CN117587640A - High-strength degradable leather based on mycelium fibers and preparation method thereof - Google Patents

High-strength degradable leather based on mycelium fibers and preparation method thereof Download PDF

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Publication number
CN117587640A
CN117587640A CN202311555632.XA CN202311555632A CN117587640A CN 117587640 A CN117587640 A CN 117587640A CN 202311555632 A CN202311555632 A CN 202311555632A CN 117587640 A CN117587640 A CN 117587640A
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mycelium
leather
fibers
polylactic acid
fiber
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袁久刚
徐进
马博谋
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Jiangnan University
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Jiangnan University
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    • D—TEXTILES; PAPER
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
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    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
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    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
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    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
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    • D06M2101/16—Synthetic fibres, other than mineral fibres
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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention relates to a high-strength degradable leather based on mycelium fibers and a preparation method thereof, belonging to the technical field of biological base materials. The preparation method comprises the following steps: the invention takes high-strength polylactic acid filaments as core yarns, natural or regenerated cellulose staple fibers as cladding yarns, the core yarns are spun into the core yarns with the surface layers of the cellulose staple fibers and the core layers of the polylactic acid filaments, and then the core yarns are woven to obtain mesh fabrics; and then stacking the substrate with the grown mycelium for solid state fermentation, after the cultivation, carrying out hot pressing, modification, crosslinking, plasticization, polyurethane impregnation, drying and the like to obtain the mycelium leather bass, and finally carrying out sanding, veneering, vacuum grain suction or embossing to obtain the enhanced degradable element leather product taking the mycelium fiber as the main body. The leather obtained by the invention has excellent water vapor permeability, bending resistance, abrasion resistance, mechanical property and biodegradability, and the product has application prospect in the fields of fashion, bags, home furnishings, clothing decoration and the like.

Description

High-strength degradable leather based on mycelium fibers and preparation method thereof
Technical Field
The invention relates to a mycelium fiber-based high-strength degradable leather and a preparation method thereof, belonging to the technical field of biological base materials.
Background
Natural leather products have been widely used in daily life for people because of their excellent elasticity, abrasion resistance, water vapor permeability and mechanical properties. However, the development of natural leather is limited due to the problems of lack of animal resources, high price of products and the like. Meanwhile, with the development of technology and the progress of technology, the quality of synthetic leather products is greatly improved, wherein the quality and the types of superfine fiber synthetic leather products are rapidly developed, the performances of the superfine fiber synthetic leather products can be comparable with those of natural leather, and even exceed those of the natural leather, and the superfine fiber synthetic leather is gradually replaced by the natural leather at present and is widely used in home sofas, automobile seats, clothing, shoes, caps and the like. However, the synthetic fiber and polyurethane which are the main components of the preparation and synthesis are prepared from petroleum products, the degradation period is long after the petroleum products are abandoned, and a large amount of organic solvents are used in the production process, so that the environment is greatly influenced. In this context, the development of environmentally friendly degradable leather products is of great importance.
The plant fiber is a natural fiber material with abundant reserves in nature, and is an ideal substitute for petroleum-based chemical fiber raw materials in synthetic leather. Patent CN115418866a reports a method for producing degradable artificial leather by sequentially laminating from bottom to top using plant bast fibers such as pineapple leaf fibers and coconut shell fibers. Patent CN111455681a reports a method for preparing degradable artificial leather by steaming and pulping by using agricultural and forestry wastes such as crop straw and wood. In addition, natural material or waste based leather such as apple, pineapple, cactus and mycelium is receiving increasing attention, wherein mycelium leather having a small fiber diameter (about 1-5 μm), soft touch, good air permeability, more similar to the fiber structure in animal leather, and excellent degradability is considered as one of the most developed pure leather materials. However, the existing mycelium material has poor bending resistance, abrasion resistance and mechanical property and is easy to delaminate and tear under the action of pressure. Therefore, improving the comprehensive performance of the mycelium material is a key for expanding the application of the mycelium material.
Disclosure of Invention
In view of the above problems, the inventors have devised an invention with a view to improving bending resistance, abrasion resistance and mechanical properties by combining the growth characteristics of mycelium. Considering that mycelium fibers are favored to grow on hydrophilic materials, microorganisms can degrade and destroy the hydrophilic materials in the growth process, so that the mechanical properties are reduced. The hydrophilic cellulose fiber and the synthetic fiber are compounded in a core-spun yarn mode to prepare the mesh fabric, the cellulose fiber part is utilized to promote the growth of mycelium, and the synthetic fiber part ensures the mechanical property of the product. Meanwhile, the mycelium and the cellulose fiber are mutually wound in situ, and the cellulose fiber and the synthetic fiber are mutually wound in situ, so that the interface adhesion performance is effectively improved. In addition, the hydrophilic characteristics of mycelium fibers and cellulose fibers and the interfacial compatibility of the mycelium fibers and the cellulose fibers with polyurethane materials are considered, and polylactic acid macromolecule chain segments are grafted on the surfaces of the fibers in an in-situ grafting mode, so that the bending resistance, abrasion resistance, mechanical properties and the like of the final product are further ensured.
