A mycelial fiber skin and its preparation method

Abstract

The present invention belongs to the technical field of mycelial fiber leather, and particularly relates to a mycelial fiber leather and a preparation method thereof. The preparation method of the mycelial fiber leather comprises the following steps: trimming; soaking in water; pickling; tanning; deliming; retanning; finishing. In the soaking step of the above method, a zinc salt is added for reaction, and through the zinc-chromium combination tanning method, the strength and toughness of the mycelium are improved, so that it has the use characteristics similar to those of traditional animal leather. The obtained mycelial fiber leather has a soft surface, good heat resistance, and strength and toughness that meet the use requirements.

Description

Technical Field

[0001] The present invention belongs to the technical field of mycelial fiber leather, and particularly relates to a mycelial fiber leather and a preparation method thereof. Background Art

[0002] Mycelium is the vegetative part of a mushroom, composed of a large number of branches, fibers and natural composite materials, with controllable physical and mechanical properties and a certain strength; during the cultivation of edible mushrooms such as mushrooms, a large amount of mycelial substrate is produced. In the prior art, through chemical and physical treatment methods, mycelium can be turned into plant leather with potential application, and its performance is expected to be similar to that of traditional animal and synthetic leather products; however, compared with traditional leather, mycelial fiber leather has the characteristics of high growth efficiency and easier directional regulation.

[0003] Currently in the leather industry, the chrome tanning method has a history of more than one hundred years. Chrome-tanned leather has high resistance to heat and humidity, good hand feeling, good use performance, and the chrome tanning process is easy to operate, and it is the most widely used tanning method. By simply treating mycelium with the chrome tanning method, the obtained mycelial fiber leather has low physical and chemical properties, a yellowish color, and poor fullness. Zn 2+ can form coordination bonds with a variety of ligands, and its chemical reaction principle is basically the same as that of Cr 3+ 、Al 3+ 、Zr 4+ 、Ti 4+ Basically the same, and the addition of zinc salt has an obvious effect on the strength of its mycelial leather. Therefore, compared with a single metal tanning agent, the mycelial leather tanned with chromium-zinc combination has no worse softness, fullness, hand feeling, etc. than conventional chrome-tanned leather, thus further improving the tanning effect. Summary of the Invention

[0004] The present application discovers that Zn 2+ Compared with chromium salts, the coordination bonding reaction functional groups in leather making are different. In order to solve the problem of insufficient strength existing in the prior art, the present application introduces zinc salt into the chrome tanning method and treats the mycelium, and finds that zinc salt and chromium salt can play a synergistic role, which can effectively improve the physical and chemical properties of mycelial fiber leather.

[0005] The purpose of the present invention is to provide a mycelial fiber leather and a preparation method thereof. Through the chromium-zinc combination tanning method, the strength and toughness of the mycelium are improved, so that it has the use characteristics similar to those of traditional animal leather. The obtained mycelial fiber leather has a soft surface, good heat resistance, and the strength and toughness that meet the use requirements.

[0006] In order to achieve the above purpose, the present invention provides the following technical solutions:

[0007] A preparation method of a mycelial fiber leather, comprising the following steps:

[0008] (1) Trimming: Trim the mycelium neatly by cutting, and remove the culture medium residues attached to the surface. Weigh the wet weight of the inactivated mycelium, and use this as the tare weight benchmark.

[0009] (2) Soaking: Soak the mycelium after the treatment in step (1). The soaking temperature is 20 - 25°C. During the soaking process, first add soaking aids such as calcium chloride, calcium oxide, glycerol or olive oil to disperse the mycelium fibers, and then add zinc salt to continue the reaction. After the treatment is completed, weigh it, and the obtained weight is used as the reagent addition amount benchmark in acid pickling and tanning.

[0010] (3) Acid pickling: After washing the mycelium soaked in step (2), carry out acid pickling. The pH of the acid pickling system is 2.0 - 3.0, and sodium chloride is added to the system.

[0011] (4) Tanning, add a concealer and a chrome tanning agent to promote the full penetration of the tanning agent into the interior of the mycelium for tanning.

[0012] (5) Raising the alkalinity, raise the alkalinity of the tanned mycelium in a bath solution with a pH of 3.8 - 4.0. After the reaction is completed, carry out water washing, and let it stand for 24 - 48 h after water washing.

