CN117188041B - A method for preparing mycelial vegan leather - Google Patents
A method for preparing mycelial vegan leatherInfo
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- CN117188041B CN117188041B CN202311087116.9A CN202311087116A CN117188041B CN 117188041 B CN117188041 B CN 117188041B CN 202311087116 A CN202311087116 A CN 202311087116A CN 117188041 B CN117188041 B CN 117188041B
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Abstract
The invention discloses a preparation method of mycelium pure leather, and belongs to the technical field of new materials. The mycelium is treated by a physical or chemical method, and finally the pure leather with the performance strength comparable with that of animal leather and environmental friendliness is obtained. The method mainly comprises the following steps of deacetylating, filling, vat dye dyeing, crosslinking and plasticizing, spraying and coloring, further fixation and finally finishing a coating. The invention has the advantages of less environmental pollution in the fermentation process and the preparation process, short production period and low production cost.
Description
Technical Field
The invention relates to a preparation method of mycelium pure leather, belonging to the technical field of new materials.
Background
Conventional leather manufacturing methods generally involve the use of animal leather, but such methods have concerns of animal rights, environmental pollution, and waste of resources. Therefore, the search for alternative, environmentally friendly leather materials is an important area of research.
In recent years, researchers have begun to explore the use of biowaste and renewable materials to make leather substitutes. Among them, the use of solid state fermentation mycelium materials for the manufacture of fiber textiles is a method of great interest. Solid state fermentation is a process whereby mycelia are grown on a solid substrate to form a network of fibers. The mycelium has fibrous structure and plasticity, so that the mycelium becomes a potential leather substitute material.
Leather substitutes made using solid state fermentation mycelium have many advantages. First, they are renewable, using waste or agricultural byproducts as substrates, reducing resource consumption. Secondly, the production process of the material is relatively environment-friendly, and the use of harmful chemical substances involved in the traditional leather manufacturing is avoided. In addition, the solid state fermentation mycelium can obtain an appearance and performance similar to that of dermis through different treatment methods such as filling, dyeing, crosslinking plasticization, etc.
The development of the technology has important significance for promoting sustainable development and strengthening environmental awareness. The method can provide an alternative choice for textile and leather industries, reduce dependence on animal leather, reduce environmental burden and meet the requirements of consumers on sustainable products.
However, the preparation of the pure leather by solid state fermentation has the problems of poor mechanical property, uneven color, difficult degradation, complex process and the like.
Disclosure of Invention
In order to solve the problems, the invention carries out a series of treatments such as deacetylation treatment, filling, dyeing, crosslinking, plasticization, hot pressing, spray painting and coloring, coating finishing and the like on the mycelium material obtained by solid fermentation.
The first object of the invention is to provide a method for preparing mycelium pure leather, which comprises the following steps:
(1) Deacetylation
And (3) putting the mycelium material obtained by solid state fermentation into a baking oven at 20-160 ℃, drying and inactivating, putting the mycelium material into a deacetylated solution with the mass fraction of 2-20%, soaking for 12-24 hours, taking out clear water, and washing to remove redundant solution.
The deacetylation function is to convert chitin in hyphae into chitosan, and then the chitosan is crosslinked through the subsequent steps so as to improve the crosslinking degree and the mechanical property of the material.
(2) Filling
And (3) drying the mycelium material treated in the step (1) at 40 ℃ to obtain a spongy porous material, soaking the spongy porous material in a filler solution with the mass fraction of 2-20%, taking out after soaking for 24 hours, and airing.
The filling function is that the dried mycelium is fluffy, the quality is lighter, the leather texture is not provided, more gaps exist among mycelium fibers, the material feel is plump after filling, and the strength is improved.