The technical scheme is as follows:
the invention provides a method for preparing high-strength degradable leather based on mycelium fibers, which comprises the following steps:
(1) Preparation of mesh fabrics
Taking polylactic acid filaments as core yarns and natural or regenerated cellulose staple fibers as cladding yarns, spinning to obtain cellulose polylactic acid core-spun yarns, and then carrying out structural design and weaving to obtain mesh fabrics;
(2) Preparation of mycelium leather bass
Stacking the mesh fabric prepared in the step (1) on a culture medium containing spores for solid state fermentation, and after the fermentation is finished, sequentially carrying out hot pressing, modification, crosslinking treatment, plasticization treatment, polyurethane impregnation and drying to obtain mycelium leather bass;
(3) Preparation of high-strength degradable leather
Polishing, veneering, absorbing lines or embossing the mycelium leather bass prepared in the step (2) to prepare a high-strength degradable leather finished product based on mycelium fibers.
In one embodiment of the present invention, the polylactic acid filaments of step (1) are polylactic acid filaments having a total denier of 100D to 300D.
In one embodiment of the present invention, the natural fibers of step (1) are cotton fibers, and the regenerated cellulose staple fibers include viscose staple fibers and tencel staple fibers.
In one embodiment of the present invention, the mass ratio of the cellulose staple fiber to the polylactic acid in the cellulose polylactic acid core-spun yarn in the step (1) is 1:1-2.
In one embodiment of the invention, the mesh fabric of step (1) has a mesh size of 2-5mm and a fabric gram weight of 100-200g/m 2 . Further, the mesh size of the mesh fabric is 3-5mm.
In one embodiment of the present invention, the spore-containing medium in the step (2) is prepared by the following method: will be
Mixing corncob, bran, flour and water, sterilizing, spraying sterile water with spores onto the surface of the culture medium, and culturing at 28deg.C under 65% humidity for 5 days in dark.
In one embodiment of the invention, the spores refer to, but are not limited to, any one or more of the following combinations: ganoderma lucidum, oyster mushroom, lentinus Edodes, straw mushroom, kou mushroom, needle mushroom, hericium Erinaceus, white beech mushroom, pleurotus eryngii, agaric bisporus, tremella, oletum Trogopterori, morchella, north America, dictyophora Indusiata, and Schizophyllum commune spores.
In one embodiment of the invention, the mass ratio of the corncob to the bran to the flour is 3:1:1.
in one embodiment of the invention, the percentage of water relative to the total mass of cob, bran and flour is 60%.
In one embodiment of the present invention, the hot pressing in the step (2) has a temperature of 60 to 120 ℃ for 1 to 3 minutes.
In one embodiment of the present invention, the modification in the step (2) is to impregnate the catalyst with the hot-pressed mycelium fiber/mesh fabric composite base fabric, then soak the catalyst in 120 ℃ lactide, graft-modify the surface of the mycelium fiber with polylactic acid molecular chain segments by in-situ ring-opening polymerization of lactide on the surface of the mycelium fiber, and wash the surface with ethanol to remove unreacted lactide monomers.
In one embodiment of the present invention, the crosslinking treatment of the step (2) means that the modified mycelium fiber/mesh fabric composite base fabric is triple-padded in 1-10 (w/w)% of an aqueous solution of citric acid, butane tetracarboxylic acid or ethylene glycol diglycidyl ether, and then dried at 100-120 ℃ for 30-60min.
In one embodiment of the present invention, the plasticizing treatment of the step (2) refers to three padding the crosslinked composite base fabric in 1-10 (w/w)% of an aqueous solution of glycerol, propylene glycol or dibutyl phthalate, and then drying to remove water.
In one embodiment of the present invention, the impregnating polyurethane in the step (2) refers to three-impregnating and three-rolling the plasticized composite base fabric in a mixed solution containing 20-80wt% of bio-based aqueous polyurethane, 0.5-2wt% of thickener carboxymethyl cellulose and 1-5wt% of pore-forming agent salt particles.
Further, the mixed solution contains 40-60wt% of bio-based aqueous polyurethane.
