Treatment method of mycelium leather

Abstract

The invention discloses a treatment method of mycelium leather, and relates to the field of leather, and the treatment method comprises the following steps: 1, carrying out deacetylation treatment on a freshly harvested mycelium material obtained by solid fermentation; 2, washing the mycelia subjected to deacetylation treatment with water, and keeping the pH value at 5.5-7; 3, tanning treatment is conducted on the mycelium material through a cyanuric chloride derivative type tanning agent; 4, retanning is conducted after washing is conducted again; 5, the mycelium leather is filled; according to the method, when a freshly harvested mycelium material is obtained through solid fermentation, a culture medium is coated with gelatin, hydrogen bond and electrostatic interaction can be generated between the gelatin and a chitin / glucan network on the outer wall of mycelia in the growth period of the mycelia, and then the mycelia are subjected to fat liquoring; and a'albumen glue layer 'formed by gelatin can also be used as a template structure to promote ordered growth of hyphae, so that the overall density is improved, and holes and weak binding areas are reduced on a microstructure.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of leather, in particular to a treatment method of mycelium leather. BACKGROUND

[0002] Mycelium is a kind of mycelium generated by fungi, which is similar to blood vessels. Fungi are actually closer to animals in gene sequencing, so mycelium leather can be more similar to animal leather than other plant leather, and mycelium leather has the advantage of environmental protection.

[0003] Mycelium leather is a leather substitute that does not use plastic as a core component. It is made of three organic materials, namely water, wood chips and mycelium, so the carbon emissions during production are very low. Through cultivation, mycelium grows into a large brick, and the top layer looks like an animal leather. When it is peeled off, it can be tanned or colored like leather.

[0004] The existing mycelium leather has poor tensile and tear resistance, and the treatment reagent cannot meet the environmental protection requirements, therefore, a treatment method of mycelium leather is proposed to solve the above problems. SUMMARY

[0005] In order to solve the above technical problems, the present application provides a treatment method of mycelium leather.

[0006] The purpose of the present application can be achieved by the following technical solutions: A treatment method of mycelium leather, comprising the following steps: Step 1: deacetylation treatment of fresh harvested mycelium material obtained by solid fermentation; Step 2: water washing of the deacetylated mycelium, keeping the pH value at 5.5-7; Step 3: tanning treatment of the mycelium material using tricyanocyanine derivative type tanning agent; Step 4: re-water washing and re-tanning; Step 5: filling of the mycelium leather; Step 6: fatliquoring of the mycelium leather.

[0007] Preferably, the treatment method of the fresh harvested mycelium material obtained by solid fermentation in step 1 is specifically: 2-4 parts of gelatin are dissolved in 70-90℃ water, cooled to 40℃, and then uniformly sprayed into the culture medium. After stirring evenly, sterilize in a bag, then perform solid fermentation, then immerse the harvested mycelium layer in a PVA solution with a concentration of 3-5%, soak for 30 minutes, then spray a chitosan solution with a concentration of 0.5%, and finally obtain the fresh harvested mycelium material obtained by solid fermentation.

[0008] Preferably, the deacetylation solution comprises any one of a chitin deacetylase solution, a sodium bicarbonate solution, a sodium carbonate solution or a sodium hydroxide solution.

[0009] Preferably, the chitin deacetylase solution is a 10% chitin deacetylase solution by mass fraction.

[0010] Preferably, the retanning uses any one of a non-chromium metal tanning agent, a tannin tanning agent or a phenolic synthetic tanning agent.

[0011] Preferably, the filling uses any one or more of an acrylic resin filler, a melamine resin retanning agent, an aromatic sulfonate condensate retanning agent and a protein filler.

