Ecological mycelium leather and green preparation method thereof

Abstract

The invention belongs to the field of mycelium materials, and provides ecological mycelium leather and a green preparation method thereof, and the method comprises the following steps: (1) carrying out deacetylation treatment on flaky mycelium; (2) adjusting the pH value of the deacetylated flaky mycelium, then placing the deacetylated flaky mycelium in a bath lotion containing a cross-linking agent for permeation, and then adjusting the pH value of the bath lotion for cross-linking; (3) putting the flaky cross-linked mycelia into bath liquid for filling and dyeing; and (4) soaking the filled and dyed flaky cross-linked mycelia in a bath lotion containing a plasticizer which is composed of a natural grease modified product and polyhydric alcohol, then taking out the mycelia, and throwing water to obtain the flaky cross-linked mycelia. The processing process of the method conforms to the green chemical process, the ecological property and biodegradability of the mycelium leather can be improved, and the sensory quality of the mycelium leather is improved.

Description

Technical Field

[0001] The invention belongs to the field of mycelium materials and relates to ecological mycelium leather and a green preparation method thereof. Background Art

[0002] In recent years, the use of mycelium as a biomaterial to replace petroleum-based plastics has opened a new era of mycelium materials. In particular, MycoWorks Biotechnology Company has used Fine Mycelium TM Technology developed by Reishi TM The material has a polymer content of less than 1%, has high tensile strength, good tear resistance and durability, and its performance is comparable to that of animal leather, making it a potential substitute for leather.

[0003] Fungal mycelium is composed of a network of tubular microfilaments called hyphae. The main components of the mycelial cell wall are polysaccharides, followed by proteins and lipids, and the cell wall accounts for 30% of the cell dry matter. The polysaccharides that make up the cell wall mainly include polymers such as chitin (chitin), cellulose, glucan, and mannan. Among them, chitin is a polysaccharide composed of N-acetylglucosamine molecules connected by β-(1,4) glucosidic bonds. It is a tough, elastic, inert and water-insoluble polysaccharide substance. Mycelial materials or mycelial sheets can be processed into leather-like products, or form composites with other materials, such as cotton textiles and macromolecular polymer materials. Such composites can be used as textiles, packaging materials, and building materials.

[0004] The properties of mycelium materials can be regulated by chemical modification methods. For example, some important properties of mycelium leather can be improved by cross-linking, including tensile strength, tear strength and wear resistance, and it also helps to improve the stability of mycelium leather. Although there are literatures at home and abroad that disclose different methods of cross-linking and modifying fungal composite materials, most of these methods are based on the processing ideas of animal leather, which may bring some environmental problems and cause the presence of harmful chemical components in the products.

[0005] In the prior art, the preparation of mycelium leather is mainly divided into three types: the first type follows the idea and process of traditional leather manufacturing, and the mycelium undergoes a process of deacetylation-tanning agent cross-linking-dyeing-fatting and finishing, and the tanning agents used include metal tanning agents such as chromium and aldehyde tanning agents; the second type is to first crush, cross-link and plasticize the mycelium, and then add macromolecular binding materials, such as alcohol-soluble proteins, polypeptides, adhesives (latex, water-based polyurethane, guar gum, sodium carboxymethyl cellulose, etc.), and then heat-press and shape them to make sheet materials (similar to the base of synthetic leather), and further transfer or resin coating is performed on them; the third type is to directly coat a layer of textile material on one side of the mycelium, or to implant a textile cloth base during the solid-state cultivation of the mycelium to improve the mechanical properties of the mycelium leather, especially the tensile strength and tear strength. However, the above methods have the following shortcomings: (1) The processing process will use and emit harmful chemicals, such as metal tanning agents or aldehyde tanning agents, plasticizers such as dibutyl phthalate, and the use of these chemicals will also lead to the risk of residual ingredients harmful to consumer health in the end product; (2) There are too many polymer or fabric components in the product, resulting in the product not being completely biodegradable after the end of its life cycle; (3) It is easy to cause defects in product performance. For example, the use of adhesives such as water-based polyurethane, guar gum, and sodium carboxymethyl cellulose can easily produce cross-linking and make the leather board hard. For example, transfer film or resin coating can easily cause poor air permeability.

[0006] Therefore, for the preparation of mycelium leather similar to animal leather by chemical cross-linking modification of mycelium materials, there is an urgent need to develop a preparation method for ecological mycelium leather whose preparation process is more in line with the green chemical process and can give the end product good biodegradability and sensory quality. Summary of the invention

[0007] In view of the problems that existing mycelium leather products are difficult to completely biodegrade after the end of their life cycle and there is a risk of residual harmful substances in the products, as well as the problem that existing mycelium leather uses and emits harmful chemicals during the preparation process, the present invention provides an ecological mycelium leather and a green preparation method thereof, so that the processing of mycelium leather is more in line with the green chemical process, the ecology and biodegradability of the product are increased, and the sensory quality of the product is improved.

[0008] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention is as follows:

[0009] The process route of the green preparation method of the ecological mycelium leather of the present invention is as follows: Figure 1 shown.

[0010] The present invention provides a green preparation method of ecological mycelium leather, comprising the following steps:

[0011] (1) Deacetylation

[0012] 100 parts by weight of sheet-like mycelium, 100 to 400 parts by weight of water and 0.5 to 10 parts by weight of an inorganic base are placed in a reaction container, and the mixture is immersed at 35 to 100° C. for 1 to 20 hours for deacetylation treatment, and then washed with water and centrifuged for dehydration to obtain deacetylated sheet-like mycelium;

[0013] (2) Cross-linking

[0014] 100 parts by weight of deacetylated mycelium and 100 to 300 parts by weight of an aqueous solution of an organic acid are added into a reaction container, and when the pH value of the deacetylated mycelium reaches a pH value level conducive to the penetration of a crosslinking agent, 1 to 10 parts by weight of a crosslinking agent is added for sufficient penetration, and then the pH value of the bath solution is adjusted to 5.5 to 8.0 for a crosslinking reaction to obtain a crosslinked mycelium sheet;

