CN115162013A - Biodegradable TPU synthetic leather and preparation method thereof - Google Patents

Biodegradable TPU synthetic leather and preparation method thereof Download PDF

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Publication number
CN115162013A
CN115162013A CN202210662329.9A CN202210662329A CN115162013A CN 115162013 A CN115162013 A CN 115162013A CN 202210662329 A CN202210662329 A CN 202210662329A CN 115162013 A CN115162013 A CN 115162013A
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CN
China
Prior art keywords
synthetic leather
tpu
biodegradable
polypropylene carbonate
coating
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Pending
Application number
CN202210662329.9A
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Chinese (zh)
Inventor
孙哲
董伊航
张克勤
周宁
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Suzhou Kaien Carbon Neutral Technology Co ltd
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Suzhou Kaien Carbon Neutral Technology Co ltd
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Priority to CN202210662329.9A priority Critical patent/CN115162013A/en
Publication of CN115162013A publication Critical patent/CN115162013A/en
Pending legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0036—Polyester fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

Abstract

The invention belongs to the technical field of synthetic leather, and particularly relates to biodegradable TPU synthetic leather and a preparation method thereof. The invention utilizes biodegradable polypropylene carbonate-based thermoplastic polyurethane elastomer, polylactic acid and poly adipic acid/butylene terephthalate-based non-woven fabrics as the surface layer and the base material respectively to manufacture the synthetic leather, thereby realizing the integral biodegradation and ecological sustainability of the synthetic leather; meanwhile, the preparation of the polypropylene carbonate is derived from industrial waste gas carbon dioxide, the preparation of the synthetic leather realizes the reutilization of waste resources, reduces the carbon emission, is natural and natural, and realizes the industrial sustainable development from the source.

