A method for preparing mycelium leather

Abstract

The present invention relates to the field of new material technology, and specifically to a method for preparing mycelium leather. In order to improve the yield and quality of mycelium leather, the present invention improves the mycelium culture process, and accelerates the time cost and culture cost of mycelium fermentation culture by combining deep fermentation with solid-state culture, thereby reducing carbon emissions. Moreover, on this basis, the present invention also introduces a polyurethane coating with fluorine elements and imidazole rings on the surface of the mycelium leather, thereby improving the defects of the mycelium leather that is not wear-resistant and water-resistant compared to traditional animal leather, and realizes antibacterial finishing of the leather, thereby improving its durability.

Description

Technical Field

[0001] The invention relates to the technical field of new materials, in particular to a method for preparing mycelium leather. Background Art

[0002] As a traditional material, leather is beautiful, durable and high-end. However, as people's awareness of environmental protection gradually increases, mycelium leather comes into being.

[0003] However, in the preparation process of existing mycelium leather, the mycelium is filtered out through deep fermentation, and some polymer adhesives are added, and then it is made through extrusion and drying. This method destroys the natural network structure of the mycelium, so the air permeability and feel are dependent on the adhesive, and it is essentially not completely degradable. Although traditional solid-state fermentation to produce mycelium leather can retain its natural network structure, the cultivation technology has high requirements on the environment, and requires electromagnetic field control and precise regulation of carbon dioxide to achieve the purpose of growing aerial mycelium taller and thicker, and there are problems such as long fermentation cycle and limited output. Summary of the invention

[0004] The object of the present invention is to provide a method for preparing mycelium leather to solve the problems raised in the above background technology.

[0005] In order to solve the above technical problems, the present invention provides the following technical solution: a method for preparing mycelium leather, comprising the following steps:

[0006] S1. Cultivate mycelium;

[0007] S11. Take the fresh fruiting body grafted in the PDA plate, culture it at a temperature of 27-29 ° C for 5-8 days, take the front hyphae, transplant it to a fresh PDA plate, and culture it again and take the front hyphae for culture. Repeat the operation 3-5 times to obtain a pure strain;

[0008] Wherein, the fresh fruiting body is any one of purple ganoderma, antler ganoderma, black ganoderma, red ganoderma, versicolor, oyster mushroom, Agaricus bisporus, Pleurotus eryngii, seafood mushroom, and schizophyllum;

[0009] S12. The pure strain was inoculated into the culture medium, and then cultured at 27-29°C for 24 hours, and then cultured under shaking at a speed of 120-150 r / min for 3-5 days to obtain shake flask seeds;

[0010] S13. The shake flask seeds were inoculated into a 5L fermenter, the pH of the culture solution in the fermenter was adjusted to 4.5-7.5, the liquid volume in the fermenter was 50-60%, the inoculation amount was 8-10%, the ventilation volume was 6-10L / min, the culture temperature was 20-30°C, and the speed was 100-250r / min. After 5 days of fermentation, the culture solution in the fermenter was transferred to an open tray, and cultured in an environment of 25-30°C in the dark for 3-8 days to obtain an aerial mycelial film;

[0011] S14. Transplanting the aerial mycelial film onto a solid substrate, continuing to culture at 25-30° C. in the dark for 5-8 days, and then collecting the mycelial layer;

[0012] S2. The mycelium layer was laid flat, hot pressed for 3-5min inactivation, and the inactivated mycelium layer was placed in a tanning finishing liquid, ultrasonically shaken, soaked at room temperature for 24-36h, removed, and the excess tanning finishing liquid on the surface was rinsed with water, and after natural drying, the inactivated mycelium layer was dyed to obtain a mycelium leather body;

[0013] S3. Apply the antibacterial modified polyurethane coating on both sides of the mycelium leather blank, raise the temperature to 115-130°C, keep the temperature for 25-30 minutes, take it out, and roll it up to obtain the mycelium leather.

[0014] Furthermore, in step S12, the culture solution is prepared by:

[0015] 80-100 parts of bran are placed in 3000 parts of boiling water and boiled for 8-12 minutes, 80-100 parts of corn flour are added, and the mixture is boiled for 20 minutes, filtered, the filtrate is collected, and 1.8-2.5% sucrose, 0.8-1.5% glucose, 0.15-0.25% peptone, 0.01% potassium dihydrogen phosphate, and 0.8-1.2% calcium chloride are added thereto respectively based on the weight of the filtrate, the mixture is evenly mixed, filtered again, the filtrate is collected, water is added to 3000 parts, the mixture is boiled at 121° C. for 30 minutes, and the mixture is cooled to obtain a culture solution.

