Polyvinyl chloride artificial leather as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of artificial leather, and provides polyvinyl chloride artificial leather and a preparation method and application thereof, and the polyvinyl chloride artificial leather comprises a compact layer and a foaming layer; the compact layer comprises the following components in percentage by mass: 50%-55% of polyvinyl chloride resin, 25%-27% of a vegetable oil plasticizer, 8%-10% of plant filler, 2%-5% of a stabilizer, 1%-2% of a pigment and the balance of 1%-14%; the foaming layer comprises the following components in percentage by mass: 45%-50% of polyvinyl chloride resin, 22%-25% of a vegetable oil plasticizer, 6%-10% of plant filler, 1%-3% of a stabilizer, 0.8%-1.5% of a foaming agent, 4%-5.5% of a flame retardant and the balance of 5%-21.2%. Sustainable raw materials are used in the compact layer and the foaming layer, namely the vegetable oil plasticizer and the plant filler are adopted, so that the requirements on petroleum-based polyvinyl chloride, the petroleum-based plasticizer and the mineral filler are reduced from the source, the emission of carbon dioxide in the preparation process of the raw materials is reduced, the toxicity risk is reduced, and the environment-friendly effect is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of artificial leather, in particular to a polyvinyl chloride artificial leather and a preparation method and application thereof. Background Art

[0002] PVC artificial leather is a primary raw material for luggage and is widely used in these applications. Its production uses key raw materials including PVC, plasticizers, stabilizers, and fillers. PVC is typically produced by cracking petroleum into ethylene or by using calcium carbide to produce acetylene. The resulting ethylene or acetylene is then chlorinated to produce vinyl chloride, which is then polymerized. Furthermore, the production of plasticizers, stabilizers, and fillers also requires significant amounts of fossil fuels and mineral resources. Furthermore, these production processes generate high levels of carbon dioxide emissions, exacerbating the greenhouse effect and negatively impacting the ecological environment. Therefore, the production of PVC, plasticizers, and fillers is highly dependent on various non-renewable fossil energy and mineral resources, making the use of such artificial leather inconsistent with sustainable development. Summary of the Invention

[0003] In view of the above-mentioned shortcomings of the prior art, the present invention provides a polyvinyl chloride artificial leather.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] In a first aspect, a polyvinyl chloride artificial leather is provided, comprising a dense layer and a foamed layer;

[0006] The dense layer comprises, by mass percentage, 50% to 55% of polyvinyl chloride resin, 25% to 27% of vegetable oil plasticizer, 8% to 10% of plant filler, 2% to 5% of stabilizer and 1% to 2% of colorant, with the balance being processing aids and unavoidable impurities, with the balance being 1% to 14% and the unavoidable impurities being less than 0.5%;

[0007] The foaming layer comprises, by mass percentage, 45% to 50% of polyvinyl chloride resin, 22% to 25% of vegetable oil plasticizer, 6% to 10% of plant filler, 1% to 3% of stabilizer, 0.8% to 1.5% of foaming agent and 4% to 5.5% of flame retardant, with the remainder being processing aids and inevitable impurities, with the remainder being 5% to 21.2%, and the inevitable impurities being less than 0.5%.

[0008] In some embodiments, the vegetable oil plasticizer is any one or more of epoxidized soybean oil, epoxidized linseed oil, acetylated monoglyceride, and butyl ricinoleate.

[0009] In some embodiments, the plant filler is configured as any one or more of wood powder, bamboo powder, flax fiber, and starch-based filler.

[0010] In some embodiments, the foaming agent in the foaming layer is set to be any one or more of azodicarbonamide, azodicarbonamide potassium formate, sodium bicarbonate and azobisisobutyronitrile.

[0011] In some embodiments, the stabilizer is configured as any one or more of calcium stearate, calcium ricinoleate, zinc ricinoleate, a calcium-zinc composite stabilizer, zinc stearate, barium stearate, or lanthanum stearate.

[0012] In some embodiments, the flame retardant is configured as any one or more of phosphate, zinc borate, boron oxide, and aluminum oxide.

[0013] In some embodiments, the colorant is configured to be any one or more of iron oxide red, iron oxide yellow, carbon black, titanium dioxide, and phthalocyanine blue.

[0014] In some embodiments, the processing aid is provided as a lubricant and / or an antioxidant.

[0015] In a second aspect, a method for preparing the polyvinyl chloride artificial leather as described in any of the above embodiments comprises the following steps:

[0016] The polyvinyl chloride resin, vegetable oil plasticizer, plant filler, stabilizer and colorant are mixed evenly, and then evenly coated on the release paper and heated to form a film material to prepare a dense layer;

[0017] The polyvinyl chloride resin, the vegetable oil plasticizer, the plant filler, the stabilizer, the foaming agent and the flame retardant are mixed evenly, and then evenly applied on the dense layer and heated to form, thereby preparing a foaming layer;

[0018] The foamed layer is embossed and coated to obtain the polyvinyl chloride artificial leather.

[0019] In a third aspect, there is provided a use of the polyvinyl chloride artificial leather as described in any of the above embodiments in the preparation of clothing, shoes, bags or decorations.

