Artificial leather and method for producing the same

Abstract

The present application relates to the leather technical field, specifically to a kind of artificial leather and its preparation method, the artificial leather of the described artificial leather with PHA as base material, can replace traditional polyurethane (PU) and polyvinyl chloride (PVC) artificial leather, the artificial leather of the present application can be degraded by microbial fermentation in seawater or soil after being discarded.

Description

Technical Field

[0001] This invention relates to the field of leather technology, specifically to an artificial leather and its preparation method. Background Technology

[0002] Artificial leather is an ideal alternative to natural leather, helping to reduce the use of animal hides. Currently, the main materials used to manufacture artificial leather include polymers such as polyvinyl chloride (PVC), polyurethane, polyolefins, and polyamides. However, there is no publicly available technology that discloses the use of polyvinyl chloride (PHA) in the manufacture of artificial leather. Summary of the Invention

[0003] This invention provides an artificial leather and its preparation method. The artificial leather uses homopolymers, copolymers, polymers, and mixtures thereof of PHA in different proportions as a base material, and can replace traditional PU and PVC synthetic leather. The fillers, foaming agents (e.g., surfactants), plasticizers, or dyes used in the preparation process of the artificial leather are natural polymers or environmentally friendly reagents. The PHA base material is prepared entirely by microbial fermentation. The fermentation process consumes excess straw, starch, and kitchen waste in nature. The fermentation wastewater is non-toxic and easy to treat. Furthermore, PHA can be naturally degraded in seawater and soil through microbial fermentation after disposal, making it very environmentally friendly.

[0004] In a first aspect, the present invention provides an artificial leather.

[0005] Preferably, the artificial leather comprises a base material and auxiliary materials, wherein the base material comprises PHA and the auxiliary materials comprise a foaming agent.

[0006] In one specific embodiment of the present invention, the artificial leather comprises 10-20 parts of base material, such as 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 parts, and 0.1-10 parts of auxiliary material, such as 0.1, 0.35, 0.5, 1, 1.05, 1.35, 1.5, 2, 2.09, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9 or 10 parts.

[0007] Preferably, the foaming agent includes, but is not limited to, surfactants, chemical foaming agents, and / or physical foaming agents. Preferably, the foaming agent is added at any mass of 0%-30% (preferably 0.5%-25%) of the base material, for example, 0%, 0.000001%, 0.5%, 0.9%, 1%, 1.25%, 1.3%, 1.4%, 1.6%, 1.7%, 3%, 3.3%, 3.4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 25%, or 30%.

[0008] In one specific embodiment of the present invention, the artificial leather comprises any number of 10-20 parts of base material, such as 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 parts, and 0.1-5 parts of foaming agent, such as 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.5, 1, 2, 3, 4 or 5 parts.

[0009] Preferably, the surfactant comprises anionic surfactant and / or nonionic surfactant. Preferably, the anionic surfactant and / or nonionic surfactant is added at any mass of 0%-20% (preferably 0.5%-12%) of the substrate, for example, 0%, 0.000001%, 0.5%, 0.6%, 0.9%, 1%, 1.6%, 1.7%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 15%, or 20%.

[0010] In one specific embodiment of the present invention, the artificial leather contains any number of 10-20 parts of a base material, such as 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 parts, and 0.1-3 parts of a surfactant, such as 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5, 1, 2 or 3 parts.

[0011] More preferably, the anionic surfactant includes, but is not limited to, one, two, or more of C-70, C-90, T-70, JFC-EP, alkali-resistant penetrant AEP, or alkali-resistant penetrant OEP-70. Among these, C-70, C-90, and T-70 are fast-penetrating anionic surfactants.

[0012] In one specific embodiment of the present invention, the anionic surfactant is a fast-penetrating agent T-70 and JFC-EP, and the mass ratio of the fast-penetrating agent T-70 and JFC-EP is 1:1.

[0013] In one specific embodiment of the present invention, the anionic surfactant is C-90.

[0014] In one specific embodiment of the present invention, the anionic surfactant is C-70.

[0015] Preferably, the nonionic surfactant includes, but is not limited to, one, two, or more of S-80, AEO-3, AEO-4, AEO-5, AEO-7, JFC-1, JFC-2, and JFC-E. Specifically, S-80 is a dehydrated sorbitol fatty acid ester nonionic surfactant; AEO-3, AEO-4, AEO-5, and AEO-7 are AEO series nonionic emulsifiers; and JFC-1, JFC-2, and JFC-E are nonionic penetrants.

[0016] In one specific embodiment of the present invention, the nonionic surfactant is JFC-1.

[0017] In one specific embodiment of the present invention, the nonionic surfactant is JFC-2.

[0018] In one specific embodiment of the present invention, the nonionic surfactant is JFC-E.

[0019] In one specific embodiment of the present invention, the nonionic surfactant is AEO-3.

[0020] In one specific embodiment of the present invention, the nonionic surfactant is S-80.

[0021] Preferably, the chemical foaming agent is added at any value between 0% and 30% (preferably 0.5% and 30%) of the base material, such as 0%, 0.000001%, 0.5%, 0.8%, 0.9%, 1%, 1.25%, 1.3%, 1.4%, 5%, 10%, 20%, 25%, 27%, 28.6%, 29%, and 30%.

[0022] In one specific embodiment of the present invention, the artificial leather comprises any number of 10-20 parts of base material, such as 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 parts, and 0.1-5 parts of chemical foaming agent, such as 0.1, 0.15, 0.2, 0.25, 0.3, 0.4, 0.5, 1, 2, 3, 4 or 5 parts.

[0023] Preferably, the chemical foaming agent includes inorganic foaming agents and organic foaming agents.

[0024] More preferably, the organic foaming agent includes, but is not limited to, one, two, or more of azo compounds, sulfonyl hydrazine compounds, or nitroso compounds.

[0025] More preferably, the inorganic foaming agent includes, but is not limited to, carbonates, sodium silicate, silicon carbide, sodium chloride, or carbon black, etc.

[0026] The carbonates mentioned include, but are not limited to, one, two or more of calcium carbonate, magnesium carbonate, ammonium bicarbonate, sodium carbonate or sodium bicarbonate.

[0027] In one specific embodiment of the present invention, the inorganic foaming agent is ammonium bicarbonate.

[0028] In one specific embodiment of the present invention, the inorganic foaming agent is sodium bicarbonate.

