Method for manufacturing leather sheet using mycelium

Abstract

The present invention relates to a method for manufacturing a leather sheet using mycelium. A leather sheet manufactured using the method for manufacturing a leather sheet of the present invention is environmentally friendly and has excellent physical properties and durability.

Description

Method for manufacturing leather sheets using mycelia

[0001] The present invention relates to a method for manufacturing a leather sheet using mycelia.

[0002] Global preference for and demand for leather is increasing. Environmental and ethical concerns are driving the development of new materials that can replace existing animal and synthetic leather. Research is currently underway on the production of leather using plant fibers, mushrooms, and silicone as potential alternatives to leather.

[0003] Meanwhile, mushroom mycelia are composed of fibers composed of chitin-glucan complexes, hydrophobic proteins, and cellulose or their composites. Leather material (Mycelium-mat) made from mushroom mycelia has a material that most closely resembles animal leather compared to other biomass materials and has the advantage of being environmentally friendly to produce. However, compared to animal proteins composed of collagen protein, its physical properties (tensile strength, elongation) and durability are weaker, and the hydrophobic protein film on the mycelial surface makes it difficult for materials applied with existing tanning processes to penetrate.

[0004] Accordingly, the inventors of the present invention have made efforts to increase the physical properties and durability while also enabling environmentally friendly production, and as a result, they have attempted to provide an environmentally friendly method for manufacturing leather sheets that improves the physical properties of mycelial leather sheets by introducing a natural polymer that matches the physicochemical structure inside mycelia without using materials such as chromium or aluminum that cause environmental pollution problems.

[0005] The purpose of the present invention is to provide an environmentally friendly method for manufacturing leather sheets by introducing a natural polymer to improve the properties of mycelial leather sheets.

[0006] Therefore, the present invention relates to a method for manufacturing leather sheets using mycelia,

[0007] 1) Step of treating a polymer on a mycelial sheet;

[0008] 2) a step of treating the mycelial sheet treated with the polymer in step 1) with an enzyme that crosslinks the polymer; and 3) a step of treating the mycelial sheet of step 2) with at least one of a plasticizer and a fatliquoring agent. A method for manufacturing a leather sheet is provided.

[0009] According to one embodiment of the present invention, the step 1) may further include a step of treating the mycelial sheet with a fungicide.

[0010] According to one embodiment of the present invention, after step 2), a step of processing the branch agent may be further included.

[0011] According to one embodiment of the present invention, after step 1), a step of treating a cross-linking agent may be further included.

[0012] According to one embodiment of the present invention, after treating the crosslinking agent, a step of treating a metallic ion may be further included.

[0013] According to one embodiment of the present invention, after step 2), a step of treating a cross-linking agent may be further included.

[0014] According to one embodiment of the present invention, the polymer may be selected from gelatin, collagen, chitosan, curdlan, casein, soy protein, gluten, cellulose, pectin, and combinations thereof.

[0015] According to one embodiment of the present invention, the enzyme may be transglutaminase.

[0016] According to one embodiment of the present invention, the plasticizer may be selected from the group consisting of glycerol, polyethylene glycol, sorbitol, xylitol, epoxidized triglyceride vegetable oil, fatty acid, ester, and combinations thereof.

[0017] According to one embodiment of the present invention, the fat may be selected from castor oil, corn oil, jojoba oil, olive oil, fish oil, oleic acid, linoleic acid, stearic acid, and combinations thereof.

[0018] According to one embodiment of the present invention, the crosslinking agent may be polyphenol.

[0019] According to one embodiment of the present invention, the crosslinking agent may be selected from the group consisting of citric acid, glyoxal, glutaraldehyde, tannic acid, genipin, vanillin, gallic acid, and combinations thereof.

[0020] In addition, the present invention,

[0021] In a method for manufacturing leather sheets using mycelia,

[0022] 1) Step of treating a polymer on a mycelial sheet;

[0023] 2) A step of treating the mycelial sheet treated with the polymer in step 1) with an enzyme that crosslinks the polymer;

[0024] 3) A step of treating the mycelial sheet of step 2) with a fungicide; and

[0025] 4) A manufacturing method can be provided, including a step of treating a plasticizer on a mycelial sheet treated with the agent of step 3).