[0016] Furthermore, in step S14, the solid matrix is ​​prepared by:

[0017] According to weight, 55-65 parts of cottonseed hulls, 10-20 parts of corn cobs, 10-20 parts of bran, 3-6 parts of soybean meal and 3-6 parts of sawdust are mixed, water is added to adjust the moisture content to 60-70%, the mixture is heated to 121° C. and sterilized for 30 minutes, and then cooled to obtain a solid matrix.

[0018] Further, in step S2, the hot pressing temperature is 80-150°C, and the hot pressing pressure is 1-1.5MPa;

[0019] The tanning finishing liquid consists of 18-22 parts of tannin extract, 8-12 parts of glycerol, 12-18 parts of lecithin, 3-7 parts of penetrant and 45-55 parts of water in parts by weight.

[0020] Furthermore, the preparation method of the antibacterial modified polyurethane coating is:

[0021] a. Dissolve 5,5-dimethylhydantoin in ethanol, heat to 70-75°C and stir to decompose, add sodium hydroxide, continue to reflux and stir for 20 minutes, stop heating, add 4-(chloromethyl)benzyl alcohol, reflux for 24-36 hours, remove excess solvent by rotary evaporation, wash the reaction product 1-3 times with deionized water at a temperature of 0-4°C, and evaporate in vacuo to constant weight to obtain an antibacterial benzyl alcohol intermediate;

[0022] b. Disperse triphenylmethane triisocyanate in DMF, disperse under ultrasonic vibration for 15-35min, add 4-trifluoromethoxybenzoic acid, raise the temperature to 78-105°C under nitrogen atmosphere, stir the reaction for 0.5-2h, and remove excess solvent by rotary evaporation to obtain fluorine-modified diisocyanate;

[0023] c. Under nitrogen atmosphere protection, 1,4-butanediol and DMF were mixed, fluorine-modified diisocyanate and 2,4-toluene diisocyanate were added, the temperature was raised to 55-65°C, and the reaction was stirred for 1.5-2h. The temperature was then raised to 70-75°C, and the antibacterial benzyl alcohol intermediate was added. The reaction was continued with stirring for 2-4h. The temperature was then lowered to 55-65°C, ethanol was added, and the reaction was continued for 0.5-1h. The heating was stopped, and DMF was added to adjust the solid content to 30wt% to obtain an antibacterial modified polyurethane coating.

[0024] Furthermore, in step a, the mass ratio of the 5,5-dimethylhydantoin, sodium hydroxide and 4-(chloromethyl)benzyl alcohol is 1:(0.15-0.3):(1-1.2).

[0025] Furthermore, in step b, the mass ratio of triphenylmethane triisocyanate to 4-trifluoromethoxybenzoic acid is 1:(0.3-0.6).

[0026] Furthermore, in step c, the mass ratio of the 1,4-butanediol, the fluorine-modified diisocyanate, and the 2,4-toluene diisocyanate is (0.8-1): (0.5-1): 3.

[0027] Furthermore, in step c, the mass ratio of the 2,4-toluene diisocyanate, the antibacterial benzyl alcohol intermediate, and ethanol is 3:(1-2):(0.5-0.8).

[0028] Furthermore, a mycelium leather is prepared by the above method.

[0029] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0030] In order to improve the yield and quality of mycelium leather, the present invention improves the mycelium culture process, and accelerates the time cost of mycelium fermentation culture by combining deep fermentation with solid-state culture. In addition, the present invention does not require precise environmental control, and only needs to be cultured in a normal mushroom culture environment and away from light to achieve the growth of aerial mycelium blanket, thereby reducing the culture cost and carbon emissions.

[0031] On this basis, the present invention also defines the processing technology of mycelium leather. The present invention first uses 5,5-dimethylhydantoin and 4-(chloromethyl)benzyl alcohol as raw materials, and in the presence of sodium hydroxide, prepares an antibacterial benzyl alcohol intermediate with antibacterial function, wherein the imidazole ring can effectively bind to the cell membrane of pathogens, thereby destroying the integrity of the cell membrane, thereby inhibiting the growth and reproduction of bacteria and fungi;