[0029] In one specific embodiment of the present invention, the inorganic foaming agent is sodium carbonate.

[0030] In one specific embodiment of the present invention, the inorganic blowing agent is sodium silicate and ammonium bicarbonate. Preferably, the physical blowing agent includes, but is not limited to, one, two, or more of carbon dioxide blowing agents, HCFC blowing agents, hydrocarbon blowing agents, or HFC blowing agents. More preferably, the PHA comprises homopolymers or copolymers of the monomers constituting the PHA.

[0031] More preferably, the PHA comprises a monomer, dimer, or polymer of the monomers constituting the PHA. The monomers constituting the PHA comprise one, two, or more of the following: 2-hydroxypropionic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvalerate, 5-hydroxyvalerate, 3-hydroxyhexanoic acid, 3-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 3-hydroxydecanoic acid, and 3-hydroxydodecanoic acid.

[0032] More preferably, the PHA comprises one, two or more of P(HB-LA), P3HP, PHB, P4HB, PHV, PHO, PHN, PHD, PHBV, P34HB, PHBHHp, PHBHHx, P3HB4HB3HV or P3HB4HB5HV.

[0033] Preferably, the PHA can be chemically synthesized, prepared by bio-fermentation, or purchased.

[0034] In one specific embodiment of the present invention, the PHA is P34HB, wherein the content of 4HB is any value between 15-20 mol%, for example 15, 16, 17, 18, 19 or 20 mol%.

[0035] In one specific embodiment of the present invention, the PHA is PHBHHx, wherein the content of 3HHx is any value of 10-15 mol%, for example 10, 11, 12, 13, 14 or 15 mol%.

[0036] In one specific embodiment of the present invention, the PHA is PHBV, wherein the content of 3HV is any value between 20-25 mol%, for example 20, 21, 22, 23, 24 or 25 mol%.

[0037] In one specific embodiment of the present invention, the substrate is a mixture of PHB and P34HB (4HB content is 20 mol%), and the mass ratio of PHB to P34HB in the substrate is 1:(3-5), for example 1:3, 1:4, 1:5.

[0038] In one specific embodiment of the present invention, the substrate is a mixture of PHB and P34HB (4HB content is 35 mol%), and the mass ratio of PHB to P34HB in the substrate is 1:(1-3), for example 1:1, 1:1.5, 1:2, 1:2.5, 1:3.

[0039] In one specific embodiment of the present invention, the substrate is a mixture of PHB and P34HB (40 mol% of 4HB), and the mass ratio of PHB to P34HB in the substrate is 1:1.

[0040] In one specific embodiment of the present invention, the substrate is a mixture of PHB and PHBV (3HV content is 25 mol%), and the mass ratio of PHB to PHBV in the substrate is 1:(5-10), for example 1:5, 1:6, 1:7, 1:8, 1:9, 1:10.

[0041] In one specific embodiment of the present invention, the substrate is a mixture of PHB and PHBHHx (the content of 3HHx is 30 mol%), and the mass ratio of PHB to PHBHHx in the substrate is 1:(1-3), for example 1:1, 1:1.5, 1:2, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:3.

[0042] Preferably, in the artificial leather, the mass content of the substrate is any value from 50% to 100% (preferably 70% to 100%), such as 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or 100%.

[0043] Preferably, the auxiliary materials include, but are not limited to, one, two or more of fillers, plasticizers and / or dyes.

[0044] Preferably, in the artificial leather, the mass content of the auxiliary material is any value from 0% to 50% (preferably 0.1% to 30%), for example, 0%, 0.1%, 0.5%, 5%, 10%, 11%, 12%, 13%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, and 50%.

[0045] in,

[0046] Preferably, the filler is added at any value between 0% and 50% (preferably 20% to 40%) of the substrate, such as 0%, 2.5%, 5%, 7.5%, 10%, 20%, 30%, 32%, 33%, 34%, 35%, 40%, and 50%.

[0047] Preferably, the filler includes, but is not limited to, one, two or more of the following: wood flour, hydrolyzed gelatin, collagen, hydrolyzed animal protein and / or cellulose acetate butyrate.

[0048] In one specific embodiment of the present invention, the filler is wood powder and collagen, and the mass ratio of wood powder to collagen added is 5:7.

[0049] In one specific embodiment of the present invention, the filler is cellulose acetate butyrate.

[0050] The filler can increase the viscosity of the slurry, reduce the amount of substrate used, thereby reducing costs, or enhance the strength of the leather.

[0051] Preferably, the plasticizer is added at any value from 0% to 50% (preferably 20% to 40%) of the base material, such as 0%, 1%, 1.5%, 2%, 2.5%, 5%, 7.5%, 10%, 20%, 30%, 32%, 33%, 34%, 35%, 40%, or 50%.

[0052] Preferably, the plasticizers include, but are not limited to, castor oil-derived ester plasticizers (e.g., acetylated ricinoleate dimethyl glycerol plasticizers), isosorbide diester plasticizers (e.g., isosorbide dioctyl ester) and / or citrate plasticizers, etc.

[0053] In one specific embodiment of the present invention, the plasticizer is a castor oil-derived ester plasticizer, specifically an acetylated dimethyl ricinoleate type plasticizer.

[0054] In one specific embodiment of the present invention, the plasticizer is an isosorbide diester plasticizer, specifically isosorbide dioctyl ester.

[0055] Preferably, the dye is added at 0%-5% (preferably 0.1%-0.6%) of the substrate, for example, 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.55%, 0.56%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%.

[0056] Preferably, the dyeing agent includes, but is not limited to, one, two or more of the following: phthalocyanine blue, lemon yellow, fast red, iron oxide red, titanium dioxide, lightfast yellow, and iron oxide yellow.

[0057] In one specific embodiment of the present invention, the dye is lemon yellow.

[0058] In one specific embodiment of the present invention, the staining agent is iron oxide red and iron oxide yellow, and the mass ratio of iron oxide red and iron oxide yellow is 1:1.

[0059] Artificial leather made with PHA as the base material is naturally milky white to pale yellow. After adding dyes, it can meet the needs of different colors. Of course, if no dyes are added during the preparation process, it can also be colored by dyeing later.

[0060] Depending on the specific implementation requirements, the artificial leather can be of any shape and thickness.