[0020] Compared with the prior art, the present invention has the following beneficial effects: the PVC artificial leather of the present application uses sustainable raw materials in the dense layer and foaming layer, namely, using plant oil plasticizers instead of traditional phthalate plasticizers and plant fillers instead of mineral fillers. This reduces the demand for petroleum-based PVC, petroleum-based plasticizers, and mineral fillers at the source, thereby reducing carbon dioxide emissions during the preparation of these raw materials, lowering toxicity risks, and being more environmentally friendly. Furthermore, using sustainable raw materials in the fillers can improve the softness of the PVC artificial leather and reduce costs compared to using mineral fillers. This resource is renewable and conforms to the concept of sustainable development. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a schematic diagram of the process of the polyvinyl chloride artificial leather of the present invention. DETAILED DESCRIPTION

[0022] To make the purpose, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. The described embodiments are only part of the embodiments of the present invention, not all of the embodiments.

[0023] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the invention as claimed, but rather merely represents selected embodiments of the present invention. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are also within the scope of protection of the present invention.

[0024] The present application provides a polyvinyl chloride artificial leather, comprising a dense layer and a foaming layer; the dense layer comprises, by mass percentage, 50% to 55% of polyvinyl chloride resin, 25% to 27% of a vegetable oil plasticizer, 8% to 10% of a plant filler, 2% to 5% of a stabilizer, and 1% to 2% of a colorant, with the remainder being processing aids and unavoidable impurities, with the remainder being 1% to 14%, and the unavoidable impurities being less than 0.5%; the foaming layer comprises, by mass percentage, 45% to 50% of a polyvinyl chloride resin, 22% to 25% of a vegetable oil plasticizer, 6% to 10% of a plant filler, 1% to 3% of a stabilizer, 0.8% to 1.5% of a foaming agent, and 4% to 5.5% of a flame retardant, with the remainder being processing aids and unavoidable impurities, with the remainder being 5% to 21.2%, and the unavoidable impurities being less than 0.5%.

[0025] Specifically, this formula can be used to produce PVC artificial leather, which conforms to the concept of sustainable development. The PVC resin can be set at 45%, 47.5%, 50%, 52.5%, or 55%; the vegetable oil plasticizer can be set at 22%, 23.5%, 25%, 26%, or 27%; the plant filler can be set at 6%, 7%, 8%, 9%, or 10%; the stabilizer can be set at 1%, 2%, 3%, 4%, or 5%; the colorant can be set at 1%, 1.5%, or 2%; the foaming agent can be set at 0.8%, 1.2%, or 1.5%; and the flame retardant can be set at 4%, 5%, or 5.5%.

[0026] It is worth noting that the PVC artificial leather of this application uses sustainable raw materials in the dense layer and foaming layer, which reduces the demand for petroleum-based PVC, petroleum-based plasticizers, and mineral fillers at the source, thereby reducing carbon dioxide emissions during the production of these raw materials and being more environmentally friendly. Furthermore, the use of sustainable raw materials in the filler can improve the softness of the PVC artificial leather and reduce costs compared to using mineral fillers.

[0027] To facilitate the use of the vegetable oil plasticizer, in some embodiments, the vegetable oil plasticizer is set to be any one or more of epoxidized soybean oil, epoxidized linseed oil, acetylated monoglyceride and butyl ricinoleate.

[0028] Specifically, this application replaces traditional phthalate plasticizers with vegetable oil plasticizers to improve flexibility and lower the glass transition temperature. The specific selection of vegetable oil plasticizers shall be based on actual production requirements:

[0029] In one embodiment, the vegetable oil plasticizer is configured as epoxidized soybean oil.

[0030] In another embodiment, the vegetable oil plasticizer is provided as epoxidized linseed oil.

[0031] In yet another embodiment, the vegetable oil plasticizer is configured as acetylated monoglyceride.

[0032] In yet another embodiment, the vegetable oil plasticizer is set to butyl ricinoleate.

[0033] In yet another embodiment, the vegetable oil plasticizer is provided as a mixture of epoxidized soybean oil and epoxidized linseed oil.

[0034] In order to facilitate the use of plant fillers, in some embodiments, the plant fillers are set to be any one or more of wood powder, bamboo powder, flax fiber, and starch-based fillers.

[0035] Specifically, plant fillers are used to increase the volume of products and reduce costs. By replacing fillers with sustainable raw materials, environmental impact is reduced. The specific selection of plant fillers should be based on actual production needs:

[0036] In one embodiment, the plant filler is set as wood powder. It can be seen that wood powder is low in cost, renewable, and can improve the rigidity and dimensional stability of the material, but excessive addition may reduce flexibility.

[0037] In another embodiment, the plant filler is bamboo powder. As can be seen, bamboo powder has low density and high strength, which can give the material good mechanical properties and natural texture, and when used, can obtain leather with better performance.

[0038] In yet another embodiment, the plant filler is provided as flax fibers.

[0039] In yet another embodiment, the plant filler is provided as a starch-based filler.

[0040] In yet another embodiment, the plant filler is provided as a mixture of wood powder and bamboo powder.

[0041] In order to facilitate the use of the foaming agent, in some embodiments, the foaming agent in the foaming layer is set to be any one or more of azodicarbonamide, azodicarbonamide potassium formate, sodium bicarbonate and azobisisobutyronitrile.