In one embodiment of the invention, the prepared mycelium leather bass also needs polishing, veneering, line absorbing or embossing to obtain a degradable leather finished product with excellent comprehensive properties such as water vapor permeability, bending resistance, abrasion resistance, mechanics and the like.
The invention provides the high-strength degradable leather based on the preparation method.
The invention also provides application of the high-strength degradable leather in the fields of home sofas, automobile seats, clothing, shoes and caps.
Advantageous effects
1. The invention designs the core spun yarn compounded by the cellulose fiber and the polylactic acid fiber, and considers the double requirements of mycelium growth and mechanical property guarantee.
2. The covering yarn is adopted to design fabrics with different mesh sizes as a three-dimensional bracket for the growth of mycelium fibers, so that the interface adhesion effect between the mycelium and the fabrics is improved, and the bending resistance, abrasion resistance and mechanical properties of the final leather product are further ensured.
3. The polylactic acid molecular chain segments are grafted on the surfaces of the mycelium fibers, so that the hydrophilic mycelium fibers are subjected to hydrophobic modification, interface adhesion with polyurethane is facilitated, and the bending resistance, abrasion resistance and mechanical properties of the final leather product are improved.
4. On the premise of improving the comprehensive performance, the invention selects cellulose fiber and degradable polylactic acid fiber as raw materials, and does not damage the integral degradable characteristic of the mycelium material. In addition, the invention uses the aqueous polyurethane to replace solvent polyurethane, is safe and environment-friendly, and has the advantage of small environmental pollution.
5. The content of degradable components in the high-strength degradable leather product prepared by the method is between 60 and 90 percent, and the water vapor permeability is between 1 and 5mg/m 2 H, the bending resistance is 1-3 ten thousand times, the abrasion resistance is 800-2500 times, the breaking strength is 30-50MPa, the breaking elongation is 50-200%, and the comprehensive performance is excellent.
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.
And (3) water vapor permeability test: the GB/T1811-1993 leather water vapor permeability test method is adopted.
Bending resistance test: the test was carried out using the method described in GB/T4689.9-1984.
Abrasion resistance performance test: the surface was observed by turning a certain number of turns under a load of 1kg with a wearing machine at 23.+ -. 2 ℃.
Mechanical property test: the sample was cut into 1X 10cm strips and subjected to a tensile test on a universal material tester at a tensile speed of 5cm/min.
Example 1
Taking cotton fiber as a covering yarn and taking 120D polylactic acid filament as a core yarn, and feeding the yarn according to a mass ratio of 1:1 to prepare cellulose/polylactic acid core-spun yarn, and then weaving to prepare the yarn with the gram weight of 150g/m 2 A mesh fabric with a mesh of 3 mm.
Preparation of the culture medium: preparing a culture medium by 60% of corncob, 20% of bran and 20% of flour, adding 60% of clear water by mass of the culture medium, uniformly stirring, and sterilizing. Then, sterile water with ganoderma lucidum spores is uniformly sprayed on the surface of the culture medium, and the culture is carried out for 5 days in dark at 28 ℃ under the condition of 65% humidity.
The culture medium is prepared from 10g/L of soluble starch, 1.5g/L of soybean peptone, 20g/L of glucose, 0.75g/L of monopotassium phosphate, 1.5g/L of magnesium sulfate and 10.1g/L of vitamin B. Immersing the mesh fabric in the culture solution for 12h, taking out, airing at room temperature, and sterilizing.
Covering the sterilized mesh fabric on a culture medium which is cultivated for 5 days, continuously cultivating for one week, and performing solid state fermentation (the mesh fabric is used as a three-dimensional grid bracket for the mycelium fiber to spread and grow in the solid state fermentation process, and cellulose components provide nutrition for the mycelium growth), wherein the mycelium fiber grows along the cotton fiber of the covering yarn fabric in the process, and is entangled and hooked with the cotton fiber. After the cultivation, the fabric and the mycelium layer were cut together and hot pressed at 80℃under 5MPa for 3min.
And then immersing the mycelium composite material obtained by hot pressing into a stannous octoate ethanol solution with the weight of 2%, taking out the mycelium composite material after ethanol is volatilized, immersing the mycelium composite material into 120 ℃ molten lactide for 10 hours, and then washing the surface unreacted lactide monomer with ethanol to obtain the modified mycelium/mesh fabric composite base cloth with the mycelium fiber surface grafted with polylactic acid macromolecule chain segments.