[0061] In one specific embodiment of the present invention, the raw materials for preparing the artificial leather include PHA and a base fabric. In another specific embodiment of the present invention, the raw materials for preparing the artificial leather include PHA and a foaming agent.

[0062] In one specific embodiment of the present invention, the raw materials for preparing the artificial leather include PHA and anionic surfactants.

[0063] In one specific embodiment of the present invention, the raw materials for preparing the artificial leather include PHA and nonionic surfactants.

[0064] In one specific embodiment of the present invention, the raw materials for preparing the artificial leather include PHA and an inorganic foaming agent.

[0065] In one specific embodiment of the present invention, the raw materials for preparing artificial leather include PHA, anionic surfactants and nonionic surfactants. Preferably, the mass ratio of anionic surfactants and nonionic surfactants in the raw materials for preparing artificial leather is any value in the range of 1:(1-3), such as 1:1, 1:1.5, 1:2, or 1:3.

[0066] In one specific embodiment of the present invention, the raw materials for preparing the artificial leather include PHA, anionic surfactants, and inorganic foaming agents.

[0067] In one specific embodiment of the present invention, the raw materials for preparing the artificial leather include PHA, nonionic surfactant and inorganic foaming agent.

[0068] Preferably, in the raw materials for preparing the artificial leather, the mass ratio of nonionic surfactant to inorganic foaming agent is any value in the range of 1:(1-3), such as 1:1, 1:1.5, 1:2, or 1:3.

[0069] In one specific embodiment of the present invention, the raw materials for preparing the artificial leather include PHA, anionic surfactant, nonionic surfactant, and inorganic foaming agent. Preferably, the mass ratio of the anionic surfactant, nonionic surfactant, and inorganic foaming agent in the raw materials for preparing the artificial leather is any value in the range of 1:(1-5):(1-5), such as 1:1:1, 1:2:2, 1:1:5, or 1:5:5.

[0070] In one specific embodiment of the present invention, the raw materials for preparing the artificial leather include one, two or more of the following: PHA, foaming agent (preferably a surfactant and an inorganic foaming agent, wherein the surfactant is anionic surfactant and / or nonionic surfactant), solvent, filler, dyeing agent, base fabric, and / or plasticizer.

[0071] The artificial leather described in this invention can be prepared using conventional methods in the prior art, such as wet or dry methods.

[0072] Preferably, the artificial leather is obtained by adding a substrate to a good solvent to obtain a slurry, and then allowing the slurry to form a film in a coagulation liquid.

[0073] Preferably, the raw materials added to the good solvent or coagulation liquid also include auxiliary materials.

[0074] Preferably, the good solvent includes, but is not limited to, one, two, or more of the following: chloroform, dichloromethane, trichloroethane, dichloroethane, 1,3-dichloropropane, trichloroethylene, tetrachloroethylene, N,N-dimethylformamide, N,N-dimethylacetamide, D-limonene, dipentene, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, propyl acetate, or n-butyl acetate.

[0075] More preferably, the good solvent includes, but is not limited to, one, two or more of chloroform, dichloromethane, N,N-dimethylformamide and / or dimethyl sulfoxide.

[0076] Preferably, the undesirable solvents include, but are not limited to, one, two, or more of water, ethanol, 1,4-butanediol, acetic acid, and / or glycerol.

[0077] Further preferably, the undesirable solvent includes, but is not limited to, water and / or ethanol (preferably anhydrous ethanol). In one specific embodiment of the present invention, the good solvent is dimethyl sulfoxide, and the undesirable solvent is water.

[0078] In one specific embodiment of the present invention, the good solvent is chloroform, and the bad solvent is anhydrous ethanol.

[0079] In one specific embodiment of the present invention, the good solvent is dichloromethane, and the poor solvent is anhydrous ethanol.

[0080] In one specific embodiment of the present invention, the good solvent is N,N-dimethylformamide, and the bad solvent is water.

[0081] Preferably, the mass ratio of the substrate to the good solvent is any value in the range of 1:(1-20), and more preferably any value in the range of 1:(3-15), such as 1:1, 1:2, 1:3, 1:4, 1:5, 1:5.5, 1:5.6, 1:6, 1:6.25, 1:6.6, 1:6.7, 1:7, 1:8, 1:8.3, 1:8.4, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or 1:20, etc.

[0082] A second aspect of the present invention provides a method for preparing the artificial leather described in the first aspect. Preferably, the artificial leather comprises a substrate and auxiliary materials, the substrate comprising PHA, and the auxiliary materials comprising a foaming agent. Preferably, the auxiliary materials further comprise one, two, or more of fillers, plasticizers, and / or dyes.

[0083] Preferably, the types and amounts of the substrate and auxiliary materials are limited in the same way as in the first aspect of the present invention.

[0084] Preferably, the preparation method includes adding a substrate to a good solvent to obtain a slurry, and then allowing the slurry to form a film in a coagulation liquid to obtain artificial leather.

[0085] Preferably, the raw materials added to the good solvent or coagulation liquid also include auxiliary materials.

[0086] Preferably, the preparation method includes coating a slurry onto a carrier and then immersing the carrier in a coagulation solution to form a film.

[0087] Preferably, the carrier comprises a base fabric, release paper, and / or a petri dish; more preferably, the base fabric comprises one, two, or more of the following: nonwoven fabric, plain woven fabric, single-sided napped fabric, or double-sided napped fabric. Preferably, when the carrier is a base fabric, the step of immersing the base fabric in a poor solvent to increase its humidity is further included before the slurry coating.

[0088] Depending on the specific implementation requirements, the carrier can be of any shape, simple or complex. Preferably, the coagulation liquid contains both good and bad solvents.

[0089] More preferably, the mass ratio of good solvent to bad solvent in the coagulation liquid is (0-1):(1-20), more preferably (0.1-1):(3-10), and even more preferably (0.2-1):(4-10), for example 0.2:10, 0.5:10, 1:10, 1.5:10, 1:4 or 1:5.

[0090] Preferably, the good solvent and the bad solvent are miscible.

[0091] Preferably, the substrate and / or auxiliary materials are soluble in a good solvent, insoluble or slightly soluble in a poor solvent, and the poor solvent can cause the substrate and / or auxiliary materials in the good solvent to precipitate out.

[0092] Preferably, the definition of good solvents and bad solvents is the same as that in the first aspect of the invention.