[0042] Specifically, the foaming agent is used to form tiny bubbles in the material, reduce the material density, and improve the thermal insulation and sound insulation. The specific selection is based on actual production needs:

[0043] In one embodiment, the foaming agent is set to azodicarbonamide. It is known that azodicarbonamide can give the product a light and soft performance in the production of PVC foam artificial leather, and increase the leather feel by improving the elasticity and feel of the product.

[0044] In another embodiment, the foaming agent is set to potassium azodicarbonamide formate. It can be seen that potassium azodicarbonamide formate can reduce the amount of stabilizer used and reduce costs.

[0045] In yet another embodiment, the blowing agent is configured as azobisisobutyronitrile.

[0046] In yet another embodiment, the foaming agent is set to sodium bicarbonate.

[0047] In yet another embodiment, the blowing agent is configured as azobisisobutyronitrile.

[0048] In yet another embodiment, the blowing agent is configured as a mixture of azodicarbonamide and potassium azodicarbonamide formate.

[0049] To facilitate the use of stabilizers, in some embodiments, the stabilizer is set to be any one or more of calcium stearate, calcium ricinoleate, zinc ricinoleate, calcium zinc composite stabilizer, zinc stearate, barium stearate or lanthanum stearate.

[0050] Specifically, stabilizers are used to prevent PVC from degrading due to factors such as heat, light, and oxygen during processing and use, thereby extending the service life of the material. The specific use of stabilizers is subject to actual production conditions:

[0051] In one embodiment, the stabilizer is provided as calcium stearate.

[0052] In another embodiment, the stabilizer is provided as a mixture of calcium ricinoleate and zinc ricinoleate.

[0053] Furthermore, the specific choice of stabilizer is not limited here, and can also be set to zinc ricinoleate, calcium zinc composite stabilizer, zinc stearate, barium stearate or lanthanum stearate, etc.

[0054] To facilitate the use of flame retardants, in some embodiments, the flame retardant is configured as any one or more of phosphate, zinc borate, boron oxide, and aluminum oxide.

[0055] Specifically, flame retardants are used to retard PVC materials, melting and sealing the surface of the burning material under high temperature conditions to form a glass covering layer. The specific selection is based on actual production needs and is not limited here:

[0056] In one embodiment, the flame retardant is configured as a phosphate.

[0057] In yet another embodiment, the flame retardant is provided as zinc borate.

[0058] In another embodiment, the flame retardant is provided as boron oxide.

[0059] In yet another embodiment, the flame retardant is provided as a mixed boron oxide and aluminum oxide.

[0060] In order to facilitate the production of polyvinyl chloride artificial leather of desired color, in some embodiments, the colorant is set to be any one or more of iron oxide red, iron oxide yellow, carbon black, titanium dioxide and phthalocyanine blue.

[0061] Specifically, the colorant is used to provide color and hiding power, thereby forming the desired color of polyvinyl chloride artificial leather. The specific selection is based on actual production needs and is not limited here:

[0062] In one embodiment, the colorant is selected from iron oxide red, iron oxide yellow, carbon black, etc. to prepare brown color.

[0063] In another embodiment, the colorant is selected from carbon black, titanium dioxide and phthalocyanine blue to formulate a blue color.

[0064] In order to facilitate the production of polyvinyl chloride artificial leather, in some embodiments, the processing aid is configured as a lubricant and / or an antioxidant.

[0065] Specifically, processing aids can promote the formation of polyvinyl chloride artificial leather. The specific selection shall be based on the actual production situation:

[0066] In one embodiment, the processing aid is configured as a lubricant. Thus, when manufacturing the foaming layer, the use of the lubricant allows the components to be mixed more evenly. The lubricant can be configured as stearic acid, zinc / calcium stearate, or paraffin / polyethylene wax.

[0067] In another embodiment, the processing aid is configured as an antioxidant. This can inhibit yellowing and degradation of the polyvinyl chloride resin due to oxidation during processing and use, thereby extending its service life. The antioxidant can be a hindered phenol antioxidant, such as BHT (2,6-di-tert-butyl-p-cresol), a phosphite antioxidant, such as a calcium-zinc composite stabilizer containing 5% phosphite, or a thioester antioxidant.

[0068] In yet another embodiment, the processing aid is provided as a lubricant and an antioxidant.

[0069] Furthermore, in order to improve the performance of the polyvinyl chloride artificial leather, ultraviolet absorbers, processing modifiers, etc. may be added accordingly. This is not limited here and the design is carried out according to actual production needs.

[0070] like Figure 1 As shown, the present application provides a method for preparing polyvinyl chloride artificial leather, comprising the following steps:

[0071] S110, uniformly mixing polyvinyl chloride resin, vegetable oil plasticizer, plant filler, stabilizer and colorant, and then evenly coating the mixture on release paper and heating the mixture to form a film material to prepare a dense layer.

[0072] Specifically, polyvinyl chloride resin: Use suspension-process PVC resin with a degree of polymerization of 1000-3000 and a K value of 65-75. Dry at 80°C for 2 hours before use, and a moisture content of ≤0.2%. Vegetable oil plasticizer: Use epoxidized soybean oil with an epoxy value of ≥6.0% and an acid value of ≤0.5 mgKOH / g. Filter to remove impurities before use. Plant filler: Use wood powder with a moisture content of ≤0.8%. Dry at 105°C for 4 hours before use. Stabilizer: Use a calcium-zinc composite stabilizer with a calcium-zinc mass ratio of (2-3):1. Colorants: Use iron oxide red, iron oxide yellow, and carbon black. Additives: Use 0.5%-3% stearic acid and 0.1%-1% hindered phenolic antioxidant.