Description

Biodegradable TPU synthetic leather and preparation method thereof
Technical Field
The invention belongs to the technical field of synthetic leather, and particularly relates to biodegradable TPU synthetic leather and a preparation method thereof.
Background
Polyurethanes are polar polymeric materials containing repeating urethane structures that are formed by polyaddition reactions of polyisocyanates and polyols. The polyurethane resin can be regarded as a block copolymer in which soft and hard segments are alternately connected to each other. The soft segment determines the elongation at break, elasticity, etc. of the resin, while the hard segment determines the strength, heat resistance, etc. of the resin, and generally contains groups such as ester bond, ether bond, urea bond, urethane bond, and aromatic ring in the molecular chain. Because of its special structure, polyurethane has many excellent properties, such as good mechanical properties, adhesion, wide adjustable range of hardness and softness, etc., and has been widely used as a main coating material in synthetic leather manufacture for a long time.
At present, solvent type polyurethane is mostly adopted as a coating material in the production of domestic polyurethane synthetic leather. However, due to the use of a large amount of organic solvents, such as N, N-dimethylformamide, toluene, etc., on the one hand, serious environmental pollution and resource waste are caused; on the other hand, the organic solvent is flammable and explosive, has a strong smell and a high toxicity, seriously harms the physical and mental health of workers, and the residual volatile organic matters in the finished leather reaches more than 1000mg/kg, which threatens the physical and mental health of consumers, so that the requirement of domestic and foreign markets on the ecological environmental protection property of the synthetic leather can not be met gradually. With the continuous development and promotion of synthetic leather cleaning production technology, the coating material for polyurethane synthetic leather begins to develop towards environmental-friendly waterborne polyurethane, solvent-free bi-component polyurethane, thermoplastic polyurethane elastomer (TPU) and the like.
Patent CN 107083690B discloses a high-performance TPU superfine fiber synthetic leather and a clean production method thereof, dipping a superfine fiber synthetic leather base cloth in a dipping tank filled with kneading liquid, and then entering a continuous type kneading machine to obtain a kneaded base cloth; a calendering production line is adopted, the calendered materials are put into a high-speed kneading machine to be stirred, and then the materials are banburied, plasticated and calendered and then are attached to release paper to obtain a release paper composite TPU film; and (3) adopting a synthetic leather dry production line provided with PUR (polyurethane) blade coating equipment, coating the PUR on a release paper composite TPU film by blade coating, then attaching the release paper to the kneaded base cloth, and stripping the release paper. The invention adopts a kneading technology to greatly improve the flexibility, air permeability and water vapor permeability of the base fabric of the superfine fiber synthetic leather, and then adopts a release paper transfer coating and reactive polyurethane hot melt adhesive blade coating composite technology to compound the thermoplastic polyurethane calendered film on the base fabric of the superfine fiber synthetic leather, thereby obtaining the TPU superfine fiber synthetic leather with soft hand feeling and good mechanical property and service performance.
The above patent does not have biodegradability, and the synthetic leather manufacturing process is loaded down with trivial details moreover, adopts the transfer coating method to make TPU synthetic leather, consumes from type paper.
Disclosure of Invention
The invention provides a preparation method of biodegradable TPU synthetic leather, which comprises the following steps:
s1: mixing the polypropylene carbonate-based TPU, the toner and the antioxidant, and banburying to obtain a TPU molten coating;
s2: coating the TPU molten coating on the surface of a textile substrate to obtain a TPU synthetic leather semi-finished product;
s3: and (3) carrying out line absorption treatment on the surface of the TPU synthetic leather semi-finished product, and cooling to obtain the biodegradable TPU synthetic leather.
Preferably, the mass ratio of the toner to the polypropylene carbonate-based TPU is 3-6:100.
preferably, the mass ratio of the antioxidant to the polypropylene carbonate-based TPU is 0.1-0.2:100.
preferably, in the step S1, a single-screw casting machine is adopted for mixing, the feeding temperature is 90-110 ℃, and the melting temperature is 130-150 ℃.
Preferably, in the step S2, the coating method is a casting method, and the die temperature is 170 to 200 ℃.
Preferably, in the step S2, the thickness of the coating is 0.8 to 1.2mm.
Preferably, in the step S3, the temperature of the texture adsorption treatment is 80-100 ℃ and the time is 8-15S.
Preferably, the content of the polypropylene carbonate in the polypropylene carbonate-based TPU is 40 to 60wt%.
Preferably, the antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite and/or pentaerythritol phosphite.
Preferably, the textile substrate is a polylactic acid non-woven fabric or a polybutylene adipate/terephthalate non-woven fabric.
The invention also provides the biodegradable TPU synthetic leather prepared by the preparation method.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The invention utilizes biodegradable polypropylene carbonate-based thermoplastic polyurethane elastomer, polylactic acid (PLA) and poly adipic acid/butylene terephthalate (PBAT) based non-woven fabrics as the surface layer and the base material respectively to manufacture the synthetic leather, thereby realizing the integral biodegradation and ecological sustainability of the synthetic leather; meanwhile, the preparation of the polypropylene carbonate is derived from industrial waste gas carbon dioxide, the preparation of the synthetic leather realizes the reutilization of waste resources, reduces the carbon emission, is natural and natural, and realizes the industrial sustainable development from the source.
(2) The invention adopts the direct coating process, effectively shortens the manufacturing flow of the synthetic leather, improves the production efficiency and greatly saves the release paper resource.
(3) The synthetic leather manufactured by the invention does not need any organic solvent in the whole process, and the final product meets the requirements of green and environmental protection.
Detailed Description
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.
Example 1
A manufacturing method of biodegradable TPU synthetic leather comprises the following steps:
(1) The preparation method comprises the steps of putting 100 parts by weight of aliphatic TPU with the content of polypropylene carbonate of 40wt%, 3.0 parts by weight of toner and 0.1 part by weight of pentaerythritol phosphite into a single-screw casting machine, controlling the temperature of a charging section charging barrel to be 90 ℃ and the temperature of a melting section charging barrel to be 130 ℃, banburying, mixing, then directly coating the TPU on the surface of PLA non-woven fabric by casting equipment, controlling the temperature of a casting die head to be 170 ℃, and controlling the thickness of a coating film to be 0.8mm, and cooling to obtain a TPU synthetic leather semi-finished product.