[0013] (6) Retanning, add a fat - type retanning agent accounting for 5% - 20% of the weight of the mycelium after the treatment in step (5), and add a surfactant to promote the penetration of the fat.

[0014] (7) Through the drying and finishing processes, the mycelium fiber leather is obtained. The drying process can adopt methods such as drying in an oven and natural drying, and subsequent finishing and coating processes are carried out according to the traditional leather production method.

[0015] The mycelium described in step (1) is cultivated from Ganoderma lucidum and then inactivated by boiling at 100°C.

[0016] Preferably, in step (2), the liquor ratio of soaking is greater than 2, and the dosage of the soaking aid is 5 - 20% of the weight of the inactivated mycelium.

[0017] Preferably, the total soaking time in step (2) is 12 - 36 h, and the zinc salt is added 8 - 18 h after adding the soaking aid.

[0018] Preferably, the zinc salt in step (2) is selected from zinc nitrate, zinc borate or zinc nitrate.

[0019] Preferably, in step (3), the acid pickling temperature is 18 - 25°C, the time is 4 - 24 h, the liquor ratio is 1 - 1.5, and the dosage of sodium chloride is 5 - 10% of the mass of the mycelium after soaking.

[0020] Preferably, in step (3), the pH of the pickling system is adjusted with an acid solution. The preparation method of the acid solution is as follows: sulfuric acid and formic acid are mixed at a volume ratio of 5:1, and the resulting mixture is mixed with water at a volume ratio of 1:(10 - 20).

[0021] Preferably, in step (4), the amount of the masking agent is 2 - 5% of the mass of the mycelium after pickling, and the amount of the chrome tanning agent is 5 - 20% of the mass of the mycelium after pickling.

[0022] More preferably, in step (4), the tanning temperature is 20 - 30 °C, and the reaction time is 3 - 8 h.

[0023] Preferably, in step (5), baking soda is used for raising the alkalinity; the reaction time for raising the alkalinity is 4 - 12 h.

[0024] Preferably, in step (6), the liquor ratio for retanning is greater than 1, the retanning temperature is 30 - 45 °C, and the retanning time is 12 - 24 h.

[0025] The present invention also provides a mycelial fiber leather prepared by the above preparation method.

[0026] Beneficial effects

[0027] The process of the present invention can produce a mycelial fiber leather with physical and chemical properties meeting the requirements of daily applications. Its appearance is similar to that of leather, and it has a unique elasticity of mycelial fiber leather in terms of hand feeling. Compared with the mycelial leather prepared by plastifying mycelium by the synthetic leather method, the present invention is closer to the traditional leather manufacturing process, and the shrinkage temperature of the mycelial fiber leather is higher than that of traditional leather, meeting the standards of vegan leather. Description of the drawings

[0028] Figure 1 It is the surface topography diagram of the mycelial fiber leather of Example 3 of the present invention;

[0029] Figure 2 It is the surface topography diagram of the mycelial fiber leather of Example 4 of the present invention;

[0030] Figure 3 It is the depth of field diagram of the mycelial fiber leather of Example 3 of the present invention;

[0031] Figure 4 It is the depth of field diagram of the mycelial fiber leather of Example 4 of the present invention;

[0032] Figure 5 It is the electron microscope diagram of the mycelial fiber leather of Example 3 of the present invention;

[0033] Figure 6 It is the electron microscope diagram of the mycelial fiber leather of Example 4 of the present invention. Detailed implementation manners

[0034] The present invention will be further described below in conjunction with specific embodiments, and the advantages and features of the present invention will become clearer as the description progresses. However, the embodiments are merely exemplary and do not constitute any limitation to the scope of the present invention. Those skilled in the art should understand that the details and forms of the technical solutions of the present invention can be modified or replaced without departing from the spirit and scope of the present invention, but such modifications and replacements all fall within the protection scope of the present invention.

[0035] The mycelium used in the examples was provided by Tianjin Meikele Biotechnology Co., Ltd.