[0012] Preferably, the specific steps for tanning the mycelium material in step three using a tricyanogen chloride derivative type tanning agent are as follows: A tricyanogen chloride derivative type tanning agent is used at a concentration of 1-15wt%, a solvent is 100% deionized water (100% is a relative weight percentage of the mycelium leather), then the solution is adjusted to PH=8.5 using sodium carbonate, the temperature is adjusted to 25-35°C, the mycelium is added to a leather drum with stirring in the tanning solution, the reaction is rotated for 40 minutes, then the solution is adjusted to PH=6.0-6.5 using sodium bicarbonate, a sodium acetate slow-release solution is added to terminate the reaction, then the temperature is increased to 45°C for continued reaction for 120 minutes, then the temperature is increased to 50°C for continued reaction for 120 minutes, the solution is adjusted to PH=6.0-6.5 using sodium bicarbonate, and the mycelium is washed with water for 3-5 times until the PH value falls back to neutral, then the mycelium is lightly pressed to remove water, the temperature is controlled at 50-60°C for hot air drying to obtain the treated mycelium material.

[0013] Preferably, the specific preparation process of the tricyanogen chloride derivative type tanning agent is as follows: Anhydrous THF solution containing tricyanogen chloride is prepared and placed in a 250ml three-necked flask, a condensation reflux device is installed, the solution is cooled to 0-5°C using an ice-salt bath, nitrogen is introduced for protection, ethylenediamine is slowly added dropwise to ensure that the temperature is maintained below 10°C, after 30 minutes of reaction, triethylamine is added to capture the generated HCL, the reaction temperature is slowly increased to 40-50°C, and the stirring reaction is continued for 2 hours, the by-product salt is filtered out, the solution is concentrated, the reaction product is precipitated using cold acetone, and the tricyanogen chloride derivative type tanning agent is obtained after filtration, washing and drying.

[0014] Preferably, the ratio of the amount of ethylenediamine to tricyanogen chloride is 1mol:2mol.

[0015] The beneficial effects of the present application are as follows: 1、The present application is a new fresh harvested mycelium material obtained by solid fermentation, which is coated with gelatin in the culture medium. During the growth of the mycelium, hydrogen bonding and electrostatic interaction occur with the chitin / glucomannan network on the outer wall of the mycelium. The "protein glue layer" formed by the gelatin also promotes the ordered growth of the mycelium, improves the overall density, reduces the pore and weakly bonded areas in the microstructure, and PVA can form hydrogen bonding cross-linking with the "-OH and -NH2 groups" in the mycelium wall. During the soaking process, PVA penetrates into the mycelium network, forming a network coating structure to improve the overall structural stability. Chitosan can form hydrogen bonding and electrostatic adsorption with the mycelium and the gelatin / PVA network through spraying.

[0016] 2、The present application uses a tricyanopyridine derivative type tanning agent to tan the mycelium material. The tricyanopyridine molecule has three active chlorine sites, which can easily form covalent bonds with amino-containing biological macromolecules, forming a dense and stable three-dimensional cross-linked lattice structure, improving the tensile strength and tear resistance, and significantly enhancing the stability of chitosan, glucan and other structures in the mycelium, inhibiting thermal expansion and hydrolytic degradation, so that the mycelium leather maintains structural integrity under high temperature processing or wet use environment. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present application will be described below. Obviously, the described embodiments are only a part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0018] Example 1: The preparation process of the mycelium leather is as follows: Step one: 2 parts of gelatin are dissolved in water at 70℃, and then uniformly sprayed into the culture medium after cooling to 40℃. After stirring evenly, sterilize in a bag, then perform solid fermentation. Then, the harvested mycelium layer is soaked in a 5% PVA solution for 30 minutes, and then a 0.5% chitosan solution is sprayed. Finally, the solid fermentation obtained fresh harvested mycelium material is obtained. The solid fermentation obtained fresh harvested mycelium material is subjected to deacetylation treatment, and the deacetylation solution is a 10% chitin deacetylase solution by mass fraction; Step two: the deacetylated mycelium is washed with water, and the PH value is maintained at 5.5; Step three: prepare a solution of anhydrous THF containing cyanuric chloride in a 250 ml three-necked flask, install a condenser reflux device, cool the solution to 5°C with an ice salt bath, protect it with nitrogen, slowly add ethylenediamine, make sure the temperature is maintained below 10°C, add triethylamine after 30 minutes of reaction to capture the generated HCL, the ratio of ethylenediamine and cyanuric chloride is 1 mol:2 mol, slowly raise the reaction temperature to 50°C, continue stirring for 2 hours, filter out the by-product salt, concentrate the solution, precipitate the reaction product using cold acetone, filter, wash and dry to obtain the cyanuric chloride derivative type tanning agent; Use a concentration of 1 wt% cyanuric chloride derivative type tanning agent, solvent is 100% deionized water (100% is the relative weight percentage of mycelium leather), then adjust the solution to PH=8.5 with sodium carbonate, adjust the temperature to 35°C, add the mycelium to the leather drum by stirring in the tanning liquid, rotate for 40 minutes, then stop the reaction by adding sodium bicarbonate to adjust the solution to PH=6.0 and adding sodium acetate slow-release solution, then raise the temperature to 45°C and continue to react for 120 minutes, then raise the temperature to 50°C and continue to react for 120 minutes, adjust the solution to PH=6.0 with sodium bicarbonate, rinse 3-5 times with water until the PH value returns to neutral, lightly press to remove water, control the temperature at 60°C for hot air drying to obtain the treated mycelium material; Step four: water wash again and then retanning, use non-chromium metal tanning agent for retanning; Step five: fill the mycelium leather with acrylic resin filler to obtain the final mycelium leather.

