A method for preparing mycelium vegan leather

Abstract

The application discloses a kind of mycelium pure leather preparation methods, belong to new material technical field.The application utilizes physical or chemical method to mycelium, finally obtains the pure leather of performance strength and animal leather comparable and environment-friendly.Mainly divided into following steps: the harvested fresh mycelium material is deacetylated, filled, reduced dye dyeing, then crosslinking plasticizing, then spraying coloring further color fixing, finally coating finishing.The application causes little pollution to environment in fermentation process and preparation process, and production cycle is short, and production cost is low.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for preparing mycelium vegan leather, belonging to the technical field of new materials. BACKGROUND

[0002] Traditional leather manufacturing methods usually involve the use of animal leather, but this method has concerns about animal rights, environmental pollution and resource waste. Therefore, finding alternative and environmentally friendly leather materials has become an important research field.

[0003] In recent years, researchers have begun to explore the use of biological waste and renewable materials to manufacture leather alternatives. Among them, the use of solid-state fermentation mycelium material to manufacture fiber textiles has become a method that has attracted much attention. Solid-state fermentation is a process in which mycelium grows on solid substrates to form a fiber network. This mycelium has a fibrous structure and plasticity, making it a potential leather alternative material.

[0004] Leather alternatives made from solid-state fermentation mycelium have many advantages. First, they are renewable, using waste or agricultural by-products as substrates, reducing resource consumption. Second, the production process of this material is relatively environmentally friendly, avoiding the use of harmful chemicals involved in traditional leather manufacturing. In addition, solid-state fermentation mycelium can be obtained through different processing methods such as filling, dyeing, cross-linking plasticization, etc., to obtain similar appearance and performance to the dermis.

[0005] The development of this technology is of great significance to promote sustainable development and the strengthening of environmental awareness. It can provide an alternative choice for the textile and leather industry, reduce dependence on animal leather, reduce environmental burden, and meet the needs of consumers for sustainable products.

[0006] However, there are still problems such as poor mechanical properties, uneven color, difficulty in degradation, and complex process in the preparation of vegan leather using solid-state fermentation. SUMMARY

[0007] To solve the above problems, the mycelium material obtained by solid-state fermentation is subjected to a series of treatments such as deacetylation, filling, dyeing, cross-linking, plasticization, hot pressing, spraying coloring, coating finishing, etc.

[0008] The first object of the present application is to provide a method for preparing mycelium vegan leather, which comprises the following steps:

[0009] (1) Deacetylation

[0010] The mycelium material obtained by solid-state fermentation is placed in an oven at 20-160°C for drying and inactivation. The mycelium material is soaked in a deacetylation solution with a mass fraction of 2-20% for 12-24 hours, and then rinsed with water to remove excess solution.

[0011] The deacetylation converts chitin in the mycelium into chitosan, and the chitosan is cross-linked in subsequent steps to increase the cross-linking degree and improve the mechanical properties of the material.

[0012] (2) Filling

[0013] The mycelium material treated in step (1) is dried at 40°C to obtain a sponge-like porous material, which is soaked in a filling solution with a mass fraction of 2-20%, taken out after 24 hours of soaking, and dried.

[0014] The filling has the following effects: the dried mycelium is fluffy and light in weight, and does not have the texture of leather, while there are many gaps between the mycelium fibers, and the material has a full hand feeling and improved strength after filling.

[0015] (3) Dyeing with a vat dye

[0016] The mass ratio of natural vat dye, reducing agent, fixing agent, and water is 5:1.25:1:125. The natural vat dye, reducing agent, and water are mixed in proportion, and after the dye is fully reduced, the mycelium material treated in step (2) is put in, soaked for 15 minutes, the fixing agent is added and stirred thoroughly, taken out after 15 minutes, and the mycelium material is oxidized in air, soaked again for 15 minutes, taken out and oxidized in air again, a total of 3 times of soaking, to obtain a mycelium material with a darker color, and then the mycelium is put into a soaping solution to wash off the floating color.

