CN109609006B - Preparation method and application method of graphene oxide-based leather finishing agent - Google Patents
Preparation method and application method of graphene oxide-based leather finishing agent Download PDFInfo
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- CN109609006B CN109609006B CN201811383286.0A CN201811383286A CN109609006B CN 109609006 B CN109609006 B CN 109609006B CN 201811383286 A CN201811383286 A CN 201811383286A CN 109609006 B CN109609006 B CN 109609006B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
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Abstract
The invention relates to the technical field of leather-making chemistry and engineering, and provides a preparation method and an application method of an oxidized graphene-based leather finishing agent. The preparation method of the graphene oxide-based leather finishing agent adopts graphene oxide, the graphene oxide has oxygen-containing groups, is good in water solubility and reactivity, can react with hydroxyl, carboxyl or amino in polyacrylate and polyurethane resin or is combined with hydroxyl, carboxyl or amino of leather collagen fiber, and is not easy to fall off, and the graphene oxide can be used for preparing the leather finishing agent of a stable homogeneous system by taking the polyacrylate and the polyurethane resin as carriers; the obtained leather finishing agent is coated on the surface of leather, and a layer of uniform film is formed on the surface of the leather by the finishing agent along with gradual volatilization of water in the finishing agent, so that the performance of a leather coating is improved.
Description
Technical Field
The invention relates to the technical field of leather-making chemistry and engineering, in particular to a preparation method and an application method of an oxidized graphene-based leather finishing agent.
Background
The leather coating is a very important workshop section in the leather manufacturing process, the leather which is not coated has rough hand feeling and is easy to damage, a layer of film is formed on the surface of the leather after the leather is coated, the hand feeling is smooth, and the leather has certain strength and is difficult to damage. Because of the limitation of leather chemicals, the leather products widely applied at present have the technical defects of poor coating strength, wear resistance, aging resistance and the like, and the current situation seriously restricts the competitiveness of the leather products in the international market in China, so the research and development of the high-performance key technology of the leather products are increased, the traditional leather industry is improved by utilizing high and new technologies, and the method is the key for improving the technical content and the international market competitiveness of the leather products in China and ensuring the advantages of the leather industry in China and the sustainable development of the industry.
In order to solve the technical problems, conventionally, ethylene glycol ether is used as a dispersion medium to prepare a graphene dispersion liquid with the graphene content of 0.1%, and then the graphene dispersion liquid is added into a leather finishing agent to prepare a graphene-based leather finishing agent, and a spraying method is adopted to be applied to a cattle napa vamp finishing section. Although the graphene is a two-dimensional nano material with the highest natural strength and has very good toughness, the application of the graphene in the leather finishing agent is beneficial to improving the strength, the wear resistance and the like of a leather coating; however, the prior method still has the following technical problems:
1. in the existing method, the graphene takes ethylene glycol monoethyl ether as a dispersion medium, and the ethylene glycol monoethyl ether is an organic solvent, so that VOC can be generated, harm is generated to human health, and the requirement of environmental protection and leather making is not met; the graphene has the technical defect of reaction inertia, is difficult to react with components of a leather finishing agent or leather collagen fibers, is agglomerated and deposited on the surface of the leather along with gradual volatilization of ethylene glycol ethyl ether, is not uniformly distributed and is easy to peel, so that the defect of different abrasion resistance of coatings at different parts of the surface of the leather is shown, the film forming stability of the finishing agent is reduced, and the practical finishing effect is reduced; the prepared finishing agent is a heterogeneous system, has poor stability and is not storage-resistant;
2. the leather finishing agent is a multi-component mixture and comprises polyacrylate, polyurethane resin and other non-resin components, the phenomenon that graphene is adsorbed with the polyacrylate and the polyurethane resin and is also adsorbed with the non-resin components can be caused by directly adding and mixing the graphene dispersion liquid and the leather finishing agent in the prior art, the wear resistance of a coating is mainly determined by the performances of the polyacrylate and the polyurethane resin in the leather finishing agent, the graphene adsorbed with the non-resin components cannot play an effective role, and the production problems of low effective utilization rate of the graphene, cost increase and the like are caused.
Disclosure of Invention
Therefore, in order to solve the problems, the invention provides a preparation method and an application method of the graphene oxide-based leather finishing agent. The preparation method of the graphene oxide-based leather finishing agent adopts graphene oxide, the graphene oxide has oxygen-containing groups, is good in water solubility and reactivity, can react with hydroxyl, carboxyl or amino in polyacrylate and polyurethane resin or is combined with hydroxyl, carboxyl or amino of leather collagen fiber, and is not easy to fall off, and the graphene oxide can be used for preparing the leather finishing agent of a stable homogeneous system by taking the polyacrylate and the polyurethane resin as carriers; the obtained leather finishing agent is coated on the surface of leather, and a layer of uniform film is formed on the surface of the leather by the finishing agent along with gradual volatilization of water in the finishing agent, so that the performance of a leather coating is improved.
