological cellulose facial mask is a facial mask product taking biological cellulose as a base material, wherein the biological cellulose is bacterial cellulose. The bacterial cellulose has a three-dimensional reticular fiber structure and is in a nanometer level, a plurality of holes are formed in the fiber, the specific surface area is higher, and a plurality of hydrophilic groups are arranged on a molecular chain, so that the bacterial cellulose has good air permeability and water binding property. In addition, the bacterial cellulose has excellent biocompatibility, tensile strength, tensile property and the like, and good plasticity, and can change the sizes of different faces in a cutting mode and the like, so that the skin surface can be highly attached. At present, facial masks with bacterial cellulose as a base material are also proposed by various brands at home and abroad; however, compared to nonwoven fabric type facial masks, there are few studies on staining of bacterial cellulose, and bacterial cellulose produced in laboratories or in industries is white or translucent in general, and has a single color and limited functions.

Therefore, the development of a method for endowing the bacterial cellulose facial mask with diversified colors 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 facial mask. The invention endows the natural bacterial cellulose facial mask with new color and functionality brought by natural pigment by adjusting the proportion of various natural pigments in three processes of fermentation, spray dyeing during fermentation and post-treatment.

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

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

(1) preparing a colored culture solution containing natural red pigment with the mass fraction of 0.005-2 wt%; the natural red pigment is more than one of natural black corn pigment, sorghum red pigment, red leaf beet pigment, lac red pigment, cochineal red pigment and safflower red pigment;

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

(3) taking the colored bacterial cellulose I film obtained in the step (2) as a substrate, and spray-painting the substrate at different positions by adopting a spray liquid every 6-12 hours (the position of each spray-painting is related to a pre-constructed three-dimensional pattern, the position of each spray-painting is different or the same, the position of each spray-painting can be single, two or more, and the positions are related to a pre-designed pattern), wherein the colored bacterial cellulose I film is positioned in a colored culture solution during the spray-painting and is kept in a standing culture state, so that colored bacterial cellulose II is obtained;

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

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

when the adopted spray liquid is the natural blue pigment extracting solution, the amount of the basic culture liquid in the culture medium is sufficient, namely the basic culture liquid can grow every 6-12 hours from the film form of 3-5 days of culture, and the bacterial cellulose is thickened;

when the used spray liquid is a mixed liquid of a natural blue pigment extracting solution and a basic culture liquid, the culture liquid in the culture medium is only in an amount which can grow a 3-5 d film, and the mixed liquid sprayed by the sprayer contains the other part of the culture liquid, so that the continuous thickening of the mixed liquid is realized;

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

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

the spray painting adopts a sprayer which can move in the spatial position in three directions of XYZ three-dimensional coordinate axes; the spray dyeing is to uniformly spray a spray solution;

the different positions on the substrate refer to positions for spray dyeing by a sprayer determined according to the pattern of the mask;

the colorful bacterial cellulose II is a mixture consisting of natural bacterial cellulose, natural red pigment and natural blue pigment which are generated by fermentation above the colorful bacterial cellulose I as a substrate; the color of each spray-dyed position on the colorful bacterial cellulose II presents a specific color along with the proportion of the natural red pigment in the colorful bacterial cellulose I and the natural blue pigment sprayed on the position, and the specific color is one of the gradual colors (also called as 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 hours under the control of the computer end, and finally, the spatial position of the natural blue pigment on each layer is stabilized through the stacking of the layers; wherein, according to the pattern of the facial mask, the digital signal is converted, the position of spray-painting on each layer is determined by a sprayer connected with a signal output end of a computer, specifically, the position of spray-painting on each layer is determined relative to a pre-constructed three-dimensional pattern, finally, the spray-painting on each layer is carried out by the spatial movement of the sprayer on three axes X, Y, Z, the color of the bacterial cellulose finally has color change along with the end of the spray-painting process, and the color change is influenced by the proportion of the red-blue pigment, thereby constructing the three-dimensional pattern on the film;

in each layer of the colored bacterial cellulose II obtained by the spray-painting process, the color of the spray-painted position can be changed, and the color of the whole colored bacterial cellulose II can be slightly changed, specifically: the color of the spray-dyed position is based on red blue, the two are adjusted in different proportions to present various colors (red, blue and less purple, when the same amount is purple, and when blue and more red are less brilliant purple; namely, various gradual colors from purple red to purple can be presented), after the spray-dyeing process is finished, the color change of the spray-dyed position on each layer is removed, the slight diffusion of the pigment on the spray-dyed position on each layer is also present (the diffusion amount and the range of the blue pigment on the spatial position point on each layer are smaller relative to each layer), the slight diffusion of the blue pigment on the spray-dyed position on each layer finally causes the color change of the colored bacterial cellulose II on the whole, and finally the spray-dyeing process is finished, and the color (the various colors from purple to brilliant purple) and the whole color (peach red, purple and brilliant purple) on the spatial position of each layer of the colored bacterial cellulose II are accompanied by the slight diffusion of the blue pigment on each layer Red, brilliant red, and their neutral colors);

(4) soaking the colored bacterial cellulose II in the step (3) in NaOH aqueous solution, uniformly mixing to obtain a mixture, mixing ethanol aqueous solution of turmeric pigment with the mixture, heating to 60-100 ℃, stirring for 30-60 min (namely a cooking process), adjusting the pH value to 4.5-6.0 when the temperature is reduced to 30-40 ℃, adjusting the pH value within the temperature range to prevent the degradation of the three pigments, adjusting the pH value to 4.5-6.0, and enabling the natural red pigment to be stable red, the natural blue pigment to be stable blue and the curcumin to be stable yellow within the pH value range, so that the coloring of the bacterial cellulose by various natural pigments can be realized by utilizing a color matching principle, and the color stability is kept to obtain the colored bacterial cellulose III;