[0017] (4) Cross-linking and plasticizing

[0018] The mycelium material treated in step (3) is put into a cross-linking agent / plasticizer mixed solution, shaken for 12-24 hours, taken out after the reaction is completed, and naturally dried.

[0019] (5) Hot pressing

[0020] The mycelium material treated in step (4) is hot pressed and shaped, with a hot pressing temperature of 50-150°C and a hot pressing time of 1-5 minutes. Preferably, the hot pressing temperature is 125°C and the hot pressing time is 2 minutes.

[0021] (6) Spraying and coloring

[0022] MD black paste, adhesive RU2100, and water are mixed in a certain proportion, sprayed on the surface of the mycelium with a spray gun, and a layer is sprayed again after drying.

[0023] (7) Coating finishing

[0024] The mycelium leather obtained in step (6) is sprayed with a finishing agent, and the leather is obtained after drying.

[0025] In one embodiment of the present application, the mycelium comprises: Ganoderma lucidum, Pleurotus ostreatus, Lentinula edodes, Volvariella volvacea, Agaricus bisporus, Flammulina velutipes, Hericium erinaceus, Pleurotus cystidiosus, Pleurotus eryngii, Agaricus bisporus, Auricularia auricular, Tremella fuciformis, Cantharis carolinensis, Morchella esculenta, Rhizoma bambusae, Schizophyllum commune.

[0026] In one embodiment of the present application, the deacetylation solution comprises: chitin deacetylase (CDA) solution, sodium bicarbonate solution, sodium carbonate solution, sodium hydroxide solution. Preferably chitin deacetylase (CDA) solution, more preferably chitin deacetylase solution with a mass fraction of 10%.

[0027] In one embodiment of the present application, the temperature of the soaking in step (1) is 50°C.

[0028] In one embodiment of the present application, the filler comprises: zein, wheat protein, barley protein, sorghum protein, chitin nanowhisker, carboxymethyl cellulose, aqueous polyurethane, guar gum.

[0029] In one embodiment of the present application, the natural mordant comprises: indigo, cochineal, lemon yellow, etc.

[0030] In one embodiment of the present application, the reducing agent can be sodium hydrosulfite, sodium formaldehyde sulfoxylate, dihydrothiourea.

[0031] In one embodiment of the present application, the fixing agent can be fixing agent DFRF-1, fixing agent SH-96, fixing agent Eccofix FD-3, fixing agent LH.

[0032] In one embodiment of the present application, in the crosslinking agent / plasticizer mixed solution, the mass fraction of the crosslinking agent is 2-12%, and the mass fraction of the plasticizer is 2.5-15%.

[0033] In one embodiment of the present application, the crosslinking agent comprises one or more of tannin, flaxseed oil, glutaraldehyde, genipin, formaldehyde, tyrosinase, acetic anhydride, sodium tripolyphosphate, or tannic acid. Preferably genipin solution with a mass fraction of 6%.

[0034] In one embodiment of the present application, the plasticizer comprises one or more of polyethylene glycol (PEG), formamide, urea, sodium nitrate, salicylic acid, dicyandiamide, thiocyanate, glycerol, sorbitol, ethylene glycol, diisooctyl sebacate, dibutyl phthalate, DES. Preferably polyethylene glycol solution with a mass fraction of 10%.

[0035] In one embodiment of the present application, the ratio of the leather pigment paste: adhesive RU2100: water is 6.5:28:65.5.

[0036] In one embodiment of the application, the coating includes but is not limited to PU coating, PVC coating, acrylic resin, phenolic resin coating, grease, silicone oil, shellac, prolamine. Preferably, the shellac.

[0037] Advantages

[0038] The present application greatly improves the performance of the mycelium leather by a series of post-finishing such as deacetylation treatment, filling, dyeing, crosslinking, plasticizing, hot pressing, spray coloring and coating finishing. The mycelium leather is a kind of leather obtained by in-situ growth of mycelium, and its mechanical properties can be greatly improved after a series of chemical and physical treatments, and it is easy to store and has a short production cycle, low cost, biodegradability and less environmental pollution compared with traditional rawhide such as pig, cow and sheep.