[0015] In this step, the temperature of the bath solution is controlled to be room temperature to 80°C during infiltration and cross-linking, and the time of the cross-linking reaction is controlled to be 2 to 5 hours; the cross-linking agent is a combination of one or more of a polyphenol cross-linking agent, a small molecule phenol cross-linking agent and a glycidyl ether cross-linking agent, and the small molecule phenol cross-linking agent and the polyphenol cross-linking agent cannot be used in the same bath with the glycidyl ether cross-linking agent; the polyphenol cross-linking agent is a vegetable tannin, including but not limited to wattle bark tannin, bayberry tannin, chestnut tannin, tara tannin or tamarind tannin, the small molecule phenol cross-linking agent is genipin, quercetin or catechin, and the glycidyl ether cross-linking agent is ethylene glycol diglycidyl ether, glycerol triglycidyl ether or polyethylene glycol glycidyl ether;

[0016] (3) Filling and dyeing

[0017] 100 parts by weight of sheet-shaped cross-linked mycelium are put into a bath for filling and dyeing, and the temperature of the bath is controlled at 35 to 60° C. to obtain sheet-shaped cross-linked mycelium that has been filled and dyed;

[0018] The filling material used during filling is a combination of one or more of a biodegradable and environmentally friendly synthetic tanning agent, a biodegradable protein filler and sodium aluminum silicate. The amount of solvent water in the bath liquid is 80 to 300 parts by weight, and the amount of the filling material is 4 to 10 parts by weight. The environmentally friendly synthetic tanning agent is a phenolic or naphthalene auxiliary synthetic tanning agent that does not release formaldehyde. The protein filler is a combination of one or more of plant protein and animal protein.

[0019] (4) Plasticization

[0020] The bath liquid after filling and dyeing in step (3) is heated to 50-80° C., 6-20 parts by weight of plasticizer is added, and the bath liquid is soaked for 1-8 hours, and then formic acid is added to adjust the pH value of the bath liquid to 3.5-4.0, and the bath liquid is taken out after soaking for 1-3 hours, and the water is shaken off to obtain ecological mycelium leather;

[0021] The plasticizer is composed of a modified product of natural oil and fat and a polyol in a mass ratio of (2-5):1.

[0022] In the above technical scheme, the deacetylation operation of step (1) is mainly aimed at the chitin contained in the mycelium cell wall. Chitin can be appropriately deacetylated in an alkaline solution, which can not only release primary amino groups, enhance the bonding between mycelium fibers and crosslinking agents and / or plasticizers, but also reduce the rigidity of chitin, giving the mycelium leather good flexibility; at the same time, part of the soluble protein in the mycelium can be dissolved under the action of alkali, which is conducive to the penetration and action of the crosslinking agent, filling material and plasticizer added in the subsequent processing process into the sheet mycelium, thereby obtaining a good leather-like effect. The crosslinking operation of step (2) is mainly to form a stable mycelium structure through chemical bonds, such as -CO-NH-, -CN-, hydrogen bonds, etc., on the amino and hydroxyl active groups in the sheet mycelium obtained by the deacetylation treatment of step (1), and appropriately block the primary amino groups, hydroxyl active groups on the mycelium fibers, so as to avoid excessive hydrogen bonds between the fibers due to water loss during drying, resulting in hard leather blanks. The filling operation in step (3) is mainly to improve the fullness and firmness of the mycelium leather, to avoid the finished leather blank being too loose, and filling also helps to improve the mechanical properties of the finished leather. The main purpose of the plasticizing operation in step (4) is to increase the flexibility of the mycelium leather and prevent it from being over-drying and forming too many hydrogen bonds between mycelium fibers due to drying, which leads to problems such as hard board and easy breakage. In order to improve the softness of the leather, in addition to adding natural oil modified products, a certain amount of polyol materials with moisturizing and plasticizing functions must be added during the plasticizing treatment. On the basis of clarifying the role and purpose of each step, more technical details are as follows:

[0023] In step (4) of the above technical solution, the modified natural oil product is a composition of one or more of sulfated oil, sulfited oil, phosphorylated oil and sulfonated oil obtained by modifying natural animal and plant oils. The natural animal and plant oils include vegetable oils and animal fats. Preferably, the modified natural oil product is a combination of one or more of Lipsol BSFR, Lipsol STS, Neopristol EWK, SYNTHOLCP996, SYNTHOL CU909 and SYNTHOL FF992.

[0024] In step (4) of the above technical solution, the polyol is preferably a combination of one or more of glycerol, ethylene glycol, polyethylene glycol, polypropylene glycol, sorbitol, and polyol esters.

[0025] In step (3) of the above technical solution, the environmentally friendly synthetic tanning agent and the biodegradable protein filler help to improve the fullness of the product, and the sodium aluminum silicate can promote the absorption of dyes and plasticizers in addition to the filling function. According to different actual application requirements, one or more of the environmentally friendly synthetic tanning agent, the biodegradable protein filler and the sodium aluminum silicate can be selected for use in combination. Preferably, the filling material used during filling is a combination of at least two of the biodegradable environmentally friendly synthetic tanning agent, the biodegradable protein filler and the sodium aluminum silicate.

[0026] In step (3) of the above technical solution, the biodegradable and environmentally friendly synthetic tanning agent may be SYNTANZLR100 or SYNTAN SMA678, the biodegradable protein filler may be SYNTAN FP888, and the sodium aluminum silicate may be MZ 8132.

[0027] In step (3) of the above technical solution, the type and amount of dyes used during dyeing are selected according to actual application requirements. The dyes can be selected from one or more combinations of acid dyes, direct dyes, reactive dyes, and leather-specific dyes commonly used in the textile or leather industry, mainly involving the color matching and tone adjustment of the dyes. The preferred dyes are acid dyes that are easier to penetrate and color evenly.

[0028] In step (3) of the above technical solution, according to the needs of actual application requirements, the sheet-like cross-linked mycelium can be dyed first and then filled, or the sheet-like cross-linked mycelium can be filled first and then dyed, or the sheet-like cross-linked mycelium can be dyed and filled at the same time.