(3) Vat dye dyeing
And (2) mixing the natural vat dye, the reducing agent, the color fixing agent and the water according to the mass ratio of 5:1.25:1:125, putting the mixture into the mycelium material obtained by the treatment in the step (2) after the dye is fully reduced, dip-dyeing for 15min, adding the color fixing agent, fully stirring for 15min, taking out, oxidizing the mycelium material in the air, dip-dyeing for 15min again, taking out, oxidizing in the air, dip-dyeing for 3 times to obtain the mycelium material with a darker color, and then putting the mycelium into a soaping liquid to wash off the flooding.
(4) Cross-linked plasticization
And (3) putting the mycelium material treated in the step (3) into a cross-linking agent/plasticizer mixed solution, oscillating for 12-24 hours, taking out after the reaction is finished, and naturally airing.
(5) Hot pressing
And (3) carrying out hot press shaping on the mycelium material obtained by the treatment in the step (4), wherein the hot press temperature is 50-150 ℃ and the hot press time is 1-5 min. Preferably, the hot pressing temperature is 125 ℃ and the hot pressing time is 2min.
(6) Spray painting coloring
The MD black paste, the adhesive RU2100 and water are mixed according to a certain proportion, sprayed on the surface of mycelium by a spray gun, and sprayed with a layer after being dried.
(7) Coating finishing
Spraying the mycelium leather obtained in the step (6) with a finishing agent, and airing to obtain the leather.
In one implementation method of the invention, the mycelium comprises mycelium of ganoderma lucidum, oyster mushroom, straw mushroom, kou mushroom, flammulina velutipes, hericium erinaceus, white beech mushroom, pleurotus eryngii, agaricus bisporus, agaric, tremella, chanterelle, morchella, north fungus, bamboo fungus and schizophyllum commune.
In one embodiment of the present invention, the deacetylation solution comprises Chitin Deacetylase (CDA) solution, sodium bicarbonate solution, sodium carbonate solution, sodium hydroxide solution. Preferably a Chitin Deacetylase (CDA) solution, more preferably a chitin deacetylase solution with a mass fraction of 10%.
In one embodiment of the invention, the soaking temperature in step (1) is 50 ℃.
In one embodiment of the invention, the filler comprises zein, wheat gliadin, barley gliadin, sorghum gliadin, chitin nanowhiskers, carboxymethyl cellulose, aqueous polyurethane, guar gum.
In one embodiment of the invention, the natural vat dye comprises indigo, carmine, lemon yellow, and the like.
In one embodiment of the invention, the reducing agent may be sodium dithionite, sodium bisulphite formaldehyde, thiourea dioxide.
In one embodiment of the present invention, the fixing agent may be fixing agent DFRF-1, fixing agent SH-96, fixing agent Eccofix FD-3, fixing agent LH.
In one implementation method of the invention, in the cross-linking agent/plasticizer mixed solution, the mass fraction of the cross-linking agent is 2-12%, and the mass fraction of the plasticizer is 2.5-15%.
In one embodiment of the invention, the cross-linking agent comprises one or more of tannin extract, linseed oil, glutaraldehyde, genipin, formaldehyde, tyrosinase, acetic anhydride, sodium tripolyphosphate, or tannic acid. Preferably genipin solution with mass fraction of 6%.
In one embodiment of the invention, 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 a polyethylene glycol solution with a mass fraction of 10%.
In one embodiment of the invention, the leather pigment paste has a binder RU2100 to water ratio of 6.5:28:65.5.
In one embodiment of the invention, the coating includes, but is not limited to, PU coating, PVC coating, acrylic, phenolic coating, grease, silicone oil, shellac, prolamin. Shellac is preferred.
Advantageous effects
According to the invention, the mycelium leather is subjected to deacetylation treatment, filling, dyeing, crosslinking, plasticization, hot pressing, spray painting and coloring, and a series of after-finishing is performed on the mycelium leather, so that the performance of the mycelium leather is greatly improved, and the application performance of the mycelium leather is greatly improved. The mycelium leather is leather obtained by in-situ growth of mycelium, can greatly improve the mechanical property after a series of chemical and physical treatments, is convenient to store, and has short manufacturing period, low cost, degradability and small environmental pollution compared with raw leather of pigs, cows, sheep and the like used for traditional tanning.