[0026] In addition, the present invention,

[0027] In a method for manufacturing leather sheets using mycelia,

[0028] 1) Step of treating the mycelium sheet with a fungicide;

[0029] 2) A step of treating the mycelial sheet treated with a polymer in step 1);

[0030] 3) A step of treating the mycelia treated with the polymer in step 2) above with an enzyme that crosslinks the polymer;

[0031] 4) A manufacturing method can be provided, including a step of treating a plasticizer on the mycelial sheet of step 3).

[0032] In addition, the present invention,

[0033] In a method for manufacturing leather sheets using mycelia,

[0034] 1) Step of treating a polymer on a mycelial sheet;

[0035] 2) A step of treating a cross-linking agent on the mycelial sheet treated with polymer in step 1);

[0036] 3) A step of treating the mycelial sheet treated with a cross-linking agent in step 2) above with metal ions;

[0037] 4) A step of treating the mycelial sheet treated with metal ions in step 3) above with an enzyme that crosslinks the polymer;

[0038] 5) A step of treating the mycelial sheet treated with the enzyme of step 4) above with a cross-linking agent; and

[0039] 6) A manufacturing method can be provided, including a step of mixing a plasticizer and a fatliquoring agent into the mycelium sheet treated with the crosslinking agent of step 5 above.

[0040] A leather seat manufactured using the method for manufacturing a leather seat of the present invention is environmentally friendly and has excellent physical properties and durability.

[0041] FIG. 1 is a flowchart schematically illustrating a method for manufacturing a leather seat according to one embodiment of the present invention.

[0042] FIG. 2 is a graph schematically illustrating the results of an experiment on the physical properties of a leather sheet manufactured by a method for manufacturing a leather sheet according to one embodiment of the present invention.

[0043] FIG. 3 is a graph schematically illustrating the results of an experiment on the physical properties of a leather sheet manufactured by a method for manufacturing a leather sheet according to another embodiment of the present invention.

[0044] Hereinafter, the present invention will be described in detail.

[0045] Referring to Fig. 1, the process for manufacturing leather sheets using mycelia can be comprised of 1) a mycelia sheet cultivation process, 2) an inactivation process after harvesting the cultivated sheets, 3) a polymerization, plasticization, and cross-linking process, and 4) a drying process.

[0046] First, 1) in order to manufacture a mycelial sheet, mycelia can be cultured using a liquid medium and a solid medium, and the medium composition can be appropriately selected and used according to optimal pH conditions, optimal temperature conditions, optimal carbon source and optimal concentration, optimal nitrogen source and optimal concentration, and optimal inorganic salt and optimal concentration, which are well known in the art.

[0047] After distributing the inoculum on the medium, the mycelial sheet can be cultured under specific temperature and humidity conditions well known in the art, and the mycelial sheet can be cultured by adjusting the conditions according to the intended use.

[0048] The "inoculating agent" of the present invention may be a mycelial fragment isolated from a woody mushroom, such as Ganoderma sp., Fomitella Sp., or Inonotus sp., and specifically, a mycelial fragment isolated from the mycelia of chaga mushroom (Inonotus obliquus), Phellinus linteus, or reishi mushroom (Ganoderma lucidum) may be used, but is not limited thereto.

[0049] After culturing and harvesting the mycelial sheets, the steps for manufacturing leather may include 1) an inactivation step, 2) a polymer / crosslinking / plasticizing step, and 3) a drying step.

[0050] The term "inactivation of mycelial sheets" as used herein may refer to a reduction or inhibition of the biological activity of mycelia. The inactivation step may utilize methods such as sterilization, sonication, or chemical treatment.

[0051] The above sterilization method is a method using an autoclave, and may be a method of sterilizing living mycelia at a temperature and pressure higher than the maximum extreme temperature at which living organisms can survive, 119°C and 1.2 atm, and specifically, the mycelia mat can be inactivated by sterilizing at 121°C and 1.5 atm for 30 minutes.

[0052] Inactivation of mycelial mats using the above ultrasound can be performed by placing living mycelia in distilled water for 2 hours at a frequency range of 35 to 50 kHz.