[0029] When the sheet-like cross-linked mycelium is first dyed and then filled, 100 parts by weight of the sheet-like cross-linked mycelium, 80 to 300 parts by weight of water and 0.2 to 10 parts by weight of dye are put into a reaction container, and after being fully immersed and dyed at 35 to 60° C., 1 to 10 parts by weight of filling material are added to fully immerse and fill, and the immersion dyeing and immersion filling time can be 2 to 6 hours; when the sheet-like cross-linked mycelium is first filled and then dyed, 100 parts by weight of the sheet-like cross-linked mycelium, 80 to 300 parts by weight of water and 1 to 10 parts by weight of filling material are added to the reaction container. The material is put into a reaction container, fully immersed and filled at 35-60° C., and then 0.2-10 parts by weight of dye is put into the reaction container for full immersion and dyeing, and the time for immersion, filling and dyeing can be 2-6 hours; when dyeing and filling the sheet-like cross-linked mycelium at the same time, 100 parts by weight of sheet-like cross-linked mycelium, 80-300 parts by weight of water, 0.2-10 parts by weight of dye and 1-10 parts by weight of filling material are put into the reaction container, and fully immersed at 35-60° C. for dyeing and filling, and the immersion time for dyeing and filling can be 2-6 hours.

[0030] In step (2) of the above technical scheme, the small molecule phenol crosslinking agent and the polyphenol crosslinking agent cannot be used in the same bath with the glycidyl ether crosslinking agent, which means that at least one of the small molecule phenol crosslinking agent and the polyphenol crosslinking agent cannot be added to the bath liquid with the glycidyl ether crosslinking agent at the same time. When it is necessary to use at least one of the small molecule phenol crosslinking agent and the polyphenol crosslinking agent in combination with the glycidyl ether crosslinking agent, it is necessary to adopt the glycidyl ether crosslinking agent and fully penetrate, then change the bath liquid and add at least one of the small molecule phenol crosslinking agent and the polyphenol crosslinking agent for crosslinking, or after adopting at least one of the small molecule phenol crosslinking agent and the polyphenol crosslinking agent to fully penetrate, change the bath liquid and add the glycidyl ether crosslinking agent for crosslinking. Using at least one of the small molecule phenol crosslinking agent and the polyphenol crosslinking agent in combination with the glycidyl ether crosslinking agent can achieve the effect of enhancing the crosslinking effect.

[0031] In the above technical solution, a secondary cross-linking operation is also included before the plasticizing operation in step (4). In particular, when a biodegradable protein filler is used for filling, the secondary cross-linking operation can further improve the tensile strength of the ecological mycelium leather. The cross-linking agent used in the secondary cross-linking operation is a fatty aldehyde or the aforementioned small molecule phenol cross-linking agent. A feasible secondary cross-linking operation is as follows:

[0032] 100 parts by weight of the sheet-like cross-linked mycelium filled and dyed in step (3) and 100 to 300 parts by weight of an aqueous solution of an organic acid having a pH value of 4.3 to 4.6 are placed in a reaction container, and then 0.3 to 1 parts by weight of a fatty aldehyde or a small molecule phenol cross-linking agent is added for sufficient penetration (the penetration time is preferably 2 to 5 hours), and then the pH value of the bath is adjusted to 5.5 to 8.5 for a cross-linking reaction.

[0033] In the above technical solution, according to the requirements of practical application, the ecological mycelium leather prepared in step (4) can be subjected to one or more of the following operations: drying, softening, shaving and surface finishing.

[0034] The sheet-like mycelium in step (1) of the above technical scheme is obtained by transplanting mycelium obtained by liquid fermentation onto a solid culture medium for cultivation. The sheet-like mycelium can be prepared according to the existing technology. Preferably, the sheet-like mycelium is obtained by transplanting mycelium obtained by liquid fermentation of a Ganoderma lucidum strain onto a solid culture medium for cultivation.

[0035] In step (1) of the above technical solution, the inorganic base includes one or more combinations of NaOH, KOH, Na2CO3 and NaHCO3.

[0036] In step (2) of the above technical solution, the organic acid includes a combination of one or more of formic acid, acetic acid, oxalic acid, and lactic acid.

[0037] The operations of the above technical solutions are all carried out in a device with controllable temperature and moderate stirring (such as a rotary drum or an inclined rotary drum).

[0038] The present invention also provides ecological mycelium leather prepared by the above technical solution.

[0039] Compared with the prior art, the technical solution of the present invention produces the following beneficial technical effects:

[0040] 1. The present invention provides a green preparation method of ecological mycelium leather, which includes deacetylation, crosslinking, dyeing, filling and plasticizing of sheet mycelium. The primary amino groups of chitin in mycelium are appropriately released by deacetylation, the combination between mycelium fiber and crosslinking agent and / or plasticizer is enhanced, and the rigidity of chitin is reduced. A stable mycelium framework is formed by crosslinking operation and the primary amino groups, hydroxyl groups and other active groups on mycelium fiber are appropriately closed to avoid excessive hydrogen bonds between fibers due to water loss during drying, resulting in hard leather blanks. The fullness and compactness of mycelium leather are improved by filling operation. Finally, the flexibility of mycelium leather is increased and mycelium leather is prevented from being hard by the coordination of natural oil modifier and polyol in the plasticizing operation process, and its softness is increased. Through the mutual cooperation of the above processes, the ecological mycelium leather finally prepared by the method of the present invention has the inherent characteristics and mechanical properties similar to animal leather. During the entire processing process of the method described in the present invention, except for acids and alkalis, the selected cross-linking agents, filling materials and plasticizers all belong to the category of green chemicals. No new harmful chemical components will be generated during the processing, and the end product does not contain any chemical substances harmful to the human body. The end product has good ecology and biodegradability, thereby realizing the sustainable green manufacturing of mycelium leather.

[0041] 2. The tensile strength of the ecological mycelium leather prepared by the method of the present invention is 4.16-9.53 MPa / mm through mechanical property test. 2 The elongation at break is 47.7% to 69.9%, which is significantly improved compared with the mechanical properties of sheet mycelium raw materials (tested after squeezing water in wet state), and can meet the requirements of practical applications.