[0032] On this basis, the present invention also uses 4-trifluoromethoxybenzoic acid containing fluorine element to react with triphenylmethane triisocyanate to prepare a diisocyanate compound containing fluorine element, and in the subsequent steps, it is cross-linked with substances such as 1,4-butanediol, and finally a polyurethane coating with antibacterial and hydrophobic properties is prepared on the leather surface, thereby improving the defects of mycelium leather that it is not wear-resistant and water-resistant compared to traditional animal leather, and realizing antibacterial finishing of leather, thereby improving its durability. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] Example 1. A method for preparing mycelium leather, comprising the following steps:

[0035] S1. Cultivate mycelium;

[0036] S11. Take the fresh fruiting body grafted in the PDA plate, culture it at a temperature of 28 ° C for 8 days, take the front hyphae, transplant it to a fresh PDA plate, culture it again, take the front hyphae culture, repeat the operation 5 times, and obtain a pure strain;

[0037] S12. The pure strain was inoculated into the culture medium, and then cultured at 28°C for 24 hours, and then cultured with shaking at a speed of 150 r / min for 5 days to obtain shake flask seeds;

[0038] The preparation method of the culture solution is as follows: according to the weight, 90g of bran is placed in 3000mL of boiling water and boiled for 10min, 90g of corn flour is added, and the water is boiled for 20min, filtered, the filtrate is collected, and 2% of sucrose, 1% of glucose, 0.2% of peptone, 0.01% of potassium dihydrogen phosphate, and 1% of calcium chloride are added thereto respectively, the mixture is evenly mixed, filtered again, the filtrate is collected, water is added to 3000mL, the filtrate is boiled at 121°C for 30min, and the culture solution is obtained after cooling;

[0039] S13. The shake flask seeds were inoculated into a 5L fermenter, the pH of the culture solution in the fermenter was adjusted to 7, the liquid volume in the fermenter was 55%, the inoculation amount was 8%, the ventilation volume was 8L / min, the culture temperature was 30°C, and the fermentation speed was 150r / min. After 5 days of culturing and fermentation, the culture solution in the fermenter was transferred to an open tray, and after culturing in a dark environment at 28°C for 5 days, an aerial mycelium film was obtained;

[0040] S14. The aerial mycelial membrane was transplanted onto a solid substrate, and cultured at 28° C. in the dark for 5 days, and then the mycelial layer was collected;

[0041] Wherein, the preparation method of the solid matrix is:

[0042] 60 parts of cottonseed hulls, 15 parts of corn cobs, 15 parts of bran, 5 parts of soybean meal, and 5 parts of sawdust were mixed by weight, water was added to adjust the moisture content to 65%, the mixture was heated to 121° C. and sterilized for 30 minutes, and then cooled to obtain a solid matrix;

[0043] S2. The mycelium layer is arranged and laid flat, and after being inactivated by hot pressing at a temperature of 120°C and a pressure of 1 MPa for 5 minutes, the inactivated mycelium layer is placed in a tanning finishing liquid, ultrasonically shaken, and soaked at room temperature for 24 hours, taken out, and the excess tanning finishing liquid on the surface is rinsed with clean water. After naturally drying, the inactivated mycelium layer is dyed to obtain a mycelium leather body;

[0044] Wherein, the tanning finishing liquid is composed of 20 parts of tannin extract, 10 parts of glycerin, 15 parts of lecithin, 5 parts of penetrant, and 50 parts of water in parts by weight;

[0045] S3. The antibacterial modified polyurethane coating is applied on both sides of the mycelium leather body, the temperature is raised to 120°C, and after keeping warm for 25 minutes, a 60 micron thick antibacterial modified polyurethane coating layer is formed, and the antibacterial modified polyurethane coating layer is removed and rolled up to obtain mycelium leather;

[0046] Wherein, the preparation method of the antibacterial modified polyurethane coating is:

[0047] a. By weight, 1 part of 5,5-dimethylhydantoin was dissolved in ethanol, heated to 70°C and stirred for decomposition, 0.2 parts of sodium hydroxide was added, and the mixture was stirred and mixed under reflux for 20 minutes, and then the heating was stopped. 1 part of 4-(chloromethyl)benzyl alcohol was added, and the reaction was refluxed for 24 hours, and then the excess solvent was removed by rotary evaporation. The reaction product was washed twice with deionized water at a temperature of 2°C, and then vacuum evaporated to constant weight to obtain an antibacterial benzyl alcohol intermediate;

[0048] b. Disperse 1 part of triphenylmethane triisocyanate in DMF, disperse under ultrasonic vibration for 30 minutes, add 0.3 parts of 4-trifluoromethoxybenzoic acid, raise the temperature to 78 ° C under nitrogen atmosphere, stir and react for 2 hours, and then remove excess solvent by rotary evaporation to obtain fluorine-modified diisocyanate;