According to the invention, the enzyme is adopted for deacetylation of the mycelium for the first time, compared with the alkali treatment for deacetylation, the chitin deacetylase is adopted for deacetylation, the reaction is milder, and the damage to the mycelium is small. The deacetylation step and the crosslinking step cooperatively improve the mechanical properties, and the filling and hot pressing cooperatively improve the mechanical properties and the hand feeling.
The invention adopts a method of dyeing before spraying to unify the internal and external colors, the dyeing and the spraying are cooperated to improve the coloring effect and the color fastness, and simultaneously, the spraying times are reduced, and the paint paste contains a small amount of PU or other non-degradable components, so the spraying times are reduced to improve the degradability to a certain extent.
The dye selected by the invention is natural vat dye, so that the sun-proof performance of leather is improved, the pollution to the environment is small, and the degradability is good. The steps of the invention are progressive layer by layer, thus ensuring the product performance.
In the processing process of the pure leather, all the used additives are degradable environment-friendly, and only a very small amount of PU is used in the final coating, so that the pure leather is wholly degradable and has little environmental pollution.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention.
Mechanical properties test the tensile strength and elongation of mycelium leather were determined according to QB/T2710-2018 determination of leather physical and mechanical test tensile Strength and elongation.
The folding endurance test refers to the standard of QB/T2714-2005 leather physical and mechanical test folding endurance test, and is modified appropriately. Cutting the sample into square with side length of 3cm, repeatedly folding, observing crease and fracture condition of leather, and recording folding times when obvious fracture trace appears on leather.
And (3) testing degradability, namely taking a part of mycelium leather, drying to constant weight, recording the quality, and burying the leather in soil 20 cm-30 cm below the ground surface under natural conditions. And taking out after 50d, washing with clear water, drying to constant weight, and calculating the weight loss ratio W.
Density testing refers to the standard of GB/T4689.10-1984 determination of apparent Density of leather, and is modified appropriately. Cutting leather into a round shape with radius D, weighing the mass m, measuring the thickness h of the leather, and calculating to obtain the density.
Wherein m is the mass of leather and g;
D, radius of leather, cm;
h, the thickness of leather, cm.
The rubbing color fastness refers to the standard of GB/T39366-2020 leather color fastness to rubbing test. The leathers were cut 140mm by 50mm and four portions were prepared for dry and wet rubbing, respectively. The test sample is placed on a cylindrical test bench, the length direction of the test sample is consistent with the running direction of a friction head, the white cotton cloth is fixed on the friction head, and the test sample is repeatedly rubbed for ten times along with the skill running. A piece of new white cotton cloth is soaked, the liquid carrying rate is 100%, the cotton cloth is fixed on a friction head, the operation is repeated, then the cotton cloth is dried, and under a standard light source, the dyeing grade of the cotton cloth is evaluated by using a dyeing evaluation card.
And (3) testing the light fastness, namely referring to the standard of Xe arc, the artificial light fastness of QB/T2727-2017 leather color fastness test, and carrying out proper improvement. Cutting leather into 30mm by 20mm samples, placing the samples in a clamp holder, covering one half of the pattern by the clamp holder, setting the sun-drying time length, placing a test card into an experiment cabin for measurement, and then comparing the samples with gray sample cards.
Air permeability test is carried out by referring to GB/T4689.22-1996 leather air permeability determination method. And (3) taking the prepared leather sample, cutting the sample into a sample of 20cm 2, and measuring the air permeability of the leather by using an air permeability instrument. Measurement conditions were 100Pa.
Waterproof test is carried out by referring to GB/T40936-2021 leather physical and mechanical test clothing leather waterproof property determination. A 1cm x 2cm leather sample with a smooth surface and no breakage was taken, 3uL of the test liquid was discharged at room temperature by a syringe, and the contact surface was photographed when the droplet contacted the sample 9s, at least 3 photographs were taken, to obtain an average value of the static contact angle of the mycelium film material.