(2) Coating line absorption and surface treatment: and (3) carrying out grain absorption treatment on the surface of the coating through a vacuum grain absorption machine, enriching the design and color variety of the synthetic leather, carrying out grain absorption temperature of 80 ℃ for 8s, cooling, and carrying out surface treatment to obtain a biodegradable TPU synthetic leather finished product.
The biodegradable TPU synthetic leather manufactured by the technology has excellent biodegradability, the biodegradation degree reaches 92% in 21 days, and the biodegradable TPU synthetic leather has good hydrolysis resistance, wear resistance and flame retardance.
Example 2
A manufacturing method of biodegradable TPU synthetic leather comprises the following steps:
(1) The preparation method comprises the steps of putting 100 parts by weight of aliphatic TPU with the polypropylene carbonate content of 50wt%, 5.0 parts by weight of toner and 0.1 part by weight of pentaerythritol phosphite into a single-screw casting machine, controlling the temperature of a charging barrel at a feeding section to be 100 ℃ and the temperature of a charging barrel at a melting section to be 140 ℃, banburying and mixing, directly coating the TPU on the surface of PLA non-woven fabric by casting equipment, controlling the temperature of a casting die head to be 180 ℃, and controlling the thickness of a coating film to be 1.0mm, and cooling to obtain a TPU synthetic leather semi-finished product.
(2) Coating line absorption and surface treatment: and (3) carrying out grain absorption treatment on the surface of the coating by using a vacuum grain absorption machine, enriching the design and color variety of the synthetic leather, carrying out grain absorption temperature of 90 ℃ for 10s, cooling, and carrying out surface treatment to obtain a biodegradable TPU synthetic leather finished product.
The biodegradable TPU synthetic leather manufactured by the technology has excellent biodegradability, the biodegradation degree reaches 96% in 21 days, and the biodegradable TPU synthetic leather has good hydrolysis resistance, wear resistance and flame retardance.
Example 3
A manufacturing method of biodegradable TPU synthetic leather comprises the following steps:
(1) The preparation method comprises the following steps of putting 100 parts by weight of aromatic TPU with the content of 60wt% of polypropylene carbonate, 6.0 parts by weight of toner and 0.2 part by weight of tri (2, 4-di-tert-butylphenyl) phosphite into a single-screw casting machine, controlling the temperature of a charging barrel at a feeding section to be 110 ℃ and the temperature of a charging barrel at a melting section to be 150 ℃, carrying out banburying and mixing, directly coating the TPU on the surface of PBAT non-woven fabric by casting equipment, controlling the temperature of a casting die head to be 200 ℃, controlling the thickness of a coating film to be 1.2mm, and cooling to obtain a TPU synthetic leather semi-finished product.
(2) Coating line absorption and surface treatment: and (3) carrying out grain absorption treatment on the surface of the coating by using a vacuum grain absorption machine, enriching the design and color variety of the synthetic leather, carrying out grain absorption temperature of 100 ℃ for 15s, cooling, and carrying out surface treatment to obtain a biodegradable TPU synthetic leather finished product.
The biodegradable TPU synthetic leather manufactured by the technology has excellent biodegradability, the biodegradation degree reaches 98 percent in 21 days, and the biodegradable TPU synthetic leather has good hydrolysis resistance, wear resistance and flame retardance.
Example 4
A manufacturing method of biodegradable TPU synthetic leather comprises the following steps:
(1) The preparation method comprises the following steps of putting 100 parts by weight of aliphatic TPU (thermoplastic polyurethane) with the content of polypropylene carbonate of 55wt%, 3.0 parts by weight of toner and 0.2 part by weight of pentaerythritol phosphite into a single-screw casting machine, controlling the temperature of a feeding section material cylinder to be 90 ℃ and the temperature of a melting section material cylinder to be 150 ℃, carrying out banburying and mixing, then directly coating the TPU on the surface of PLA (polylactic acid) non-woven fabric by casting equipment, controlling the temperature of a casting die head to be 190 ℃, and controlling the thickness of a coating film to be 0.8mm, and cooling to obtain a TPU synthetic leather semi-finished product.
(2) Coating line absorption and surface treatment: and (3) carrying out grain absorption treatment on the surface of the coating by using a vacuum grain absorption machine, enriching the design and color variety of the synthetic leather, carrying out grain absorption temperature of 95 ℃ for 12s, cooling, and carrying out surface treatment to obtain a biodegradable TPU synthetic leather finished product.
Example 5
A manufacturing method of biodegradable TPU synthetic leather comprises the following steps:
(1) The preparation method comprises the following steps of putting 100 parts by weight of aliphatic TPU (thermoplastic polyurethane) containing 49wt% of polypropylene carbonate, 5.0 parts by weight of toner and 0.1 part by weight of pentaerythritol phosphite into a single-screw casting machine, controlling the temperature of a charging barrel at a feeding section to be 95 ℃ and the temperature of a charging barrel at a melting section to be 135 ℃, banburying and mixing, directly coating the TPU on the surface of PLA (polylactic acid) non-woven fabric by casting equipment, controlling the temperature of a casting die head to be 180 ℃, and controlling the thickness of a coating film to be 1.0mm, and cooling to obtain a TPU synthetic leather semi-finished product.
(2) Coating line absorption and surface treatment: and (3) carrying out grain absorption treatment on the surface of the coating through a vacuum grain absorption machine, enriching the design and color variety of the synthetic leather, carrying out grain absorption temperature of 90 ℃ for 10s, cooling, and carrying out surface treatment to obtain a biodegradable TPU synthetic leather finished product.
Example 6
A manufacturing method of biodegradable TPU synthetic leather comprises the following steps:
(1) The preparation method comprises the following steps of putting 100 parts by weight of aliphatic TPU (thermoplastic polyurethane) with the content of polypropylene carbonate being 44wt%, 6.0 parts by weight of toner and 0.2 part by weight of pentaerythritol phosphite into a single-screw casting machine, controlling the temperature of a charging barrel at a feeding section to be 100 ℃ and the temperature of a charging barrel at a melting section to be 130 ℃, carrying out banburying and mixing, then directly coating the TPU on the surface of PLA (polylactic acid) non-woven fabric by casting equipment, controlling the temperature of a casting die head to be 200 ℃, and controlling the thickness of a coating film to be 1.0mm, and cooling to obtain a TPU synthetic leather semi-finished product.
(2) Coating line absorption and surface treatment: and (3) carrying out grain absorption treatment on the surface of the coating through a vacuum grain absorption machine, enriching the design and color variety of the synthetic leather, carrying out grain absorption temperature of 90 ℃ for 10s, cooling, and carrying out surface treatment to obtain a biodegradable TPU synthetic leather finished product.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (10)