[0036] Example 1

[0037] The specific operation steps and materials used in each process of the tanning section of the leather-making process are as follows:

[0038] (1) Trimming: Trim the Ganoderma lucidum mycelium neatly and remove the culture medium residues attached to the surface. Weigh and record the cut and inactivated Ganoderma lucidum mycelium samples, and use this as a benchmark to stipulate the dosage of subsequent fillers.

[0039] (2) Soaking: Liquid ratio 3; amount of calcium oxide added: 5%. Rotation speed 150 r / min, temperature 25 °C, after 8 h, add 10% zinc acetate, continue to react for 16 h, then wash and weigh.

[0040] (3) Pickling: Liquid ratio 1, amount of NaCl added: 5%, the acids used to adjust the pH are sulfuric acid and formic acid, and the volume ratio of the two is 5:1. Then dilute it with water, and the volume ratio of the acid solution to water is 1:20. Adjust the pH to 2.8. The pickling temperature is 25 °C and the pickling time is 4 h.

[0041] (4) Tanning: Temperature 25 °C, total time 3.0 h. Amount of formate (montanizing agent) added: 5%, after 0.5 h, amount of chromium sulfate added: 5%;

[0042] (5) Raising the alkali: Use baking soda solution to raise the alkali and adjust the pH to 3.8. Do it in two times within 30 min, total time 4 h, wash with water and then let it stand for 24 h;

[0043] (6) Retanning: Liquid ratio 3, amount of glycerol used: 5%, amount of surfactant Tween used: 2%; rotation speed 150 r / min, temperature 40 °C, time 24 h;

[0044] (7) Rinse and dry the sample, and dry it at 60 °C for 10 h. The subsequent treatment is carried out according to the conventional leather-making method.

[0045] Perform performance tests on the obtained mycelium fiber leather, and the results are shown in Table 1.

[0046] Example 2

[0047] A method for preparing a mycelial fiber leather, comprising the following steps:

[0048] (1) Trimming: Trim the Ganoderma lucidum mycelium neatly and remove the culture medium residues attached to the surface. Weigh the cut and inactivated Ganoderma lucidum mycelium samples, and based on this, specify the dosage of subsequent fillers.

[0049] (2) Immersion in water: Conducted in a rotary drum, liquor ratio 3; amount of glycerol: 10%; rotation speed 150 r / min, temperature 25 °C, after 8 h, add 10% zinc borate, continue to react for 16 h, then wash and weigh.

[0050] (3) Acid pickling: Liquor ratio 1, add 5% NaCl based on the weight of the mycelium after treatment in step (2); adjust the pH to 2.8, the acid used to adjust the pH is sulfuric acid and formic acid, and the volume ratio of the two is 5:1. Then dilute it with water to obtain an acid solution, and the volume ratio of the acid solution to water is 1:15; the acid pickling temperature is 25 °C, and the acid pickling time is 4 h.

[0051] (4) Tanning: Temperature 25 °C, time 3.0 h; add 5% sodium acetate as a masking agent based on the weight of the mycelium after treatment in step (3), and then add 5% chromium sulfate after 0.5 h.

[0052] (5) Alkali raising: Use a sodium bicarbonate solution to raise the alkali and adjust the pH to 3.8. Conduct it in two times within 30 min to make the alkali raising process milder and avoid damaging the leather surface. The total time is 4 h, wash with water and then let it stand for 24 h.

[0053] (6) Retanning: Conducted in a rotary drum, amount of glycerol: 5%, amount of surfactant Tween: 2%, temperature 40 °C, time 24 h.

[0054] (7) Naturally air-dry the samples, and subsequent treatment is carried out according to the conventional leather-making method.

[0055] Perform performance tests on the obtained mycelial fiber leather, and the results are shown in Table 1.

[0056] Example 3:

[0057] A method for preparing a mycelial fiber leather, comprising the following steps:

[0058] (1) Trimming: Trim the Ganoderma lucidum mycelium neatly and remove the culture medium residues attached to the surface. Weigh and record the cut and inactivated Ganoderma lucidum mycelium samples, and based on this, specify the dosage of subsequent fillers.

[0059] (2) Immersion: Conducted in a rotating drum, liquor ratio 3; amount of calcium oxide added: 5%; 18 h after adding calcium oxide, add zinc nitrate accounting for 2% of the weight of the mycelium; rotation speed 150 r / min, temperature 25 °C, total time 24 h; After the treatment is completed, weigh, and the obtained weight is used as the benchmark for the reagent addition amount in pickling and tanning.