[0073] The following ingredients are weighed in percentage by mass: 50% to 55% of polyvinyl chloride resin, 25% to 27% of vegetable oil plasticizer, 8% to 10% of plant filler, 2% to 5% of stabilizer, 1% to 2% of colorant and 1% to 14% of processing aid; the PVC resin is added into a high-speed mixer at a speed of 800 rpm to 1200 rpm, and the temperature is raised to 50° C. to 60° C.; the vegetable oil plasticizer is then slowly added, and the mixture is mixed for 5 to 8 minutes until the resin is uniformly swollen; the stabilizer, plant filler, colorant and processing aid are then added in sequence, and the mixture is mixed for 10 to 15 minutes until the system temperature reaches 90° C. to 100° C.; the discharged material is cooled to below 40° C., and the agglomerated particles are removed through an 80-mesh sieve to obtain a uniform dense layer mixture.

[0074] Afterwards, the dense layer mixture is evenly coated onto the release paper with a coating thickness of 0.2mm to 0.3mm at a coating speed of 10m / min to 15m / min, and a surface roughness Ra of 0.5μm to 1.0μm. The coated release paper is placed in an oven and heated and formed in stages. The preheating stage is at a temperature of 140°C to 160°C with a dwell time of 1min to 2min; the forming stage is at a temperature of 170°C to 190°C with a dwell time of 3min to 5min, allowing the PVC resin to fully gel and form a dense layer membrane. After heating and forming, the membrane is cooled to below 40°C at a cooling rate of 5°C / min to 10°C / min.

[0075] S120: Mix polyvinyl chloride resin, vegetable oil plasticizer, plant filler, stabilizer, foaming agent and flame retardant evenly, then evenly apply them on the dense layer and heat to form, so as to prepare a foaming layer.

[0076] Specifically, the selection of polyvinyl chloride resin, vegetable oil plasticizer, plant filler, and stabilizer is the same as S110. Azodicarbonamide is used as the foaming agent, with a decomposition temperature of 180°C to 200°C and a gas evolution rate of 200mL / g to 300mL / g. Zinc borate is used as the flame retardant, with a particle size D50 ≤ 5μm and a purity ≥ 99%. Weigh 45% to 50% polyvinyl chloride resin, 22% to 25% vegetable oil plasticizer, 6% to 10% plant filler, 1% to 3% stabilizer, 0.8% to 1.5% foaming agent, 4% to 5.5% flame retardant, and 5% to 21.2% processing aid. Premix the PVC resin and vegetable oil plasticizer at 60°C for 5 minutes. Then, add the stabilizer and flame retardant and mix for 8 minutes. Finally, add the foaming agent to prevent premature decomposition. Mix for 5 minutes and discharge to obtain the foam layer mixture.

[0077] Afterwards, the foaming layer mixture is evenly applied to the dense layer prepared in S110, with a coating thickness of 0.5mm to 0.8mm and a coating speed of 10m / min to 15m / min. The coated double-layer structure is placed in an oven and heated and formed in stages. The preheating stage is at a temperature of 140°C to 160°C with a dwell time of 1 to 2 minutes; the forming stage is at a temperature of 190°C to 200°C with a dwell time of 3 to 5 minutes, allowing the foaming agent to decompose and generate gas, forming the foaming layer structure. After heating and forming, the double-layer structure is cooled to below 40°C at a cooling rate of 5°C / min to 10°C / min.

[0078] S130: The foamed layer is embossed and coated to obtain polyvinyl chloride artificial leather.

[0079] Specifically, the cooled double-layer structure is fed into an embossing machine and embossed at a temperature of 120°C to 140°C and a pressure of 8MPa to 10MPa for 10 to 30 seconds to form the desired surface texture. A layer of polyurethane finishing agent is applied to the embossed surface to a thickness of 10 to 20μm, followed by curing at 80°C to 100°C for 1 to 2 minutes to improve the product's wear resistance and weather resistance.

[0080] Furthermore, the polyvinyl chloride artificial leather prepared in the above embodiment can be used in clothing, shoes, bags or decorations to obtain green and environmentally friendly products.

[0081] Example 1

[0082] This embodiment provides a polyvinyl chloride artificial leather for use in brown luggage, comprising the following steps:

[0083] Weigh by mass percentage: 54% polyvinyl chloride resin, 28% epoxy soybean oil, 9% wood flour (40-80 mesh, dried at 100°C for 4h, moisture content ≤0.8%), 4% calcium zinc composite stabilizer (Ca / Zn=3:1, containing 5% phosphite), 1% red iron oxide, 1% yellow iron oxide, 2.5% stearic acid, and 0.5% antioxidant BHT (the total of all components is 100%); add PVC resin into a high-speed mixer at a speed of 1000 rpm and raise the temperature to 55°C; slowly add epoxy soybean oil and mix for 7 minutes until the resin swells; add the remaining components in sequence and mix for 12 minutes to 95°C; cool the discharged material to ≤35°C and pass it through an 80-mesh sieve. The mixture was coated on PET release paper (Ra = 0.8 μm) with a coating thickness of 0.25 mm and a coating speed of 10 m / min; the mixture was heated in an oven in stages: 150°C × 2 min → 185°C × 4 min; and water-cooled to below 40°C at a cooling rate of 8°C / min.