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

as the cooking process is carried out, the color of the position sprayed and dyed in the colorful bacterial cellulose II is controlled by the proportion of two pigments of red and blue, and is converted into the color controlled by the proportion of three pigments of red and yellow, so that for the colorful bacterial cellulose III, the color at different positions on each layer presents different colors according to the different proportions of the natural red pigment, the natural blue pigment and the curcumin, and the colors refer to brown, brilliant green and olive green intermediate colors, brown and dark blue intermediate colors, reddish brown, brilliant orange and dark blue. Because a trace amount of blue pigment is diffused in the cooking process, the prepared colorful bacterial cellulose III has color change on the space position of each layer and slight change of the whole color; thus, the final color of the colored bacterial cellulose III has the colors at the spatial positions of each layer (brown, brilliant green, the intermediate color of brilliant green and olive green, the intermediate color of brown and dark blue, reddish brown, brilliant orange and dark blue), and the overall colors (orange yellow, orange red and the intermediate colors thereof).

The natural red pigment extracting solution and the natural blue pigment extracting solution are generally prepared by adopting a solvent extraction method, which comprises the following steps:

drying raw materials (generally branches, leaves, roots, stems and the like of natural plants) containing natural pigments at low temperature to constant weight, and then grinding; adding natural pigment powder into a solution containing 30-70 wt% of an extraction solvent by adopting an ultrasonic-assisted extraction method according to the ratio of 1g to 3-30 mL, and performing ultrasonic extraction for 5-60 min; then, the residue is filtered by suction and collected as the natural pigment extracting solution.

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

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

The extraction process of the purple cabbage pigment comprises the following steps: firstly, cleaning and chopping the purple cabbage by adopting an ultrasonic-assisted extraction method, grinding the purple cabbage after drying the purple cabbage for 4-6 min, and then placing the purple cabbage in a closed container for later use; adding the ground purple cabbage into a 0.2-0.7 mol/L hydrochloric acid aqueous solution (preferably 0.3mol/L) according to a material-to-liquid ratio of 1g: 5-25 mL (preferably 1:10g/mL), setting ultrasonic power at 70-85W, leaching at 30-70 ℃ (preferably 40 ℃) for 4-12 min (preferably 8min), leaching, removing residues through suction filtration, and collecting filtrate as a purple cabbage pigment extracting solution.

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

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

The natural red pigment and the natural blue pigment used in the formula of the colored culture solution are determined according to the maximum absorbance which can be presented by the pigment in the solution in certain wavelength ranges.

Curcumin was purified by acid-base precipitation based on crude extract, and a yellow precipitate was obtained by adjusting pH to 7.3, and the ratio of the addition of the other two pigments was quantified by yellow precipitate.

As a preferred technical scheme:

the preparation method of the colorful bacterial cellulose facial mask comprises the following specific steps of (1): firstly, degerming the natural red pigment extract by using a 0.22 mu m filter (because the natural pigment is unstable at high temperature, the natural red pigment extract is filtered by using the filter); mixing the degerming natural red pigment extracting solution with a basic culture solution subjected to high-pressure steam sterilization treatment (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:

1-6 wt% of a substance A;

0.05-1 wt% of peptone;

0.05-1 wt% of yeast extract;

0.01-0.5 wt% of citric acid;

0.04-0.4 wt% of disodium hydrogen phosphate;

0.02-0.2 wt% of monopotassium phosphate;

0.005-2 wt% of natural red pigment;

the balance of water;

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

According to the preparation method of the colorful bacterial cellulose facial mask, in the step (2), the pH value of the colored culture solution is 4-6, and the temperature is 30-38 ℃. The natural red pigment is selected and 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 natural red pigment can be prevented from being degraded, and more pigments 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 description of the state of the finally obtained culture solution is given after the process of preparing the culture solution is finished, the culture temperature in the culture process is 28-37 ℃, the normal growth of the mycoderm can be ensured, and the current temperature difference between the two processes is not related.

In the preparation method of the color bacterial cellulose facial mask, in the step (2), the static culture conditions are as follows: the culture temperature is 28-37 ℃. The culture temperature is too high or too low, and both the culture temperature and the culture temperature can affect the activity of strains, so that the yield of bacterial cellulose is affected; the temperature is 28-37 ℃ which is a suitable condition for producing the bacterial cellulose by fermenting the strain, and the yield of the bacterial cellulose can be increased along with the increase of the culture days when the bacterial cellulose is cultured at any temperature within the temperature range.

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

In the preparation method of the color bacterial cellulose facial 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:

1-6 wt% of a substance B;

0.05-1 wt% of peptone;

0.05-1 wt% of yeast extract;

0.01-0.5 wt% of citric acid;

0.04-0.4 wt% of disodium hydrogen phosphate;

0.02-0.2 wt% of monopotassium phosphate;

0.003 to 1.5 wt% of natural blue pigment;

the balance of water;

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

According to the preparation method of the colorful bacterial cellulose facial mask, the moving range in the step (3) is as follows: the X axis is 0-30 cm, the Y axis is 0-30 cm, and the Z axis is 0-34 cm.

In the preparation method of the colorful bacterial cellulose facial 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 μm.