[0093] Preferably, the preparation method further includes a step of removing a good solvent; more preferably, the removal of a good solvent from the membrane includes rinsing, and more preferably, rinsing with a bad solvent once or multiple times.

[0094] Preferably, the residual amount of good solvent in the artificial leather is no more than 10%, more preferably no more than 5%, and even more preferably no more than 1%.

[0095] Preferably, before adding the raw materials to a good solvent for dissolution, the method further includes a step of drying the substrate and / or auxiliary materials. More preferably, the drying method includes, but is not limited to, vacuum drying, freeze drying, airflow drying, microwave drying, infrared drying, and / or high-frequency drying, etc.

[0096] In one specific embodiment of the present invention, the drying method is vacuum drying.

[0097] Preferably, the vacuum drying temperature is 70–100°C.

[0098] Preferably, the vacuum drying time is 6 to 12 hours.

[0099] Preferably, the moisture content of the substrate and / or auxiliary materials after drying is less than 1%, and more preferably less than 0.5%.

[0100] Preferably, the mass content of the substrate in the slurry is any value from 50% to 100% (preferably 70% to 100%), such as 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or 100%.

[0101] Preferably, the mass content of the auxiliary material in the slurry is any value from 0% to 50% (preferably 0% to 30%), for example, 0%, 5%, 10%, 11%, 12%, 13%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%.

[0102] In one specific embodiment of the present invention, the slurry is composed of a substrate and a good solvent.

[0103] In one specific embodiment of the present invention, the slurry is composed of a substrate, auxiliary materials and a good solvent.

[0104] In one specific embodiment of the present invention, the slurry contains 10-20 parts of substrate (e.g., 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20) and 100 parts of good solvent.

[0105] In one specific embodiment of the present invention, the slurry contains any number of 10-20 parts of substrate, such as 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 parts; any number of 0.1-5 parts of auxiliary materials, such as 0.1, 0.35, 0.5, 1, 1.05, 1.35, 1.5, 2, 2.09, 2.5, 3, 3.5, 4, 4.5 or 5 parts; and 100 parts of good solvent.

[0106] In one specific embodiment of the present invention, the preparation method includes:

[0107] S1: The raw materials (substrate and / or auxiliary materials) are vacuum dried at 70-100℃ for 6-12 hours to control the moisture content to below 0.5%;

[0108] S2: Add the dried substrate to the good solution, heat and stir at 40-100℃ for 0.2-2 hours to dissolve and obtain a slurry; or,

[0109] The dried substrate and auxiliary materials are added to a good solution and heated and stirred at 40-100℃ for 0.2-2 hours to obtain a slurry; or,

[0110] S3: Prepare a coagulation solution by mixing a good solvent and a poor solvent, wherein the mass ratio of the good solvent to the poor solvent in the coagulation solution is (0-1):(1-20), more preferably (0.1-1):(3-10), and preferably further includes cooling the coagulation solution to room temperature; even more preferably, the coagulation solution also contains auxiliary materials;

[0111] S4: Coat the slurry onto the carrier, immerse the slurry-coated carrier in the coagulation liquid to form a film, and the coagulation time is 20-50 min (preferably 30 min);

[0112] S5: Rinse, dry or freeze-dry;

[0113] Preferably, if the carrier is a base fabric, the step of immersing the base fabric in a poor solvent to increase the humidity of the base fabric is included before the slurry coating.

[0114] Preferably, the rinsing is one or more rinses with a poor solvent.

[0115] Preferably, when the foaming agent in the auxiliary material is an inorganic foaming agent (e.g., carbonate, sodium silicate, silicon carbide, sodium chloride and / or carbon black), step S2 may further include:

[0116] The dried substrate and / or auxiliary materials are added to a good solution and heated and stirred at 40-100°C for 0.2-2 hours. Then an inorganic foaming agent (e.g., carbonate, sodium silicate, silicon carbide, sodium chloride and / or carbon black) is added and heated at 40-50°C (preferably 45°C) for 1-5 minutes (preferably 3 minutes) to obtain a slurry.

[0117] A third aspect of the present invention provides an artificial leather obtained by the above preparation method, or an application of the above artificial leather.

[0118] The applications include, but are not limited to, manufacturing leather products, simulated skin, or antibacterial wound dressings. Preferably, the leather products include, but are not limited to, leather shoes, leather clothing, etc.

[0119] The advantages of this invention include, but are not limited to:

[0120] First, the artificial leather described in this invention uses PHA, which has a greater "carbon-neutral" effect than traditional synthetic fibers, as its main raw material. It eliminates the use of synthetic fibers and avoids animal welfare issues. The production process of its raw materials is very environmentally friendly, and the finished product is completely biodegradable. This reduces dependence on petroleum and does not cause a net increase in atmospheric CO2, as many microorganisms in nature can hydrolyze it.

[0121] Second: The artificial leather preparation method described in this invention is flexible and versatile, and leather can be formed on various surfaces, such as traditional leather on a base fabric, pure leather that is easy to tear and transfer on release paper or petri dishes, or even coated on complex surfaces (such as spherical, polygonal, and rugged surfaces) to form leather that perfectly fits the complex surface.

[0122] Third: The artificial leather described in this invention has good post-dyeing performance, and dyeing agents can also be added during the preparation process to prepare the desired color.

[0123] Fourth: The artificial leather prepared by this invention has antibacterial properties, and its loose and porous structure is also conducive to breathability and keeping dry. In addition, it has a smooth feel and good skin-friendliness.

[0124] Fifth: The artificial leather described in this invention can not only be used to manufacture leather products such as leather shoes and leather clothing, but also be applied in new application fields such as the preparation of simulated skin and antibacterial wound dressings.

[0125] Sixth: The artificial leather preparation method described in this invention requires preparing a coagulation solution by mixing a good solvent and a bad solvent in a specific ratio in order to obtain ideal dense and elastic artificial leather.

[0126] The mass ratio of good solvent to bad solvent in the coagulation liquid is (0-1):(1-20), more preferably (0.1-1):(3-10). If the content of good solvent is too high, it will greatly slow down the coagulation speed and increase the content of PHA dissolved in the water, wasting PHA substrate. The resulting artificial leather will be loose, inelastic, and have low strength. If the content of good solvent is too low, it will not only increase the cost of recycling the good solvent but also increase the shrinkage rate of the artificial leather surface, making the surface uneven, denser and less elastic, thinner, and causing edge curling. This is because the good solvent will rapidly migrate into the bad solvent, while the bad solvent has difficulty penetrating into the material layer. The convection between the good and bad solvents is not uniformly balanced, so during the coagulation process of the slurry, the artificial leather will shrink to a certain extent, making the coating thinner and causing a certain degree of edge curling.