[0049] c. By weight, under nitrogen atmosphere, 0.8 parts of 1,4-butanediol and DMF were mixed, 0.5 parts of fluorine-modified diisocyanate and 3 parts of 2,4-toluene diisocyanate were added, the temperature was raised to 65°C, stirred and reacted for 2 hours, then the temperature was raised to 70°C, 1 part of antibacterial benzyl alcohol intermediate was added, the stirring reaction was continued for 2 hours, the temperature was lowered to 55°C, 0.5 parts of ethanol were added, the reaction was continued for 0.5 hours, the heating was stopped, DMF was added to adjust the solid content to 30wt%, and the antibacterial modified polyurethane coating was obtained.

[0050] Example 2. A method for preparing mycelium leather, comprising the following steps:

[0051] Compared with Example 1, the present embodiment increases the amount of 4-(chloromethyl)benzyl alcohol added in step a;

[0052] S3. The antibacterial modified polyurethane coating is applied on both sides of the mycelium leather body, the temperature is raised to 120°C, and after keeping warm for 25 minutes, a 60 micron thick antibacterial modified polyurethane coating layer is formed, and the antibacterial modified polyurethane coating layer is removed and rolled up to obtain mycelium leather;

[0053] Wherein, the preparation method of the antibacterial modified polyurethane coating is:

[0054] a. By weight, 1 part of 5,5-dimethylhydantoin was dissolved in ethanol, heated to 70°C and stirred for decomposition, 0.2 parts of sodium hydroxide was added, and the mixture was stirred and mixed under reflux for 20 minutes, and then the heating was stopped. 1 part of 4-(chloromethyl)benzyl alcohol was added, and the reaction was refluxed for 24 hours, and then the excess solvent was removed by rotary evaporation. The reaction product was washed twice with deionized water at a temperature of 2°C, and then vacuum evaporated to constant weight to obtain an antibacterial benzyl alcohol intermediate;

[0055] b. Disperse 1 part of triphenylmethane triisocyanate in DMF, disperse under ultrasonic vibration for 30 minutes, add 0.3 parts of 4-trifluoromethoxybenzoic acid, raise the temperature to 78 ° C under nitrogen atmosphere, stir and react for 2 hours, and then remove excess solvent by rotary evaporation to obtain fluorine-modified diisocyanate;

[0056] c. By weight, under nitrogen atmosphere, 0.8 parts of 1,4-butanediol and DMF were mixed, 0.5 parts of fluorine-modified diisocyanate and 3 parts of 2,4-toluene diisocyanate were added, the temperature was raised to 65°C, stirred and reacted for 2 hours, then the temperature was raised to 70°C, 1 part of antibacterial benzyl alcohol intermediate was added, the stirring reaction was continued for 2 hours, the temperature was lowered to 55°C, 0.5 parts of ethanol were added, the reaction was continued for 0.5 hours, the heating was stopped, DMF was added to adjust the solid content to 30wt%, and the antibacterial modified polyurethane coating was obtained.

[0057] Example 3. A method for preparing mycelium leather, comprising the following steps:

[0058] Compared with Example 1, this example increases the amount of 4-trifluoromethoxybenzoic acid added in step b;

[0059] S3. The antibacterial modified polyurethane coating is applied on both sides of the mycelium leather body, the temperature is raised to 120°C, and after keeping warm for 25 minutes, a 60 micron thick antibacterial modified polyurethane coating layer is formed, and the antibacterial modified polyurethane coating layer is removed and rolled up to obtain mycelium leather;

[0060] Wherein, the preparation method of the antibacterial modified polyurethane coating is:

[0061] a. By weight, 1 part of 5,5-dimethylhydantoin was dissolved in ethanol, heated to 70°C and stirred for decomposition, 0.2 parts of sodium hydroxide was added, and the mixture was stirred and mixed under reflux for 20 minutes, and then the heating was stopped. 1 part of 4-(chloromethyl)benzyl alcohol was added, and the reaction was refluxed for 24 hours, and then the excess solvent was removed by rotary evaporation. The reaction product was washed twice with deionized water at a temperature of 2°C, and then vacuum evaporated to constant weight to obtain an antibacterial benzyl alcohol intermediate;

