Green and environment-friendly polyvinyl chloride artificial leather and preparation method thereof

Abstract

The invention relates to the technical field of artificial leather, and provides green and environment-friendly polyvinyl chloride artificial leather, which is prepared from the following ingredients in parts by mass: 100 parts of polyvinyl chloride, 40 to 60 parts of polyester polyadipic acid-1, 2-propylene glycol ester plasticizers, 3 to 5 parts of stabilizers, 10 to 30 parts of filling materials, 5 to 10 parts of vegetable oil plasticizers, 1 to 3 parts of lubricating agents, 10 to 25 parts of adsorption decomposition agents, 1 to 3 parts of foaming agents and 1 to 3 parts of coloring agents. The green and environment-friendly polyvinyl chloride artificial leather has good environmental protection performance, and the polyester polyadipic acid-1, 2-propylene glycol ester plasticizer and the vegetable oil plasticizer are used for replacing a traditional phthalate plasticizer, so that the release of harmful substances is remarkably reduced. Meanwhile, the added adsorption and decomposition agent can effectively adsorb and decompose harmful gas possibly generated in the use process of the artificial leather, and the environmental protection performance of the product is further improved.

Description

Technical Field

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

[0002] PVC (Polyvinyl chloride) leather is the main raw material for luggage and is widely used in luggage. The polyvinyl chloride used in PVC leather has performance defects such as low strength, easy aging, poor thermal stability, and easy decomposition and release of harmful gases at high temperatures. Therefore, different additives need to be added for modification. Among them, plasticizers are one of the indispensable additives.

[0003] There are many types of plasticizers, and the most commonly used are phthalates, particularly dioctyl phthalate. However, dioctyl phthalate is toxic to humans and poses a risk of cancer. When PVC products plasticized with it are exposed to external conditions such as heat or solvents, small molecules of dioctyl phthalate easily migrate out, impacting not only human health but also the environment and the product's lifespan. Summary of the Invention

[0004] In view of the above-mentioned shortcomings of the prior art, the present invention provides a green and environmentally friendly polyvinyl chloride artificial leather and a preparation method thereof.

[0005] To achieve the above object, the present invention provides the following technical solution:

[0006] In a first aspect, a green and environmentally friendly polyvinyl chloride artificial leather is provided, comprising, by weight:

[0007] 100 parts of polyvinyl chloride, 40 to 60 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 3 to 5 parts of stabilizer, 10 to 30 parts of filler, 5 to 10 parts of vegetable oil plasticizer, 1 to 3 parts of lubricant, 10 to 25 parts of adsorption decomposition agent, 1 to 3 parts of foaming agent and 1 to 3 parts of colorant.

[0008] In some embodiments, the foaming agent is set to supercritical CO2, and also includes 2 to 3 parts of nano talc powder as a nucleating agent.

[0009] In some embodiments, 5 to 8 parts of ethylene vinyl acetate are further included.

[0010] In some embodiments, the stabilizer is configured as any one or more of calcium stearate, calcium zinc composite stabilizer, and zinc stearate.

[0011] In some embodiments, the filler is configured as light calcium carbonate or wollastonite powder.

[0012] In some embodiments, the vegetable oil plasticizer is any one or more of epoxidized soybean oil and epoxidized linseed oil.

[0013] In some embodiments, the lubricant is configured as a stearic acid or paraffin lubricant.

[0014] In some embodiments, the adsorption decomposition agent is configured as modified activated carbon-supported nano nitrogen-doped titanium dioxide.

[0015] In some embodiments, 1 to 3 parts of organic reversible thermochromic microcapsules and 0.5 to 1 part of graphene nanosheets are also included.

[0016] In a second aspect, a method for preparing green and environmentally friendly polyvinyl chloride artificial leather is provided, comprising:

[0017] Weigh the raw materials according to the formula;

[0018] Add polyvinyl chloride into a high-speed mixer, and sequentially add polyester polyadipate-1,2-propylene glycol ester plasticizer, stabilizer, filler, vegetable oil plasticizer, lubricant, adsorption decomposition agent, foaming agent and colorant, and stir at 90°C to 130°C for 120 seconds to 200 seconds to uniformly disperse the materials to obtain a mixture;

[0019] The mixture is mixed with a solvent to form a slurry with a solid content controlled at 30% to 50%, and the slurry is coated on a base fabric by a coating machine. After coating, the slurry is placed in an oven at 150° C. to 200° C. for foaming to obtain a formed artificial leather;

[0020] The formed artificial leather is then cooled, shaped, printed, embossed and laminated to obtain a product.