[0127] To prevent curling and uneven surfaces, and to ensure that artificial leather maintains both elasticity and stiffness, it is necessary to control the concentration of the good solvent in the coagulation tank. This achieves a foaming-like effect through the dynamic convection balance between the good and bad solvents in the substrate. Furthermore, surfactants, chemical foaming agents, and / or physical foaming agents must be added during formulation to enhance and synergistically reinforce this effect. Surfactants enhance the penetration of both good and bad solvents into the substrate, opening and accelerating the convection channels and speeds of both solvents in the slurry system. Chemical or physical foaming agents can further refine the pores and improve the uniformity of the internal porous structure.

[0128] The term "slightly soluble" as used in this invention refers to the ability to dissolve 0.01g-1g of solute in 100g of solution at a certain temperature (e.g., 20°C).

[0129] The terms “comprising” or “including” in this invention are open-ended descriptions that include the specified ingredients or steps described, as well as other specified ingredients or steps that do not materially affect them.

[0130] The term "and / or" as used in this invention encompasses all combinations of items connected by the term, and should be considered as if each combination had been individually listed herein. For example, "A and / or B" includes "A", "A and B", and "B". As another example, "A, B and / or C" includes "A", "B", "C", "A and B", "A and C", "B and C", and "A and B and C".

[0131] The English abbreviation and the full Chinese name of this application are shown in Table 1.

[0132] Table 1: Comparison of English Abbreviations and Full Chinese Names

[0133] Attached image description:

[0134] Figure 1 A comparative illustration of traditional synthetic leather and synthetic leather with complex shapes. Detailed Implementation

[0135] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the present invention will be described in more detail below through specific embodiments and comparative examples, but the present invention is by no means limited to these examples. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0136] It should be noted that, unless otherwise specified, the parts and percentages mentioned below are based on quality.

[0137] Some of the materials used in the examples are from:

[0138] Rapid penetrants T-70, JFC-EP, JFC-1, JFC-2, and JFC-E were purchased from Haian Petrochemical Plant in Jiangsu Province; C-70 and C-90 were purchased from Zhangjiagang Free Trade Zone Kaimirui International Trade Co., Ltd.

[0139] S-80, AEO-3, AEO-4, AEO-5, AEO-7: purchased from Guangzhou Taili Chemical Co., Ltd.

[0140] Wood powder: purchased from Lingshou County Jia'ao Mineral Products Co., Ltd.; item number: porosity 0.01;

[0141] Collagen: Purchased from Hongjiu Native Peptide (Shanxi) Co., Ltd.;

[0142] Cellulose acetate butyrate: purchased from Eastman Chemical Company, USA; Product No.: CAB 381-0.2;

[0143] The various PHAs used in this invention are sourced from Beijing Microstructure Workshop Biotechnology Co., Ltd.

[0144] Evaluation criteria for the tests used in the examples

[0145] (1) Touch sensation: Two groups of people were selected as subjects using the subjective evaluation method.

[0146] A panel of 10 experts or experienced participants, weighted at 1, was formed. They were familiar with the scales and descriptive terms used in subjective testing, understood the human sensations corresponding to each level of the terminology, and were able to quickly and accurately assess and quantify the performance of artificial leather.

[0147] Another group consisted of 10 consumers with minimal training, weighted at 0.5. Prior to the experiment, these participants received instruction on the properties of synthetic leather and the terminology used in evaluation metrics to ensure accurate assessments of its performance and the rigor of the results.

[0148] Experimental conditions: temperature 20℃±2℃, relative humidity 65%±2%, wind speed ≤0.1m / s.

[0149] The tactile evaluation scale and descriptive terms are shown in Table 2, so the closer the score is to 3, the better.

[0150] Table 2: Subjective Evaluation Scale for Tactile Feel

[0151]

[0152] (2) Strength: It is evaluated by "tensile load", and the method refers to the standard GB / T 8948-2008 "Polyvinyl Chloride Artificial Leather".

[0153] (3) Viscosity (mPa·s): The viscosity was tested using an NDJ-1 rotational viscometer. At 25°C, with rotor No. 1 and 12 rpm, the leather quality was better when the viscosity was 150-500 mPa·s.

[0154] Example 1: A method for preparing artificial leather using P34HB as a substrate

[0155] P34HB (with a 4HB content of 16 mol%) was vacuum dried at 70–100 °C for 6–12 h to control the moisture content to below 0.5%.

[0156] Weigh 10 parts of dried P34HB and add them to 100 parts of DMSO. Heat and stir at 40-100℃ for 0.2-2 hours to fully dissolve P34HB and obtain solution L2, which is a DMSO solution of P34HB. Cool solution L2 to room temperature.

[0157] A coagulation solution was prepared by mixing DMSO and water at a mass ratio of 1:10, with 0.1 wt% C-70 and 0.15 wt% S-80 added to the water.

[0158] Solution L2 was evenly coated onto a glass petri dish using a brush or scraper. The coated petri dish was then immersed in a coagulation bath containing a coagulation solution at room temperature for 30 minutes. After coagulation, the petri dish was washed multiple times to ensure that the residual DMSO content did not exceed 1%. After washing, the petri dish was dried at 60°C for 24 hours to obtain the artificial leather.

[0159] Example 2: A method for preparing artificial leather using PHBHHx as a substrate

[0160] PHBHHx (of which the content of 3HHx is 12 mol%) is vacuum dried at 70-100℃ for 6-12 hours to control the moisture content to below 0.5%;

[0161] Weigh 12 parts of dried PHBHHx and 0.1 parts of C-90, 0.1 parts of JFC-2, and 0.3 parts of acetylated ricinoleic acid dimethyl ester plasticizer and add them to 100 parts of DMSO. Heat and stir at 40-100℃ for 0.2-2 hours to fully dissolve PHBHHx and the excipients, and obtain solution L2, which is the DMSO solution of PHBHHx. Cool solution L2 to room temperature.