[0062] b. Disperse 1 part of triphenylmethane triisocyanate in DMF, disperse under ultrasonic vibration for 30 minutes, add 0.6 parts of 4-trifluoromethoxybenzoic acid, raise the temperature to 78 ° C under nitrogen atmosphere, stir and react for 2 hours, and then remove excess solvent by rotary evaporation to obtain fluorine-modified diisocyanate;

[0063] c. By weight, under nitrogen atmosphere, 0.8 parts of 1,4-butanediol and DMF were mixed, 0.5 parts of fluorine-modified diisocyanate and 3 parts of 2,4-toluene diisocyanate were added, the temperature was raised to 65°C, stirred and reacted for 2 hours, then the temperature was raised to 70°C, 1 part of antibacterial benzyl alcohol intermediate was added, the stirring reaction was continued for 2 hours, the temperature was lowered to 55°C, 0.5 parts of ethanol were added, the reaction was continued for 0.5 hours, the heating was stopped, DMF was added to adjust the solid content to 30wt%, and the antibacterial modified polyurethane coating was obtained.

[0064] Example 4. A method for preparing mycelium leather, comprising the following steps:

[0065] Compared with Example 1, this example increases the amount of fluorine-modified diisocyanate added in step c;

[0066] S3. The antibacterial modified polyurethane coating is applied on both sides of the mycelium leather body, the temperature is raised to 120°C, and after keeping warm for 25 minutes, a 60 micron thick antibacterial modified polyurethane coating layer is formed, and the antibacterial modified polyurethane coating layer is removed and rolled up to obtain mycelium leather;

[0067] Wherein, the preparation method of the antibacterial modified polyurethane coating is:

[0068] a. By weight, 1 part of 5,5-dimethylhydantoin was dissolved in ethanol, heated to 70°C and stirred for decomposition, 0.2 parts of sodium hydroxide was added, and the mixture was stirred and mixed under reflux for 20 minutes, and then the heating was stopped. 1 part of 4-(chloromethyl)benzyl alcohol was added, and the reaction was refluxed for 24 hours, and then the excess solvent was removed by rotary evaporation. The reaction product was washed twice with deionized water at a temperature of 2°C, and then vacuum evaporated to constant weight to obtain an antibacterial benzyl alcohol intermediate;

[0069] b. Disperse 1 part of triphenylmethane triisocyanate in DMF, disperse under ultrasonic vibration for 30 minutes, add 0.3 parts of 4-trifluoromethoxybenzoic acid, raise the temperature to 78 ° C under nitrogen atmosphere, stir and react for 2 hours, and then remove excess solvent by rotary evaporation to obtain fluorine-modified diisocyanate;

[0070] c. By weight, under nitrogen atmosphere, 0.8 parts of 1,4-butanediol and DMF were mixed, 1 part of fluorine-modified diisocyanate and 3 parts of 2,4-toluene diisocyanate were added, the temperature was raised to 65°C, stirred and reacted for 2 hours, then the temperature was raised to 70°C, 1 part of antibacterial benzyl alcohol intermediate was added, the stirring reaction was continued for 2 hours, the temperature was lowered to 55°C, 0.5 parts of ethanol were added, the reaction was continued for 0.5 hours, the heating was stopped, DMF was added to adjust the solid content to 30wt%, and the antibacterial modified polyurethane coating was obtained.

[0071] Example 5. A method for preparing mycelium leather, comprising the following steps:

[0072] Compared with Example 1, this example increases the amount of antibacterial benzyl alcohol intermediate added in step c;

[0073] S3. The antibacterial modified polyurethane coating is applied on both sides of the mycelium leather body, the temperature is raised to 120°C, and after keeping warm for 25 minutes, a 60 micron thick antibacterial modified polyurethane coating layer is formed, and the antibacterial modified polyurethane coating layer is removed and rolled up to obtain mycelium leather;

[0074] Wherein, the preparation method of the antibacterial modified polyurethane coating is:

[0075] a. By weight, 1 part of 5,5-dimethylhydantoin was dissolved in ethanol, heated to 70°C and stirred for decomposition, 0.2 parts of sodium hydroxide was added, and the mixture was stirred and mixed under reflux for 20 minutes, and then the heating was stopped. 1 part of 4-(chloromethyl)benzyl alcohol was added, and the reaction was refluxed for 24 hours, and then the excess solvent was removed by rotary evaporation. The reaction product was washed twice with deionized water at a temperature of 2°C, and then vacuum evaporated to constant weight to obtain an antibacterial benzyl alcohol intermediate;

