Chitosan-based mycelium leather finishing agent as well as preparation method and application thereof

Abstract

The invention belongs to the field of production of mycelium fiber-based leather materials, and particularly relates to a preparation method and an application method of a chitosan-based mycelium leather finishing agent. The preparation method comprises the following steps: carrying out graft copolymerization on any one of glucose, cyclodextrin and amino acid and a chitosan-based material, and blending with at least one of collagen, sodium alginate and konjac glucomannan to obtain the chitosan-based mycelium leather finishing agent. The mycelium fiber-based leather can be used as a base layer or a middle layer to be applied to base coating and floating coating in the coating stage, the strength, toughness and other properties of mycelium crust leather are improved, the mycelium crust leather enables a mycelium fiber-based leather material to be attractive in appearance, have a matte effect and soft and natural hand feeling, the appearance of the mycelium fiber-based leather material is similar to that of traditional leather, and daily application requirements can be met.

Description

Technical Field

[0001] The invention belongs to the field of mycelium fiber-based leather material production, and specifically relates to a chitosan-based mycelium leather finishing agent and a preparation method and application thereof. Background Art

[0002] Traditional leather production has caused serious environmental pollution, so the demand for environmentally friendly leather-like materials has gradually increased. In recent years, a series of plant-based leather-like materials have been developed; however, compared with plant-based fibers, mycelium fibers have a better Similar microscopic properties, high growth efficiency, and easy to control in a directional manner. Traditional leather finishing agents are a general term for a class of additives used for leather surface finishing, protection, and beautification. Its use can increase the beauty of leather, extend the service life of leather, significantly improve the quality and grade of leather products, and increase commercial value. However, due to the large difference between the components of mycelium and the collagen fiber components that constitute conventional leather, the finishing agents used for traditional leather are prone to shedding and delamination when applied to mycelium leather; on this basis, this method uses chitosan-based materials to prepare finishing agents that can be used for mycelium leather, and can be applied to the top coating and middle coating stages in mycelium leather production. Since chitosan-based materials have good affinity with mycelium fibers, they can effectively improve the performance of mycelium leather. Summary of the invention

[0003] The purpose of the present invention is to provide a chitosan-based mycelium leather finishing agent and a preparation method and application thereof. The chitosan-based material is used in the preparation of the mycelium leather finishing agent, which can be used as a base layer or middle layer for primer and mid-coat in the finishing stage to improve the strength and toughness of the mycelium leather and make the surface of the mycelium leather soft.

[0004] In order to achieve the above object, the present invention provides the following technical solutions: A method for preparing a chitosan-based mycelium leather finishing agent comprises the following steps: (1) Dissolving: dissolving the chitosan-based material in a solvent under stirring to obtain a homogenized chitosan-based material; when the chitosan-based material is high-deacetylated chitosan, carboxymethyl chitosan, chitosan hydrochloride or chitosan quaternary ammonium salt, the solvent is deionized water; when the chitosan-based material is low-deacetylated chitosan, the solvent is a dilute acetic acid solution or a dilute hydrochloric acid solution with a volume fraction of 0.5% to 1.2%; (2) Modification: adding bio-based material A to the homogenized chitosan-based material obtained in step (1), stirring until completely dissolved, adjusting the pH and performing graft copolymerization to obtain solution A; the bio-based material A is any one of glucose, cyclodextrin, and amino acid; (3) Compounding: After adjusting the pH of solution A, bio-based material B is added to solution A for blending and reacting with stirring to obtain a chitosan-based mycelium leather finishing agent; the bio-based material B is at least one of collagen, sodium alginate, and konjac gum. Preferably, in step (1), the solid-liquid ratio of the chitosan-based material to the solvent is 1:20-1:160.

[0005] Preferably, in step (2), the mass ratio of chitosan-based material to bio-based material A is 1:2-1:5, the pH is adjusted to 3-7, the graft copolymerization temperature is 40°C-90°C, and the graft copolymerization time is 4 h-72 h.

[0006] Preferably, in step (3), the pH of solution A is adjusted to 6-8; the mass ratio of chitosan-based material to bio-based material B is 1:1-1:10, the blending temperature is 50°C-70°C, and the blending time is 2 h-24 h.