Chitin deacetylases were purchased from Shanghai screening quasi-biotechnology Co., ltd and had an enzyme activity of 1442.3U/mL.
EXAMPLE 1 preparation of pure mycelium leather
(1) Deacetylation
Preparing mycelium material by solid state fermentation:
Preparing corncob, wood chips, wheat bran, flour and water into a solid culture medium according to the mass ratio of 4:2:2:2:7, adding 1% of monopotassium phosphate, 1% of calcium carbonate, 10% of glucose and 1% of magnesium sulfate into the solid culture medium, uniformly stirring, subpackaging into polypropylene fermentation bags, sterilizing, inoculating mushroom strains into the fermentation bags to prepare fungus bags, culturing at 28 ℃ for 15 days until the fungus bags are full of mycelia, smashing and spreading the fungus bags into a fermentation tank, culturing for about 10 days under the conditions of 28 ℃ and 70% of humidity, 88% of nitrogen concentration, irradiation of red light (650 nm), 30KV/m of electric field intensity and 50mT of magnetic field intensity, and finally harvesting a layer of mycelia material on the surface.
And (3) putting the mycelium material obtained by solid state fermentation into an 80 ℃ oven for drying and inactivating, then putting the mycelium material into 10% Chitin Deacetylase (CDA) solution, carrying out shaking soaking for 24 hours at 50 ℃, taking out clear water, and washing to remove redundant enzyme liquid.
(2) Filling
And (3) drying the mycelium material obtained after the treatment in the step (1) at 40 ℃ to obtain a spongy porous material, soaking the spongy porous material in 5% (w/w) zein solution, taking out the spongy porous material after soaking for 24 hours, and airing the spongy porous material.
(3) Vat dye dyeing
And (2) mixing the natural indigo dye, sodium dithionite, a fixing agent LH and water according to the mass ratio of 5:1.25:1:125, fully reducing the dye, then placing the mycelium treated in the step (2) into a dye bath for dip dyeing for 15min, adding the fixing agent LH, fully stirring for 15min, taking out, oxidizing in air, putting into the dye bath again for dip dyeing for 15min, oxidizing in air after taking out, and repeating the operation for 3 times to obtain a darker color. The mycelium is then placed in a soap wash to wash off the flooding.
(4) Cross-linked plasticization
And (3) putting the mycelium material treated in the step (3) into a genipin/PEG mixed solution (the mass fraction of genipin is 6 percent, the mass fraction of PEG is 10 percent), oscillating for 12-24 hours, taking out after the reaction is finished, and naturally airing.
(5) Hot pressing
And (3) hot-pressing and shaping the mycelium material obtained by the treatment in the step (4), wherein the hot-pressing temperature is 125 ℃ and the hot-pressing time is 2min.
(6) Spray painting coloring
The MD black paste, the adhesive RU2100 and water are mixed according to the mass ratio of 6.5:28:65.5, sprayed on the surface of mycelium by a spray gun, and sprayed with a layer after being dried.
(7) Coating finishing
And (3) coating shellac on the surface of the mycelium leather obtained in the step (6), and airing to obtain the leather.
Example 2:
The specific implementation method is the same as that of example 1, except that the drying and inactivation in the step (1) is changed into hot-pressing (80 ℃ for 5 min) inactivation.
The results show that:
The density and mechanical properties of the leather in step (4) were measured and the results are shown in table 1 below:
TABLE 1
| Density (g/cm 3) | Tensile Strength (MPa) | Elongation (%) | |
| Example 1 | 0.522 | 11.2 | 47.8 |
| Example 2 | 0.357 | 6.3 | 64.5 |
Example 2 is treated by a hot-pressing inactivation mode, the density and tensile strength of the finally obtained leather are reduced compared with those of example 1, and the elongation is improved. Fresh hyphae are compacted by hot pressing, gaps among the hyphae are reduced, the entering of subsequent fillers is not facilitated, the density and the tensile strength are reduced, and the fibers can freely slide due to the lack of fixation of the fillers among the hyphae, so that the elongation is high.