In order to realize the technical problem, the solution scheme adopted by the invention is as follows: a preparation method of a graphene oxide-based leather finishing agent comprises the following steps:
step 1, preparing a graphene oxide dispersion liquid: dissolving graphene oxide powder in water, performing ultrasonic dispersion for 20-30min at the ultrasonic power of 300-350W, and then adjusting the pH to 6.5-9 by using 2-4% ammonia water to prepare graphene oxide dispersion liquid;
step 2, preparing the graphene oxide-based polyacrylate resin emulsion: mixing the graphene oxide dispersion liquid with the polyacrylate resin emulsion, and dispersing for 30-45min by ultrasonic waves with the ultrasonic power of 450-500W to prepare graphene oxide-based polyacrylate resin emulsion with the graphene oxide mass fraction of 0.05-0.1%;
step 3, preparing the graphene oxide-based polyurethane resin emulsion: mixing the graphene oxide dispersion liquid with the polyurethane resin emulsion, and dispersing for 30-45min by ultrasonic waves with the ultrasonic power of 450-500W to prepare the graphene oxide-based polyurethane resin emulsion with the graphene oxide mass fraction of 0.05-0.1%;
step 4, preparing the graphene oxide-based leather finishing agent: according to the parts by weight, 0-160 parts of graphene oxide-based polyacrylate resin emulsion, 85-125 parts of graphene oxide-based polyurethane resin emulsion and a coating auxiliary agent are dissolved in water, and the mixture is stirred for 5-10min at the stirring speed of 900-1200r/min to prepare the graphene oxide-based leather coating agent.
Wherein the finishing auxiliary agent in the step 4 comprises casein, an auxiliary agent and pigment paste, and the graphene oxide-based leather finishing agent prepared in the step 4 is a middle-layer graphene oxide-based leather finishing agent.
Step 4, the preparation of the middle layer graphene oxide-based leather finishing agent specifically comprises the following steps: according to the parts by weight, 160 parts of oxidized graphene-based polyacrylate resin emulsion, 85-100 parts of oxidized graphene-based polyurethane resin emulsion, 45-60 parts of casein, 85-100 parts of auxiliary agent and 65-80 parts of pigment paste are dissolved in 450 parts of water with the temperature of 300-.
Wherein the finishing auxiliary agent in the step 4 comprises an oil wax auxiliary agent and a cross-linking agent, and the graphene oxide-based leather finishing agent prepared in the step 4 is a top layer graphene oxide-based leather finishing agent.
Step 4, the preparation of the top layer graphene oxide-based leather finishing agent specifically comprises the following steps: according to the parts by weight, 0 part of graphene oxide-based polyacrylate resin emulsion, 100 parts of graphene oxide-based polyurethane resin emulsion, 5-10 parts of oil wax additive and 2-5 parts of cross-linking agent are dissolved in 100 parts of water, and the mixture is stirred for 5-10min at the stirring speed of 900-1200r/min to obtain the top layer graphene oxide-based leather finishing agent.
An application method of the graphene oxide-based leather finishing agent sequentially comprises the following steps: crust leather bottoming coating → ironing → middle layer oxidized graphene-based leather coating → ironing → top layer oxidized graphene-based leather coating → ironing → vibration softening → stretching plate drying → ironing → vibration softening → dry vacuum; the middle-layer graphene oxide-based leather finishing agent comprises the following components in parts by weight: 125-160 parts of oxidized graphene-based polyacrylate resin emulsion, 85-100 parts of oxidized graphene-based polyurethane resin emulsion, 45-60 parts of casein, 85-100 parts of an auxiliary agent, 65-80 parts of a pigment paste and 300-450 parts of water; the top layer graphene oxide-based leather finishing agent comprises the following components in parts by weight: 100-125 parts of graphene oxide-based polyurethane resin emulsion, 5-10 parts of oil wax auxiliary agent, 2-5 parts of cross-linking agent and 100-150 parts of water.
Wherein the coating amount of the middle-layer graphene oxide-based leather finishing agent coating is 10-15 g/sf; the coating amount of the top layer graphene oxide-based leather finishing agent coating is 8-10 g/sf; the ironing condition is 120-; the intensity of the oscillation softening is 5-6 levels; the milling time is 8-12 h; the drying condition of the toggling plate is 45-50 ℃/4-6cm/20-25min, and the dry vacuum condition is 65-80 ℃/15-30 seconds/vacuum degree- (0.05-0.1) MPa.