[0007] The present invention also includes the use of the chitosan-based mycelium leather finishing agent in the mycelium leather base layer, and the specific steps are as follows: Water, chitosan-based finishing agent, cross-linking agent and pigment paste are compounded and evenly distributed on the surface of mycelium leather by roller coating or spraying, and then dried.

[0008] Preferably, water is 200-350 parts, chitosan-based finishing agent is 30-100 parts, cross-linking agent is 0-100 parts, pigment paste is 0-50 parts, drying temperature is 25°C-120°C, and drying time is 5 min-24 h.

[0009] The present invention also includes the application of a chitosan-based mycelium leather finishing agent in the middle layer of mycelium leather, and the specific steps are as follows: Water, chitosan finishing agent, dye water and other film-forming materials are compounded, evenly distributed on the surface of mycelium leather by roller coating or spraying, and then dried.

[0010] Preferably, water is 350-600 parts, chitosan coating agent is 50-70 parts, dye water is 0-30 parts, other film-forming materials are 0-50 parts, and the drying temperature is 25°C - 120°C.

[0011] Compared with the prior art, the present invention has the following advantages: (1) The chitosan-based mycelium leather finishing agent provided by the present invention makes the mycelium fiber-based leather material beautiful in appearance, has a matte effect, and feels soft and natural. It is similar to traditional leather in appearance and can meet daily application needs.

[0012] (2) Compared with conventional leather making auxiliaries, the chitosan-based mycelium leather finishing agent of the present invention has better affinity with mycelium fibers, is less likely to delaminate or peel off, and has better biodegradability. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 This is the effect picture of the mycelium leather after finishing in Example 1; Figure 2 This is a picture of the mycelium leather product after coating in Example 1. DETAILED DESCRIPTION

[0014] The above contents of the present invention are further described in detail below through examples, but the contents of the present invention are not limited thereto.

[0015] Example 1 A method for preparing chitosan-based mycelium leather finishing agent (1) Weigh 5.0 g of carboxymethyl chitosan and dissolve it in deionized water under stirring to make the volume 250 ml so that the concentration of the chitosan solution is 20 mg / ml to obtain a homogenized chitosan-based material; (2) Add β-cyclodextrin (12.0 g) to the homogenized chitosan-based material in step (1) to a total volume of 500 mL; react at 85 °C for 1 h until completely dissolved (the pH of the solution is 6-7), then cool to 60 °C and continue to react for 4 h to obtain solution A; (3) Solution A was adjusted to pH 8, 10 g of collagen was added at 50 °C, and the reaction was continued with stirring for 2 h to obtain a chitosan-based mycelium leather finishing agent.

[0016] The obtained coating agent was coated on a polytetrafluoroethylene plate and dried at room temperature to form a film, and its tensile strength was measured to be 0.82 Mpa.

[0017] Application of chitosan-based mycelium leather finishing agent in mycelium leather base layer The finishing agent obtained by the above preparation method was mixed in a spray pot according to the mass ratio of 80 parts of chitosan finishing agent, 200 parts of water, and 10 parts of cross-linking agent, and then sprayed on the surface of mycelium leather as a base layer, and dried at 100 °C for 5 minutes. The tensile strength of mycelium leather was measured to be 8.14 Mpa.

[0018] Embodiment 2: (1) Weigh 10.0 g of low-deacetylated chitosan and dissolve it in 0.8% acetic acid solution under stirring to make the concentration of the chitosan solution 10 mg / ml to obtain a homogenized chitosan-based material; (2) Glucose (20.0 g) was added to the homogenized chitosan-based material obtained in step (1) and stirred until completely dissolved; the pH of the solution was adjusted to 5.5, and the reaction was carried out at 65 °C for 72 h to obtain solution A.

[0019] (3) Solution A was adjusted to pH 8, 10 g of collagen was added at 55 °C, and the reaction was continued with stirring for 2 h to obtain a chitosan-based mycelium leather finishing agent.

[0020] Application of chitosan-based mycelium leather finishing agent in mycelium leather base layer After 100 parts of the obtained finishing agent and 200 parts of water were evenly mixed, the mixture was roller-coated on the surface of mycelium leather as a base layer, dried at 100°C for 15 min, and softened at room temperature. The strength of the mycelium leather material after coating was measured to be 8.53 Mpa.