[0019] Example 2: A process for preparing mycelium leather is as follows: Step one: dissolve 4 parts of gelatin in water at 90°C, cool to 40°C, and evenly spray onto the culture medium, stir evenly, sterilize in a bag, then perform solid state fermentation, then soak the harvested mycelium layer in a 5% PVA solution for 30 minutes, then spray a 0.5% chitosan solution, finally obtain the fresh harvested mycelium material obtained by solid state fermentation, and perform deacetylation on the fresh harvested mycelium material obtained by solid state fermentation, the deacetylation solution is a 10% chitin deacetylase solution; Step two: water wash the deacetylated mycelium, keep the PH value at 7; Step three: prepare a solution of anhydrous THF containing cyanuric chloride in a 250 ml three-necked flask, install a condenser reflux device, cool the solution to 5°C with an ice salt bath, protect it with nitrogen, slowly add ethylenediamine, make sure the temperature is maintained below 10°C, add triethylamine after 30 minutes of reaction to capture the generated HCL, the ratio of ethylenediamine to cyanuric chloride is 1 mol:2 mol, slowly raise the reaction temperature to 50°C, continue stirring for 2 hours, filter out the by-product salt, concentrate the solution, precipitate the reaction product using cold acetone, and obtain the cyanuric chloride derivative type tanning agent after filtration, washing, and drying; Use a concentration of 3wt% cyanuric chloride derivative type tanning agent, with 100% deionized water as the solvent (100% is the relative weight percentage of the mycelium leather), then adjust the solution to PH=8.5 with sodium carbonate, adjust the temperature to 35°C, add the mycelium to the leather drum by stirring it in the tanning solution, rotate for 40 minutes, then stop the reaction by adding sodium bicarbonate to adjust the solution to PH=6.0 and adding sodium acetate to slow down the reaction, then raise the temperature to 45°C and continue the reaction for 120 minutes, then raise the temperature to 50°C and continue the reaction for 120 minutes, adjust the solution to PH=6.5 with sodium bicarbonate, rinse 3-5 times with water until the PH value returns to neutral, lightly press to remove water, and then dry at a temperature of 60°C with hot air to obtain the treated mycelium material; Step four: water wash again and then retanning, using non-chromium metal tanning agent for retanning; Step five: fill the mycelium leather with acrylic resin filler to obtain the final mycelium leather.