By adopting the technical scheme, the invention has the beneficial effects that: compared with the prior art, the preparation method of the graphene oxide-based leather finishing agent has the following advantages:
1. water is used as a dispersion medium, so that no VOC is generated, and the method is green and environment-friendly and meets the requirement of environmental protection and leather making; the graphene oxide is a reactive material, can react with hydroxyl, carboxyl or amino in polyacrylate and polyurethane resin or can be combined with hydroxyl, carboxyl or amino of leather collagen fiber, and is not easy to fall off, and the prepared graphene oxide-based leather finishing agent is a homogeneous system, has good stability and is storage-resistant; the finishing agent is coated on the surface of the leather and gradually volatilizes along with water, and the graphene oxide can be uniformly distributed on the surface of the leather and firmly combined, so that the characteristic of consistent coating performance at different parts of the surface of the leather is shown.
2. The graphene oxide takes polyacrylate and polyurethane resin as carriers to form a stable homogeneous system, the effect is obvious, and the graphene oxide dispersion liquid is compounded with the polyacrylate and polyurethane resin emulsion and then added into the coating agent, so that the effective utilization rate of the graphene oxide can be greatly improved, and the cost is reduced.
3. The graphene oxide-based leather finishing agent is used for leather finishing, so that the strength, the wear resistance and the aging resistance of a leather coating are greatly improved, the tearing strength of the leather coating is improved by 8-12%, and the elongation at break is reduced by 6-8%; the wear resistance of the leather coating is improved by 16-18%; the ageing resistance of the leather coating is improved by 4-8%.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, so that how to apply technical means to solve technical problems and achieve technical effects can be fully understood and implemented, and it should be noted that the embodiments are only used for further description of the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make modifications and adjustments according to the above disclosure.
Unless otherwise indicated, the techniques employed in the examples are conventional and well known to those skilled in the art, and the reagents and products employed are also commercially available. Various procedures and methods not described in detail are conventional methods well known in the art, and the source, trade name, and if necessary, the constituents of the reagents used are indicated at the first appearance.
Example 1
A preparation method of a graphene oxide-based leather finishing agent comprises the following steps:
step 1, preparing a graphene oxide dispersion liquid: dissolving 10.0 parts of graphene oxide powder in 1000 parts of water, performing ultrasonic dispersion for 30min at the ultrasonic power of 300W, and then adjusting the pH to 7.5 by using 2% ammonia water to prepare a graphene oxide dispersion liquid;
step 2, preparing the graphene oxide-based polyacrylate resin emulsion:
mixing 8 parts of the graphene oxide dispersion liquid obtained in the step 1 with 500 parts of polyacrylate resin emulsion (RA-2356, the solid content is 20%, Statel Fine coating (Suzhou) Co., Ltd.), and ultrasonically dispersing for 30min at the ultrasonic power of 450W to prepare graphene oxide-based polyacrylate resin emulsion RA-2356 with the graphene oxide mass fraction of 0.08%;
mixing 14 parts of the graphene oxide dispersion liquid obtained in the step 1 with 500 parts of polyacrylate resin emulsion (RA-1079, the solid content is 35%, Sutaer Fine coating (Suzhou) Co., Ltd.), and ultrasonically dispersing for 30min at the ultrasonic power of 500W to obtain graphene oxide-based polyacrylate resin emulsion RA-1079 with the graphene oxide mass fraction of 0.08%;
step 3, preparing the graphene oxide-based polyurethane resin emulsion:
mixing 14 parts of the graphene oxide dispersion liquid obtained in the step 1 with 500 parts of polyurethane resin emulsion (RU-3910, the solid content is 35%, and the Steyr fine coating (Suzhou) Co., Ltd.), and performing ultrasonic dispersion for 30min at the ultrasonic power of 500W to obtain graphene oxide-based polyurethane resin emulsion RU-3910 with the graphene oxide mass fraction of 0.08%;
mixing 14 parts of the graphene oxide dispersion liquid obtained in the step 1 with 500 parts of polyurethane resin emulsion (Aqualen Top LN.A, the solid content is 35%, Stal Fine paint (Suzhou) Co., Ltd.), and performing ultrasonic dispersion for 30min at the ultrasonic power of 500W to obtain graphene oxide-based polyurethane resin emulsion Aqualen Top LN.A with the graphene oxide mass fraction of 0.08%;
step 4, preparing the graphene oxide-based leather finishing agent:
dissolving 60 parts of oxidized graphene-based polyacrylate resin emulsion RA-2356, 80 parts of oxidized graphene-based polyacrylate resin emulsion RA-1079, 100 parts of oxidized graphene-based polyurethane resin emulsion RU-3910, 60 parts of casein (RODA bound TU 688/B, Delphi skin chemical Co., Ltd.), 40 parts of wax additive (48416-GAA, Shanghai Pierca Bravayi chemical Co., Ltd.), 50 parts of Soft additive (EUDERM Nappa Soft S-C, Langsheng group), 80 parts of pigment paste (PPE DEEP BLACK A-ID, Steyr fine paint (Suzhou)) in 400 parts of water, stirring for 8min at a stirring speed of 950r/min to prepare a middle-layer oxidized graphene-based leather finishing agent;
② 100 parts of oxidized graphene-based polyurethane resin emulsion Aqualen Top LN.A, 10 parts of oil wax additive (KO 2311, Xiamen Haodeya trade Co., Ltd.), 5 parts of cross-linking agent (Aqualen AKU liq, Steyr fine paint (Suzhou) Co., Ltd.) were dissolved in 120 parts of water, and stirred for 8min at a stirring rotation speed of 950r/min to obtain a Top layer oxidized graphene-based leather finishing agent.