[0042] 3. The present invention has found through natural degradation test experiments that the leather prepared by the method of the present invention has good biodegradability. After the ecological mycelium leather is kept in the soil for 30 days, the degradation rate can reach more than 35%. After being kept in the soil for 60 days, the degradation rate can reach more than 70%. After being kept in the soil for 90 days, it can be basically completely degraded into fine particles, and finally can achieve complete biodegradation, with excellent biodegradability.

[0043] 4. The ecological mycelium leather prepared by the method of the present invention has good fullness, good softness, uniform coloring, delicate and smooth surface, and is very similar to cowhide leather in feel and appearance, and has good sensory quality. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 It is a process route map of the green preparation method of the ecological mycelium leather of the present invention. DETAILED DESCRIPTION

[0045] The ecological mycelium leather and the green preparation method thereof provided by the present invention are further described by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. The technical personnel in the relevant field can make some non-essential improvements and adjustments to the present invention based on the above invention content, which still fall within the scope of protection of the present invention.

[0046] In the following embodiments, SYNTAN FP888, SYNTAN SMA678, SYNTAN ZLR100, and MZ 8132 are commercial products of Smit&Zoom of the Netherlands, which are biodegradable and environmentally friendly filling materials or biodegradable protein fillers, environmentally friendly synthetic tanning agents or silicate tanning agents; Lipsol BSFR, Lipsol STS, and Neopristol EWK are all commercial products of Schill+Seilacher of Germany, and SYNTHOL CP996, SYNTHOL CU909, and SYNTHOL FF992 are all commercial products of Smit&Zoom of the Netherlands.

[0047] In the following embodiments, the mechanical properties test was carried out according to the method in "QB / T 2710-2018 Determination of tensile strength and elongation of leather physical and mechanical tests", specifically testing the tensile strength and elongation of mycelium leather.

[0048] In the following embodiments, the test method of natural degradation performance is as follows:

[0049] A small sample was cut from the mycelium leather sample, weighed, and recorded as M1. The small sample was dried to constant weight, recorded as M2. Three samples of the same size were taken from the mycelium leather prepared in the same embodiment, weighed, and recorded as W1 and W3 respectively. Two samples were buried in garden soil about 30 cm below the surface under natural conditions. One sample was taken out on the 30th day and one on the 60th day respectively, washed with clean water to remove mud and sand, and dried to constant weight, recorded as W2 and W4 respectively. The 30-day degradation rate D1 and the 60-day degradation rate D2 were calculated according to the following formula.

[0050] Sample moisture content a = (M1-M2) / M1 × 100%

[0051] Sample degradation rate D1 = [(W1 × a)] - W2 / [(W1 × a)] × 100%

[0052] D2=[(W3×a)]-W4 / [(W3×a)]×100%

[0053] Example 1

[0054] In this embodiment, a green preparation method of ecological mycelium leather is provided, and the steps are as follows:

[0055] (1) Deacetylation

[0056] 100 parts by mass of sheet mycelium, 300 parts by mass of water and 5 parts by mass of sodium hydroxide were put into a drum, and immersed at 60° C. for 3 hours under the condition of rotating the drum for deacetylation treatment, and then washed with water and centrifuged for dehydration to obtain deacetylated sheet mycelium.

[0057] The sheet-like mycelium is from Tianjin Meikexin Biotechnology Co., Ltd., and is obtained by transplanting mycelium obtained by liquid fermentation of Ganoderma lucidum strains onto solid culture medium for cultivation.

[0058] (2) Cross-linking

[0059] 100 parts by mass of deacetylated flaky mycelium and 200 parts by mass of a 1.5 wt% formic acid aqueous solution are put into a drum, and the drum is rotated for 90 minutes until the pH value of the deacetylated flaky mycelium reaches 3.8-4.0. 1 part by mass of catechin is added, and the drum is rotated for 1 hour. Then, 5 parts by mass of bayberry tannin are added, and the drum is rotated for 6 hours to allow the catechin and bayberry tannin to fully penetrate into the deacetylated flaky mycelium. Then, the pH value of the bath liquid is adjusted to 5.5-5.6 with a 20% sodium bicarbonate solution, and the drum is rotated for 2 hours for a cross-linking reaction to obtain flaky cross-linked mycelium.

[0060] In this step, after adding catechins, the temperature of the bath liquid is controlled to be room temperature.

[0061] (3) Filling and coloring

[0062] 100 parts by mass of sheet-like cross-linked mycelium, 200 parts by mass of water and 0.2 parts by mass of dye acid orange were put into a drum, and the drum was rotated for 1 hour. Then 4 parts by mass of SYNTAN FP888 and 3 parts by mass of MZ 8132 were added, and the drum was rotated for 6 hours to obtain sheet-like cross-linked mycelium that had been filled and dyed.

[0063] In this step, after adding acid orange, the temperature of the bath liquid is controlled to be 35°C.

[0064] (4) Plasticization

[0065] The bath liquid after filling and dyeing in step (3) is heated to 50°C, 3 parts by mass of Lipsol BSFR, 5 parts by mass of Neopristol EWK and 2 parts by mass of glycerol are added, and the drum is rotated for 8 hours, and then formic acid solution is added several times to adjust the pH value of the bath liquid to 3.8-4.0, and the bath liquid is taken out after rotating the drum for 2 hours, and the water is removed, dried, softened and shaved to obtain ecological mycelium leather. According to different actual application requirements, the ecological mycelium leather can be further subjected to post-processing operations such as surface finishing with reference to the preparation process of animal leather.