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

According to the preparation method of the colorful bacterial cellulose facial mask, in the mixture in the step (4), the mass ratio of the colorful bacterial cellulose II to the NaOH aqueous solution is 1-10: 100; in the ethanol aqueous solution of the curcumin, the concentration of ethanol in the ethanol aqueous solution is 70-95 wt%, when the ethanol aqueous solution of the curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of the 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 NaOH aqueous solution and ethanol aqueous solution of curcumin.

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

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

The concentration of ethanol in the aqueous ethanol solution is 70-95 wt%, and the concentration range is used for the solubility of the curcumin, and the maximum dissolution of the curcumin is ensured in the range.

The mechanism of the invention is as follows:

the method comprises the steps of firstly preparing a haematochrome culture solution, obtaining a colored bacterial cellulose I film substrate through a culture stage, then preparing colored bacterial cellulose II through a spray dyeing process, finally adding curcumin in an alkali liquor dipping process, and adjusting pH to obtain the colored bacterial cellulose III.

The spray dyeing process comprises the steps that on one hand, relatively unstable blue pigments are dyed in a relatively mild mode, and are not damaged to the maximum extent through spraying, so that the relatively unstable blue pigments can be reserved; the blue pigment sprayed on the bacterial cellulose has the advantages that the pigment sites can not move obviously, on one hand, the hydroxyl groups or hydrogen bonds of the bacterial cellulose can adsorb pigment molecules, on the other hand, next spraying is carried out at a certain time interval, and a certain time is provided, so that more pigment molecules can be adsorbed on the bacterial cellulose. The layered spray-painting is to obtain a three-dimensional pattern, and the three-dimensional pattern is finally constructed as a whole by stacking layers by using the spray-painting sites of each layer.

In the dipping process of the alkali liquor, on one hand, curcumin can be better diffused, so that the coloring of curcumin on the colorful bacterial cellulose II is improved, on the other hand, the final process of the alkali liquor dipping is the final adjustment of the color, the red-blue pigment can generate the color change due to the increase of the pH value in the alkali liquor dipping process, and the red-blue-yellow three pigments are adjusted to the state of three primary colors through the adjustment back of the final pH value, so that the desired color is achieved; the position of the pigment sprayed and dyed in the colored bacterial cellulose II can not move at the end of the alkali liquor dipping process, the position fixation of the pigment sprayed and dyed in the colored bacterial cellulose II is mainly realized through the following two aspects, firstly, the hydroxyl or hydrogen bond of the bacterial cellulose is used for firmly adsorbing pigment molecules, secondly, the colored bacterial cellulose I film is used as a substrate, the spraying and dyeing is carried out once every 6-12 hours, the spraying and dyeing is carried out at different positions of each layer by controlling a computer digital signal output end to spraying equipment, and finally, the layers are overlapped to generate the colored bacterial cellulose II, the superposition of the layers also has a fixing effect on the position of the pigment, so that the position of the pigment sprayed and dyed after being cooked by alkali liquor has no obvious change compared with the prior position through the fixing effect of the two layers;

the nature of natural pigments is not stable, which also leads to a change in their colour. In the prior art, a natural pigment is generally added into bacterial cellulose to prepare colorful bacterial cellulose, the colorful bacterial cellulose has a single color, the addition of a single natural pigment can easily present the expected color through the control of temperature and pH value, and the addition of a plurality of natural pigments can mix the plurality of natural pigments because the respective color changes are affected by different pH values and temperatures, so that the respective color presentation of the natural pigments is not easy under the same condition, thereby limiting the combination of the plurality of natural pigments and the dyeing of certain substances to a great extent.

The invention adopts a plurality of natural pigments for color matching, and controls the proportion of the added natural pigments based on the three-primary color matching principle, so that the color of the finally obtained colored bacterial cellulose can be close to the target color designed by color matching, and the natural pigments are prevented from forming an unstable structure in the process of preparing the colored bacterial cellulose to cause larger deviation with the target color.

The method specifically comprises the following steps: the invention selects three specific natural pigments which are respectively natural red pigments (natural black corn pigment, sorghum red pigment, red leaf beet pigment, lac red pigment, cochineal red pigment and safflower red pigment), natural blue pigments (purple cabbage pigment, gardenia blue pigment, blueberry pigment and algae blue pigment) and curcumin, and the three pigments can meet the color requirement of three primary colors for color matching; in addition, the invention also divides the color matching process into three steps, which are respectively as follows: firstly, adding natural red pigment into a bacterial cellulose fermentation culture stage to prepare the colored bacterial cellulose I, wherein the natural red pigment is added into 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, actually, the relationship between the first step and the second step is tight, the spray dyeing is carried out on the colored bacterial cellulose I by taking a colored bacterial cellulose I film fermented for 3-5 days as a substrate, 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 the spray dyeing at different positions on each layer, the control time is 6-12 hours, a thin layer cannot grow out if the time is too short, the time is too long, the next layer required for spray dyeing is likely to thicken, and is not beneficial to the construction of the three-dimensional patterns, in addition, a certain time interval exists, which is also beneficial to fixing the natural blue pigment;

the natural red and blue pigments contain anthocyanin, and the anthocyanin has different structures at different pH values, so that the pigment has different colors at different pH values only when the anthocyanin structures exist in different modes due to the pH values, but the existence mode of the anthocyanin structures can have reversible change due to the different pH values, and the change is the basis of the color change brought by the change back of the pH value of subsequent alkali liquor treatment (namely, the three pigments can show color change along with the pH values, and the color tones of the three pigments are in the state of three primary colors through the adjustment of the pH value in the subsequent treatment); and then the prepared colored bacterial cellulose II and curcumin are subjected to color matching in alkali liquor, and the temperature, time and pH value of the alkali liquor of the color matching 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 and the time of color matching and the pH value of the alkali liquor are controlled, the determination method comprises the following steps:

and adjusting the pH value to 4.5-6.0, wherein the natural red pigment is stable red, the natural blue pigment is stable blue and the curcumin is stable yellow within the pH value range, so that the bacterial cellulose can be colored by various natural pigments by utilizing the three-primary-color matching principle, and the color stability is kept. Before the process of adjusting the pH value, the third pigment is dyed by heating and stirring at the temperature of 60-100 ℃ for 30-60 min, the pH value is adjusted to be reduced to 30-40 ℃, the pH value is adjusted to be 4.5-6.0 at the relatively low temperature, and the color and the property of the pigment are relatively stable.