[0039] The present application first uses enzyme to deacetylate mycelium, which is more mild and less damaging to mycelium compared with alkali treatment and chitin deacetylase.

[0040] The mycelium material may have uneven color during growth, and it is difficult to make the color uniform by using dye alone. In the present application, the method of dyeing first and then spraying is used to unify the color inside and outside, and dyeing and spray coloring are used to improve the coloring effect and color fastness, and also reduce the number of spraying. Since the pigment paste contains a small amount of PU or other non-degradable components, reducing the number of spraying improves the degradability to some extent.

[0041] The dye selected in the present application is a natural vat dye, which improves the light resistance of the leather, has less environmental pollution and good degradability. The steps in the present application are progressive, which ensures the performance of the product.

[0042] In the processing of the pure leather, all the auxiliaries used are degradable and environmentally friendly. Only a small amount of PU is used in the final coating. The whole pure leather is degradable and has less environmental pollution. DETAILED DESCRIPTION

[0043] The preferred embodiments of the present application are described below, and it should be understood that the embodiments are used to better explain the present application and are not used to limit the present application.

[0044] Mechanical property test: the tensile strength and elongation of the mycelium leather are determined according to QB / T 2710-2018 Leather Physical and Mechanical Test Determination of Tensile Strength and Elongation.

[0045] Folding resistance test: refer to the standard of QB / T 2714-2005 Leather physical and mechanical test Determination of folding resistance, and make appropriate improvements. Cut the sample into a square with a side length of 3 cm, repeatedly fold it, and observe the creases and breakage of the leather. When the leather shows obvious signs of breakage, record the number of folds.

[0046] Degradation test: take a portion of mycelium leather and dry it to constant weight. Record the mass, bury the leather in soil 20-30 cm below the surface under natural conditions. After 50 days, remove it, wash it thoroughly with clean water, and dry it to constant weight. Calculate the weight loss rate W.

[0047] Density test: refer to the standard of GB / T 4689.10-1984 Leather Determination of apparent density, and make appropriate improvements. Cut the leather into a circle with a radius of D, weigh it m, measure the thickness h of the leather, and calculate the density.

[0048]

[0049] where m is the mass of the leather, g;

[0050] D is the radius of the leather, cm;

[0051] h is the thickness of the leather, cm.

[0052] Friction color fastness: refer to the standard of GB / T 39366-2020 Leather Color fastness test Color fastness to rubbing. Cut the leather into 140mm*50mm, prepare four copies, and use them for dry rubbing and wet rubbing respectively. Place the sample on the cylindrical test bench, with the length direction of the sample consistent with the running direction of the rubbing head. Fix a piece of white cotton cloth on the rubbing head and rub it repeatedly ten times. Soak a piece of white cotton cloth with a liquid rate of 100%, fix it on the rubbing head, and after repeating the above operation, dry it. Under standard light source, use the evaluation of staining with a card to evaluate the staining grade of the cotton cloth.

[0053] Sunlight resistance test: refer to the standard of QB / T 2727-2017 Leather Color fastness test Color fastness to artificial light: xenon arc, and make appropriate improvements. Cut the leather into 30mm*20mm samples, place the sample in the clamping device, cover half of the sample with the clamping device, set the sunlight duration, place the test card in the experimental chamber for determination, and then compare the sample with the gray sample card.

[0054] Air permeability test: refer to GB / T 4689.22-1996 Leather Determination of air permeability for testing. Take the prepared leather sample, cut it into 20cm 2 samples, and use the air permeability instrument to measure the air permeability of the leather. Test conditions: 100 Pa.