[0162] Prepare a coagulation solution by mixing DMSO and water at a mass ratio of 0.5:10.

[0163] Apply solution L2 evenly to the bottom of a glass petri dish using a brush or scraper. Immerse the petri dish coated with solution L2 into a coagulation bath containing a coagulation solution for 30 minutes. The coagulation solution should be at room temperature.

[0164] After solidification, the material undergoes multiple washes to ensure that the residual DMSO content does not exceed 1%. After washing, it is dried at 60℃ for 24 hours to obtain artificial leather.

[0165] Example 3: A method for preparing artificial leather using PHBV as a substrate

[0166] PHBV (with a 3HV content of 22 mol%) was vacuum dried at 70–100 °C for 6–12 h to control the moisture content to below 0.5%.

[0167] Weigh 16 parts of dried PHBV, 0.15 parts of JFC-E, 0.5 parts of wood powder, and 0.7 parts of collagen, add them to 100 parts of chloroform, heat and stir at 40-100℃ for 0.2-2 hours to fully dissolve PHBV and excipients, and obtain solution L2, which is the chloroform solution of PHBV. Cool solution L2 to room temperature.

[0168] Chloroform and anhydrous ethanol were mixed in a mass ratio of 1.5:10 to prepare a coagulating solution.

[0169] Solution L2 was evenly coated onto the bottom of a glass petri dish using a brush or scraper. The coated petri dish was then immersed in a coagulation bath containing a coagulation solution at room temperature for 30 minutes. After coagulation, the petri dish was washed multiple times with ethanol to ensure that the residual chloroform content did not exceed 1%. The petri dish was then freeze-dried for 24 hours to obtain artificial leather.

[0170] Example 4: A method for preparing artificial leather using PHB and P34HB as substrates

[0171] The PHA mixture with a mass ratio of PHB:P34HB (where the content of 4HB is 20 mol%) of 2:8 was vacuum dried at 70-100℃ for 6-12 hours to control the moisture content to below 0.5%.

[0172] Weigh 15 parts of dried PHA mixed raw materials and 0.1 parts of C-70, 0.2 parts of AEO-3, and 0.2 parts of sodium bicarbonate, add them to 100 parts of dichloromethane, heat and stir at 40-100℃ for 0.2-2 hours to fully dissolve the PHA mixed raw materials and excipients, and obtain solution L2, which is the dichloromethane solution of PHA mixed raw materials. Cool solution L2 to room temperature.

[0173] Dichloromethane and anhydrous ethanol were mixed at a mass ratio of 0.2:10 to prepare a coagulated solution.

[0174] Solution L2 was evenly coated onto the bottom of a glass petri dish using a brush or scraper. The coated glass petri dish was then immersed in a coagulation bath containing a coagulation solution at room temperature for 30 minutes. After coagulation, the petri dish was washed multiple times with ethanol to ensure that the residual dichloromethane content did not exceed 1%, and then dried at 60°C for 24 hours to obtain artificial leather.

[0175] Example 5: A method for preparing artificial leather using PHB and P34HB as substrates

[0176] The PHA mixture with a mass ratio of PHB:P34HB (of which the content of 4HB is 35 mol%) of 4:6 was vacuum dried at 70-100℃ for 6-12 hours to control the moisture content to below 0.5%.

[0177] Weigh 20 parts of dried PHA mixed raw materials and 0.25 parts of sodium carbonate, 0.5 parts of cellulose acetate butyrate, and 0.3 parts of isosorbide dioctyl ester, add them to 100 parts of DMSO, heat and stir at 40-100℃ for 0.2-2 hours to fully dissolve the PHA mixed raw materials and excipients, and obtain solution L2, which is the DMSO solution of PHA mixed raw materials. Cool solution L2 to room temperature.

[0178] Prepare a coagulation solution by mixing DMSO and water at a mass ratio of 1:10.

[0179] Solution L2 was evenly coated onto the bottom of a glass petri dish using a brush or scraper. The coated petri dish was then immersed in a coagulation bath containing a coagulation solution at room temperature for 30 minutes. After coagulation, the petri dish was washed multiple times to ensure that the residual DMSO content did not exceed 1%. After washing, the petri dish was dried at 60°C for 24 hours to obtain the artificial leather.

[0180] Example 6: A method for preparing artificial leather using PHB and PHBV as substrates

[0181] The PHA mixture with a PHB:PHBV (of which the 3HV content is 25 mol%) mass ratio of 1:9 was vacuum dried at 70-100℃ for 6-12 hours to control the moisture content to below 0.5%.

[0182] Weigh 18 parts of dried PHA mixed raw materials, 0.1 parts of JFC-1, 0.15 parts of sodium silicate, and 0.1 parts of lemon yellow, add them to 100 parts of DMSO, heat and stir at 40-100℃ for 0.2-2 hours to fully dissolve the PHA mixed raw materials and excipients, and obtain solution L2, which is the DMSO solution of PHA mixed raw materials. Cool solution L2 to room temperature.

[0183] Prepare a coagulation solution by mixing DMSO and water at a mass ratio of 1:10. Apply solution L2 evenly to the bottom of a glass petri dish using a brush or scraper. Immerse the coated glass petri dish in a coagulation bath containing the coagulation solution for 30 minutes. The coagulation solution is kept at room temperature.

[0184] After solidification, the material undergoes multiple washes to ensure that the residual DMSO content does not exceed 1%. After washing, it is dried at 60℃ for 24 hours to obtain artificial leather.

[0185] Example 7: A method for preparing artificial leather using PHB and PHBHHx as substrates

[0186] The PHA mixture with a mass ratio of PHB:PHBHHx (of which the content of 3HHx is 30 mol%) of 3:7 was vacuum dried at 70-100℃ for 6-12 hours to control the moisture content to below 0.5%.

[0187] Weigh 20 parts of dried PHA mixed raw material and add it to 100 parts of N,N-dimethylformamide (DMF). Heat and stir at 40-100℃ for 0.2-2 hours to fully dissolve the PHA mixed raw material. Then add 5 parts of ammonium bicarbonate and heat at 45℃ for 3 minutes to obtain DMF solution L2 of PHA mixed raw material. Cool solution L2 to room temperature.

[0188] DMF and water were mixed in a mass ratio of 1:5 to prepare a coagulation solution.