[0076] b. Disperse 1 part of triphenylmethane triisocyanate in DMF, disperse under ultrasonic vibration for 30 minutes, add 0.3 parts of 4-trifluoromethoxybenzoic acid, raise the temperature to 78 ° C under nitrogen atmosphere, stir and react for 2 hours, and then remove excess solvent by rotary evaporation to obtain fluorine-modified diisocyanate;

[0077] c. By weight, under nitrogen atmosphere, 0.8 parts of 1,4-butanediol and DMF were mixed, 1 part of fluorine-modified diisocyanate and 3 parts of 2,4-toluene diisocyanate were added, the temperature was raised to 65°C, stirred and reacted for 2 hours, then the temperature was raised to 70°C, 2 parts of antibacterial benzyl alcohol intermediate were added, the stirring reaction was continued for 2 hours, the temperature was lowered to 55°C, 0.5 parts of ethanol were added, the reaction was continued for 0.5 hours, the heating was stopped, DMF was added to adjust the solid content to 30wt%, and the antibacterial modified polyurethane coating was obtained.

[0078] Comparative Example 1. A method for preparing mycelium leather, comprising the following steps:

[0079] Compared with Example 1, this comparative example did not prepare an antibacterial modified polyurethane coating;

[0080] S1. Cultivate mycelium;

[0081] S11. Take the fresh fruiting body grafted in the PDA plate, culture it at a temperature of 28 ° C for 8 days, take the front hyphae, transplant it to a fresh PDA plate, culture it again, take the front hyphae culture, repeat the operation 5 times, and obtain a pure strain;

[0082] S12. The pure strain was inoculated into the culture medium, and then cultured at 28°C for 24 hours, and then cultured with shaking at a speed of 150 r / min for 5 days to obtain shake flask seeds;

[0083] The preparation method of the culture solution is as follows: according to the weight, 90g of bran is placed in 3000mL of boiling water and boiled for 10min, 90g of corn flour is added, and the water is boiled for 20min, filtered, the filtrate is collected, and 2% of sucrose, 1% of glucose, 0.2% of peptone, 0.01% of potassium dihydrogen phosphate, and 1% of calcium chloride are added thereto respectively, the mixture is evenly mixed, filtered again, the filtrate is collected, water is added to 3000mL, the filtrate is boiled at 121°C for 30min, and the culture solution is obtained after cooling;

[0084] S13. The shake flask seeds were inoculated into a 5L fermenter, the pH of the culture solution in the fermenter was adjusted to 7, the liquid volume in the fermenter was 55%, the inoculation amount was 8%, the ventilation volume was 8L / min, the culture temperature was 30°C, and the fermentation speed was 150r / min. After 5 days of culturing and fermentation, the culture solution in the fermenter was transferred to an open tray, and after culturing in a dark environment at 28°C for 5 days, an aerial mycelium film was obtained;

[0085] S14. The aerial mycelial membrane was transplanted onto a solid substrate, and cultured at 28° C. in the dark for 5 days, and then the mycelial layer was collected;

[0086] Wherein, the preparation method of the solid matrix is:

[0087] 60 parts of cottonseed hulls, 15 parts of corn cobs, 15 parts of bran, 5 parts of soybean meal, and 5 parts of sawdust were mixed by weight, water was added to adjust the moisture content to 65%, the mixture was heated to 121° C. and sterilized for 30 minutes, and then cooled to obtain a solid matrix;

[0088] S2. The mycelium layer is laid flat, inactivated by hot pressing at a temperature of 120°C and a pressure of 1 MPa for 5 min, and the inactivated mycelium layer is placed in a tanning finishing liquid, ultrasonically shaken, and soaked at room temperature for 24 h, then taken out, and the excess tanning finishing liquid on the surface is rinsed with water, and after natural drying, the inactivated mycelium layer is dyed to obtain mycelium leather;

[0089] Wherein, the tanning finishing liquid is composed of 20 parts of tannin extract, 10 parts of glycerin, 15 parts of lecithin, 5 parts of penetrant and 50 parts of water in parts by weight.