Then in 5% citric acid aqueous solution, after three soaking and three rolling, drying for 30min under 120 ℃ under the action of tension, and utilizing unreacted hydroxyl groups on the surface of mycelium fibers and residual hydroxyl groups on the surface of cellulose to make the mycelium fibers, cotton fibers and mycelia and cotton fibers undergo cross-linking reaction so as to fix the relative positions of the fibers. And immersing the crosslinked mycelium composite material into 5% glycerol aqueous solution, and drying and dewatering after three-soaking and three-padding to obtain the plasticized mycelium composite material.
Preparing a mixed solution consisting of 40wt% of bio-based aqueous polyurethane, 1wt% of carboxymethyl cellulose and 2wt% of salt particles, soaking and padding the plasticized mycelium composite material in the mixed solution three times, and drying under a tension condition to remove water to obtain the mycelium leather bass.
Polishing, veneering and embossing the bass according to a conventional processing method of microfiber leather to obtain a high-strength degradable leather finished product based on mycelium fibers.
The content of the degradable component in the leather product is measured to be about 85 percent, and the water vapor permeability is measured to be 3.8mg/m 2 H, bending resistance is 2.2 ten thousand times, abrasion resistance is 1700 times, breaking strength is 36MPa, and breaking elongation is 78%.
Comparative example 1
The cotton fiber/polylactic acid core-spun yarn mesh fabric in example 1 is replaced by polylactic acid filament mesh fabric with the same specification (same gram weight and same mesh size), and other preparation processes and methods are unchanged, so that the degradable leather product is obtained. The content of the degradable component in the leather product is measured to be about 55 percent, and the water vapor permeability is measured to be 0.8mg/m 2 H, elongation at break 60%. The content of degradable components and the water vapor permeability are greatly reduced mainly because a hydrophilic environment for the growth of mycelium fibers is difficult to provide in the pure polylactic acid fabric, so that the mycelium fibers grow slowly and grow little, a porous structure between the fibers cannot be formed, and the polylactic acid mesh fabric and the PU composite material are formed after PU is immersed, so that the water vapor permeability is obviously reduced.
Comparative example 2
The cotton fiber/polylactic acid core-spun yarn mesh fabric in example 1 is replaced by a cotton fiber mesh fabric with the same specification (same gram weight and same mesh size), and other preparation processes and methods are unchanged, so that the degradable leather product is obtained. The bending resistance is 1.5 ten thousand times, the abrasion resistance is 500 times, the breaking strength is 12MPa, and the breaking elongation is 35%. It is speculated that cotton fibers are susceptible to microbial decomposition during hyphal growth, which also results in significant reductions in flex, abrasion and mechanical properties of the final leather product.
Comparative example 3
The cotton fiber/polylactic acid core-spun yarn grid fabric in the example 1 is replaced by grid fabric (same gram weight and same mesh size) with the same specification made of cotton fiber polylactic acid twisted yarn, and other preparation processes and methods are unchanged, so that the degradable leather product is obtained. The abrasion resistance was 650 times, the breaking strength was 28MPa, and the elongation at break was 65%. The reason for the abrasion resistance and the mechanical deterioration may be that microorganisms decompose portions of cotton fibers to different extents during the cultivation of mycelium fibers, so that the structure of the mesh fabric becomes loose, resulting in the abrasion resistance and the mechanical deterioration.
Comparative example 4
The modification step after the hot pressing of the mycelium fiber/mesh fabric composite base cloth in example 1 is removed, and the crosslinking and other steps are directly performed to obtain the degradable leather product. The bending resistance is 1.8 ten thousand times, the abrasion resistance is 1500 times, the breaking strength is 25MPa, and the breaking elongation is 55%. The reason for the reduced flex, abrasion, and mechanical properties compared to example 1 may be the poor interfacial compatibility between the hydrophilic mycelium fibers, the residual cotton fibers, and the polyurethane.
Comparative example 5
The mesh size of the mesh fabric was increased to 10mm on the basis of example 1, and other preparation procedures and methods were unchanged, resulting in a degradable leather product. Abrasion resistance was measured 600 times.
Example 2
The mesh size of the mesh fabric was increased to 5mm on the basis of example 1, and other preparation procedures and methods were unchanged, resulting in a degradable leather product. The content of the degradable component in the leather product was found to be about 85% as in example 1, and the water vapor permeability was found to be 4.0mg/m 2 H, bending resistance is 2.2 ten thousand times, abrasion resistance is 1000 times, breaking strength is 38MPa, and breaking elongation is 95%.
Example 3
The concentration of the impregnated bio-based aqueous polyurethane is increased to 60% on the basis of the example 1, and other preparation processes and methods are unchanged, so that the degradable leather product is obtained. The content of the degradable component in the leather product was slightly reduced compared with example 1, about 80%, and the water vapor permeability was 3.6mg/m 2 H, bending resistance is 2.5 ten thousand times, abrasion resistance is 2200 times,the breaking strength was 43MPa and the breaking elongation was 72%.