[0020] Example 3: A process for preparing mycelium leather is as follows: Step one: dissolve 3 parts of gelatin in water at 85°C, cool to 40°C, and evenly spray onto the culture medium, stir evenly, sterilize in a bag, then perform solid state fermentation, then soak the harvested mycelium layer in a 5% PVA solution for 30 minutes, then spray a 0.5% chitosan solution, and finally obtain the fresh harvested mycelium material obtained by solid state fermentation, and then deacetylate the fresh harvested mycelium material obtained by solid state fermentation, using a 10% chitin deacetylase solution as the deacetylation solution; Step two: wash the deacetylated mycelium with water, keeping the PH value at 5.5; Step three: prepare a solution of anhydrous THF containing cyanuric chloride in a 250 ml three-necked flask, install a condenser reflux device, cool the solution to 2°C with an ice salt bath, protect it with nitrogen, slowly add ethylenediamine, make sure the temperature is maintained below 10°C, add triethylamine after 30 minutes of reaction to capture the generated HCL, the ratio of ethylenediamine and cyanuric chloride is 1 mol:2 mol, slowly raise the reaction temperature to 45°C, continue stirring for 2 hours, filter out the by-product salt, concentrate the solution, use cold acetone to precipitate the reaction product, filter, wash and dry to obtain the cyanuric chloride derivative type tannin; Use a concentration of 5 wt% cyanuric chloride derivative type tannin, solvent is 100% deionized water (100% is the relative weight percentage of mycelium leather), adjust the temperature to 25°C, add the mycelium and tanning solution into the leather drum, rotate for 40 minutes, then adjust the solution to PH=6.0 with sodium bicarbonate, then heat to 45°C and continue to react for 120 minutes, then heat to 50°C and continue to react for 120 minutes, adjust the solution to PH=6.0 with sodium bicarbonate, rinse 3-5 times with water until the PH value falls to neutral, control the temperature at 60°C for hot air drying to obtain the treated mycelium material; Step four: water washing again and retanning, use non-chromium metal tannin for retanning; Step five: fill the mycelium leather with acrylic resin filler to obtain the final mycelium leather.

[0021] Example 4: a process for preparing mycelium leather as follows: Step one: dissolve 4 parts of gelatin in water at 90°C, cool to 40°C, evenly spray onto the culture medium, stir evenly, then sterilize in a bag, then perform solid state fermentation, then soak the harvested mycelium layer in a 4% PVA solution for 30 minutes, then spray a 0.5% chitosan solution, finally obtain the fresh harvested mycelium material obtained by solid state fermentation, deacetylate the fresh harvested mycelium material obtained by solid state fermentation, the deacetylation solution is a 10% chitin deacetylase solution; Step two: water wash the deacetylated mycelium, keep the PH value at 6; Step three: prepare a solution of cyanuric chloride in anhydrous THF, place it in a 250 ml three-necked flask, install a condenser reflux device, cool the solution to 3°C with an ice salt bath, protect it with nitrogen, slowly add ethylenediamine, make sure the temperature is maintained below 10°C, add triethylamine after 30 minutes of reaction to capture the generated HCL, the ratio of ethylenediamine to cyanuric chloride is 1 mol:2 mol, slowly raise the reaction temperature to 50°C, continue stirring for 2 hours, filter out the by-product salt, concentrate the solution, precipitate the reaction product using cold acetone, filter, wash, and dry to obtain the cyanuric chloride derivative type tanning agent; Use a concentration of 12 wt% cyanuric chloride derivative type tanning agent, with 100% deionized water as the solvent (100% is the relative weight percentage of mycelium leather), adjust the temperature to 30°C, add the mycelium and tanning solution into the leather drum, rotate for 40 minutes, then adjust the solution to PH=6.5 with sodium bicarbonate, then heat to 45°C and continue to react for 120 minutes, then heat to 50°C and continue to react for 120 minutes, adjust the solution to PH=6.0 with sodium bicarbonate, rinse 3-5 times with water until the PH value returns to neutral, lightly press to remove water, control the temperature at 55°C for hot air drying to obtain the treated mycelium material; Step four: water wash again and then retanning, use non-chromium metal tanning agent for retanning; Step five: fill the mycelium leather with acrylic resin filler to obtain the final mycelium leather.