[0090] Comparative Example 2. A method for preparing mycelium leather, comprising the following steps:

[0091] This comparative example did not prepare the addition of antibacterial benzyl alcohol intermediate;

[0092] S3. The antibacterial modified polyurethane coating is applied on both sides of the mycelium leather body, the temperature is raised to 120°C, and after keeping warm for 25 minutes, a 60 micron thick antibacterial modified polyurethane coating layer is formed, and the antibacterial modified polyurethane coating layer is removed and rolled up to obtain mycelium leather;

[0093] Wherein, the preparation method of the antibacterial modified polyurethane coating is:

[0094] a. Disperse 1 part of triphenylmethane triisocyanate in DMF, disperse under ultrasonic vibration for 30 minutes, add 0.3 parts of 4-trifluoromethoxybenzoic acid, raise the temperature to 78 ° C under nitrogen atmosphere, stir and react for 2 hours, and then remove excess solvent by rotary evaporation to obtain fluorine-modified diisocyanate;

[0095] b. By weight, under nitrogen atmosphere, 0.8 parts of 1,4-butanediol and DMF were mixed, 0.5 parts of fluorine-modified diisocyanate and 3 parts of 2,4-toluene diisocyanate were added, the temperature was raised to 65°C, stirred and reacted for 2 hours, then the temperature was lowered to 55°C, 0.5 parts of ethanol were added, the reaction was continued for 0.5 hours, the heating was stopped, DMF was added to adjust the solid content to 30wt%, and an antibacterial modified polyurethane coating was obtained.

[0096] Testing: Performance testing was performed on Examples 1-5 and Comparative Examples 1-2;

[0097] Mechanical properties test: The tensile strength and elongation of mycelium leather were measured according to "QB / T 2710-2018 Leather physical and mechanical testing - Determination of tensile strength and elongation";

[0098] Air permeability test: refer to GB / T 4689.22-1996 "Leather air permeability test method" for testing. Take the prepared leather sample, cut the sample into 20cm2 samples, and use the air permeability meter to measure the air permeability of the leather. Test conditions: 100Pa;

[0099] Waterproof test: refer to GB / T 40936-2021 Physical and mechanical tests of leather - Determination of waterproof performance of garment leather. Take a 1cm*2cm smooth and undamaged leather sample, use a syringe to discharge 3uL of the test liquid at room temperature, take a photo of the contact surface when the droplet contacts the sample for 9s, take at least 3 photos, and obtain the average value of the static contact angle of the mycelium membrane material;

[0100] Antibacterial test: Cut the leather sample into a circle with a diameter of about 20 mm, put it into a culture medium containing Escherichia coli, Staphylococcus aureus, Aspergillus niger, and Penicillium, place it in a constant temperature and humidity chamber (temperature 30 ℃) for 2 days, and measure the diameter of the inhibition circle. The size of the inhibition circle diameter is used as a standard to measure the antibacterial performance of leather. The larger the inhibition circle, the better the antibacterial performance of the leather;

[0101] Tear force test: Tear force refers to QB / T 2711-2018 "Determination of tear force of leather physical and mechanical tests: bilateral tearing";

[0102] The test results are shown in the table below:

[0103]

[0104] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing mycelium leather, characterized in that: The following steps are involved: S1. Cultivate mycelium; S11. Take fresh fruiting bodies and inoculate them in a PDA plate. After culturing them at a temperature of 27-29°C for 5-8 days, take the front hyphae and transplant them to a fresh PDA plate. After culturing them again, take the front hyphae and culture them. Repeat the operation 3-5 times to obtain a pure strain. Wherein, the fresh fruiting body is any one of purple ganoderma, antler ganoderma, black ganoderma, red ganoderma, versicolor, oyster mushroom, Agaricus bisporus, Pleurotus eryngii, seafood mushroom, and schizophyllum; S12. The pure strain was inoculated into the culture medium, and then cultured at 27-29°C for 24 hours, and then cultured under shaking at a speed of 120-150 r / min for 3-5 days to obtain shake flask seeds; S13. The shake flask seeds were inoculated into a 5L fermenter, the pH of the culture solution in the fermenter was adjusted to 4.5-7.5, the liquid volume in the fermenter was 50-60%, the inoculation amount was 8-10%, the ventilation volume was 6-10L / min, the culture temperature was 20-30°C, and the speed was 100-250r / min. After 5 days of fermentation, the culture solution in the fermenter was transferred to an open tray, and cultured in a dark environment at 25-30°C for 3-8 days to obtain an aerial mycelial film; S14. transplanting the aerial mycelium film onto a solid substrate, continuing to culture at 25-30° C. in the dark for 5-8 days, and then collecting the mycelium layer; S2. The mycelium layer is arranged and laid flat, and after being inactivated by hot pressing for 3-5 minutes, the inactivated mycelium layer is placed in a tanning finishing liquid, ultrasonically shaken, and soaked at room temperature for 24-36 hours, taken out, and the excess tanning finishing liquid on the surface is rinsed with water. After naturally drying, the inactivated mycelium layer is dyed to obtain a mycelium leather blank; S3. Apply the antibacterial modified polyurethane coating on both sides of the mycelium leather blank, raise the temperature to 115-130°C, keep warm for 25-30 minutes, take out, and roll up to obtain mycelium leather; Wherein, the preparation method of the antibacterial modified polyurethane coating is: a. Dissolve 5,5-dimethylhydantoin in ethanol, heat to 70-75°C and stir to decompose, add sodium hydroxide, continue to reflux and stir for 20 minutes, stop heating, add 4-(chloromethyl)benzyl alcohol, reflux for 24-36 hours, remove excess solvent by rotary evaporation, wash the reaction product 1-3 times with deionized water at a temperature of 0-4°C, and evaporate in vacuo to constant weight to obtain an antibacterial benzyl alcohol intermediate; b. Disperse triphenylmethane triisocyanate in DMF, disperse under ultrasonic vibration for 15-35min, add 4-trifluoromethoxybenzoic acid, raise the temperature to 78-105°C under nitrogen atmosphere, stir and react for 0.5-2h, and then remove excess solvent by rotary evaporation to obtain fluorine-modified diisocyanate; c. Under nitrogen atmosphere protection, 1,4-butanediol and DMF were mixed, fluorine-modified diisocyanate and 2,4-toluene diisocyanate were added, the temperature was raised to 55-65°C, and the reaction was stirred for 1.5-2h, then the temperature was raised to 70-75°C, the antibacterial benzyl alcohol intermediate was added, the reaction was continued with stirring for 2-4h, the temperature was lowered to 55-65°C, ethanol was added, the reaction was continued for 0.5-1h, the heating was stopped, and DMF was added to adjust the solid content to 30wt% to obtain an antibacterial modified polyurethane coating.