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

Advantageous effects

(1) The preparation method of the colored bacterial cellulose comprises the first step of obtaining a film matrix of the colored bacterial cellulose I by culture and fermentation, endowing the film matrix of the colored bacterial cellulose I with new colors at different sites through a spray-painting process of the second step so as to obtain colored bacterial cellulose II with different colors, adding a third pigment in the third step of post-treatment so as to change the colors at the spray-painting sites so as to obtain colored bacterial cellulose III, and finally adding the colored bacterial cellulose with the colors of different proportions into the bacterial cellulose so as to achieve the purpose of generating new colors;

(2) the spray-painting process is added, and a method for realizing three-dimensional patterning of the bacterial cellulose is provided on the basis of generating new colors by the bacterial cellulose by utilizing the growth process of the bacterial cellulose;

(3) the colorized bacterial cellulose provided by the invention not only can achieve the purpose of color controllability, but also can enable the bacterial cellulose to have the function of natural pigment, and the color is controllable and functionalized, so that the application field of the colorized bacterial cellulose is wider.

Drawings

FIG. 1 is a schematic diagram of a spray painting process and corresponding area positions of a sprayer according to the present invention;

FIG. 2 is a schematic diagram of the positions of the colorized bacterial cellulose II with different colors in the invention.

Detailed Description

The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the teachings of the present invention, and such equivalents also fall within the scope of the appended claims.

The extraction process of the curcumin comprises the following steps: firstly, slicing the cleaned turmeric medicinal material, placing the sliced turmeric medicinal material in a vacuum drying oven at 45 ℃ to be dried to constant weight, sieving the sliced turmeric medicinal material by a 50-mesh sieve, wrapping a certain amount of turmeric powder by using filter paper, placing the filter paper in a Soxhlet extractor filled with 350mL of petroleum ether (the boiling range is 60 ℃) until the solution is colorless, opening the filter paper, drying the filter paper in the shade in a fume hood to obtain degreased turmeric powder, then adding the degreased turmeric powder into 50% ethanol water solution according to the solid-to-liquid ratio of 1g to 10mL, extracting at 60 ℃ for 2.5h, wherein the pH value is 4.0, the yield of curcumin is 5.78%, and finally, further purifying the extracting solution by using 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, i.e. curcumin.

The spray painting adopts a sprayer which can move in the spatial position in three directions of XYZ three-dimensional coordinate axes; and the range of movement is: the X axis is 0-30 cm, the Y axis is 0-30 cm, and the Z axis is 0-34 cm. If a CREALITY3D printer is adopted, the model adopts end-3 max, the printing size is 300mm x 340mm, the spray head used for melting by the original instrument is changed into the spray head for spraying the solution by modification, the spray head is connected with a small metering pump, and the metering pump controls the amount of the solution sprayed by the spray head.

The colored culture solution containing the natural red pigment comprises the following components: firstly, degerming the natural red pigment extracting solution by using a 0.22 mu m filter; mixing the degerming natural red pigment extracting solution with the basic culture solution subjected to high-pressure steam sterilization treatment; the formulas of the colored culture solutions containing natural red pigments are shown in tables 1-3.

TABLE 1

TABLE 2

TABLE 3

The invention adopts a spraying liquid prepared by a mixed liquid of a natural blue pigment extracting solution and a basic culture solution, and the formula of the spraying liquid is shown in the following table 4:

TABLE 4

The term names for colors in the present invention refer to the 37 color regions in GB 3899.2.

Example 1A

preparing raw materials:

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

preparing a spraying liquid: the content of the natural blue pigment is 0.0075 wt% of the natural blue pigment extract; the natural blue pigment is purple glycyl blue pigment;

(1) preparing a colorful bacterial cellulose I film: inoculating the strain into A1# colored culture solution, wherein the cell density of the strain is 10⁵Standing and culturing for 3d to obtain the extract per ml;

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

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

areas

1, 2 and 3 respectively;

the colorful bacterial cellulose II is a mixture consisting of natural bacterial cellulose, natural red pigment and natural blue pigment which are generated by fermentation above the colorful bacterial cellulose I as a substrate; and each spray-dyeing position (position number referring to fig. 2) on the colorized bacterial cellulose II and the corresponding color (as shown in the following table) are:

location numbering	Colour(s)
		5	Pink color
1、2、3、4	Intermediate color of purple red and purple

FIG. 2 is a schematic view of the whole of the colored bacterial cellulose II, wherein 1 and 4 correspond to two positions of a region 1 in FIG. 1, 2 corresponds to

regions

2 and 3 in FIG. 1, and regions 3 and 5 in FIG. 1 correspond to the colors of the whole body of the bacterial cellulose;

(3) firstly, soaking the colorful bacterial cellulose II in a3 wt% 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 colorful bacterial cellulose III;