[0066] The sensory evaluation of the ecological mycelium leather prepared in this example is: good fullness, relatively soft, uniform coloring, smooth and fine surface, and very similar to cow leather in feel and appearance. The mechanical properties of the ecological mycelium leather prepared in this example were tested, and the results showed that its tensile strength was 4.35MPa / mm 2 The elongation at break was 47.7%. The mechanical property test of the sheet mycelium used in step (1) (tested after squeezing water in a wet state) showed that the tensile strength of the sheet mycelium was 0.14±0.06MPa / mm 2, the elongation at break was 142.2±15.9%. In contrast, the mechanical properties of the ecological mycelium leather prepared in this embodiment were significantly improved. The natural degradation test found that the degradation rates of the ecological mycelium leather prepared in this embodiment in the soil for 30 days and 60 days reached 36.4% and 72.8%, respectively, and it was almost completely degraded into fine particles in 90 days.

[0067] Example 2

[0068] In this example, the effects of cross-linking agent selection on the performance of ecological mycelium leather were compared, and the following multiple groups of experiments were set up:

[0069] The first group of experiments: The operation was basically the same as that in Example 1, except that the cross-linking agent in Example 1 was replaced by 6 parts by mass of wattle bark tannin extract.

[0070] The second group of experiments: The operation was basically the same as that in Example 1, except that the cross-linking agent in Example 1 was replaced by 3 parts by mass of genipin.

[0071] The third group of experiments: The operation was basically the same as that of Example 1, except that the cross-linking agent in Example 1 was replaced by 3 parts by mass of propylene glycol triglycidyl ether.

[0072] The fourth group of experiments: The operation was basically the same as that of Example 1, except that the cross-linking agent in Example 1 was replaced by 4 parts by mass of wattle bark tannin extract and 2 parts by mass of genipin.

[0073] The fifth group of experiments: The operation is basically the same as that in Example 1, except that the cross-linking agent in Example 1 is replaced by 3 parts by mass of wattle bark tannin, 1 part by mass of genipin and 1 part by mass of glycerol triglycidyl ether. The specific operation is: 100 parts by mass of deacetylated sheet mycelium and 200 parts by mass of 1.5wt% formic acid aqueous solution are put into a drum, and the drum is rotated for 90 minutes, the pH value of the deacetylated sheet mycelium reaches 3.8-4.0, 1 part by mass of genipin is put into the drum, and the drum is rotated for 1 hour, and then 5 parts by mass of bayberry tannin are put into the drum, and the drum is rotated for 3 hours, the bath liquid is removed, and then 100 parts by mass of water and 1 part by mass of glycerol triglycidyl ether are added, and the drum is rotated for 3 hours, and then the pH value of the bath liquid is adjusted to 5.5-5.6 with 20% sodium bicarbonate solution, and the drum is rotated for 2 hours for cross-linking reaction.

[0074] The ecological mycelium leather prepared in each group of experiments was compared, and the results showed that when the first group of experiments used plant polyphenol tannin cross-linking agents for cross-linking, the cross-linking agent could be filled more between the mycelium fibers, and the prepared leather was firm, but the flexibility and strength were poor; when the second group of experiments used the small molecule cross-linking agent genipin for cross-linking, the prepared leather was relatively flat and thin, and the feel was poor; the third group of experiments used propylene glycol triglycidyl ether for cross-linking, and the prepared leather had good softness and fullness, and the strength of the leather was good; the fourth group of experiments used plant polyphenol tannin cross-linking agents and small molecule cross-linking agents in combination, and the prepared leather was full and had good strength; the fifth group of experiments used plant polyphenol tannin cross-linking agents, small molecule cross-linking agents and glycidyl ether cross-linking agents in combination, and the prepared leather had excellent softness and fullness, and the strength was significantly improved. From the above experimental results, it can be seen that the use of appropriate cross-linking agents can achieve more surprising results, especially better improving the hand feel and tensile strength of the prepared ecological mycelium leather. In practical applications, according to the requirements for the hand feel and strength of the mycelium leather, multiple combinations of the above three types of cross-linking agents can be selected for use.

[0075] Example 3

[0076] In this example, the effects of the selection of filling materials on the performance of ecological mycelium leather were compared, and the following multiple groups of experiments were set up:

[0077] The first group of experiments: The operation was basically the same as that in Example 1, except that the filling material in Example 1 was replaced with 5 parts by weight of protein filler SYNTAN FP888.

[0078] The second group of experiments: The operation is basically the same as that of Example 1, except that the filling material in Example 1 is replaced by 5 parts by mass of synthetic tanning agent SYNTAN ZLR 100.

[0079] The third group of experiments: The operation was basically the same as that of Example 1, except that the filler material in Example 1 was replaced with 5 parts by mass of sodium aluminum silicate MZ 8132.

[0080] The fourth group of experiments: The operation is basically the same as that of Example 1, except that the filling material in Example 1 is replaced by 3 parts by mass of protein filler SYNTAN FP888 and 2 parts by mass of sodium aluminum silicate MZ 8132.

[0081] The fifth group of experiments: The operation is basically the same as that of Example 1, except that the filling material in Example 1 is replaced by 3 parts by mass of protein filler SYNTAN FP888 and 2 parts by mass of sodium aluminum silicate MZ 8132.

[0082] The sixth group of experiments: The operation is basically the same as that of Example 1, except that the filling material in Example 1 is replaced by 2 parts by mass of protein filler SYNTAN FP888, 2 parts by mass of protein filler SYNTAN FP888 and 1 part by mass of sodium aluminum silicate MZ 8132.

[0083] The ecological mycelium leather prepared in each group of experiments was compared. The results showed that the use of protein materials for filling can help improve the fullness of the leather, and the leather can maintain a certain sense of moisture and is not easy to break due to excessive drying; the use of synthetic tanning agents for filling can also help improve the fullness of the leather, but compared with the first group of experiments, the tear resistance of the leather has not been significantly improved; the use of sodium aluminum silicate for filling, although the fullness of the leather is poor, can promote the absorption of dyes and plasticizers by the leather, increase the uniformity of coloring during dyeing and improve the feel of the leather. The combination of protein fillers and synthetic tanning agents can improve the fullness and tear resistance of the leather, and the combination of protein fillers and / or synthetic tanning agents with sodium aluminum silicate can further improve the sensory quality of the leather. In practical applications, multiple combinations of the above three types of cross-linking agents can be selected according to the requirements of the sensory quality and tear resistance of mycelium leather.