2. The method for preparing mycelium leather according to claim 1, characterized in that: In step S12, the culture solution is prepared by: 80-100 parts of bran are placed in 3000 parts of boiling water and boiled for 8-12 minutes, 80-100 parts of corn flour are added, and the mixture is boiled for 20 minutes, filtered, the filtrate is collected, and 1.8-2.5% of sucrose, 0.8-1.5% of glucose, 0.15-0.25% of peptone, 0.01% of potassium dihydrogen phosphate, and 0.8-1.2% of calcium chloride are added thereto respectively based on the weight of the filtrate, the mixture is evenly mixed, filtered again, the filtrate is collected, water is added to 3000 parts, the mixture is boiled at 121° C. for 30 minutes, and the mixture is cooled to obtain a culture solution.

3. The method for preparing mycelium leather according to claim 1, characterized in that: In step S14, the solid matrix is ​​prepared by: According to weight, 55-65 parts of cottonseed hulls, 10-20 parts of corn cobs, 10-20 parts of bran, 3-6 parts of soybean meal and 3-6 parts of sawdust are mixed, water is added to adjust the water content to 60-70%, the mixture is heated to 121° C. and sterilized for 30 minutes, and then cooled to obtain a solid matrix.

4. The method for preparing mycelium leather according to claim 1, characterized in that: In step S2, the hot pressing temperature is 80-150°C and the hot pressing pressure is 1-1.5MPa; The tanning finishing liquid consists of 18-22 parts of tannin extract, 8-12 parts of glycerin, 12-18 parts of lecithin, 3-7 parts of penetrant and 45-55 parts of water in parts by weight.

5. The method for preparing mycelium leather according to claim 1, characterized in that: In step a, the mass ratio of 5,5-dimethylhydantoin, sodium hydroxide and 4-(chloromethyl)benzyl alcohol is 1:(0.15-0.3):(1-1.2).

6. The method for preparing mycelium leather according to claim 1, characterized in that: In step b, the mass ratio of triphenylmethane triisocyanate to 4-trifluoromethoxybenzoic acid is 1:(0.3-0.6).

7. The method for preparing mycelium leather according to claim 1, characterized in that: In step c, the mass ratio of the 1,4-butanediol, the fluorine-modified diisocyanate, and the 2,4-toluene diisocyanate is (0.8-1): (0.5-1):

3.

8. The method for preparing mycelium leather according to claim 1, characterized in that: In step c, the mass ratio of the 2,4-toluene diisocyanate, the antibacterial benzyl alcohol intermediate and the ethanol is 3:(1-2):(0.5-0.8).

9. Mycelium leather prepared by the preparation method according to any one of claims 1 to 8.

Images