[0022] Example 5: A process for preparing mycelium leather is as follows: Step one: dissolve 4 parts of gelatin in water at 90°C, cool to 40°C, and evenly spray onto the culture medium, stir evenly, then sterilize in a bag, then perform solid state fermentation, then soak the harvested mycelium layer in a 5% PVA solution for 30 minutes, then spray a 0.5% chitosan solution, finally obtain the fresh harvested mycelium material obtained by solid state fermentation, and perform deacetylation on the fresh harvested mycelium material obtained by solid state fermentation, the deacetylation solution is a 10% chitin deacetylase solution; Step two: water wash the deacetylated mycelium, keep the PH value at 6; Step three: prepare a solution of cyanuric chloride in anhydrous THF, place it in a 250ml three-necked flask, install a condenser reflux device, cool the solution to 3°C with an ice-salt bath, protect it with nitrogen, slowly add ethylenediamine, make sure the temperature is below 10°C, add triethylamine after 30 minutes of reaction to capture the generated HCL, the ratio of ethylenediamine and cyanuric chloride is 1mol:2mol, slowly raise the reaction temperature to 45°C, continue stirring for 2 hours, filter out the by-product salt, concentrate the solution, precipitate the reaction product with cold acetone, filter, wash, and dry to obtain the cyanuric chloride derivative type tanning agent; Use a concentration of 10 wt% cyanuric chloride derivative type tanning agent, solvent is 100% deionized water (100% is the relative weight percentage of mycelium leather), adjust the temperature to 25°C, add the mycelium and tanning solution into the leather drum, rotate for 40 minutes, then adjust the solution to PH=6.0 with sodium bicarbonate, then raise the temperature to 45°C and continue to react for 120 minutes, then raise the temperature to 50°C and continue to react for 120 minutes, adjust the solution to PH=6.3 with sodium bicarbonate, rinse 3-5 times with water until the PH value falls to neutral, dry under light pressure, control the temperature at 50°C for hot air drying, and obtain the treated mycelium material; Step four: water wash again and retanning, use non-chromium metal tanning agent for retanning; Step five: fill the mycelium leather with acrylic resin filler to obtain the final mycelium leather Comparative Example 1: Compared with Example 1, this comparative example lacks Step three and Step four in Example 1.

[0023] Comparative Example 2: Compared with Example 1, the difference lies in the following process, and the rest is exactly the same: Step two: water wash the deacetylated mycelium, keep the PH value at 5; Step three: prepare a solution of cyanuric chloride in anhydrous THF, place it in a 250ml three-necked flask, install a condenser reflux device, cool the solution to 3°C with an ice-salt bath, protect it with nitrogen, slowly add ethylenediamine, make sure the temperature is below 10°C, add triethylamine after 30 minutes of reaction to capture the generated HCL, the ratio of ethylenediamine and cyanuric chloride is 1mol:2mol, slowly raise the reaction temperature to 45°C, continue stirring for 2 hours, filter out the by-product salt, concentrate the solution, precipitate the reaction product with cold acetone, filter, wash, and dry to obtain the cyanuric chloride derivative type tanning agent; The hyphae and tanning liquid are added into the leather drum using a concentration of 0.5 wt% of the cyanuric chloride derivative type tanning agent, a solvent of 100% deionized water (100% is the relative weight percentage of the hyphae leather), the temperature is adjusted to 35°C, the reaction is rotated for 40 minutes, then the solution is adjusted to PH = 6.0 using sodium bicarbonate, and then the temperature is raised to 45°C to continue the reaction for 120 minutes, the solution is adjusted to PH = 6.0 using sodium bicarbonate, and then washed 3-5 times with water until the PH value falls back to neutral, after light pressure dewatering, the temperature is controlled at 60°C for hot air drying, to obtain the treated hyphae material.

[0024] The properties of the hyphae leather prepared in Examples 1-5 and Comparative Examples 1-2 are tested, and the results are shown in Table 1 below: Table 1 As can be seen from Table 1 above, the hyphae leather prepared in Examples 1-5 of the present application has excellent tensile properties and tear resistance, so after tanning with the cyanuric chloride derivative type tanning agent, the cyanuric chloride derivative can form stable covalent bonds with the amino groups in the hyphae, and the connection between the hyphae network is changed from the original weak non-covalent interaction to stable chemical bond connection. This chemical crosslinking effectively limits the sliding and tensile deformation of the molecular chain, and under external force, the material exhibits higher tensile strength, and the trifunctional structure of the cyanuric chloride molecule can realize three-dimensional crosslinking, thereby limiting the local crack from expanding in a single direction. This multidirectional crosslinking structure has stronger buffering and dispersing effect on the tearing force, and under the treatment of the tanning agent, the composite crosslinking network formed includes mechanical entanglement structure, physical combination of chitin, and chemical crosslinking induced by the tanning agent, which synergistically stabilizes the interface structure of the material, significantly improving the tear resistance.