[0189] After thoroughly wetting the base fabric with water, remove it and squeeze out the water. Then, scald the base fabric until it is semi-dry. Apply solution L2 evenly to the base fabric using a brush or scraper. Immerse the coated base fabric in a coagulation tank containing a coagulation solution for 30 minutes. The temperature of the coagulation solution is room temperature.

[0190] After solidification, the material undergoes multiple washes to ensure that the residual DMF content does not exceed 1%. After washing, it is dried at 60℃ for 24 hours to obtain artificial leather.

[0191] Example 8: A method for preparing artificial leather using PHB and P34HB as substrates

[0192] The PHA mixture with a mass ratio of PHB:P34HB (of which the content of 4HB is 40 mol%) of 5:5 was vacuum dried at 70-100℃ for 6-12 hours to control the moisture content to below 0.5%.

[0193] Weigh 100 parts of N,N-dimethylformamide (DMF) by mass, add 1 part of rapid penetration agent T-70 and 1 part of JFC-EP, stir thoroughly for 30 minutes to obtain solution L1.

[0194] Weigh 18 parts of dried PHA mixed raw material, 0.045 parts of iron oxide red, and 0.045 parts of iron oxide yellow, add them to solution L1, heat and stir at 40-100℃ for 0.2-2 hours to fully dissolve the PHA mixed raw material, and obtain solution L2. Cool solution L2 to room temperature.

[0195] DMF and water were mixed in a mass ratio of 1:4 to prepare a coagulation solution.

[0196] After thoroughly wetting the base fabric with water, remove it and squeeze out the water. Then, scald the base fabric until it is semi-dry. Apply solution L2 evenly to the base fabric using a brush or scraper. Immerse the coated base fabric in a coagulation tank containing a coagulation solution for 30 minutes. The temperature of the coagulation solution is room temperature.

[0197] After solidification, the material undergoes multiple washes to ensure that the residual DMF content does not exceed 1%. After washing, it is dried at 60℃ for 24 hours to obtain artificial leather.

[0198] Comparative Example 1: A method for preparing artificial leather using P34HB as a substrate

[0199] Compared to Example 1, DMSO was replaced with chloroform. Since water was used as the unsuitable solvent in Example 1, and chloroform and water are immiscible, the condition that a good solvent (chloroform) and an unsuitable solvent (water) must be miscible was not met, and therefore artificial leather could not be formed.

[0200] Comparative Example 2: A method for preparing artificial leather using PHB and P34HB as substrates. Compared to Example 5, the proportion of PHA mixed raw materials was reduced from 15 parts to 5 parts. Due to the low PHA content, the viscosity of the PHA DMSO solution was low, only 87 mPa·s, resulting in poor leveling properties during coating and easy formation of defects during curing. The resulting artificial leather had rough edges, could not maintain its complete shape, and was of poor quality.

[0201] Comparative Example 3: A method for preparing artificial leather using PHB and P34HB as substrates. Compared to Example 8, after coagulation, the washing was insufficient, and the residual DMF content exceeded 10%. After washing, the artificial leather was dried at 60°C for 24 hours. In Comparative Example 3, because the residual DMF exceeded 10%, the DMF had a corrosive effect on the artificial leather during the drying process, resulting in low leather strength.

[0202] Comparative Example 4: A method for preparing artificial leather using PHB and P34HB as substrates, compared to Example 4, does not add any foaming agents such as C-70, AEO-3, or sodium bicarbonate. The resulting artificial leather has a harder surface and poor overall molding effect. Although it has fewer internal pores, it is very soft due to the large amount of residual solvent, and is difficult to wash due to surface hardening, resulting in low strength and poor uniformity of the artificial leather.

[0203] Comparative Example 5: A method for preparing artificial leather using PHBHHx as a base material, compared to Example 2, does not add any foaming agents such as C-90 or JFC-2. The resulting artificial leather has a harder surface and poor overall molding effect. Although the internal pores are few, it is very soft due to the large amount of residual solvent, and is difficult to wash due to surface hardening, resulting in low strength and poor uniformity of the artificial leather.

[0204] Comparative Example 6: A method for preparing artificial leather using PHB and PHBHHx as base materials, compared to Example 7, does not add any foaming agents such as ammonium bicarbonate. The resulting artificial leather has a harder surface and poor overall molding effect. Although there are not many internal pores, it is very soft due to the large amount of residual solvent, and is difficult to wash due to the relative hardening of the surface, resulting in low strength and poor uniformity of the artificial leather.

[0205] Comparative Example 7: A method for preparing artificial leather using PHB and P34HB as substrates. Compared to Example 5, the proportion of PHA mixed raw materials was increased from 15 parts to 40 parts. Due to the high PHA content, the DMSO solution of PHA has a high viscosity, reaching 762 mPa·s. This results in poor leveling properties during coating, a slow curing process, and, because the poor solvent and the good solvent cannot penetrate each other, a large amount of residual solvent remains inside the artificial leather, making it softer. The surface is relatively hardened, curls at the edges, and has low strength and poor uniformity.

[0206] Comparative Example 8: A method for preparing artificial leather using PHB and PHBV as substrates. Compared with Example 6, the coagulation solution is prepared with DMSO and water in a mass ratio of 3:7. Due to the excessively high content of good solvents, a long coagulation time is required, and the content of PHA dissolved in the water increases, resulting in waste of substrates and low strength of the obtained artificial leather.

[0207] Comparative Example 9: A method for preparing artificial leather using PHB and PHBV as substrates. Compared with Example 6, the coagulating liquid is water. The resulting artificial leather has a larger surface shrinkage rate, an uneven surface, and becomes denser and less elastic. Therefore, the coating becomes thinner and causes curling.

[0208] Comparative Example 10: A method for preparing artificial leather using PHB and P34HB as substrates. Compared with Example 4, this method employs conventional techniques, uniformly coating solution L2 onto the bottom of a glass petri dish using a brush or scraper. The coated glass petri dish is then placed in a foaming oven and foamed at 60°C for 1 hour, followed by drying at 60°C in a vacuum drying oven for 24 hours, ensuring that the residual dichloromethane content does not exceed 1%, thus obtaining the artificial leather.

[0209] The resulting artificial leather had large surface pores, was uneven, had inconsistent foaming, and low strength. Test results for each embodiment and control example are shown in Tables 3 and 4.