[0053] The above chemical treatment method may be a method of inactivating the mycelial mat using hydrogen peroxide (H2O2), sodium hypochlorite (NaClO), sodium hydroxide (NaOH), etc.

[0054] The above hydrogen peroxide solution is a substance that can react with enzymes to generate active oxygen or oxygen radicals and dissolve cell walls or cell membranes, and a 3% hydrogen peroxide solution is commonly used for medical purposes.

[0055] In the treatment method using a hydrogen peroxide solution of the present invention, the concentration of hydrogen peroxide may be 5 to 30% of the total volume of the hydrogen peroxide solution, and the treatment may be performed by immersing the mycelial mat in the solution at a temperature of 25 to 60°C for 1 minute to 2 hours. At this time, if the concentration of hydrogen peroxide is 10 to 30% of the total volume of the solution, ultrasonic treatment must be performed for 1 hour or more prior to the hydrogen peroxide solution treatment.

[0056] The above sodium hypochlorite is known as the main component of bleach, and can be diluted and used for sterilization purposes depending on the intended use.

[0057] In the treatment method using a sodium hypochlorite solution of the present invention, the concentration of sodium hypochlorite may be 0 to 30% of the total solution volume, and the mycelial mat may be immersed in the solution at a temperature of 25 to 60°C for 1 minute to 2 hours. At this time, in order to inactivate the mycelia, it is preferable to immerse the mycelia mat using an ultrasonic treatment for 1 hour or more in a solution containing 5% or more sodium hypochlorite, or to immerse the mycelia mat in a 5% or more sodium hypochlorite solution for 2 hours or more without ultrasonic treatment.

[0058] After inactivating the mycelial sheet, it may undergo polymer treatment, cross-linking, and plasticization, and may additionally include a step of adding a branching agent.

[0059] The polymer treatment step of the present invention means a step of treating a polymer for crosslinking, and the polymer may be selected from gelatin, collagen, chitosan, curdlan, casein, soy protein, gluten, cellulose, pectin, and combinations thereof.

[0060] The polymer of the present invention can be treated on a mycelial sheet as a 1 to 20 wt% solution, and preferably, the mycelial sheet can be impregnated with a 5 wt% solution.

[0061] The crosslinking step of the present invention refers to a process that strengthens the bonds between polymers during the leather manufacturing process, thereby increasing the durability and strength of the leather. The crosslinking step may utilize an enzyme that binds polymers together, preferably transglutaminase.

[0062] Additionally, durability and strength can be enhanced by adding an additional cross-linking agent during the cross-linking step. In the present invention, the cross-linking agent may be a polyphenol and may be selected from the group consisting of citric acid, glyoxal, glutaraldehyde, tannic acid, genipin, vanillin, gallic acid, and combinations thereof.

[0063] Additionally, a metal ion may be added in the cross-linking step, preferably aluminum sulfate.

[0064] In the present invention, the enzyme for crosslinking can be impregnated into the mycelia sheet as a 0.01 to 0.2 wt% solution, and the crosslinking agent can be applied to the mycelia sheet as a 3 to 6 wt% solution. Additionally, the metal ion can be applied to the mycelia sheet as a 2 to 6 wt% solution.

[0065] The plasticizing step of the present invention is a step that provides flexibility to leather manufacturing, and can make the surface of the leather soft and increase dyeability.

[0066] The term “plasticizer” used in the present invention may refer to a substance added to change physical properties such as softening point, glass transition point, thermal and mechanical properties of a polymer, as an additive that reduces viscosity or plasticity of a material, and may be a substance commonly used in the production of plastics.

[0067] The above plasticizer solution may be selected from the group consisting of glycerol, polyethylene glycol, sorbitol, xylitol, epoxidized triglycerides vegetable oils, fatty acids, esters and combinations thereof, and in the case of the plasticizer, it may be applied to the mycelium sheet at 5 to 20 v / v%.

[0068] The present invention may include a step of treating a branch agent.

[0069] In addition, the term "leather oil" in the present invention may mean a vegetable oil for protecting leather and increasing the flexibility of leather. The leather oil may be selected from castor oil, corn oil, jojoba oil, olive oil, fish oil, oleic acid, linoleic acid, stearic acid, and combinations thereof.