[0084] Example 4

[0085] In this example, the effect of using the modified natural oil product in combination with the polyol in the plasticizing process was investigated, and the following multiple groups of experiments were set up:

[0086] The first group of experiments: The operation was basically the same as in Example 1, except that glycerol was not added in step (4).

[0087] The second group of experiments: The operation was basically the same as that of Example 1, except that 2 parts by mass of Lipsol BSFR, 2 parts by mass of Neopristol EWK and 4 parts by mass of glycerol were added in step (4).

[0088] The third group of experiments: The operation was basically the same as that of Example 1, except that in step (4), Lipsol BSFR and Neopristol EWK were not added, and only 5 parts by weight of polyethylene glycol 400 were added.

[0089] The fourth group of experiments: The operation was basically the same as that of Example 1, except that 3 parts by mass of Lipsol BSFR, 5 parts by mass of Neopristol EWK and 2 parts by mass of polyethylene glycol 400 were added in step (4).

[0090] The ecological mycelium leather prepared in each group of experiments was compared and subjected to subsequent surface finishing. The results showed that the leather blank prepared in the first group of experiments felt dry and did not affect the subsequent surface finishing, but the leather blank was easy to break and had low strength; the leather blank prepared in the second group of experiments felt soft and slippery, but would have an adverse effect on the subsequent surface finishing process; the leather blank prepared in the third group of experiments was moist and plump, but the plasticizer was not completely absorbed during the plasticization process, which would also have an adverse effect on the subsequent surface finishing process; the leather blank prepared in the fourth group of experiments felt soft, plump, moist, and had good strength, and did not affect the subsequent surface finishing. This shows that the use of natural oil modified products and polyols in appropriate proportions can improve the sensory quality of the prepared ecological mycelium leather and avoid adverse effects on the subsequent surface finishing process.

[0091] Example 5

[0092] In this embodiment, a green preparation method of ecological mycelium leather is provided, and the steps are as follows:

[0093] (1) Deacetylation

[0094] 100 parts by mass of sheet mycelium, 300 parts by mass of water and 5 parts by mass of sodium carbonate were put into a drum, and immersed at 60° C. for 8 hours under the condition of rotating the drum for deacetylation treatment, and then washed with water and centrifuged for dehydration to obtain deacetylated sheet mycelium.

[0095] The sheet-like mycelium is from Tianjin Meikexin Biotechnology Co., Ltd., and is obtained by transplanting mycelium obtained by liquid fermentation of Ganoderma lucidum strains onto solid culture medium for cultivation.

[0096] (2) Cross-linking

[0097] 100 parts by mass of deacetylated flaky mycelium and 200 parts by mass of 1.0 wt% formic acid aqueous solution are put into a drum, and the drum is rotated for 90 minutes until the pH value of the deacetylated flaky mycelium reaches 3.8-4.0. 1.5 parts by mass of quercetin are added, and the drum is rotated for 1 hour. Then, 4 parts by mass of bayberry tannin are added, and the drum is rotated for 4 hours to allow quercetin and bayberry tannin to fully penetrate into the deacetylated flaky mycelium. Thereafter, the pH value of the bath liquid is adjusted to 5.5-5.6 with a 20% sodium bicarbonate solution, and the drum is rotated for 2 hours for a cross-linking reaction to obtain flaky cross-linked mycelium.

[0098] In this step, after adding quercetin, the temperature of the bath liquid was controlled to be 50°C.

[0099] (3) Filling and coloring

[0100] 100 parts by mass of sheet-like cross-linked mycelium, 150 parts by mass of water, 0.2 parts by mass of dye acid orange, 3 parts by mass of SYNTAN SMA678, 4 parts by mass of SYNTAN ZLR100 and 1 part by mass of MZ 8132 were put into a drum, and the drum was rotated for 5 hours to obtain sheet-like cross-linked mycelium that had been filled and dyed.

[0101] In this step, after adding acid orange, the temperature of the bath liquid is controlled to be 50°C.

[0102] (4) Plasticization

[0103] The bath liquid after filling and dyeing in step (3) is heated to 60°C, 5 parts by mass of SYNTHOL CU909, 5 parts by mass of SYNTHOL FF992 and 3 parts by mass of polyol polyethylene glycol 200 are added, the drum is rotated for 4 hours, and then formic acid aqueous solution is added several times to adjust the pH value of the bath liquid to 3.8-4.0, the drum is rotated for 1 hour, and then taken out, water is shaken, dried, softened, and shaved to obtain ecological mycelium leather. According to different actual application requirements, the ecological mycelium leather can be further subjected to post-treatment operations such as surface finishing with reference to the preparation process of animal leather.

[0104] The sensory evaluation of the ecological mycelium leather prepared in this example is: good fullness, good softness, uniform coloring, fine and smooth surface, and very similar to cow leather in feel and appearance. Compared with the ecological mycelium leather prepared in Example 1, the ecological mycelium leather prepared in this example is softer and fuller. The mechanical properties of the ecological mycelium leather prepared in this example were tested, and the results showed that its tensile strength was 4.16MPa / mm 2 , elongation at break was 48.4%. The natural degradation test found that the degradation rates of the ecological mycelium leather prepared in this example in the soil after 30 days and 60 days were 37.8% and 70.2%, respectively, and it was almost completely degraded into fine particles after 90 days.

[0105] Example 6

[0106] In this embodiment, a green preparation method of ecological mycelium leather is provided, and the steps are as follows:

[0107] (1) Deacetylation

[0108] 100 parts by mass of sheet mycelium, 100 parts by mass of water, 0.5 parts by mass of sodium hydroxide and 1 part by mass of sodium carbonate were put into a drum, and immersed at 80° C. for 1 hour under the condition of rotating the drum for deacetylation treatment, and then washed with water and centrifuged for dehydration to obtain deacetylated sheet mycelium.

[0109] The sheet-like mycelium is from Tianjin Meikexin Biotechnology Co., Ltd., and is obtained by transplanting mycelium obtained by liquid fermentation of Ganoderma lucidum strains onto solid culture medium for cultivation.