[0084] Weigh the following by mass percentage: 50% polyvinyl chloride resin, 25% epoxy linseed oil, 10% bamboo powder (60-100 mesh, dried at 100°C for 4 hours, moisture content ≤0.8%, modified with 1.5% KH-550 silane coupling agent), 3% calcium stearate, 1.5% azodicarbonamide, 5% zinc borate, 2% zinc oxide, 3% stearic acid, and 0.5% zinc stearate (total of all components 100%). Premix the PVC resin and epoxy linseed oil at 60°C for 5 minutes. Add the calcium stearate, zinc borate, and zinc oxide and mix for 8 minutes. Finally, add the azodicarbonamide and the remaining stearic acid and mix for 5 minutes before discharging. Apply the foaming layer mixture to the dense layer to a thickness of 0.6 mm at a speed of 10 m / min. Heat in an oven in stages: 150°C for 2 minutes → 195°C for 4 minutes. Air cool to below 40°C at a cooling rate of 8°C / min.

[0085] The double-layer structure was embossed at 130° C. and 9 MPa for 20 seconds; a polyurethane finishing agent (solid content 30%) was applied to a coating thickness of 15 μm, and the coating was cured at 90° C. for 2 minutes.

[0086] Example 2

[0087] This embodiment provides a polyvinyl chloride artificial leather for use in brown luggage, comprising the following steps:

[0088] Weigh by mass percentage: 53% polyvinyl chloride resin, 27% epoxy soybean oil, 9% wood flour (60 mesh, dried at 100°C for 4h, moisture content ≤0.8%), 4% calcium zinc composite stabilizer (Ca / Zn=3:1, containing 5% phosphite), 0.8% red iron oxide, 0.7% yellow iron oxide, 2.5% stearic acid, and 0.5% antioxidant BHT (the total of all components is 100%); add PVC resin into a high-speed mixer at a speed of 1000 rpm and raise the temperature to 55°C; slowly add epoxy soybean oil and mix for 7 minutes until the resin swells; add the remaining components in sequence and mix for 12 minutes to 95°C; cool the discharged material to ≤35°C and pass it through an 80-mesh sieve. The mixture was coated on PET release paper (Ra = 0.8 μm) with a coating thickness of 0.25 mm and a coating speed of 10 m / min; the mixture was heated in an oven in stages: 150°C × 2 min → 185°C × 4 min; and water-cooled to below 40°C at a cooling rate of 8°C / min.

[0089] Weigh the following by mass percentage: 50% polyvinyl chloride resin, 25% epoxy linseed oil, 10% bamboo powder (80 mesh, dried at 100°C for 4 hours, moisture content ≤ 0.8%, modified with 1.5% KH-550 silane coupling agent), 3% calcium stearate, 1.5% azodicarbonamide, 5% zinc borate, 2% zinc oxide, 3% stearic acid, and 0.5% zinc stearate (total 100%). Premix the PVC resin and epoxy linseed oil at 60°C for 5 minutes. Add the calcium stearate, zinc borate, and zinc oxide and mix for 8 minutes. Finally, add the azodicarbonamide and the remaining stearic acid and mix for 5 minutes before discharging. Apply the foaming layer mixture to the dense layer at a thickness of 0.6 mm at a speed of 10 m / min. Heat in an oven in stages: 150°C for 2 minutes → 195°C for 4 minutes. Air cool to below 40°C at a cooling rate of 8°C / min.

[0090] The double-layer structure was embossed at 130° C. and 9 MPa for 20 seconds; a polyurethane finishing agent (solid content 30%) was applied to a coating thickness of 15 μm, and the coating was cured at 90° C. for 2 minutes.

[0091] Example 3

[0092] This embodiment provides a polyvinyl chloride artificial leather for use in blue bags, comprising the following steps:

[0093] Weigh by mass percentage: 53% polyvinyl chloride resin, 27% epoxy soybean oil, 9% wood flour (60 mesh, dried at 100°C for 4h, moisture content ≤0.8%), 4% calcium zinc composite stabilizer (Ca / Zn=3:1, containing 5% phosphite), 1.2% phthalocyanine blue, 0.3% carbon black, 2.5% stearic acid, and 0.5% antioxidant BHT (the total of all components is 100%); add PVC resin into a high-speed mixer at a speed of 1000 rpm and raise the temperature to 55°C; slowly add epoxy soybean oil and mix for 7 minutes until the resin swells; add the remaining components in sequence and mix for 12 minutes to 95°C; cool the discharged material to ≤35°C and pass it through an 80-mesh sieve. The mixture was coated on PET release paper (Ra = 0.8 μm) with a coating thickness of 0.25 mm and a coating speed of 10 m / min; the mixture was heated in an oven in stages: 150°C × 2 min → 185°C × 4 min; and water-cooled to below 40°C at a cooling rate of 8°C / min.