[0055] Waterproof test: The test was carried out according to GB / T 40936-2021 Leather-Physical and mechanical tests-Determination of waterproof performance of garment leather. Take 1 cm*2 cm surface smooth, no damage leather sample, at room temperature, use a syringe to discharge 3uL of test solution, take a picture when the droplet contacts the sample for 9s, take at least 3 pictures to get the average value of the static contact angle of the mycelium membrane material.

[0056] Chitin deacetylase was purchased from Shanghai Zhenjun Biotechnology Co., Ltd., and the enzyme activity was 1442.3 U / mL.

[0057] Example 1: Preparation of pure mycelium leather

[0058] (1) Deacetylation

[0059] Preparation of mycelium material by solid state fermentation:

[0060] Corn cob, sawdust, bran, flour and water were configured into a solid culture medium according to a mass ratio of 4:2:2:2:7, and 1% potassium dihydrogen phosphate, 1% calcium carbonate, 10% glucose and 1% magnesium sulfate were added to the solid culture medium, which was stirred uniformly and then divided into polypropylene fermentation bags. After sterilization, the mushroom spores were inoculated into the fermentation bags to make a fungus bag, which was cultured at 28℃ for 15 days until the mycelium covered the fungus bag. Then the fungus bag was crushed and laid flat in a fermentation box. The culture was carried out under the conditions of temperature 28℃, humidity 70%, nitrogen concentration 88%, red light (650nm) irradiation, electric field intensity 30KV / m, and magnetic field intensity 50mT for about 10 days, and finally the surface layer of mycelium material was harvested.

[0061] The mycelium material obtained by solid state fermentation was placed in an 80℃ oven for drying and inactivation, and then the mycelium material was placed in a 10% chitin deacetylase (CDA) solution and soaked at 50℃ for 24h. The excess enzyme solution was removed by rinsing with water.

[0062] (2) Filling

[0063] The mycelium material obtained after step (1) was dried at 40℃ to obtain a sponge-like porous material, which was soaked in a 5% (w / w) zein solution for 24h, then taken out and dried.

[0064] (3) Dyeing with vat dyes

[0065] The mass ratio of natural indigo dye, sodium dithionite, fixing agent LH, and water is 5:1.25:1:125. After mixing the natural indigo dye, sodium dithionite, and water in the ratio and allowing the dye to fully reduce, the mycelium obtained in step (2) is immersed in the dye bath for 15 minutes. The fixing agent LH is added and stirred thoroughly. After 15 minutes, it is removed and oxidized in the air. It is then immersed in the dye bath again for 15 minutes. After removal, it is oxidized in the air. This process is repeated 3 times to obtain a darker color. Then, the mycelium is washed in soaping solution to remove the excess dye.

[0066] (4) Crosslinking plasticization

[0067] The mycelial material treated in step (3) was placed in a genipin / PEG mixture (genipin mass fraction of 6% and PEG mass fraction of 10%), shaken for 12-24 hours, and then removed and air-dried after the reaction was completed.

[0068] (5) Hot pressing

[0069] The mycelial material obtained in step (4) was hot-pressed and shaped at a temperature of 125°C for 2 minutes.

[0070] (6) Spraying coloring

[0071] Mix MD black paste, adhesive RU2100 and water in a mass ratio of 6.5:28:65.5, spray the mixture onto the mycelial surface with a spray gun, let it dry, and then spray another layer.

[0072] (7) Coating finishing

[0073] The surface of the mycelium leather obtained in step (6) is coated with shellac and dried to obtain leather.

[0074] Example 2:

[0075] The specific implementation method is the same as in Example 1, except that "place in an 80°C oven for drying and inactivation" in step (1) is replaced with hot pressing (80°C, 5 min) for inactivation.

[0076] The results show:

[0077] The density and mechanical properties of the leather tested in step (4) are shown in Table 1 below:

[0078] Table 1

[0079] Density (g / cm 3 )]]> Tensile strength (MPa) Elongation (%) Example 1 Example 2 0.522 11.2 47.8 Deacetylating agent 0.357 6.3 64.5

[0080] Example 2 uses heat-pressing inactivated way, the final density of the leather, tensile strength of Example 1 decreased, elongation increased. Fresh mycelium through heat-pressing, become compact, the gap between the mycelium is less, not conducive to the subsequent filler into, so the density and tensile strength decreased, due to the lack of filler between the mycelium fixed, fiber can freely slip, so the elongation is high.