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

The colored bacterial cellulose III is a mixture consisting of colored bacterial cellulose II and curcumin, and the color of each spray-dyeing position on the colored bacterial cellulose II corresponds to the color, and after the curcumin is added, the specific color is presented by the proportion of three pigments at the position, and the specific color is shown in the following table:

location numbering	Colour(s)
		5	Intermediate color of orange red and orange
1、2、3、4	Brown colour

Example 2A

preparing raw materials:

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 spraying liquid: a natural blue pigment extract solution containing 0.600 wt% of natural blue pigment; the natural blue pigment is a mixture of purple cabbage pigment and blueberry pigment in a mass ratio of 1: 1;

(1) preparing a colorful bacterial cellulose I film: inoculating the strain into A2# colored culture solution, wherein the cell density of the strain is 10³Standing and culturing for 5 days to obtain the strain per ml;

(2) the colored bacterial cellulose I film is used as a substrate, a sprayer is adopted to uniformly spray spraying liquid (spray-painting) at different positions on the substrate every 12 hours, the spray-painting 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 film of the colorful bacterial cellulose I is positioned in a colorful culture solution during the spray-dyeing and is kept in a static fermentation state (the static culture conditions are that the culture temperature is 28 ℃ and the culture days are 7d) to obtain colorful bacterial cellulose II;

the colorful bacterial cellulose II is a mixture consisting of natural bacterial cellulose, natural red pigment and natural blue pigment which are generated by fermentation above the colorful bacterial cellulose I which is used as a substrate; and each spray-dyeing position (position number referring to fig. 2) on the colorful bacterial cellulose II and the corresponding color (as shown in the following table) are as follows:

(3) firstly, soaking the colorful bacterial cellulose II in a 5 wt% 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 60min, and adjusting the pH value to 4.5 when the temperature is reduced to 30 ℃ to obtain colorful bacterial cellulose III;

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

location numbering	Colour(s)
		5	Orange red
1、2、3、4	Brilliant green

Example 3A

preparing raw materials:

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

preparing a spraying liquid: natural blue pigment extractive solution with natural blue pigment content of 0.12 wt%; the natural blue pigment is prepared from the following components in a mass ratio of 1: 3a mixture of gardenia blue pigment and phycoblue pigment;

(1) preparing a colorful bacterial cellulose I film: mixing the strainsInoculating into A3# colored culture solution, and the cell density of the strain is 10⁶Standing and culturing for 4 days to obtain the strain per ml;

(2) the colored bacterial cellulose I film is used as a substrate, a sprayer is adopted to uniformly spray spraying liquid (spray-painting) at different positions on the substrate every 7 hours, the spray-painting 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 film of the colorful bacterial cellulose I is positioned in the colorful culture solution during the spray-dyeing period and is kept in a static fermentation state (the static culture condition is that the culture temperature is 32 ℃, the culture days are 7 d;), so as to obtain the colorful bacterial cellulose II;

(3) firstly, soaking the colored bacterial cellulose II in NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing the ethanol aqueous solution of curcumin with the mixture, heating to 70 ℃, stirring for 40min, and regulating 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 colorful bacterial cellulose II to the NaOH aqueous solution is 1: 30; in the ethanol aqueous solution of the curcumin, the concentration of ethanol in the ethanol aqueous solution is 85 wt%, when the ethanol aqueous solution of the curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of the curcumin to the NaOH aqueous solution is 1:100, and the final mass percent of the curcumin in the system is 0.01 wt%; the system consists of NaOH aqueous solution and ethanol aqueous solution of curcumin.

location numbering	Colour(s)
		5	Intermediate color of orange red and orange
1、2、3、4	Intermediate color between brilliant green and olive green

Example 4A

preparing raw materials:

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 spraying liquid: a natural blue pigment extract solution containing 0.600 wt% of natural blue pigment; the natural blue pigment is a mixture of purple cabbage pigment, gardenia blue pigment and algae blue pigment in a mass ratio of 1:1: 1;

(1) preparing a colorful bacterial cellulose I film: inoculating the strain into A4# colored culture solution, wherein the cell density of the strain is 10⁷Standing and culturing for 5 days to obtain the strain per ml;

(2) the colored bacterial cellulose I film is used as a substrate, a sprayer is adopted to uniformly spray spraying liquid (spray-painting) at different positions on the substrate every 8 hours, the spray-painting process is the same as that of the embodiment 1A, and the difference is that: spray-dyeing speed is 1mL/min, the diameter of liquid drop sprayed by a sprayer is 0.5 μm, and the film of the colorful bacterial cellulose I is positioned in a colorful culture solution during spray-dyeing and is kept in a static fermentation state (the static culture condition is that the culture temperature is 31 ℃, the culture days are 8 d;), so as to obtain colorful bacterial cellulose II;

location numbering	Colour(s)
		5	Red colour
1、2、3、4	Purple color

(3) Firstly, soaking the colored bacterial cellulose II in NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing the ethanol aqueous solution of curcumin with the mixture, heating to 68 ℃, stirring for 50min, and regulating 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 colorized bacterial cellulose II to 3.5 wt% of NaOH aqueous solution is 1: 40; in the ethanol water solution of the curcumin, the concentration of ethanol in the ethanol water solution is 80 wt%, when the ethanol water solution of the curcumin is mixed with the mixture, the volume ratio of the ethanol water solution of the curcumin to the NaOH water solution is 1:200, and the final mass percent of the curcumin in the system is 0.02 wt%; the system consists of NaOH aqueous solution and ethanol aqueous solution of curcumin.

location numbering	Colour(s)
		5	Orange red
1、2、3、4	Intermediate colors of brown and dark blue