[0094] Weigh the following by mass percentage: 50% polyvinyl chloride resin, 25% epoxy linseed oil, 10% bamboo powder (80 mesh, dried at 100°C for 4 hours, moisture content ≤ 0.8%, modified with 1.5% KH-550 silane coupling agent), 3% calcium stearate, 1.5% azodicarbonamide, 5% zinc borate, 2% zinc oxide, 3% stearic acid, and 0.5% zinc stearate (total 100%). Premix the PVC resin and epoxy linseed oil at 60°C for 5 minutes. Add the calcium stearate, zinc borate, and zinc oxide and mix for 8 minutes. Finally, add the azodicarbonamide and the remaining stearic acid and mix for 5 minutes before discharging. Apply the foaming layer mixture to the dense layer at a thickness of 0.6 mm at a speed of 10 m / min. Heat in an oven in stages: 150°C for 2 minutes → 195°C for 4 minutes. Air cool to below 40°C at a cooling rate of 8°C / min.

[0095] The double-layer structure was embossed at 130° C. and 9 MPa for 20 seconds; a polyurethane finishing agent (solid content 30%) was applied to a coating thickness of 15 μm, and the coating was cured at 90° C. for 2 minutes.

[0096] Example 4

[0097] This embodiment provides a polyvinyl chloride artificial leather for use in yellow bags, comprising the following steps:

[0098] Weigh the following ingredients by mass percentage: 51% polyvinyl chloride resin, 27% epoxy linseed oil, 9% wood flour (60-100 mesh, dried at 105°C for 5h, moisture content ≤0.7%), 4% calcium stearate and zinc stearate composite stabilizer (mass ratio 3:2), 1.8% yellow iron oxide, 0.2% titanium dioxide, 2.5% stearic acid, and 0.5% antioxidant 168 (the total of all components is 100%); add the PVC resin into a high-speed mixer at a speed of 1100 rpm and raise the temperature to 58°C; slowly add the epoxy linseed oil and mix for 8 minutes until the resin swells; add the remaining components in sequence and mix for 13 minutes until the temperature reaches 98°C; cool the discharged material to ≤33°C and pass it through a 90-mesh sieve. The mixture was coated on PET release paper (Ra = 0.7 μm) with a coating thickness of 0.23 mm and a coating speed of 11 m / min. The mixture was heated in an oven in stages: 155°C × 2.5 min → 188°C × 4.5 min; and water-cooled to below 38°C at a cooling rate of 9°C / min.

[0099] Weigh by mass percentage: 47% polyvinyl chloride resin, 24% butyl ricinoleate, 10% bamboo powder (80-120 mesh, dried at 105°C for 5h, moisture content ≤0.7%, modified with 2% KH-570 silane coupling agent), 2% calcium zinc composite stabilizer (containing 5% phosphite), 1.3% azodicarbonamide, 5% zinc borate and aluminum oxide compound flame retardant (mass ratio 3:2), 1.7% zinc oxide, 2.5% stearic acid, and 0.5% zinc stearate (the total of all components is 100%); premix the PVC resin and butyl ricinoleate at 62°C for 6 minutes; add the calcium zinc composite stabilizer, compound flame retardant, and zinc oxide, and mix for 9 minutes; finally, add azodicarbonamide and the remaining stearic acid, mix for 6 minutes, and discharge. The foaming layer mixture was coated on the dense layer with a coating thickness of 0.55 mm and a speed of 11 m / min; the oven was heated in stages: 155°C × 2.5 min → 198°C × 4.5 min; and air-cooled to below 38°C at a cooling rate of 9°C / min.

[0100] The double-layer structure was embossed at 135° C. and 10 MPa for 18 seconds; a water-based polyurethane finishing agent (solid content 32%) was applied with a coating thickness of 13 μm, and the coating was cured at 88° C. for 2.5 minutes.

[0101] Example 5

[0102] This embodiment provides a polyvinyl chloride artificial leather for use in blue bags, comprising the following steps:

[0103] Weigh the following by mass percentage: 52% polyvinyl chloride resin, 26% acetylated monoglyceride, 10% flax fiber (80-120 mesh, dried at 105°C for 5h, moisture content ≤0.7%), 3.5% calcium ricinoleate and zinc ricinoleate composite stabilizer (mass ratio 2:1), 1.3% phthalocyanine blue, 0.2% carbon black, 2.5% stearic acid, and 0.5% antioxidant 1010 (the total of all components is 100%); add the PVC resin into a high-speed mixer at a speed of 1100 rpm and raise the temperature to 58°C; slowly add the acetylated monoglyceride and mix for 8 minutes until the resin swells; add the remaining components in sequence and mix for 13 minutes until the temperature reaches 98°C; cool the discharged material to ≤33°C and pass it through a 90-mesh sieve. The mixture was coated on PET release paper (Ra = 0.7 μm) with a coating thickness of 0.23 mm and a coating speed of 11 m / min. The mixture was heated in an oven in stages: 155°C × 2.5 min → 188°C × 4.5 min; and water-cooled to below 38°C at a cooling rate of 9°C / min.