[0081] Example 3:

[0082] The specific implementation method is the same as Example 1, the difference is that the chitin deacetylase (CDA) in step (1) is replaced by sodium bicarbonate, sodium carbonate, sodium hydroxide and ammonia respectively.

[0083] The results show that:

[0084] The mechanical properties of the leather in step (4) are detected, and the results are shown in Table 2 below:

[0085] Table 2

[0086] Tensile strength (MPa) Elongation (%) Example 1 CDA Sodium bicarbonate 11.2 47.8 Sodium carbonate 6.8 71.6 Sodium hydroxide 7.3 59.7 Ammonia 1.2 10.6 Concentration (%) 7.1 62.1

[0087] The deacetylation in step (1) directly affects the cross-linking effect in step (4). Using CDA for deacetylation, the reaction is mild and the damage to the mycelium is small, and the mechanical properties of the prepared leather are best. Sodium hydroxide is too strong, which causes too much damage to the mycelium fibers, so the tensile strength and elongation decrease greatly. Sodium bicarbonate, sodium carbonate and ammonia have weak alkalinity and insufficient deacetylation.

[0088] Example 4:

[0089] The specific implementation method is the same as Example 1, the difference is that the chitin deacetylase (CDA) in step (1) is replaced by 2.5%, 5%, 12.5% and 15% respectively.

[0090] The results show that:

[0091] The mechanical properties of the leather in step (4) are detected, and the results are shown in Table 3 below:

[0092] Table 3

[0093] Tensile strength (MPa) 2.5 5 7.5 10 12.5 15 Elongation (%) Example 1 6.5 7.4 9.5 11.2 11.2 11.1 Reaction temperature (°C) 72.1 65.2 53.1 47.8 45.2 46.4

[0094] With the increase of enzyme preparation, the degree of deacetylation of mycelium increases, and the cross-linking effect is enhanced, so the tensile strength increases and the elongation decreases. When the concentration is 10%, the tensile strength is the largest, and when the concentration exceeds 10%, the mechanical properties of the leather tend to be stable.

[0095] Example 5:

[0096] The specific implementation method is the same as example 1, except that the 50℃ oscillation in step (1) is replaced by 20℃, 30℃, 40℃, 60℃, and 70℃, respectively.

[0097] The results show that:

[0098] The mechanical properties of the leather in step (4) are detected, and the results are shown in Table 4 below:

[0099] Table 4

[0100] Tensile strength (MPa) 20 30 40 50 60 70 Elongation (%) Example 1 4.6 7.2 9.5 11.2 4.8 3.2 Dye 66.4 59.2 54.1 47.8 62.4 67.2

[0101] Temperature changes can affect the activity of CDA enzyme, thereby affecting the deacetylation effect and in turn affecting the degree of cross-linking. When the temperature reaches 50℃, the mechanical properties of the prepared leather are best. When the temperature is too low, the enzyme activity is low, and the degree of deacetylation is not enough. When the temperature is too high, the enzyme is inactivated, which also affects the deacetylation. Therefore, 50℃ should be selected as the reaction temperature.

[0102] Example 6:

[0103] The specific implementation method is the same as example 1, except that the reduction dyeing in step (3) is replaced by reactive, direct, and acid dyeing, respectively.

[0104] Reactive dyeing step: reactive meta-cyanide, sodium sulfate, and water are configured according to a mass ratio of 5:1.5:100. The mycelium material is placed in the dye bath and immersed for 30 minutes at 60℃, and then the temperature is raised to 80℃ for 30 minutes. Take out and wash thoroughly, then put it in the soaping solution to remove the floating color, and dry.