[0021] Embodiment 3: (1) Weigh 5.0 g of low-deacetylated chitosan and dissolve it in 0.8% dilute acetic acid solution under stirring to make the concentration of the chitosan solution 10 mg / ml to obtain a homogenized chitosan-based material; (2) Add 10.0 g of glucose to the homogenized chitosan-based material obtained in step (1), stir until completely dissolved (the pH value of the solution is 6-7), and react at 65°C for 72 h to obtain solution A; (3) The pH of solution A was adjusted to 6.5, and 5 g of sodium alginate and 5 g of collagen were added to solution A and mixed. The mixture was stirred at 55 °C for 2 h to obtain a chitosan-based mycelium leather finishing agent.

[0022] The obtained solution was poured into a petri dish, dried at 40 °C for 6 h, and softened at room temperature. The tensile strength was measured to be 0.61 MPa.

[0023] Application of chitosan-based mycelium leather finishing agent in the middle layer of mycelium leather 350 parts of water, 70 parts of chitosan coating agent, 30 parts of natural resin and 5 parts of dye water were compounded and used in the middle layer at a drying temperature of 100 °C and a drying time of 10 min. The tensile strength of the mycelium leather after coating was measured to be 9.07 Mpa.

Claims

1. A method for preparing a chitosan-based mycelium leather finishing agent, characterized in that: The preparation method comprises the following steps: (1) Dissolving: dissolving the chitosan-based material in a solvent under stirring to obtain a homogenized chitosan-based material; when the chitosan-based material is high-deacetylated chitosan, carboxymethyl chitosan, chitosan hydrochloride or chitosan quaternary ammonium salt, the solvent is deionized water; when the chitosan-based material is low-deacetylated chitosan, the solvent is a dilute acetic acid solution or a dilute hydrochloric acid solution with a volume fraction of 0.5% to 1.2%; (2) Modification: adding bio-based material A to the homogenized chitosan-based material obtained in step (1), stirring until completely dissolved, adjusting the pH and performing graft copolymerization to obtain solution A; the bio-based material A is any one of glucose, cyclodextrin, and amino acid; (3) Compounding: After adjusting the pH of solution A, bio-based material B is added to solution A for blending and reacting with stirring to obtain a chitosan-based mycelium leather finishing agent; the bio-based material B is at least one of collagen, sodium alginate, and konjac gum.

2. The preparation method according to claim 1, characterized in that: In the step (1), the solid-liquid ratio of the chitosan-based material to the solvent is 1:20-1:

160.

3. The preparation method according to claim 1, characterized in that: In the step (2), the mass ratio of chitosan-based material to bio-based material A is 1:2-1:5, the pH is adjusted to 3-7, the graft copolymerization temperature is 40°C-90°C, and the graft copolymerization time is 4 h-72 h.

4. The preparation method according to claim 1, characterized in that: In the step (3), the pH of solution A is adjusted to 6-8; the mass ratio of chitosan-based material to bio-based material B is 1:1-1:10, the blending temperature is 50°C-70°C, and the blending time is 2h-24h.

5. A chitosan-based mycelium leather finishing agent obtained by the preparation method according to any one of claims 1 to 4.

6. Use of the chitosan-based mycelium leather finishing agent as claimed in claim 5 in a mycelium leather base layer, characterized in that: The specific steps are as follows: Water, chitosan-based finishing agent, cross-linking agent and pigment paste are compounded and evenly distributed on the surface of mycelium leather by roller coating or spraying, and then dried.

7. Use of the chitosan-based mycelium leather finishing agent according to claim 6 in a mycelium leather base layer, characterized in that: The water comprises 200-350 parts, the chitosan-based finishing agent comprises 30-100 parts, the cross-linking agent comprises 0-100 parts, and the pigment paste comprises 0-50 parts; the drying temperature comprises 25° C. to 120° C., and the drying time comprises 5 min to 24 h.

8. The use of the chitosan-based mycelium leather finishing agent as claimed in claim 5 in the middle layer of mycelium leather, characterized in that: The specific steps are as follows: Water, chitosan finishing agent, dye water and other film-forming materials are compounded, evenly distributed on the surface of mycelium leather by roller coating or spraying, and then dried.

9. The use of the chitosan-based mycelium leather finishing agent according to claim 8 in the middle layer of mycelium leather, characterized in that: The water is 350-600 parts, the chitosan coating agent is 50-70 parts, the dye water is 0-30 parts, and the other film-forming materials are 0-50 parts. The drying temperature is 25°C - 120°C.

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