[0025] The above is merely an example and description of the concept of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace them, as long as they do not deviate from the concept of the present application or exceed the scope defined by the present claims, and should belong to the protection scope of the present application.

Claims

1. A method for treating mycelium leather, characterized by, It comprises the following steps: Step one: the fresh harvested mycelium material obtained by solid fermentation is subjected to deacetylation treatment; Step two: the deacetylated mycelium is washed with water, and the PH value is maintained at 5.5-7; Step three: the mycelium material is subjected to tanning treatment using a tricyanogen chloride derivative type tanning agent; Step four: after re-washing, re-tanning is performed; Step five: the mycelium leather is filled; Step six: the mycelium leather is fat-liquored.

2. A method for processing mycelium leather according to claim 1, characterized in that: The treatment method of the fresh harvested mycelium material obtained by solid fermentation in step one is as follows: 2-4 parts of gelatin are dissolved in 70-90°C water, cooled to 40°C, and then uniformly sprayed onto the culture medium. After uniform stirring, the medium is sterilized in a bag, and then subjected to solid fermentation. Subsequently, the harvested mycelium layer is soaked in a PVA solution with a concentration of 3-5% for 30 minutes, and then sprayed with a chitosan solution with a concentration of 0.5%. Finally, the fresh harvested mycelium material obtained by solid fermentation is obtained.

3. A method for processing mycelium leather according to claim 1, characterized in that: The deacetylation solution comprises any one of a chitin deacetylase solution, a sodium bicarbonate solution, a sodium carbonate solution, or a sodium hydroxide solution.

4. A method for processing mycelium leather according to claim 3, characterized in that: The chitin deacetylase solution is a chitin deacetylase solution with a mass fraction of 10%.

5. A method for processing mycelium leather according to claim 1, characterized in that: The re-tanning agent is any one of a non-chromium metal tanning agent, a tannin tanning agent, or a phenolic synthetic tanning agent.

6. A method for processing mycelium leather according to claim 1, characterized in that: The filler is any one or more of an acrylic resin filler, a melamine resin re-tanning agent, an aromatic sulfonate condensate re-tanning agent, and a protein filler.

7. A method for processing mycelium leather according to claim 1, characterized in that: The specific steps for tanning treatment of the mycelium material using a tricyanogen chloride derivative type tanning agent in step three are as follows: A tricyanogen chloride derivative type tanning agent with a concentration of 1-15 wt% is used as the solvent, and the temperature is adjusted to 25-35°C. The mycelium and the tanning solution are added to a leather drum, and the reaction is rotated for 40 minutes. Subsequently, the solution is adjusted to PH= 6.0-6.5 using sodium bicarbonate, and then heated to 45°C for continuous reaction for 120 minutes. Then, the temperature is increased to 50°C for continuous reaction for 120 minutes. The solution is adjusted to PH= 6.0-6.5 using sodium bicarbonate, and then washed with water for 3-5 times until the PH value returns to neutral. After light pressure dewatering, the temperature is controlled at 50-60°C for hot air drying to obtain the treated mycelium material.

8. A method for processing mycelium leather according to claim 7, characterized by: The specific preparation process of the tricyanogen chloride derivative type tanning agent is as follows: Anhydrous THF solution containing tricyanogen chloride is prepared in a 250ml three-necked flask, and a condensation reflux device is installed. The solution is cooled to 0-5°C using an ice-salt bath, and nitrogen is introduced for protection. Ethylenediamine is slowly added while ensuring that the temperature is maintained below 10°C. After 30 minutes of reaction, triethylamine is added to capture the generated HCL. The reaction temperature is slowly increased to 40-50°C, and the stirring is continued for 2 hours. The by-product salt is filtered out, the solution is concentrated, and the reaction product is precipitated using cold acetone. After filtration, washing, and drying, the tricyanogen chloride derivative type tanning agent is obtained.

9. A method for processing mycelium leather according to claim 8, characterized by: The amount ratio of ethylenediamine to tricyanogen chloride is 1mol:2mol.

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