Example 1B

preparing raw materials:

b1# colored culture solution, wherein the pH value of the colored culture solution is adjusted to 6, and the temperature is 30 ℃;

b1# spray solution;

(1) preparing a colorful bacterial cellulose I film: inoculating the strain into B1# colored culture solution, wherein the cell density of the strain is 10¹³Standing and culturing for 5 days to obtain the strain per ml;

(2) the colored bacterial cellulose I film is used as a substrate, a sprayer is adopted to uniformly spray liquor (spray-painting) at different positions on the substrate by adopting b1# spray liquor every 11 hours, the spray-painting 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 film of the colorful bacterial cellulose I is positioned in the colorful culture solution during the spray-dyeing and is kept in a static fermentation state (the static culture condition is that the culture temperature is 28 ℃, the culture days are 11d), so that the colorful bacterial cellulose II is obtained;

location numbering	Colour(s)
		5	Brilliant red
1、2、3、4	Purplish red color

(3) Firstly, soaking the colorful bacterial cellulose II in a3 wt% 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 colorful bacterial cellulose III;

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

location numbering	Colour(s)
		5	Orange red
1、2、3、4	Reddish brown color

Example 2B

preparing raw materials:

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

b2# spray solution;

(1) preparing a colorful bacterial cellulose I film: inoculating the strain into B2# colored culture solution, wherein the cell density of the strain is 10⁸Per ml, standingCulturing for 4 d;

(2) the colored bacterial cellulose I film is used as a substrate, a sprayer is adopted to uniformly spray liquor (spray-painting) at different positions on the substrate by adopting b2# spray liquor every 6 hours, the spray-painting process is the same as that of the embodiment 1A, and the difference is that: the spray-dyeing speed is 9mL/min, the diameter of the liquid drop sprayed by the sprayer is 2 μm, and the colored bacterial cellulose I film is positioned in the colored culture solution during the spray-dyeing period and is kept in a static fermentation state (the static culture condition is that the culture temperature is 30 ℃, the culture days are 7 d;), so as to obtain colored bacterial cellulose II;

location numbering	Colour(s)
		5	Peach red
1、2、3、4	Intermediate color of purple red and purple

(3) Firstly, soaking the colorful bacterial cellulose II in a4 wt% 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 colorful bacterial cellulose III;

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

location numbering	Colour(s)
		5	Orange yellow
1、2、3、4	Bright orange

Example 3B

preparing raw materials:

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

b3# spray solution;

(1) preparing a colorful bacterial cellulose I film: inoculating the strain into B3# colored culture solution,the cell density of the strain is 10⁸Standing and culturing for 3d to obtain the extract per ml;

(2) the colored bacterial cellulose I film is used as a substrate, a sprayer is adopted to uniformly spray liquor (spray-painting) at different positions on the substrate by adopting b3# spray liquor every 9 hours, the spray-painting 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 film of the colorful bacterial cellulose I is positioned in the colorful culture solution during the spray-dyeing period and is kept in a static fermentation state (the static culture condition is that the culture temperature is 37 ℃, the culture days are 9 d;), so as to obtain the colorful bacterial cellulose II;

location numbering	Colour(s)
		5	Intermediate color between pink and red
1、2、3、4	Brilliant purple

(3) Firstly, soaking the colorful bacterial cellulose II in a 3.5 wt% 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 colorful bacterial cellulose III;

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

location numbering	Colour(s)
		5	Orange red
1、2、3、4	Deep blue color

Example 4B

preparing raw materials:

b4# colored culture solution, wherein the pH value of the colored culture solution is 4, and the temperature is 33 ℃;

b4# spray solution;

(1) preparation of colored bacteriaCellulose I film: inoculating the strain into B4# colored culture solution, wherein the cell density of the strain is 10⁹Standing and culturing for 5 days to obtain the extract per ml;

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

location numbering	Colour(s)
		5	Intermediate of red and brilliant red
1、2、3、4	Intermediate color of purple red and purple

(3) Firstly, soaking the colored bacterial cellulose II in NaOH aqueous solution, uniformly mixing to obtain a mixture, then mixing the ethanol aqueous solution of curcumin with the mixture, heating to 63 ℃, stirring for 40min, and regulating 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 colorized bacterial cellulose II to the 4.5 wt% NaOH aqueous solution is 1: 100; in the ethanol aqueous solution of the curcumin, the concentration of ethanol in the ethanol aqueous solution is 95 wt%, when the ethanol aqueous solution of the curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of the curcumin to the NaOH aqueous solution is 1:1000, and the final mass percent of the curcumin in the system is 0.009 wt%; the system consists of NaOH aqueous solution and ethanol aqueous solution of curcumin.

The colorful bacterial cellulose III is a mixture consisting of colorful bacterial cellulose II and curcumin, and the color of each spray-dyeing position on the colorful bacterial cellulose II corresponds to the color, and after the curcumin is added, the specific color is presented by the proportion of three pigments at the position, and the specific color is shown in the following table:

location numbering	Colour(s)
		5	Orange yellow
1、2、3、4	Intermediate colors of brown and dark blue

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

TABLE 5

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

TABLE 6

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

In examples 1A to 4A and examples 1B to 4B, the color of the spray-dyed spot of each layer of the colored bacterial cellulose II obtained after the spray-dyeing process and the color of the spray-dyed spot of the colored bacterial cellulose III obtained after the cooking process are identical, and based on the method in the above examples, the colored bacterial cellulose of each layer having different colors can be obtained, for example, in examples 2A and 3A, the color of the whole colored bacterial cellulose II obtained after the spray-dyeing process is a pink-red intermediate color and a red intermediate color, and the color of the spray-dyed spot of the colored bacterial cellulose II is a brilliant violet intermediate color, a purple intermediate color and a brilliant violet intermediate color, respectively. The integral colors of the obtained colorful bacterial cellulose III after the cooking process are respectively orange red and intermediate colors of orange red and orange, and the site colors of the colorful bacterial cellulose III are respectively brilliant green, brilliant green and intermediate colors of olive green.