[0210] Table 3

[0211]

[0212] Table 4

[0213]

[0214]

[0215] Furthermore, the results show that the artificial leather manufactured using PHA homopolymers, copolymers, polymers, or mixtures thereof as a base material according to the present invention can be formed by coating a base fabric with PHA slurry using conventional methods to form conventional artificial leather; it can also be formed in the absence of a base fabric or a spherical base, such as with a complex-shaped base (e.g., spherical, polygonal, or rugged surfaces) to form artificial leather with complex shapes (see the schematic diagram comparing conventional artificial leather and complex-shaped artificial leather). Figure 1 ).

Claims

1. A type of artificial leather, characterized in that, The artificial leather comprises a base material and auxiliary materials, wherein the base material comprises PHA and the auxiliary materials comprise a foaming agent; The artificial leather is obtained by adding the substrate to the good solvent at a mass ratio of substrate to good solvent of 1:(3-15) to obtain a slurry, then allowing the slurry to form a film in a coagulation liquid, removing the good solvent from the film, and obtaining the artificial leather. The coagulation solution contains a good solvent and a poor solvent, and the mass ratio of the good solvent to the poor solvent in the coagulation solution is (0.1-1):(3-10). Raw materials added to good solvents and / or coagulation solutions also include auxiliary materials; The good solvent and the bad solvent are miscible. The substrate and auxiliary materials are soluble in the good solvent and insoluble or slightly soluble in the bad solvent. The bad solvent can cause the substrate and auxiliary materials in the good solvent to precipitate out.

2. The artificial leather according to claim 1, characterized in that, The PHA comprises homopolymers or copolymers of the monomers that make up the PHA.

3. The artificial leather according to claim 2, characterized in that, The monomers constituting PHA include one or more of the following: 2-hydroxypropionic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvalerate, 5-hydroxyvalerate, 3-hydroxyhexanoic acid, 3-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 3-hydroxydecanoic acid, and 3-hydroxydodecanoic acid.

4. The artificial leather according to claim 1, characterized in that, The PHA includes one or more of P(HB-LA), P3HP, PHB, P4HB, PHV, PHO, PHN, PHD, PHBV, P34HB, PHBHHp, PHBHHx, P3HB4HB3HV, or P3HB4HB5HV.

5. The artificial leather according to claim 1, characterized in that, The mass ratio of good solvent to bad solvent in the coagulation liquid is (0.2-1):(4-10).

6. The artificial leather according to claim 1, characterized in that, The foaming agent includes surfactants, chemical foaming agents, and / or physical foaming agents.

7. The artificial leather according to claim 6, characterized in that, The surfactants mentioned include anionic surfactants and / or nonionic surfactants.

8. The artificial leather according to claim 7, characterized in that, The anionic surfactant comprises one or more of C-70, C-90, rapid penetrant T-70, JFC-EP, alkali-resistant penetrant AEP, or alkali-resistant penetrant OEP-70.

9. The artificial leather according to claim 7, characterized in that, The nonionic surfactant comprises one or more of S-80, AEO-3, AEO-4, AEO-5, AEO-7, JFC-1, JFC-2 or JFC-E.

10. The artificial leather according to claim 6, characterized in that, The chemical foaming agent includes inorganic foaming agents and organic foaming agents.

11. The artificial leather according to claim 10, characterized in that, The inorganic foaming agent comprises carbonate, sodium silicate, and / or silicon carbide.

12. The artificial leather according to claim 11, characterized in that, The carbonate comprises one or more of calcium carbonate, magnesium carbonate, ammonium bicarbonate, sodium carbonate, or sodium bicarbonate.

13. The artificial leather according to claim 1, characterized in that, The auxiliary materials also include one or more of fillers, plasticizers, or dyes.

14. The artificial leather according to claim 13, characterized in that, The filler comprises one or more of the following: wood powder, hydrolyzed gelatin, collagen, hydrolyzed animal protein, or cellulose acetate butyrate.

15. The artificial leather according to claim 13, characterized in that, The plasticizer comprises one or more of castor oil-derived ester plasticizers, isosorbide diester plasticizers, or citrate ester plasticizers.

16. The artificial leather according to claim 13, characterized in that, The dyeing agent comprises one or more of the following: phthalocyanine blue, lemon yellow, fast red, iron oxide red, titanium dioxide, lightfast yellow, or iron oxide yellow.

17. A method for preparing artificial leather according to any one of claims 1-16, characterized in that, The artificial leather comprises a base material and auxiliary materials, wherein the base material comprises PHA and the auxiliary materials comprise a foaming agent; The preparation method includes adding a substrate to a good solvent to obtain a slurry, and then allowing the slurry to form a film in a coagulation liquid to obtain artificial leather; the raw materials added to the good solvent and / or coagulation liquid also include auxiliary materials.

18. The preparation method according to claim 17, characterized in that, The good solvent comprises one or more of chloroform, dichloromethane, trichloroethane, dichloroethane, 1,3-dichloropropane, trichloroethylene, tetrachloroethylene, N,N-dimethylformamide, N,N-dimethylacetamide, D-limonene, dipentene, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, propyl acetate, or n-butyl acetate.

19. The preparation method according to claim 17, characterized in that, The undesirable solvents include one or more of water, ethanol, 1,4-butanediol, acetic acid, or glycerol.

20. The preparation method according to claim 17, characterized in that, The preparation method includes coating a slurry onto a carrier and then immersing the carrier in a coagulation solution to form a film.

21. The preparation method according to claim 20, characterized in that, The carrier comprises a base fabric, release paper, and / or a petri dish.

22. The preparation method according to claim 21, characterized in that, The base fabric includes one or more of the following: nonwoven fabric, plain woven fabric, single-sided napped fabric, or double-sided napped fabric.

23. The preparation method according to claim 17, characterized in that, The good solvent for removing the membrane is obtained by rinsing with a bad solvent once or multiple times.

24. The preparation method according to claim 17, characterized in that, The residual amount of good solvent in the artificial leather shall not exceed 10%.

25. The application of the artificial leather according to any one of claims 1-16 and / or the artificial leather prepared by the preparation method according to any one of claims 17-24, characterized in that, The applications include those used in the manufacture of leather products, artificial skin, or antibacterial wound dressings.

26. The application according to claim 25, characterized in that, The leather products mentioned include leather shoes and leather clothing.

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