[0105] Direct dyeing step: direct turquoise blue GL and water are configured according to a mass ratio of 1:100. Prepare 15g / L of sodium sulfate. First add half of the sodium sulfate, put the mycelium material into the dye bath and immerse for 15 minutes, then add the other half of the sodium sulfate and stir well. Take out after 15 minutes, wash in the soaping solution to remove the floating color, and dry.

[0106] Acid dyeing step: acid blue and water are configured according to a mass ratio of 3:100. Adjust the pH to about 4 with acetic acid, immerse for 30 minutes at 90℃, take out and wash thoroughly, and dry.

[0107] The results show that:

[0108] The lightfastness in step (4) is detected, and the results are shown in Table 5 below:

[0109] Table 5

[0110] Vat dye Reactive dye Direct dye Acid dye Sunfast rating Concentration (%) 4-5 3 4 3-4

[0111] The deacetylated mycelium contains chitin, chitosan, protein, glucan, so it can be dyed with vat, reactive, direct and acid dyes. Considering its light resistance, vat dyes should be selected.

[0112] Example 7

[0113] The specific embodiment is the same as example 1, except that the concentration of genipin in step (4) is changed from 6% to 2%, 4%, 8%, 10%, and 12%, respectively.

[0114] The results show that:

[0115] The mechanical properties of the leather in step (4) are detected, and the results are shown in Table 6 below:

[0116] Table 6

[0117] Tensile strength (MPa) 2 4 6 8 10 12 Elongation (%) Example 1 3.5 7.3 11.2 12.9 13.2 13.1 Concentration (%) 62.3 52.1 47.8 32.4 21.4 10.9

[0118] With the increase of the concentration of genipin, the crosslinking points increase, and the tensile strength of the leather increases, and the elongation decreases. When the concentration exceeds 6%, the crosslinking is excessive, making the leather brittle and hard, and the hand feeling and elongation decrease sharply. Therefore, the concentration of genipin is selected as 6%.

[0119] Example 8

[0120] The specific embodiment is the same as example 1, except that the concentration of PEG in step (4) is changed from 10% to 2.5%, 5%, 7.5%, 12.5%, and 15%, respectively.

[0121] The results show that:

[0122] The mechanical properties of the leather in step (4) are detected, and the results are shown in Table 7 below:

[0123] Table 7

[0124] Tensile strength (MPa) 2.5 5 7.5 10 12.5 15 Elongation (%) Example 1 13.5 12.6 11.6 11.2 8.6 7.1 Temperature (°C) 10.9 19.8 27.6 47.8 52.3 60.7

[0125] With the increase of the concentration of PEG, the interaction between chitin and glucan molecules decreases, and the intermolecular deformation and movement ability increases, so the tensile strength decreases and the elongation increases. When the concentration exceeds 10%, the tensile strength decreases sharply, and the hand feeling is sticky, so 10% is selected as appropriate.

[0126] Example 9

[0127] The specific embodiment is the same as example 1, except that the hot pressing temperature in step (5) is changed from 125°C to 25°C, 50°C, 75°C, 100°C, 150°C, 175°C, and 200°C, respectively.

[0128] The results show that:

[0129] The mechanical properties of the leather in step (5) were detected, and the results are shown in Table 8 below.

[0130] Table 8

[0131] Tensile strength (MPa) 25 50 75 100 125 150 175 200 Elongation (%) Example 1 5.2 5.4 7.2 9.2 11.2 8.2 5.1 2.3 Time (min) 62.1 60.4 54.7 50.5 47.8 32.1 25.7 12.4

[0132] The mycelium material obtained in step (4) was hot-pressed, and the hot-pressed mycelium material became compact and the mycelium leather became flat and uniform. When the temperature increased, the tensile strength increased and the elongation decreased. When the temperature exceeded 125°C, the mycelium fibers were damaged and carbonized, resulting in a sharp decrease in strength and elongation. Therefore, the hot-pressing temperature should be 125°C.