[0070] The above-mentioned agent can be treated simultaneously with the plasticizer or in separate steps, and can be applied to the mycelial sheet as a solution of 1 to 5 wt%.

[0071] In the drying step of the present invention, it is preferable to dry at 30°C to 50°C, preferably 40°C, for one day.

[0072] Hereinafter, the present invention will be described in detail through examples and experimental examples.

[0073] However, the following examples and experimental examples are only illustrative of the present invention, and the content of the present invention is not limited by the following examples and experimental examples.

[0074]

[0075] Example 1. Mycelial sheet culture

[0076] The tray and nutrient source were sterilized, the nutrient source was dispensed, and the inoculum was dispensed.

[0077] After this, the mycelia sheets were cultured at appropriate temperature and humidity, the mycelia sheets were harvested, and then experiments were conducted using the mycelia sheets.

[0078]

[0079] Example 2. Method for manufacturing leather sheets using mycelia.

[0080] 1. Check the physical properties of leather seats according to the order of natural polymer processing.

[0081] Biofilm surfaces are hydrophobic, and solutions with high hydrophobic properties exhibit high absorption rates and absorption rates. Therefore, we aimed to improve polymer penetration by using highly hydrophobic materials, and to investigate the effects of the method and order of application of hydrophobic materials on biofilms.

[0082] To this end, after removing the medium compositions from the mycelia manufactured in Example 1, an inactivation process was performed, and then polymerization, cross-linking, plasticization, and drying processes were performed according to the conditions in Tables 1 and 2 below. The inactivation process was performed by boiling at 90 degrees or ultrasonic treatment in 10 v / v% NaOH, H2O2, or NaOCL at 60 degrees.

[0083] Here, in the conditions of Table 2, in the case of Fish collagen, it may be preferable that the concentration is 0.1 to 10 wt%, the time is 1 to 48 (h), and the temperature is 20 to 100 °C; in the case of Transglutaminase, it may be preferable that the concentration is 0.01 to 5 wt%, the time is 0.5 to 6 (h), and the temperature is 20 to 100 °C; in the case of Fatliquor, it may be preferable that the concentration is 0.1 to 10 wt%, the time is 1 to 48 (h), and the temperature is 20 to 100 °C; in the case of PEG400, it may be preferable that the concentration is 0.1 to 10 wt%, the time is 1 to 48 (h), and the temperature is 20 to 100 °C; in the case of Fish collagen, it may be preferable that the concentration is 0.1 to 10 wt%, the time is 1 to 48 (h), and the temperature is 20 to 100 °C; however, specific examples of these conditions are given in Table It is shown in 2.

[0084] In addition, in the case of the polymer / crosslinking / plasticization process, after going through the washing process in flowing water at least 5 times under the conditions of Table 2, the mycelial sheet was impregnated with each solution of Table 2.

[0085] To verify the physical properties of the leather sheets manufactured under the above conditions, tensile strength and elongation were measured. Six samples were sampled from two samples and measured six times. The maximum and minimum values ​​were excluded and the average was calculated. The results are shown in Fig. 2.

[0086] Category processing order 1234CtrlPEG400T1Fish collagenTransglutaminaseFatliquorPEG400T2MSGFish collagenTransglutaminasePEG400T3Fish collagen + FatliquorTransglutaminasePEG400T4Fish collagen + TransglutaminaseFatliquorPEG400T5FatliquorFish collagen + TransglutaminasePEG400T6Fatliquor + Transglutaminase + FatliquorPEG400T7Fatliquor + Transglutaminase + Fatliquor + PEG400

[0087] Solution concentration (wt%) Time (h) Temperature (℃) Use Fish collagen 3 1 2 6 0 Natural polymer Transglutaminase 0.5 2 4 0 Crosslinker Fatliquor 1.5 1 2 2 0 Fatliquoring PEG 4 0 0 5 1 2 2 0 Plasticization

[0088] As shown in Fig. 2, leather sheets manufactured in the order of T1 and T2 exhibited significantly superior weighted properties, and it was confirmed that dividing each solution into steps was effective. In particular, when the solution was processed in a single step, such as T7, the biofilm was confirmed to be hard and cracked, confirming that each solution had a mutually disruptive effect. Therefore, it was confirmed that the order of T1 and T2 was the most suitable order.