Application example 1
An application method of the graphene oxide-based leather finishing agent sequentially comprises the following steps: coating the bottom of crust leather → ironing → coating the middle layer of oxidized graphene-based leather coating agent obtained in example 1 → ironing → coating the top layer of oxidized graphene-based leather coating agent obtained in example 1 → ironing → shaking for softening → drying of the stretching plate → ironing → shaking for softening → dry vacuum; wherein the coating amount of the middle-layer graphene oxide-based leather finishing agent coating is 15 g/sf; the coating amount of the top layer graphene oxide-based leather finishing agent coating is 8 g/sf; the ironing condition is 120 ℃/30 kgf; the intensity of the oscillation softening is 5 levels; the milling time is 10 h; the drying condition of the toggling plate is 50 ℃/4cm/25min, and the dry vacuum condition is 80 ℃/15 seconds/vacuum degree-0.1 MPa.
After the graphene oxide-based leather finishing agent is coated, the tearing strength of a leather coating is improved by 8-12%, and the elongation at break is reduced by 6-8%; the wear resistance of the leather coating is improved by 16-18%; the ageing resistance of the leather coating is improved by 4-8%.
In conclusion, the preparation method and the application method of the graphene oxide-based leather finishing agent introduce the graphene oxide nano material as the reinforcing agent of the leather coating aiming at the technical defects of poor strength, wear resistance and aging resistance of the traditional leather coating, the graphene oxide has higher specific surface area and richer oxygen-containing functional groups, and can be blended with polyacrylate and polyurethane leather film-forming agents under the action of ultrasonic waves to prepare the graphene oxide-based leather film-forming agent with good uniformity and stability; the graphene oxide has excellent strength and toughness, so that the mechanical properties of polyacrylate and polyurethane leather film forming agents can be enhanced and toughened, and a high-performance leather coating is obtained.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (7)
1. The preparation method of the graphene oxide-based leather finishing agent is characterized by comprising the following steps:
step 1, preparing a graphene oxide dispersion liquid: dissolving graphene oxide powder in water, performing ultrasonic dispersion for 20-30min at the ultrasonic power of 300-350W, and then adjusting the pH to 6.5-9 by using 2-4% ammonia water to prepare graphene oxide dispersion liquid;
step 2, preparing the graphene oxide-based polyacrylate resin emulsion: mixing the graphene oxide dispersion liquid with the polyacrylate resin emulsion, and dispersing for 30-45min by ultrasonic waves with the ultrasonic power of 450-500W to prepare graphene oxide-based polyacrylate resin emulsion with the graphene oxide mass fraction of 0.05-0.1%;
step 3, preparing the graphene oxide-based polyurethane resin emulsion: mixing the graphene oxide dispersion liquid with the polyurethane resin emulsion, and dispersing for 30-45min by ultrasonic waves with the ultrasonic power of 450-500W to prepare the graphene oxide-based polyurethane resin emulsion with the graphene oxide mass fraction of 0.05-0.1%;
step 4, preparing the graphene oxide-based leather finishing agent: according to the parts by weight, 0-160 parts of graphene oxide-based polyacrylate resin emulsion, 85-125 parts of graphene oxide-based polyurethane resin emulsion and a coating auxiliary agent are dissolved in water, and the mixture is stirred for 5-10min at the stirring speed of 900-1200r/min to prepare the graphene oxide-based leather coating agent.