[0133] Example 10:

[0134] The specific implementation is the same as that of Example 1, except that the hot-pressing time in step (5) is changed from 2 min to 1 min, 3 min, 4 min, and 5 min, respectively.

[0135] The results are shown in Table 8.

[0136] The density of the leather in step (5) was detected, and the results are shown in Table 9 below.

[0137] Table 9

[0138] Density (g / cm3) 1 2 3 4 5 Coating adhesion (N / 10 mm) 0.423 0.512 0.563 0.611 0.635

[0139] With the increase of hot-pressing time, the mycelium leather becomes more compact. When the time exceeds 2 min, the mycelium leather feels stiff and rigid, so the hot-pressing time of 2 min is appropriate.

[0140] Example 11:

[0141] The specific implementation is the same as that of Example 1, except that the shellac in step (7) is replaced by polyurethane, acrylic resin, prolamine, and beeswax, respectively.

[0142] The results are shown in Table 10.

[0143] The adhesion and hydrophobic properties of the leather in step (7) were detected, and the results are shown in Table 10 below.

[0144] Table 10

[0145] Water contact angle (°) Shellac Polyurethane 4.53 117.6 Acrylic resin 4.98 92.3 Prolamine 3.78 101.5 Beeswax 4.11 95.2 Tensile strength (MPa) 2.01 90.2

[0146] From the adhesion, polyurethane and shellac are the best. From the hydrophobicity, shellac and acrylic resin are the best. However, polyurethane and acrylic resin are difficult to degrade. Considering the degradation performance of the final leather, shellac is selected as the finishing agent.

[0147] Comparative Example 1:

[0148] Step (1) deacetylation was omitted, and the rest was consistent with Example 1.

[0149] Comparative Example 2:

[0150] Step (2) filling was omitted, and the rest was consistent with Example 1.

[0151] The test results are shown in Table 11 below:

[0152] Table 11

[0153] Density (g / cm 3 )]]> Elongation (%) Example 1 Comparative Example 1 Comparative Example 2 / 7.2 69.5 ​ 0.196 6.9 56.1

[0154] The deacetylation step was omitted in Comparative Example 1, resulting in insufficient subsequent cross-linking, so the mechanical properties were poor. In Comparative Example 2, the filling was omitted, and the density and mechanical properties decreased. Mycelium itself is a kind of porous material similar to sponge, with low density and light weight, making it difficult to achieve the feel of leather. In Example 1, the leather density after filling reached 0.522 g / cm 3 , the feel was full, and the mechanical properties were greatly improved.

[0155] Comparative Example 3:

[0156] The zein in step (2) of Example 1 was changed to water-based polyurethane, and the rest was consistent with Example 1.

[0157] Comparative Example 4:

[0158] The zein in step (2) of Example 1 was changed to wheat protein, and the rest was consistent with Example 1.

[0159] Comparative Example 5:

[0160] The zein in step (2) of Example 1 was changed to guar gum, and the rest was consistent with Example 1.

[0161] The test results are shown in Table 12 below:

[0162] Table 12

[0163]

[0164]

[0165] In Comparative Example 3, the filler was changed to waterborne polyurethane, which significantly improved the mechanical properties, but reduced the air permeability. The weight loss rate in soil was only 49.2%, and the degradation performance was significantly reduced. In Comparative Example 4, the filler was changed to wheat gliadin, which had lower mechanical properties than Example 1, but air permeability and weight loss rate were comparable to Example 1, and the hydrophobicity was poor. In Comparative Example 5, the filler was changed to guar gum, which had poor mechanical properties, good air permeability and degradation performance, but because guar gum is hydrophilic, the treated leather had poor hydrophobicity.

[0166] Comparative Example 6:

[0167] Step (3) of vat dyeing in Example 1 is omitted, and the rest is the same as in Example 1.

[0168] Comparative Example 7:

[0169] The adhesive in step (6) of Example 1 is omitted, and the rest is consistent with Example 1.