[0104] The following components were weighed in percentage by mass: 48% polyvinyl chloride resin, 23% butyl ricinoleate, 10% starch-based filler (modified with 2% surfactant), 2% calcium zinc composite stabilizer (containing 5% phosphite), 1.2% potassium azodicarbonamide formate, 5% phosphate flame retardant (melamine polyphosphate), 1.8% zinc oxide, 2.5% stearic acid, and 0.5% zinc stearate (the total of all components is 100%); the PVC resin and butyl ricinoleate were premixed at 62° C. for 6 minutes; the calcium zinc composite stabilizer, phosphate flame retardant, and zinc oxide were added and mixed for 9 minutes; finally, the potassium azodicarbonamide formate and the remaining stearic acid were added and mixed for 6 minutes before discharging. The foaming layer mixture was coated on the dense layer with a coating thickness of 0.55 mm and a speed of 11 m / min; the oven was heated in stages: 155°C × 2.5 min → 198°C × 4.5 min; and air-cooled to below 38°C at a cooling rate of 9°C / min.

[0105] The double-layer structure was embossed at 135° C. and 10 MPa for 18 seconds; a water-based polyurethane finishing agent (solid content 32%) was applied with a coating thickness of 13 μm, and the coating was cured at 88° C. for 2.5 minutes.

[0106] Comparative Example 1

[0107] The polyvinyl chloride artificial leather is prepared by conventional recipe.

[0108] Examples 1 to 5 and Comparative Example 1 were subjected to leather color fastness test, abrasion resistance test and bending resistance test.

[0109] Among them, when testing the color fastness of leather, the test is carried out by dry rubbing 50 times and wet rubbing 10 times; the gray sample card for evaluating discoloration in GB 251-2008 is used to determine the grade of the test piece; and the qualification of the test piece is determined by referring to QB / T1333-2018 (backpacks) and QB / T1619-2018 (wallets).

[0110] In the abrasion resistance test, the samples were abraded 150 times with a CS10 grinding wheel with a load of 500g. According to GB / T 250-2008 "Textiles - Tests for Colour Fastness - Grey Scale for Assessment of Colour Change", the colour change degree of the samples after the experiment was evaluated by comparing with the standard colour chart under the D65 light source in a light box.

[0111] During the bending resistance test, bend the sample 5000 times at -10℃. Flatten the sample after testing and observe it carefully under a fluorescent light. The sample is qualified if there is no crack on the surface. The worst value of the two samples in each direction is taken as the result in that direction.

[0112] The results are as follows:

[0113] Leather & Skin Color Fastness Test Wear resistance test Bending resistance test Example 1 Level 5 Level 5 No abnormalities Example 2 Level 5 Level 5 No abnormalities Example 3 Level 5 Level 5 No abnormalities Example 4 Level 5 Level 5 No abnormalities Example 5 Level 5 Level 5 No abnormalities Comparative Example 1 Level 5 Level 5 No abnormalities

[0114] It can be seen that compared with Comparative Example 1, the leather color fastness test, abrasion resistance test, and bending resistance test results of Examples 1 to 5 are also good. However, it is understandable that the formula of the comparative example contains a variety of raw materials that are not friendly to the ecological environment. In terms of raw material selection, Examples 1 to 5 use plant oil plasticizers such as epoxidized soybean oil and epoxidized linseed oil to replace traditional phthalate plasticizers to reduce toxicity risks; the use of natural plant fillers such as wood flour and bamboo powder not only reduces the consumption of petroleum-based materials, but also improves compatibility with resins through modification with silane coupling agents. The use of calcium-zinc composite stabilizers avoids heavy metal pollution such as lead and cadmium. In addition, the iron oxide pigments in Examples 1 and 2 or the combination of phthalocyanine blue and carbon black in Example 3 are non-toxic and harmless while meeting color requirements. These environmentally friendly raw materials cooperate with processing aids such as antioxidants and lubricants to ensure stable physical properties while reducing environmental pollution. Therefore, the polyvinyl chloride artificial leather of the present application significantly improves the green environmental protection performance and product quality of the polyvinyl chloride artificial leather through the synergy of multiple components in the formula design, which is in line with the concept of sustainable development.

[0115] Furthermore, Example 5 is a preferred embodiment. In Example 5, acetylated monoglyceride is used as a vegetable oil plasticizer in the dense layer. Compared with traditional plasticizers, it has better biodegradability and can reduce potential harm to the environment. In addition, flax fiber is selected as a plant filler. It is understandable that flax fiber has high strength and can improve the mechanical properties of artificial leather. At the same time, it is renewable and degradable, which is in line with environmental protection. In addition, a starch-based filler modified with a surfactant is used in the foaming layer to enhance the binding force with the resin and reduce filler agglomeration. The starch-based filler is widely available and environmentally friendly. In addition, by using a combination of calcium ricinoleate and zinc ricinoleate and a calcium-zinc composite stabilizer, while ensuring the stabilization effect, the risk of heavy metals is reduced and the product safety is improved. Melamine polyphosphate is selected as a flame retardant. It has high flame retardant efficiency and can form an expanded carbon layer during combustion, effectively preventing the spread of flames, improving the flame retardant properties of artificial leather, and meeting the fire safety requirements of luggage. Therefore, the luggage prepared from the polyvinyl chloride artificial leather of Example 5 has better performance and greater practicality.