Example 3:
the specific implementation method is the same as that of example 1, except that the Chitin Deacetylase (CDA) in the step (1) is changed into sodium bicarbonate, sodium carbonate, sodium hydroxide and ammonia water respectively.
The results show that:
the leather mechanical properties in step (4) were examined and the results are shown in table 2 below:
TABLE 2
| Deacetylation reagent | Tensile Strength (MPa) | Elongation (%) |
| CDA | 11.2 | 47.8 |
| Sodium bicarbonate | 6.8 | 71.6 |
| Sodium carbonate | 7.3 | 59.7 |
| Sodium hydroxide | 1.2 | 10.6 |
| Ammonia water | 7.1 | 62.1 |
The deacetylation in the step (1) directly influences the crosslinking effect in the step (4), the deacetylation by CDA has mild reaction and little damage to hyphae, and the prepared leather has optimal mechanical properties. The sodium hydroxide has strong alkalinity and too much damage to hypha fibers, so the tensile strength and the elongation are greatly reduced. Sodium bicarbonate, sodium carbonate and ammonia water are weak in alkalinity and insufficient in deacetylation degree.
Example 4:
the specific implementation method is the same as that of example 1, except that 10% of Chitin Deacetylase (CDA) in the step (1) is changed to 2.5%, 5%, 12.5% and 15% respectively.
The results show that:
the mechanical properties of the leather in step (4) were measured and the results are shown in table 3 below:
TABLE 3 Table 3
| Concentration (%) | 2.5 | 5 | 7.5 | 10 | 12.5 | 15 |
| Tensile strength (MPa) | 6.5 | 7.4 | 9.5 | 11.2 | 11.2 | 11.1 |
| Elongation (%) | 72.1 | 65.2 | 53.1 | 47.8 | 45.2 | 46.4 |
With increasing enzyme preparation dosage, the deacetylation degree of mycelium is increased, the crosslinking effect is enhanced, and therefore the tensile strength is increased and the elongation is reduced. The tensile strength is maximum when the concentration is 10%, and the mechanical properties of leather tend to be stable after the concentration exceeds 10%.
Example 5:
The specific implementation method is the same as that of example 1, except that 50 ℃ oscillation in the step (1) is changed into 20 ℃, 30 ℃, 40 ℃, 60 ℃ and 70 ℃ respectively.
The results show that:
the leather mechanical properties in step (4) were examined and the results are shown in table 4 below:
TABLE 4 Table 4
| Reaction temperature (°c) | 20 | 30 | 40 | 50 | 60 | 70 |
| Tensile Strength (MPa) | 4.6 | 7.2 | 9.5 | 11.2 | 4.8 | 3.2 |
| Elongation (%) | 66.4 | 59.2 | 54.1 | 47.8 | 62.4 | 67.2 |
The temperature change can influence the activity of CDA enzyme, thereby influencing the deacetylation effect and further influencing the crosslinking degree, when the temperature reaches 50 ℃, the mechanical property of the prepared leather is optimal, when the temperature is too low, the enzyme activity is low, the deacetylation degree is insufficient, the temperature is too high, the enzyme is inactivated, and the deacetylation is also influenced. Thus 50 ℃ should be chosen as the reaction temperature.
Example 6:
The specific implementation method is the same as that of example 1, except that the vat dye dyeing in the step (3) is changed into reactive, direct and acid dye dyeing respectively.
And (3) dyeing with reactive dye, namely preparing active metacyan, sodium sulfate and water according to the mass ratio of 5:1.5:100, putting the mycelium material into a dye bath, dip-dyeing for 30 minutes at 60 ℃, heating to 80 ℃ for dip-dyeing for 30 minutes, taking out and fully washing with water, putting into soap washing liquid to wash off floating color, and airing.