[0060] (3) Pickling: After washing the mycelium after immersion in step (2) with water, conduct pickling; add NaCl accounting for 5% of the weight of the mycelium after immersion; the acids used to adjust the pH are sulfuric acid and formic acid, and the volume ratio of the two is 5:1 to obtain an acid solution, and then dilute it with water, and the volume ratio of the acid solution to water is 1:20; adjust the pH to 2.8; pickling temperature is 25 °C, pickling time 4 h. Liquor ratio is 1.

[0061] (4) Tanning: Temperature 25 °C, time 3.0 h; amount of sodium citrate as a masking agent added: 5%, amount of chromium sulfate added 0.5 h later: 10%.

[0062] (5) Alkali raising: Use baking soda to raise the alkali and raise the pH to 3.8. Conduct in two times within 30 min to make the alkali raising process relatively gentle and avoid damaging the leather surface., total time 4 h. After the reaction is complete, wash with water and let it stand for 24 h after washing.

[0063] (6) Retanning: Conducted in a rotating drum, liquor ratio 3, amount of glycerol: 5%, amount of surfactant Tween: 2%. Rotation speed 150 r / min, temperature 40 °C, time 24 h.

[0064] (7) Rinse the sample, dry it, and dry it at 60 °C for 8 h. Subsequent treatment is carried out according to the conventional leather-making method.

[0065] The surface morphology diagram of the obtained mycelial fiber leather is as shown in Figure 1 shown in; the depth of field diagram is as shown in Figure 3 shown in; the scanning electron microscope diagram is as shown in Figure 5 shown in. It can be seen from the figure that: This method can obtain mycelial fiber leather similar to the leather grain surface, and the micro-structure of the mycelial fiber is made more compact through tanning, thereby effectively improving the strength of the mycelial fiber leather.

[0066] Perform performance tests on the obtained mycelial fiber leather, and the results are shown in Table 1.

[0067] Example 4

[0068] A method for preparing mycelial fiber leather, comprising the following steps:

[0069] (1) Trimming: Trim the Ganoderma lucidum mycelium regularly and remove the culture medium residues attached to the surface. Weigh and record the cut and inactivated Ganoderma lucidum mycelium samples, and use this as a benchmark to stipulate the dosage of subsequent fillers.

[0070] (2) Immersion in water: Immerse the mycelium after the treatment in step (1) in water in a rotary drum with a liquor ratio of 3. First, add glycerol accounting for 10% of the weight of the mycelium, and add 10% of zinc borate after 18 h. The temperature is 25 °C and the total time is 24 h. After the treatment, weigh it, and the obtained weight is used as the benchmark for the reagent addition amount in acid pickling and tanning.

[0071] (3) Acid pickling: After washing the mycelium immersed in water in step (2), carry out acid pickling. Add NaCl accounting for 5% of the weight of the mycelium. Adjust the pH to 2.8. The acids used are sulfuric acid and formic acid, and the volume ratio of the two is 5:1. Then dilute it with water to obtain an acid solution, and the volume ratio of the acid solution to water is 1:20. The acid pickling temperature is 25 °C and the acid pickling time is 4 h. The liquor ratio is 1.

[0072] (4) Tanning: The temperature is 25 °C and the time is 3.0 h. Add 5% of the mycelium weight of the masking agent sodium citrate, and add 10% of the mycelium weight of chromium sulfate after 0.5 h.

[0073] (5) Alkali raising: Use a sodium bicarbonate solution to raise the alkali and raise the pH to 3.8. Carry out it in two times within 30 min to make the alkali raising process milder and avoid damaging the leather surface. The total time is 4 h. After the reaction is completed, carry out water washing and let it stand for 24 h after water washing.

[0074] (6) Retanning: Carry out it in a rotary drum with a liquor ratio of 3. Add 2% of the amount of the surfactant Tween accounting for 5% of the weight of the mycelium. The temperature is 40 °C and the time is 24 h.

[0075] (7) Rinse the sample, dry it in the air, and dry it at 60 °C for 10 h. The subsequent treatment is carried out according to the conventional leather-making method.