The above examples are not intended to limit the scope of the invention nor the order of execution of the steps described. The present invention is obviously modified by a person skilled in the art in combination with the prior common general knowledge, and falls within the scope of protection defined by the claims of the present invention.

Claims (10)

1. A method for preparing high-strength degradable leather based on mycelium fibers, which is characterized by comprising the following steps:
(1) Preparation of mesh fabrics
Taking polylactic acid filaments as core yarns and natural or regenerated cellulose staple fibers as cladding yarns, spinning to obtain cellulose polylactic acid core-spun yarns, and then carrying out structural design and weaving to obtain mesh fabrics;
(2) Preparation of mycelium leather bass
Stacking the mesh fabric prepared in the step (1) on a culture medium containing spores for solid state fermentation, and after the fermentation is finished, sequentially carrying out hot pressing, modification, crosslinking treatment, plasticization treatment, polyurethane impregnation and drying to obtain mycelium leather bass;
(3) Preparation of high-strength degradable leather
Polishing, veneering, absorbing lines or embossing the mycelium leather bass prepared in the step (2) to prepare a high-strength degradable leather finished product based on mycelium fibers.
2. The method of claim 1, wherein the polylactic acid filaments of step (1) are polylactic acid filaments having a total denier of 100D to 300D; the natural fibers are cotton fibers; the regenerated cellulose short fibers comprise viscose short fibers and tencel short fibers; the mass ratio of the cellulose short fiber to the polylactic acid in the cellulose polylactic acid core-spun yarn is 1:1-2.
3. The method according to claim 1, wherein the mesh fabric of step (1) has a mesh size of 2-5mm and a fabric grammage of 100-200g/m 2 。
4. The method of claim 1, wherein the medium containing spores in step (2) is prepared by: mixing corncob, bran, flour and water, sterilizing, spraying sterile water with spores onto the surface of culture medium, and culturing at 28deg.C under 65% humidity for a period of time in dark place.
5. The method according to claim 1, wherein the hot pressing in step (2) is performed at a temperature of 60 to 120 ℃ for a time of 1 to 3 minutes; the modification is to dip the hot pressed mycelium fiber/mesh fabric composite base cloth into a catalyst, then dip the catalyst into 120 ℃ lactide, realize graft modification of polylactic acid molecular chain segments on the surface of the mycelium fiber by in-situ ring-opening polymerization of lactide on the surface of the mycelium fiber, and wash the surface of the mycelium fiber with ethanol to remove unreacted lactide monomers.
6. The method according to claim 1, wherein the crosslinking treatment of the step (2) means that the modified mycelium fiber/mesh fabric composite base fabric is triple-padded in an aqueous solution of 1-10wt% of citric acid, butane tetracarboxylic acid or ethylene glycol diglycidyl ether, and then dried at 100-120 ℃ for 30-60min.
7. The method according to claim 1, wherein the plasticizing treatment means that the crosslinked composite base fabric is three-padded in an aqueous solution of 1-10wt% of glycerin, propylene glycol or dibutyl phthalate, and then dried to remove water.
8. The method according to any one of claims 1 to 7, wherein the impregnating polyurethane of step (2) means three-impregnating and three-rolling the plasticized composite base fabric in a mixed solution containing 20 to 80wt% of bio-based aqueous polyurethane, 0.5 to 2wt% of thickener carboxymethyl cellulose, and 1 to 5wt% of pore-forming agent salt particles.
9. A high strength degradable leather made by the method of any one of claims 1-8.
10. Use of the high strength degradable leather of claim 9 in the fields of home sofas, car seats, clothing footwear and caps.
CN202311555632.XA 2023-11-21 2023-11-21 High-strength degradable leather based on mycelium fibers and preparation method thereof Pending CN117587640A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118581742A (en) * 2024-08-02 2024-09-03 上海禾向健康科技发展有限公司 Ganoderma lucidum mycelium leather and preparation method thereof
CN118581742B (en) * 2024-08-02 2024-11-19 上海禾向健康科技发展有限公司 Ganoderma lucidum mycelium leather and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118581742A (en) * 2024-08-02 2024-09-03 上海禾向健康科技发展有限公司 Ganoderma lucidum mycelium leather and preparation method thereof
CN118581742B (en) * 2024-08-02 2024-11-19 上海禾向健康科技发展有限公司 Ganoderma lucidum mycelium leather and preparation method thereof

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