1. A preparation method of biodegradable TPU synthetic leather is characterized by comprising the following steps:
s1: mixing the polypropylene carbonate-based TPU, the toner and the antioxidant, and banburying to obtain a TPU molten coating;
s2: coating the TPU molten coating on the surface of a textile substrate to obtain a TPU synthetic leather semi-finished product;
s3: and (3) carrying out line absorption treatment on the surface of the TPU synthetic leather semi-finished product, and cooling to obtain the biodegradable TPU synthetic leather.
2. The production method according to claim 1, wherein the mass ratio of the toner to the polypropylene carbonate based TPU is 3 to 6:100.
3. the method according to claim 1, wherein the ratio of the antioxidant to the polypropylene carbonate-based TPU is from 0.1 to 0.2:100.
4. the method of claim 1, wherein the mixing in step S1 is performed by using a single screw casting machine, and the feeding temperature is 90 to 110 ℃ and the melting temperature is 130 to 150 ℃.
5. The method of claim 1, wherein the coating thickness in step S2 is 0.8 to 1.2mm.
6. The method according to claim 1, wherein in the step S3, the temperature of the blotting treatment is 80 to 100 ℃ and the time is 8 to 15 seconds.
7. The method of claim 1, wherein the content of the polypropylene carbonate in the polypropylene carbonate based TPU is 40 to 60wt%.
8. The method according to claim 1, wherein the antioxidant is tris (2, 4-di-t-butylphenyl) phosphite and/or pentaerythritol phosphite.
9. The method of claim 1, wherein the textile substrate is a polylactic acid nonwoven fabric or a polybutylene adipate/terephthalate nonwoven fabric.
10. A biodegradable TPU synthetic leather prepared by the method of any one of claims 1-9.
CN202210662329.9A 2022-06-13 2022-06-13 Biodegradable TPU synthetic leather and preparation method thereof Pending CN115162013A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210662329.9A CN115162013A (en) 2022-06-13 2022-06-13 Biodegradable TPU synthetic leather and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210662329.9A CN115162013A (en) 2022-06-13 2022-06-13 Biodegradable TPU synthetic leather and preparation method thereof

Publications (1)

Publication Number Publication Date
CN115162013A true CN115162013A (en) 2022-10-11

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210662329.9A Pending CN115162013A (en) 2022-06-13 2022-06-13 Biodegradable TPU synthetic leather and preparation method thereof

Country Status (1)

Country Link
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