And (3) a direct dye dyeing step, namely preparing direct turquoise blue GL and water according to a mass ratio of 1:100, preparing 15g/L sodium sulfate, firstly adding half of sodium sulfate, putting the mycelium material into a dye bath for dip dyeing for 15min, then adding the other half of sodium sulfate, fully stirring for 15min, taking out, washing off floating color in soap washing liquid, and airing.
And (3) acid dye dyeing, namely preparing acid blue and water according to a mass ratio of 3:100, regulating the pH to be about equal to 4 by acetic acid, dip-dyeing for 30 minutes at 90 ℃, taking out, washing with water fully, and airing.
The results show that:
The light fastness in the step (4) was measured, and the results are shown in the following table 5:
TABLE 5
| Dye | Vat dye | Reactive dyes | Direct dyes | Acid dyes |
| Sun resistance grade | 4-5 | 3 | 4 | 3-4 |
The deacetylated mycelium contains chitin, chitosan, protein and glucan, so that vat, reactive, direct and acid dyes can dye the mycelium, and the vat dye is selected in consideration of the sun-proof performance of the mycelium.
Example 7:
The specific embodiment is the same as in example 1, except that the genipin concentration in the step (4) is changed to 2%, 4%, 8%, 10% and 12% respectively.
The results show that:
the leather mechanical properties in step (4) were examined and the results are shown in Table 6 below:
TABLE 6
| Concentration (%) | 2 | 4 | 6 | 8 | 10 | 12 |
| Tensile Strength (MPa) | 3.5 | 7.3 | 11.2 | 12.9 | 13.2 | 13.1 |
| Elongation (%) | 62.3 | 52.1 | 47.8 | 32.4 | 21.4 | 10.9 |
As the concentration of genipin increases, the cross-linking point increases, the tensile strength of leather increases, the elongation decreases, and when the concentration exceeds 6%, the cross-linking is excessive, so that the leather is brittle and hard, and the hand feeling and the elongation suddenly decrease, so that the genipin concentration is selected to be 6%.
Example 8:
The specific embodiment is the same as example 1, except that the PEG concentration in step (4) is changed to 2.5%, 5%, 7.5%, 12.5% and 15% respectively.
The results show that:
the mechanical properties of the leather in step (4) were measured and the results are shown in table 7 below:
TABLE 7
| Concentration (%) | 2.5 | 5 | 7.5 | 10 | 12.5 | 15 |
| Tensile Strength (MPa) | 13.5 | 12.6 | 11.6 | 11.2 | 8.6 | 7.1 |
| Elongation (%) | 10.9 | 19.8 | 27.6 | 47.8 | 52.3 | 60.7 |
With the increase of PEG concentration, the acting force between molecules such as chitin and dextran is weakened, the intermolecular deformation and mobility are enhanced, and the tensile strength is reduced and the elongation is increased. When the concentration exceeds 10%, the tensile strength is suddenly lowered and the feel is sticky, so that 10% is preferable.
Example 9:
the specific embodiment is the same as in example 1, except that the hot-pressing temperature in step (5) is changed to 25 ℃, 50 ℃, 75 ℃, 100 ℃, 150 ℃, 175 ℃ and 200 ℃ respectively.
The results show that:
The leather mechanical properties in step (5) were examined and the results are shown in Table 8 below:
TABLE 8
| Temperature (° C) | 25 | 50 | 75 | 100 | 125 | 150 | 175 | 200 |
| Tensile Strength (MPa) | 5.2 | 5.4 | 7.2 | 9.2 | 11.2 | 8.2 | 5.1 | 2.3 |
| Elongation (%) | 62.1 | 60.4 | 54.7 | 50.5 | 47.8 | 32.1 | 25.7 | 12.4 |
And (3) hot-pressing the mycelium material obtained in the step (4), wherein the mycelium material after hot-pressing becomes compact, and the mycelium leather becomes flat and uniform. When the temperature is increased, the tensile strength is increased, the elongation is reduced, and when the temperature exceeds 125 ℃, the mycelium fibers are damaged and carbonized, resulting in the sudden reduction of the strength and the elongation, so that the hot pressing temperature is 125 ℃.