[0089]

[0090] 2. Experiment to improve the properties of leather seats using naturally derived polymers

[0091] In the same manner as Example 2-1, 1) increasing the amount of enzyme treatment, 2) adding secondary polymers (Gelatin, Carboxymethyl cellulose (CMC), Hydroxyethyl cellulose (HEC)), and 3) adding polyphenol and metallic ions (dyeing) were performed under the conditions of Tables 3 and 4 (when mixing solutions, treatment was performed based on maximum temperature and time). The properties of the manufactured leather sheets were then confirmed, and the results are shown in Fig. 3.

[0092] Here, in the conditions of Table 4, for Fish collagen, the concentration may be preferably 0.1 to 10 (wt%), the time may be 1 to 48 (h), and the temperature may be 20 to 100°C; for Transglutaminase ①, the concentration may be preferably 0.01 to 5 (wt%), the time may be 0.5 to 6 (h), and the temperature may be 20 to 100°C; for Transglutaminase ②, the concentration may be preferably 0.01 to 5 (wt%), the time may be 0.5 to 6 (h), and the temperature may be 20 to 100°C; for Gelatin, the concentration may be preferably 0.5 to 10 (wt%), the time may be 1 to 48 (h), and the temperature may be 20 to 100°C; for CMC, the concentration may be 0.1 to 1.5 (wt%), the time may be 1 to 48 (h), and the temperature may be 20 to It may be preferable that the temperature is 100℃, and for HEC, the concentration may be 0.1 to 1.5 (wt%), the time may be 1 to 48 (h), and the temperature may be 20 to 100℃, and for citric acid, the concentration may be 0.5 to 10 (wt%), the time may be 0.5 to 6 (h), and the temperature may be 20 to 100℃, and for tannic acid, the concentration may be 0.1 to 10 wt% in EtOH, the time may be 0.5 to 6 (h), and the temperature may be 20 to 100℃, and for aluminum sulfate, the concentration may be 0.5 to 10 (wt%), the time may be 0.5 to 6 (h), and the temperature may be 20 to 100℃, and for Fatliquor + PEG400, the concentration may be 1 to 50 v / v%, the time may be 1 to 48(h), the temperature may be preferably 20 to 100℃, but specific examples of these conditions are shown in Table 4.

[0093]

[0094] Classification process1234T1Fish collagenTransglutaminase ①Citric acidFatliquor + PEG400T2Fish collagenTransglutaminase ②Citric acidFatliquor + PEG400T3Fish collagen + GelatinTransglutaminase ①Citric acidFatliquor + PEG400T4Fish collagen + GelatinTransglutaminase ②Citric acidFatliquor + PEG400T5Fish collagenTransglutaminase ①Citric acidFatliquor + PEG400 + Tannic acid + Aluminum sulfateT6Fish collagenTransglutaminase ②Citric acidFatliquor + PEG400 + Tannic acid + Aluminum sulfateT7Fish collagenTransglutaminase ①Citric acidTannic acidAluminium sulfateFatliquor + PEG400T8Fish collagenTransglutaminase ②Citric acidTannic acidAluminium sulfateFatliquor + PEG400T9Fish collagenTannic acidAluminium sulfateTransglutaminase ①Citric acidFatliquor + PEG400T10Fish collagenTannic acidAluminium sulfateTransglutaminase ②Citric acidFatliquor + PEG400T11Fish collagen + CMC + HECTransglutaminase ①Citric acidFatliquor + PEG400T12Fish collagen + CMC + HECTransglutaminase ②Citric acidFatliquor + PEG400

[0095] Solution concentration (wt%) Time (h) Temperature (℃) UseFish collagen31260Natural polymerTransglutaminase ①0.5240CrosslinkerTransglutaminase ②1240CrosslinkerGelatin51240Second polymerCMC0.51220Second polymerHEC0.51220Second polymerCitric acid2260CrosslinkerTannic acid3260PolyphenolAluminium sulfate2460Metal ionFatliquor + PEG400251220Fatliquoring + Plasticization

[0096] As shown in Fig. 3, it was confirmed that there was no difference in physical properties according to small increases (T2, T4, T6, T8, T10, T12) and addition of secondary polymers (T3, T4, T11, T12). In addition, it was confirmed that the effects according to addition of polyphenols and metal ions (T5, T6, T7, T8, T9, T10) varied depending on the processing order.