[0116] In terms of process, Examples 1 through 5 all employ a mixing and molding process with segmented heating and precise temperature control, ensuring the full effectiveness of environmentally friendly additives while reducing energy consumption. Strict control of the cooling rate further improves product quality and production efficiency. Compared to the conventional formulation of Comparative Example 1, Examples 1 through 5 achieve the multiple advantages of low toxicity, environmental protection, resource conservation, and high performance through the coordinated optimization of formulation and process.

[0117] In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "connect," "fixed," etc. should be understood broadly. For example, they may refer to fixed connection, detachable connection, or integration; mechanical connection or electrical connection; direct connection or indirect connection through an intermediate medium; internal communication between two components or interaction between two components. Those skilled in the art will understand the specific meanings of the above terms in the present invention based on specific circumstances.

[0118] In the description of the present invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer" and the like indicate positions or locations based on the positions shown in the accompanying drawings, or the positions or locations in which the inventive product is typically placed when in use. These terms are intended solely to facilitate the description of the present invention and to simplify the description, and are not intended to indicate or imply that the devices or components referred to must have a specific orientation, be constructed, or operate in a specific orientation. Therefore, they should not be construed as limitations on the present invention. Furthermore, the terms "first," "second," and "third," etc., are used solely to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0119] Furthermore, terms such as "horizontal," "vertical," and "overhanging" do not necessarily imply that a component must be absolutely horizontal or overhanging, but rather that it can be slightly tilted. For example, "horizontal" simply means that its direction is more horizontal than "vertical," and does not mean that the structure must be completely horizontal, but rather that it can be slightly tilted.

[0120] In the present invention, unless otherwise expressly specified or limited, a first feature being above or below a second feature may include the first and second features being in direct contact, or may include the first and second features being in contact not directly but through another feature between them. Furthermore, a first feature being above, above, and above the second feature includes the first feature being directly above and obliquely above the second feature, or simply means that the first feature is higher in level than the second feature. A first feature being below, below, and below the second feature includes the first feature being directly below and obliquely below the second feature, or simply means that the first feature is lower in level than the second feature.

[0121] Although the present invention has been described with reference to the above specific embodiments, it will be apparent to those skilled in the art that many substitutions, modifications, and variations can be made based on the above. Therefore, all such substitutions, modifications, and variations are intended to be encompassed within the spirit and scope of the appended claims.

Claims

1. A polyvinyl chloride artificial leather, characterized in that including a dense layer and a foamed layer; The dense layer comprises, by mass percentage, 50% to 55% of polyvinyl chloride resin, 25% to 27% of vegetable oil plasticizer, 8% to 10% of plant filler, 2% to 5% of stabilizer and 1% to 2% of colorant, with the balance being processing aids and unavoidable impurities, with the balance being 1% to 14% and the unavoidable impurities being less than 0.5%; The foaming layer comprises, by mass percentage, 45% to 50% of polyvinyl chloride resin, 22% to 25% of vegetable oil plasticizer, 6% to 10% of plant filler, 1% to 3% of stabilizer, 0.8% to 1.5% of foaming agent and 4% to 5.5% of flame retardant, with the remainder being processing aids and inevitable impurities, with the remainder being 5% to 21.2%, and the inevitable impurities being less than 0.5%.

2. The polyvinyl chloride artificial leather according to claim 1, characterized in that: The vegetable oil plasticizer is any one or more of epoxidized soybean oil, epoxidized linseed oil, acetylated monoglyceride and butyl ricinoleate.

3. The polyvinyl chloride artificial leather according to claim 1, characterized in that: The plant filler is any one or more of wood powder, bamboo powder, flax fiber, and starch-based filler.

4. The polyvinyl chloride artificial leather according to claim 1, characterized in that: The foaming agent in the foaming layer is set to be any one or more of azodicarbonamide, azodicarbonamide potassium formate, sodium bicarbonate and azobisisobutyronitrile.

5. The polyvinyl chloride artificial leather according to claim 1, characterized in that: The stabilizer is any one or more of calcium stearate, calcium ricinoleate, zinc ricinoleate, a calcium-zinc composite stabilizer, zinc stearate, barium stearate or lanthanum stearate.

6. The polyvinyl chloride artificial leather according to claim 1, characterized in that: The flame retardant is any one or more of phosphate, zinc borate, boron oxide and aluminum oxide.

7. The polyvinyl chloride artificial leather according to claim 1, characterized in that: The colorant is any one or more of iron oxide red, iron oxide yellow, carbon black, titanium dioxide and phthalocyanine blue.

8. The polyvinyl chloride artificial leather according to claim 1, characterized in that: The processing aid is configured as a lubricant and / or an antioxidant.

9. A method for preparing the polyvinyl chloride artificial leather according to any one of claims 1 to 8, characterized in that: The following steps are involved: The polyvinyl chloride resin, vegetable oil plasticizer, plant filler, stabilizer and colorant are mixed evenly, and then evenly coated on the release paper and heated to form a film material to prepare a dense layer; The polyvinyl chloride resin, the vegetable oil plasticizer, the plant filler, the stabilizer, the foaming agent and the flame retardant are mixed evenly, and then evenly applied on the dense layer and heated to form, thereby preparing a foaming layer; The foamed layer is embossed and coated to obtain the polyvinyl chloride artificial leather.

10. Use of the polyvinyl chloride artificial leather according to any one of claims 1 to 8 in the preparation of clothing, shoes, bags or decorations.

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