[0110] (2) Cross-linking

[0111] 100 parts by weight of deacetylated mycelium and 100 parts by weight of a 10 wt% formic acid aqueous solution are put into a drum, and the drum is rotated for 60 minutes. When the pH value of the deacetylated mycelium reaches 4.0-4.2, 1.5 parts by weight of quercetin are added, and the drum is rotated for 4 hours, and the bath liquid is discharged. Then, 100 parts by weight of water and 2 parts by weight of ethylene glycol diglycidyl ether are added to the drum, and the drum is rotated for 8 hours. Then, the pH value of the bath liquid is adjusted to 8.0-8.5 with a 20% sodium bicarbonate solution, and the drum is rotated for 5 hours for cross-linking reaction to obtain a sheet-like cross-linked mycelium.

[0112] In this step, after adding quercetin and ethylene glycol diglycidyl ether, the temperature of the bath liquid is controlled to be 40°C.

[0113] (3) Filling and dyeing

[0114] 100 parts by mass of sheet-like cross-linked mycelium, 300 parts by mass of water, 0.2 parts by mass of dye acid orange, 2 parts by mass of SYNTAN FP888, 4 parts by mass of SYNTAN SMA678 and 4 parts by mass of SYNTAN ZLR100 were put into a drum, and the drum was rotated for 6 hours to obtain sheet-like cross-linked mycelium that had been filled and dyed.

[0115] In this step, after adding acid orange, the temperature of the bath liquid is controlled to be 55°C.

[0116] (4) Plasticization

[0117] The bath liquid after filling and dyeing in step (3) is heated to 60°C, 4 parts by mass of SYNTAN SMA678, 5 parts by mass of Lipsol STS and 4 parts by mass of polyethylene glycol 400 are added, and the drum is rotated for 6 hours, and then formic acid aqueous solution is added several times to adjust the pH value of the bath liquid to 3.8-4.0, and the bath liquid is taken out after rotating the drum for 2 hours, and the water is shaken, dried, softened and shaved to obtain ecological mycelium leather. According to different actual application requirements, the ecological mycelium leather can be further subjected to post-processing operations such as surface finishing with reference to the preparation process of animal leather.

[0118] The sensory evaluation of the ecological mycelium leather prepared in this example is: good fullness, extremely soft, uniform coloring, light color, delicate and smooth surface, and very similar to cow leather in feel and appearance. Compared with the ecological mycelium leather prepared in Example 1, the ecological mycelium leather prepared in this example is softer and fuller. The mechanical properties of the ecological mycelium leather prepared in this example were tested, and the results showed that its tensile strength was 8.33MPa / mm 2 , the elongation at break was 57.2%. The improvement in tensile strength in this embodiment is mainly due to the use of small molecule phenol cross-linking agents in combination with glycidyl ether cross-linking agents. The natural degradation test found that the degradation rates of the ecological mycelium leather prepared in this embodiment in the soil for 30 days and 60 days reached 35.5% and 70.7% respectively, and it was almost completely degraded into fine particles in 90 days.

[0119] Example 7

[0120] In this embodiment, a green preparation method of ecological mycelium leather is provided, and the steps are as follows:

[0121] (1) Deacetylation

[0122] 100 parts by mass of sheet mycelium, 400 parts by mass of water and 10 parts by mass of sodium bicarbonate were put into a drum, and immersed at 35° C. for 20 hours under the condition of rotating the drum for deacetylation treatment, and then washed with water and centrifuged for dehydration to obtain deacetylated sheet mycelium.

[0123] The sheet-like mycelium is from Tianjin Meikexin Biotechnology Co., Ltd., and is obtained by transplanting mycelium obtained by liquid fermentation of Ganoderma lucidum strains onto solid culture medium for cultivation.

[0124] (2) Cross-linking

[0125] 100 parts by mass of deacetylated flaky mycelium and 300 parts by mass of 5 wt% lactic acid aqueous solution are put into a drum, and the drum is rotated for 90 minutes until the pH value of the deacetylated flaky mycelium reaches 4.0-4.2. 1 part by mass of propylene triglycidyl ether is added, and the drum is rotated for 3 hours to allow the propylene triglycidyl ether to fully penetrate into the deacetylated flaky mycelium. Then, the pH value of the bath is adjusted to 8.0-8.5 with a 20% sodium bicarbonate solution, and the drum is rotated for 3 hours for a cross-linking reaction to obtain flaky cross-linked mycelium.

[0126] In this step, after adding glycerol triglycidyl ether, the temperature of the bath liquid is controlled to be 35°C.

[0127] (3) Filling and coloring

[0128] 100 parts by mass of sheet-like cross-linked mycelium, 80 parts by mass of water, 0.2 parts by mass of dye acid orange, 2 parts by mass of SYNTAN FP888 and 2 parts by mass of SYNTAN ZLR100 were put into a drum, and the drum was rotated for 2 hours to obtain sheet-like cross-linked mycelium that had been filled and dyed.

[0129] In this step, after adding acid orange, the temperature of the bath liquid is controlled to be 55°C.

[0130] (4) Secondary crosslinking

[0131] 100 parts by weight of the filled and dyed sheet-like cross-linked mycelium prepared in step (3) was put into a formic acid aqueous solution with a pH value of 4.5, the temperature of the bath was controlled at 42°C, 0.3 parts by weight of glutaraldehyde was added and the mixture was immersed in the solution for 3 hours, and then the pH value of the bath was adjusted to 7.0, and the mixture was immersed in the solution for another 2 hours for secondary cross-linking.

[0132] (5) Plasticization

[0133] The bath liquid after the secondary crosslinking in step (4) is heated to 70°C, 4 parts by mass of SYNTAN SMA678, 5 parts by mass of Neopristol EWK, 5 parts by mass of Lipsol BSFR, 4 parts by mass of sorbitol, and 2 parts by mass of ethylene glycol are added, and the drum is rotated for 1 hour, and then formic acid aqueous solution is added several times to adjust the pH value of the bath liquid to 3.8-4.0, and the drum is rotated for 3 hours, and then taken out, water is removed, dried, softened, and shaved to obtain ecological mycelium leather. According to different actual application requirements, the ecological mycelium leather can be further subjected to post-processing operations such as surface finishing with reference to the preparation process of animal leather.