Example 10:
the specific embodiment is the same as example 1, except that the hot pressing time in the step (5) is changed to 1min, 3min, 4min and 5min respectively.
The results show that:
the density of the leather in step (5) was measured and the results are shown in table 9 below:
TABLE 9
| Time (min) | 1 | 2 | 3 | 4 | 5 |
| Density (g/cm 3) | 0.423 | 0.512 | 0.563 | 0.611 | 0.635 |
As the hot pressing time increases, the mycelium leather becomes more compact, and when the time exceeds 2 minutes, the mycelium leather feels stiff and dead, so the hot pressing time is preferably 2 minutes.
Example 11:
the specific embodiment is the same as in example 1, except that the shellac in step (7) is changed into polyurethane, acrylic resin, prolamin and beeswax respectively.
The results show that:
The leather of step (7) was tested for its coating adhesion fastness and hydrophobic properties and the results are shown in table 10 below:
Table 10
| Coating adhesion fastness (N/10 mm) | Water contact angle (°) | |
| Shellac | 4.53 | 117.6 |
| Polyurethane | 4.98 | 92.3 |
| Acrylic resin | 3.78 | 101.5 |
| Prolamin proteins | 4.11 | 95.2 |
| Beeswax (Cera flava) | 2.01 | 90.2 |
Polyurethane and shellac are optimal from the viewpoint of adhesion fastness, and shellac and acrylic resin are optimal from the viewpoint of hydrophobicity, but polyurethane and acrylic resin are difficult to degrade, and shellac is preferably selected as a finishing agent in consideration of degradation performance of the final leather.
Comparative example 1:
Step (1) of deacetylation was omitted and the remainder remained the same as in example 1.
Comparative example 2:
Step (2) filling was omitted and the remainder remained the same as in example 1.
The test results are shown in table 11 below:
TABLE 11
| Density (g/cm 3) | Tensile Strength (MPa) | Elongation (%) | |
| Comparative example 1 | / | 7.2 | 69.5 |
| Comparative example 2 | 0.196 | 6.9 | 56.1 |
The omission of the deacetylation step in comparative example 1 resulted in insufficient subsequent crosslinking and thus poor mechanical properties. In comparative example 2, filling is omitted, density and mechanical properties are reduced, mycelium is a porous material similar to sponge, density is low, quality is light, and leather feel is difficult to achieve. The density of the leather filled in the embodiment 1 reaches 0.522g/cm 3, the hand feeling is plump, and the mechanical property is greatly improved.
Comparative example 3:
the zein in step (2) of example 1 was changed to aqueous polyurethane, the remainder remaining in accordance with example 1.
Comparative example 4:
the zein in step (2) of example 1 was changed to wheat gliadin, the remainder remaining in accordance with example 1.
Comparative example 5:
The zein in step (2) of example 1 was changed to guar gum, the remainder remaining in accordance with example 1.
The test results are shown in table 12 below:
Table 12
In comparative example 3, the filler is changed into aqueous polyurethane, the mechanical property is greatly improved, but the air permeability is reduced, the weight loss rate in soil is only 49.2%, and the degradation property is greatly reduced. In comparative example 4, the filler was changed to wheat gliadin, the mechanical properties were inferior to those of example 1, the air permeability and the weight loss rate were equivalent to those of example 1, and the hydrophobicity was inferior. In comparative example 5, the filler was changed to guar gum, which had poor mechanical properties, good air permeability and good degradability, but the treated leather was poor in hydrophobicity due to the hydrophilicity of guar gum.