[0097] In addition, when comparing [T5 / T6], [T7 / T8], and [T9 / T10], it was confirmed that the properties of T9 and T10 were the best.

Claims

1. In a method for manufacturing leather sheets using mycelia, 1) Step of treating a polymer on a mycelial sheet; 2) A method for manufacturing a leather sheet, comprising: a step of treating the mycelial sheet treated with the polymer in step 1) with an enzyme that crosslinks the polymer; and 3) a step of treating the mycelial sheet of step 2) with at least one of a plasticizer and a fatliquoring agent.

2. A method for manufacturing a leather sheet, further comprising, in the first paragraph, a step of treating a mycelial sheet with a fungicide prior to step 1).

3. A method for manufacturing a leather sheet, comprising, in the first paragraph, a step of treating a branch agent after step 2).

4. A method for manufacturing a leather sheet, comprising, in the first paragraph, further comprising a step of treating a cross-linking agent after step 1).

5. A method for manufacturing a leather sheet, further comprising a step of treating a metallic ion after treating the crosslinking agent in the fourth paragraph.

6. A method for manufacturing a leather sheet, further comprising, after step 2), a step of treating a cross-linking agent.

7. A method for manufacturing a leather sheet in the first paragraph, wherein the polymer is selected from gelatin, collagen, chitosan, curdlan, casein, soy protein, gluten, cellulose, pectin, and combinations thereof.

8. A method for manufacturing a leather sheet, wherein the enzyme in paragraph 1 is transglutaminase.

9. In the first paragraph, the plasticizer is selected from the group consisting of glycerol, polyethylene glycol, sorbitol, xylitol, epoxidized triglyceride vegetable oil, fatty acid, ester and combinations thereof, a method for manufacturing a leather sheet.

10. A method for manufacturing a leather sheet, wherein the excipient is selected from among castor oil, corn oil, jojoba oil, olive oil, fish oil, oleic acid, linoleic acid, stearic acid, and combinations thereof.

11. A method for manufacturing a leather sheet, wherein the cross-linking agent in paragraph 4 is polyphenol.

12. A method for manufacturing a leather sheet, wherein the cross-linking agent in paragraph 4 is selected from the group consisting of citric acid, glyoxal, glutaraldehyde, tannic acid, genipin, vanillin, gallic acid, and combinations thereof.

13. In a method for manufacturing leather sheets using mycelia, 1) Step of treating a polymer on a mycelial sheet; 2) A step of treating the mycelial sheet treated with the polymer in step 1) with an enzyme that crosslinks the polymer; 3) A step of treating the mycelium sheet of step 2) with a fungicide; and 4) A manufacturing method comprising a step of treating a plasticizer on a mycelial sheet treated with the agent of step 3).

14. In a method for manufacturing leather sheets using mycelia, 1) Step of treating the mycelium sheet with a fungicide; 2) A step of treating a polymer on the mycelial sheet treated with a ligand in the above step 1); 3) A step of treating the mycelia treated with the polymer in step 2) above with an enzyme that crosslinks the polymer; 4) A manufacturing method comprising a step of treating a plasticizer on the mycelium sheet of step 3).

15. In a method for manufacturing leather sheets using mycelia, 1) Step of treating a polymer on a mycelial sheet; 2) A step of treating a cross-linking agent on the mycelium sheet treated with polymer in step 1); 3) A step of treating the mycelial sheet treated with a cross-linking agent in step 2) above with metal ions; 4) A step of treating the mycelial sheet treated with metal ions in step 3) above with an enzyme that crosslinks the polymer; 5) A step of treating the mycelium sheet treated with the enzyme of step 4) above with a cross-linking agent; and 6) A manufacturing method comprising a step of mixing a plasticizer and a fatliquoring agent into the mycelium sheet treated with the crosslinking agent of step 5 above.

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