[0076] The surface morphology diagram of the obtained mycelium fiber leather is as shown in Figure 2 as shown in; the depth of field diagram is as shown in Figure 4 as shown in; the scanning electron microscope diagram is as shown in Figure 6 as shown in. It can be seen from the figure that: This method can obtain mycelium fiber leather similar to the leather grain surface. Through tanning, the microstructure of the mycelium fiber becomes more compact, thereby effectively improving the strength of the mycelium fiber leather.

[0077] Perform performance tests on the obtained mycelium fiber leather, and the results are shown in Table 1.

[0078] Table 1. Physical and chemical properties of mycelium fiber leather

[0079]

Claims

1. A preparation method of a mycelial fiber skin, characterized in that, It includes the following steps: (1) Trimming: Trim the mycelium neatly by cutting, and remove the culture medium residues attached to the surface. Weigh the wet weight of the inactivated mycelium, and use this as the tare weight benchmark; the mycelium is cultivated from Ganoderma lucidum and then inactivated by boiling at 100°C; (2) Soaking: Soak the mycelium after the treatment in step (1). The soaking temperature is 20 - 25°C. During the soaking process, first add soaking aids such as calcium chloride, calcium oxide, glycerol or olive oil, and then add zinc salt to continue the reaction. After the treatment is completed, weigh it, and the obtained weight is used as the reagent addition amount benchmark in acid pickling and tanning; (3) Acid pickling: After washing the mycelium soaked in step (2), perform acid pickling; the pH of the acid pickling system is 2.0 - 3.0, and sodium chloride is added to the system; (4) Tanning: Add a masking agent and a chrome tanning agent to promote the full penetration of the tanning agent into the interior of the mycelium for tanning; (5) Raising the alkalinity: Raise the alkalinity of the tanned mycelium in a bath solution with a pH of 3.8 - 4.

0. After the reaction is completed, wash it with water, and let it stand for 24 - 48 h after washing; (6) Retanning: Add an oil - based retanning agent accounting for 5% - 20% of the weight of the mycelium after the treatment in step (5), and add a surfactant to promote the penetration of the oil, and perform retanning; (7) Obtain the mycelium fiber leather through drying and finishing processes; In step (2), the zinc salt is selected from zinc acetate, zinc borate or zinc nitrate; In step (4), the dosage of the chrome tanning agent is 5 - 20% of the mass of the mycelium after acid pickling.

2. The preparation method of the mycelial fiber skin according to claim 1, wherein, In step (2), the liquor ratio of soaking is greater than 2, and the dosage of the soaking aid is 5% - 20% of the weight of the inactivated mycelium.

3. The preparation method of the mycelial fiber skin according to claim 1, characterized in that, The total soaking time in step (2) is 12 - 36 h, and the zinc salt is added 8 - 18 h after adding the soaking aid.

4. The preparation method of the mycelial fiber skin according to claim 1, characterized in that, In step (3), the acid pickling temperature is 18 - 25°C, the time is 4 - 24 h, the liquor ratio is 1 - 1.5, and the dosage of sodium chloride is 5% - 10% of the mass of the mycelium after soaking.

5. The preparation method of the mycelial fiber skin according to claim 1, characterized in that, In step (3), the pH of the acid pickling system is adjusted with an acid solution. The preparation method of the acid solution: Mix sulfuric acid and formic acid in a volume ratio of 5:1, and mix the obtained mixed solution with water in a volume ratio of 1:(10 - 20).

6. The preparation method of the mycelial fiber skin according to claim 1, characterized in that, In step (4), the dosage of the masking agent is 2 - 5% of the mass of the mycelium after acid pickling; In step (4), the tanning temperature is 20 - 30°C, and the reaction time is 3 - 8 h.

7. The preparation method of the mycelial fiber skin according to claim 1, characterized in that, In step (5), baking soda is used for raising the alkalinity; the raising - alkalinity reaction time is 4 - 12 h.

8. The preparation method of the mycelial fiber skin according to claim 1, characterized in that, In step (6), the liquor ratio of retanning is greater than 1, the retanning temperature is 30 - 45°C, and the retanning time is 12 - 24 h.

9. The mycelium fiber leather prepared by the preparation method according to any one of claims 1 - 8.

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