The invention can also adopt the spray-painting method of the embodiment 2A on the first layer, and the spray-painting method of the embodiment 3A on the second layer, that is, in the environment with similar substrate color, the spray-painting with different blue pigment concentrations is carried out on different layers, so that the color difference of the spray-painting sites between different layers of the colored bacterial cellulose II is achieved, and the color difference of the spray-painting sites between different layers can be obtained through the colored bacterial cellulose III obtained in the final post-treatment stage. In fact, the difference of the colors of the spray-painting sites among different layers is obtained by the combination of spray-painting modes among various embodiments.

Example 1C

preparing raw materials:

c1# colored culture solution, wherein the pH value of the colored culture solution is adjusted to 5, and the temperature is 32 ℃;

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

(1) preparing a colorful bacterial cellulose I film: inoculating the strain into C1# colored culture solution, wherein the cell density of the strain is 10⁷Standing and culturing for 4 days to obtain the strain per ml;

(2) taking a colorful bacterial cellulose I film as a substrate, uniformly spraying spray liquor (spray-dyeing) on different positions on the substrate by adopting 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 refer to the positions, namely an area 1, an area 2 and an area 3, of the spray-dyeing of the sprayer determined according to the pattern (shown in figure 1) of the mask; the spray-dyeing process of the colorful bacterial cellulose I film is divided into three layers, wherein the spray-dyeing positions corresponding to the 1 st layer, the 2 nd layer and the 3 rd layer are

areas

1, 2 and 3 respectively; the first layer was spray-dyed every 8h using the spray solution of example 2A, the spray-dyeing process lasted for 3d, the second layer was spray-dyed every 8h using the spray solution of example 3A, the spray-dyeing process lasted for 4d, and the third layer was spray-dyed every 8h using the spray solution of example 2A, the spray-dyeing process lasted for 3 d. During the spray-painting period, the film of the colorful bacterial cellulose I is positioned in a colored culture solution and is kept in a static fermentation state (the static culture condition is that the culture temperature is 36 ℃), and the colorful bacterial cellulose II is obtained;

location numbering	Colour(s)
		5	Pink and red intermediate color
1、2、4	Brilliant purple
		3	Purple and brilliant purple intermediate

(3) Firstly, soaking the colorful bacterial cellulose II in a4 wt% 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 colorful bacterial cellulose III;

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

location numbering	Colour(s)
		5	Intermediate color of orange red and orange
1、2、、4	Olive green
		3	Intermediate colors of brown and deep blue

Example 2C

preparing raw materials:

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 spraying liquid: the spraying liquid adopts the spraying liquid in 3A and 3B in the embodiment;

(1) preparing a colorful bacterial cellulose I film: inoculating the strain into C2# colored culture solution, wherein the cell density of the strain is 10⁸Standing and culturing for 5 days to obtain the extract per ml;

(2) the colorful bacterial cellulose I film is used as a substrate, a sprayer is adopted to uniformly spray the spray liquor (spray-painting) at different positions on the substrate, the spray-painting speed is 9mL/min, the diameter of liquid drops sprayed by the sprayer is 3 mu m, the different positions on the substrate and the spray-painting process are basically the same as those in the embodiment 1C, and the difference is that: the first layer was spray-dyed every 6h using the spray of example 3A, the spray-dyeing process continued for 2d, the second layer was spray-dyed every 6h using the spray of example 3B, the spray-dyeing process continued for 3d, and the third layer was spray-dyed every 6h using the spray of example 3A, the spray-dyeing process continued for 3 d. During the spray-painting period, the film of the colorful bacterial cellulose I is positioned in a colorful culture solution and is kept in a static fermentation state (the condition of static culture is that the culture temperature is 31 ℃), and then colorful bacterial cellulose II is obtained;

(3) firstly, soaking the colorful bacterial cellulose II in a 5 wt% 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 colorful bacterial cellulose III;

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

location numbering	Colour(s)
		5	Orange yellow
1、2、4	Intermediate colors of brown and deep blue
		3	Brown and reddish brown intermediate

Example 3C

preparing raw materials:

c3# colored culture solution, wherein the pH value of the colored culture solution is adjusted to 6, and the temperature is 32 ℃;

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

(1) preparing a colorful bacterial cellulose I film: inoculating the strain into C3# colored culture solutionThe cell density of the strain is 10⁵Standing and culturing for 4 days to obtain the strain per ml;

(2) the colorful bacterial cellulose I film is used as a substrate, a sprayer is adopted to uniformly spray the spray liquor (spray-painting) at different positions on the substrate, the spray-painting speed is 7mL/min, the diameter of liquid drops sprayed by the sprayer is 6 mu m, the different positions on the substrate and the spray-painting process are basically the same as those in the embodiment 1C, and the difference is that: the first layer was spray-dyed every 10h using the spray of example 1B for a duration of 3d, the second layer was spray-dyed every 10h using the spray of example 2B for a duration of 3d, and the third layer was spray-dyed every 10h using the spray of example 1B for a duration of 2 d. During the spray-painting period, the film of the colorful bacterial cellulose I is positioned in a colorful culture solution and is kept in a static fermentation state (the condition of static culture is that the culture temperature is 31 ℃), and then colorful bacterial cellulose II is obtained;

location numbering	Colour(s)
		5	Pink color
1、2、4	Intermediate colors of purple and red
		3	Purplish red color