[0170] Comparative Example 8:

[0171] Step (6) of spraying and coloring in Example 1 is omitted, and the rest is the same as in Example 1.

[0172] Table 13

[0173]

[0174] Example 1 combines dyeing with coating, improving the rubbing fastness of the leather. Comparative Example 6 omits the dyeing step, resulting in decreased rubbing fastness. Comparative Example 8 omits the spray coloring, losing the coating protection, leading to a faster decrease in wet rubbing fastness, but improved breathability.

[0175] Comparative Example 9:

[0176] The shellac in step (7) of Example 1 is omitted, and the rest is the same as in Example 1.

[0177] Table 14

[0178]

[0179]

[0180] In Comparative Example 7, omitting the adhesive significantly reduced the adhesion of the coating. In Comparative Example 9, omitting shellac reduced the hydrophobicity. Although the mycelium contains hydrophobic proteins, the surface roughness was too high, resulting in poor hydrophobicity.

Claims

1. A process for the preparation of mycelium-based vegan leather, characterized in that, The method comprises the following steps: (1) deacetylation The mycelium material obtained by solid fermentation is put into an 80 C oven for drying and inactivation. The mycelium material is put into a 10% chitin deacetylase solution by mass fraction and soaked at 50°C for 12-24 hours. After being taken out, the mycelium material is washed with water to remove the excess solution. (2) padding The mycelium material treated by step (1) is dried at 40 C dried to obtain a sponge-like porous material, which is soaked in a 5% zein solution by mass fraction, taken out after soaking for 24 h, and dried. (3) dyeing with vat dyes The mass ratio of natural vat dyes, reducing agent, fixing agent and water is 5:1.25:1:

125. The natural vat dyes, reducing agent and water are mixed in proportion, and after the dyes are fully reduced, the mycelium material obtained in step (2) is put in for dyeing. The fixing agent is added and stirred thoroughly. The mycelium material is taken out and oxidized in air. It is dyed again and taken out for oxidation in air. The dyeing is repeated for 3 times. The mycelium material with deep color is obtained. Then the mycelium is put into a soaping solution to remove the floating color; (4) cross-linking and plasticizing The mycelium material treated in step (3) is put into a genipin / PEG mixed solution. The mass fraction of genipin is 6%, and the mass fraction of PEG is 10%. The solution is shaken for 12-24 hours. After the reaction is completed, the mycelium material is taken out and naturally dried; (5) hot pressing The mycelium material obtained in step (4) was hot-pressed and shaped, the hot-pressing temperature was 125 C, the hot-pressing time was 2 min. (6) spraying coloring MD black paste, adhesive RU2100 and water are mixed in a mass ratio of 6.5:28:65.

5. The mixture is sprayed on the surface of the mycelium with a spray gun. After drying, another layer of the mixture is sprayed. (7) coating finishing The mycelium leather obtained in step (6) is sprayed with shellac. After drying, the leather is obtained. The density of the leather is 0.522 g / cm 3 tensile strength of 11.2 MPa, elongation of 47.8%, fastness to sunlight of 4-5, coating adhesion of 4.53 N / 10 mm, water contact angle of 117.6°, air permeability of 629.6 mm / s, and weight loss rate of 98.2%.

2. A process for the production of mycelium-based vegan leather as claimed in claim 1, wherein, The mycelium comprises the mycelium of Ganoderma lucidum, Pleurotus ostreatus, Lentinula edodes, Volvariella volvacea, Agaricus bisporus, Auricularia auricular, Tremella fuciformis, Hypsizygus marmoreus, Agaricus blazei, Agaricus bisporus, Auricularia auricular, Tremella fuciformis, Morchella esculenta, Morchella angusticeps, Rhizopus stolonifer, Dictyophora indusiata and Schizophyllum commune.

3. A process for the production of mycelium-based vegan leather as claimed in claim 1, wherein, The natural vat dyes comprise indigo, carmine and lemon yellow.

4. The mycelium leather prepared by the method of any one of claims 1-3.

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