2. The method for preparing the graphene oxide-based leather finishing agent according to claim 1, wherein: and 4, coating auxiliaries comprise casein, auxiliaries and pigment paste, and the graphene oxide-based leather coating agent prepared in the step 4 is a middle-layer graphene oxide-based leather coating agent.
3. The method of preparing the graphene oxide-based leather finishing agent according to claim 2, wherein the step 4 of preparing the graphene oxide-based leather finishing agent is: according to the parts by weight, 160 parts of oxidized graphene-based polyacrylate resin emulsion, 85-100 parts of oxidized graphene-based polyurethane resin emulsion, 45-60 parts of casein, 85-100 parts of auxiliary agent and 65-80 parts of pigment paste are dissolved in 450 parts of water of 300-10 min, and the stirring is carried out for 5-10min at the stirring speed of 900-1200r/min, thus obtaining the middle-layer oxidized graphene-based leather finishing agent.
4. The method for preparing the graphene oxide-based leather finishing agent according to claim 1, wherein: and 4, coating auxiliaries comprise an oil wax auxiliary and a cross-linking agent, and the graphene oxide-based leather coating agent prepared in the step 4 is a top layer graphene oxide-based leather coating agent.
5. The method of preparing the graphene oxide-based leather finishing agent according to claim 4, wherein the step 4 of preparing the graphene oxide-based leather finishing agent is: according to the parts by weight, 0 part of graphene oxide-based polyacrylate resin emulsion, 100 parts of graphene oxide-based polyurethane resin emulsion, 5-10 parts of oil wax additive and 2-5 parts of cross-linking agent are dissolved in 100 parts of water, and the mixture is stirred for 5-10min at the stirring speed of 900-1200r/min to obtain the top layer graphene oxide-based leather finishing agent.
6. The application method of the graphene oxide-based leather finishing agent as claimed in claim 1, wherein the method sequentially comprises the following steps: crust leather bottoming coating → ironing → middle layer oxidized graphene-based leather coating → ironing → top layer oxidized graphene-based leather coating → ironing → vibration softening → stretching plate drying → ironing → vibration softening → dry vacuum; the middle-layer graphene oxide-based leather finishing agent comprises the following components in parts by weight: 125-160 parts of oxidized graphene-based polyacrylate resin emulsion, 85-100 parts of oxidized graphene-based polyurethane resin emulsion, 45-60 parts of casein, 85-100 parts of an auxiliary agent, 65-80 parts of a pigment paste and 300-450 parts of water; the top layer graphene oxide-based leather finishing agent comprises the following components in parts by weight: 100-125 parts of graphene oxide-based polyurethane resin emulsion, 5-10 parts of oil wax auxiliary agent, 2-5 parts of cross-linking agent and 100-150 parts of water.
7. The method of applying the graphene oxide-based leather finishing agent according to claim 6, wherein: the coating amount of the middle-layer graphene oxide-based leather finishing agent coating is 10-15 g/sf; the coating amount of the top layer graphene oxide-based leather finishing agent coating is 8-10 g/sf; the ironing condition is 120-; the intensity of the oscillation softening is 5-6 levels; the milling time is 8-12 h; the drying condition of the toggling plate is 45-50 ℃/4-6cm/20-25min, and the dry vacuum condition is 65-80 ℃/15-30 seconds/vacuum degree- (0.05-0.1) MPa.
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| CN110804875A (en) * | 2019-11-01 | 2020-02-18 | 清远市齐力合成革有限公司 | Graphene high-physical-property synthetic leather, preparation method and equipment |
| CN111501366A (en) * | 2020-05-13 | 2020-08-07 | 常州雅美特窗饰股份有限公司 | Curtain fabric containing graphene improved coating and preparation method thereof |
| CN113214632B (en) * | 2021-04-20 | 2023-04-28 | 兴业皮革科技股份有限公司 | Flame-retardant cyanuric chloride modified graphene/polyurethane composite material and preparation method and application thereof |
| CN113969097A (en) * | 2021-10-27 | 2022-01-25 | 兴业皮革科技股份有限公司 | Green coating method based on heavy metal-free tanned cattle crust leather |
| CN114318889A (en) * | 2021-12-14 | 2022-04-12 | 无锡市曼优丽新型复合材料有限公司 | High-physical-property military belt leather and preparation method thereof |
| CN116213226A (en) * | 2023-04-21 | 2023-06-06 | 兴业皮革科技股份有限公司 | Leather coating process with high water resistance |
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