(3) Firstly, soaking the colorful bacterial cellulose II in a4 wt% 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 colorful bacterial cellulose III;

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

location numbering	Colour(s)
		5	Orange and orange intermediate color
1、2、4	Brown colour
		3	Brilliant orange and brown intermediate color

Example 4C

preparing raw materials:

c4# colored culture solution, wherein the pH value of the colored culture solution is adjusted to be 4, and the temperature is 29 ℃;

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

(1) preparing a colorful bacterial cellulose I film: inoculating the strain into C3# colored culture solution, wherein the cell density of the strain is 10⁷Standing and culturing for 3d to obtain the extract per ml;

(2) the colorful bacterial cellulose I film is used as a substrate, a sprayer is adopted to uniformly spray the spray liquor (spray-painting) at different positions on the substrate, the spray-painting speed is 9mL/min, the diameter of liquid drops sprayed by the sprayer is 10 mu m, the different positions on the substrate and the spray-painting process are basically the same as those in the embodiment 1C, and the difference is that: the first layer was spray-dyed every 12h using the spray solution of example 1B for a duration of 3d, the second layer was spray-dyed every 12h using the spray solution of example 4B for a duration of 2d, and the third layer was spray-dyed every 12h using the spray solution of example 1B for a duration of 2 d. During the spray-painting period, the film of the colorful bacterial cellulose I is positioned in a colorful culture solution and is kept in a static fermentation state (the condition of static culture is that the culture temperature is 35 ℃), and the colorful bacterial cellulose II is obtained;

location numbering	Colour(s)
		5	Intermediate color of red and brilliant red
1、2、4	Purplish red color
		3	Purplish red and purple intermediate

(3) Firstly, soaking the colorful bacterial cellulose II in a 5 wt% 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 colorful bacterial cellulose III;

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

location numbering	Colour(s)
		5	Orange red
1、2、4	Brown and reddish brown intermediate
		3	Intermediate colors of dark blue and brown

Claims

1. A preparation method of a colorful bacterial cellulose facial mask is characterized by comprising the following steps:

(3) taking the colored bacterial cellulose I film obtained in the step (2) as a substrate, and spray-painting the colored bacterial cellulose I film at different positions on the substrate by adopting a spray liquid every 6-12 hours, wherein the colored bacterial cellulose I film is positioned in a colored culture liquid during the spray-painting and is kept in a standing culture state to obtain colored bacterial cellulose II;

the spray painting adopts a sprayer which can move in the spatial position in three directions of XYZ three-dimensional coordinate axes; the spray dyeing is to uniformly spray liquid;

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

(4) soaking the colorful bacterial cellulose II in the step (3) in NaOH aqueous solution, uniformly mixing to obtain a mixture, mixing the ethanol aqueous solution of curcumin 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 colorful bacterial cellulose III;

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

2. The preparation method of the colorful bacterial cellulose facial mask as claimed in claim 1, wherein the specific process of the step (1) is as follows: firstly, degerming the natural red pigment extracting solution by using a 0.22 mu m filter; mixing the degerming natural red pigment extracting solution with the basic culture solution subjected to high-pressure steam sterilization treatment;

the formula of the colored culture solution is as follows:

1-6 wt% of a substance A;

0.05-1 wt% of peptone;

0.05-1 wt% of yeast extract;

0.01-0.5 wt% of citric acid;

0.04-0.4 wt% of disodium hydrogen phosphate;

0.02-0.2 wt% of monopotassium phosphate;

0.005-2 wt% 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 the colorful bacterial cellulose facial mask according to claim 1, wherein in the step (2), the pH value of the colorful culture solution is 4-6, and the temperature is 30-38 ℃.

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

5. The method for preparing a colorful bacterial cellulose facial mask according to claim 1, wherein in the step (3), the spraying solution is a mixed solution of a natural blue pigment extracting solution and a basic culture solution.

6. The method for preparing a colorful bacterial cellulose facial mask according to claim 1, wherein 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:

1-6 wt% of a substance B;

0.05-1 wt% of peptone;

0.05-1 wt% of yeast extract;

0.01-0.5 wt% of citric acid;

0.04-0.4 wt% of disodium hydrogen phosphate;

0.02-0.2 wt% of monopotassium phosphate;

0.003 to 1.5 wt% of natural blue pigment;

the balance of water;

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

7. The method for preparing a colorful bacterial cellulose facial mask according to claim 1, wherein the moving range in the step (3) is as follows: the X axis is 0-30 cm, the Y axis is 0-30 cm, and the Z axis is 0-34 cm.

8. The method for preparing the colorful bacterial cellulose facial 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 drop sprayed by the sprayer is 0.5-6 μm.

9. The method for preparing a colorful bacterial cellulose facial mask as claimed in claim 1, wherein the static culture conditions in step (3) are the same as the static culture conditions in step (2).

10. The preparation method of the colorful bacterial cellulose facial mask according to claim 1, wherein in the mixture in the step (4), the mass ratio of the colorful bacterial cellulose II to the NaOH aqueous solution is 1-10: 100; in the ethanol aqueous solution of the curcumin, the concentration of ethanol in the ethanol aqueous solution is 70-95 wt%, when the ethanol aqueous solution of the curcumin is mixed with the mixture, the volume ratio of the ethanol aqueous solution of the 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 NaOH aqueous solution and ethanol aqueous solution of curcumin.