Comparative example 6:
step (3) vat dye dyeing of example 1 was omitted, and the remainder remained the same as example 1.
Comparative example 7:
the adhesive in step (6) of example 1 was omitted, and the remainder remained the same as in example 1.
Comparative example 8:
The spray coloration of step (6) of example 1 was omitted, the remainder remaining the same as in example 1.
TABLE 13
Example 1 combines dyeing with a coating to improve the crocking fastness of leather. Comparative example 6 omitted dyeing step, reduced crocking fastness, comparative example 8 omitted spray-applied coloration, lost coating protection, faster wet crocking fastness, but increased air permeability.
Comparative example 9:
Shellac in step (7) of example 1 was omitted, and the remainder remained the same as in example 1.
TABLE 14
Comparative example 7 the coating tack strength was significantly poorer after omitting the binder. In comparative example 9, the hydrophobicity was poor after shellac was omitted, and hydrophobin was contained in the hypha, but the hydrophobicity was poor due to the excessive surface roughness.
Claims (4)
1. A method for preparing mycelium pure leather, which is characterized by comprising the following steps:
(1) Deacetylation
Placing mycelium material obtained by solid state fermentation into 80C, drying and inactivating, namely putting the mycelium material into a chitin deacetylase solution with the mass fraction of 10% for oscillation and soaking for 12-24 hours at 50 ℃, and taking out clear water for washing to remove redundant solution;
(2) Filling
The mycelium material treated by the step (1) is treated by 40C, drying to obtain a spongy porous material, soaking the spongy porous material in a zein solution with the mass fraction of 5%, taking out the spongy porous material after soaking for 24 hours, and airing the spongy porous material;
(3) Vat dye dyeing
Mixing natural vat dye, reducing agent, color fixing agent and water according to the mass ratio of 5:1.25:1:125, fully reducing the dye, then placing the mixture into the mycelium material obtained by the treatment in the step (2), dip-dyeing, adding the color fixing agent, fully stirring, taking out the mycelium material, oxidizing in the air, dip-dyeing again, taking out, oxidizing in the air, dip-dyeing for 3 times to obtain the mycelium material with darker color, and then placing the mycelium into soaping liquid to wash off flooding;
(4) Cross-linked plasticization
Putting the mycelium material treated in the step (3) into a genipin/PEG mixed solution, wherein the mass fraction of genipin is 6%, the mass fraction of PEG is 10%, oscillating for 12-24 h, taking out after the reaction is finished, and naturally airing;
(5) Hot pressing
Performing hot-press setting on the mycelium material obtained in the step (4) at a hot-press temperature of 125 DEG CC, hot pressing for 2min;
(6) Spray painting coloring
Mixing MD black paste, an adhesive RU2100 and water according to the mass ratio of 6.5:28:65.5, spraying on the surface of mycelium by using a spray gun, and spraying a layer after airing;
(7) Coating finishing
Spraying shellac to the mycelium leather obtained in the step (6), and airing to obtain leather;
the leather has the density of 0.522g/cm 3, the tensile strength of 11.2MPa, the elongation of 47.8%, the sunlight resistance grade of 4-5, the coating adhesion fastness of 4.53N/10mm, the water contact angle of 117.6%, the air permeability of 629.6mm/s and the weight loss rate of 98.2%.
2. The method for preparing mycelium pure leather according to claim 1, wherein the mycelium comprises mycelium of ganoderma lucidum, oyster mushroom, straw mushroom, kou mushroom, flammulina velutipes, hericium erinaceus, white beech mushroom, pleurotus eryngii, agaricus bisporus, agaricus, tremella, chanterelle, morchella, north-wind fungus, bamboo fungus and schizophyllum commune.
3. A process for preparing mycelium pure leather according to claim 1, wherein the natural vat dyes comprise indigo, carmine, lemon yellow.
4. Mycelium pure leather prepared by the method of any one of claims 1-3.
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