[0134] The sensory evaluation of the ecological mycelium leather prepared in this example is: good fullness, good softness, relatively obvious bubble feeling, uniform coloring, smooth and fine surface, and very similar to cow leather in feel and appearance. The mechanical properties of the ecological mycelium leather prepared in this example were tested, and the results showed that its tensile strength was 9.53MPa / mm 2 , the elongation at break was 69.9%. The improvement in tensile strength in this embodiment is mainly due to the secondary cross-linking operation after the protein filler material is used. The natural degradation test found that the degradation rates of the ecological mycelium leather prepared in this embodiment in the soil for 30 days and 60 days reached 36.3% and 70.5% respectively, and it can be basically completely degraded into fine particles in 90 days.

Claims

1. A green preparation method of ecological mycelium leather, characterized in that: The following steps are involved: (1) Deacetylation 100 parts by weight of sheet-like mycelium, 100 to 400 parts by weight of water and 0.5 to 10 parts by weight of an inorganic base are placed in a reaction container, and the mixture is immersed at 35 to 100° C. for 1 to 20 hours for deacetylation treatment, and then washed with water and centrifuged for dehydration to obtain deacetylated sheet-like mycelium; (2) Cross-linking 100 parts by weight of deacetylated mycelium and 100 to 300 parts by weight of an aqueous solution of an organic acid are added into a reaction container, and when the pH value of the deacetylated mycelium reaches a pH value level conducive to the penetration of a crosslinking agent, 1 to 10 parts by weight of a crosslinking agent is added for sufficient penetration, and then the pH value of the bath solution is adjusted to 5.5 to 8.0 for a crosslinking reaction to obtain a crosslinked mycelium sheet; In this step, the temperature of the bath solution is controlled to be room temperature to 80°C during infiltration and cross-linking, and the time of the cross-linking reaction is controlled to be 2 to 5 hours; the cross-linking agent is a combination of one or more of a polyphenol cross-linking agent, a small molecule phenol cross-linking agent and a glycidyl ether cross-linking agent, and the small molecule phenol cross-linking agent and the polyphenol cross-linking agent cannot be used in the same bath with the glycidyl ether cross-linking agent; the polyphenol cross-linking agent is a plant tannin including but not limited to wattle bark tannin, bayberry tannin, chestnut tannin, tara tannin or kelp tannin, the small molecule phenol cross-linking agent is genipin, quercetin or catechin, and the glycidyl ether cross-linking agent is ethylene glycol diglycidyl ether, glycerol triglycidyl ether or polyethylene glycol glycidyl ether; (3) Filling and coloring 100 parts by weight of sheet-shaped cross-linked mycelium are put into a bath for filling and dyeing, and the temperature of the bath is controlled at 35 to 60° C. to obtain sheet-shaped cross-linked mycelium that has been filled and dyed; The filling material used during filling is a combination of one or more of a biodegradable and environmentally friendly synthetic tanning agent, a biodegradable protein filler and sodium aluminum silicate. The amount of solvent water in the bath liquid is 80 to 300 parts by weight, and the amount of the filling material is 4 to 10 parts by weight. The environmentally friendly synthetic tanning agent is a phenolic or naphthalene auxiliary synthetic tanning agent that does not release formaldehyde. The protein filler is a combination of one or more of plant protein and animal protein. (4) Plasticization The bath liquid after filling and dyeing in step (3) is heated to 50-80° C., 6-20 parts by weight of plasticizer is added, and the bath liquid is soaked for 1-8 hours, and then formic acid is added to adjust the pH value of the bath liquid to 3.5-4.0, and the bath liquid is taken out after soaking for 1-3 hours, and the water is shaken off to obtain ecological mycelium leather; The plasticizer is composed of a modified product of natural oil and fat and a polyol in a mass ratio of (2-5):

1.

2. The green preparation method of ecological mycelium leather according to claim 1, characterized in that: In step (4), the natural oil modified product is a composition of one or more of sulfated oil, sulfited oil, phosphorylated oil and sulfonated oil obtained by modifying natural animal and plant oils.

3. The green preparation method of ecological mycelium leather according to claim 2, characterized in that: In step (4), the natural oil modified product is a combination of one or more of Lipsol BSFR, Lipsol STS, Neopristol EWK, SYNTHOL CP996, SYNTHOLCU909, and SYNTHOL FF992.

4. The green preparation method of ecological mycelium leather according to claim 1, characterized in that: In step (4), the polyol is a combination of one or more of glycerol, ethylene glycol, polyethylene glycol, polypropylene glycol, sorbitol, and polyol ester.

5. The green preparation method of ecological mycelium leather according to claim 1, characterized in that: The filling material in step (3) is a combination of one or more of SYNTAN ZLR100, SYNTAN FP888, SYNTAN SMA678, and MZ 8132.

6. The green preparation method of ecological mycelium leather according to any one of claims 1 to 5, characterized in that: Before the plasticizing operation in step (4), a secondary cross-linking operation is also included.

7. The green preparation method of ecological mycelium leather according to any one of claims 1 to 5, characterized in that: In step (3), the sheet-like cross-linked mycelium is first dyed and then filled, or the sheet-like cross-linked mycelium is first filled and then dyed, or the sheet-like cross-linked mycelium is dyed and filled at the same time.

8. The green preparation method of ecological mycelium leather according to any one of claims 1 to 5, characterized in that: The ecological mycelium leather prepared in step (4) is subjected to one or more of the following operations: drying, softening, shaving and surface finishing.

9. The green preparation method of ecological mycelium leather according to any one of claims 1 to 5, characterized in that: The sheet-like mycelium in step (1) is obtained by transplanting mycelium obtained by liquid fermentation onto a solid culture medium for cultivation.

10. Ecological mycelium leather prepared by the method according to any one of claims 1 to 9.

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