[0021] Compared with the prior art, the present invention has the beneficial effect of improving environmental performance by significantly reducing the release of harmful substances by replacing traditional phthalate plasticizers with polyester polypropylene adipate and vegetable oil plasticizers. Furthermore, the added adsorption and decomposition agent effectively absorbs and decomposes harmful gases that may be generated during use, further improving the environmental performance of the product and ensuring its service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The present invention is a flow chart of the method for preparing the green and environmentally friendly polyvinyl chloride artificial leather. DETAILED DESCRIPTION

[0023] 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.

[0024] 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.

[0025] The present application provides a green and environmentally friendly polyvinyl chloride artificial leather, which includes, by mass: 100 parts of polyvinyl chloride, 40 to 60 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 3 to 5 parts of stabilizer, 10 to 30 parts of filler, 5 to 10 parts of vegetable oil plasticizer, 1 to 3 parts of lubricant, 10 to 25 parts of adsorption decomposition agent, 1 to 3 parts of foaming agent and 1 to 3 parts of colorant.

[0026] Specifically, the specific settings of each recipe are subject to actual production needs and are not limited here. Examples are as follows:

[0027] The polyvinyl chloride is set to a PVC resin with a K value of 65-70.

[0028] Polyester polyadipate-1,2-propylene glycol ester plasticizer: For example, the polyester polyadipate-1,2-propylene glycol ester plasticizer is set to 40 parts; for another example, the polyester polyadipate-1,2-propylene glycol ester plasticizer is set to 50 parts; for another example, the polyester polyadipate-1,2-propylene glycol ester plasticizer is set to 60 parts.

[0029] Stabilizer: For example, the stabilizer is set to 3 parts; for another example, the stabilizer is set to 3.5 parts; for another example, the stabilizer is set to 5 parts.

[0030] Filler: For example, the filler is set to 10 parts; for another example, the filler is set to 25 parts; for another example, the filler is set to 30 parts.

[0031] Vegetable oil plasticizer: For example, the vegetable oil plasticizer is set to 5 parts; for another example, the vegetable oil plasticizer is set to 6 parts; for another example, the vegetable oil plasticizer is set to 10 parts.

[0032] Lubricant: For example, the lubricant is set to 1 part; for another example, the lubricant is set to 1.2 parts; for another example, the lubricant is set to 3 parts.

[0033] Adsorption decomposition agent: For example, the adsorption decomposition agent is set to 10 parts; for another example, the adsorption decomposition agent is set to 20 parts; for another example, the adsorption decomposition agent is set to 25 parts.

[0034] Foaming agent: For example, the foaming agent is set to 1 part; for another example, the foaming agent is set to 1.5 parts; for another example, the foaming agent is set to 3 parts.

[0035] Colorant: For example, the colorant is set to 1 part; for another example, the colorant is set to 2.2 parts; for another example, the colorant is set to 3 parts.

[0036] In some embodiments, the foaming agent can be replaced with supercritical CO2, and 2 to 3 parts of nano-talc powder as a nucleating agent can be added. The amount of nano-talc powder as a nucleating agent can be 2 parts, 2.7 parts, or 3 parts.

[0037] Furthermore, it further comprises 5 to 8 parts of ethylene vinyl acetate, wherein the amount of ethylene vinyl acetate can be set to 5 parts, 6.8 parts or 8 parts.

[0038] In other embodiments, 1 to 3 parts of reversible thermochromic microcapsules and 0.5 to 1 part of graphene nanosheets may be added. The reversible thermochromic microcapsules may be provided in an amount of 1 part, 2.3 parts, or 3 parts, and the graphene nanosheets may be provided in an amount of 0.5 part, 0.8 part, or 1 part.

[0039] In the above embodiments, the specific selection of the auxiliary agent shall be based on the actual production situation and is not limited here. Examples are as follows:

[0040] The stabilizer is configured as calcium stearate, calcium zinc composite stabilizer, zinc stearate, mixed calcium stearate, calcium zinc composite stabilizer, mixed calcium zinc composite stabilizer and zinc stearate, or mixed calcium zinc composite stabilizer and zinc stearate.

[0041] The filler can be configured as light calcium carbonate or wollastonite powder.

[0042] The vegetable oil plasticizer is configured as epoxidized soybean oil, epoxidized linseed oil, or a mixture of epoxidized soybean oil and epoxidized linseed oil.

[0043] The lubricant is configured as stearic acid or paraffin lubricant.

[0044] The adsorption decomposition agent is configured as modified activated carbon loaded with nano nitrogen-doped titanium dioxide.

[0045] The foaming agent is set to be any one or more of azodicarbonamide, azodicarbonamide potassium formate, sodium bicarbonate and azobisisobutyronitrile.

[0046] like Figure 1 As shown, the preparation method of green and environmentally friendly polyvinyl chloride artificial leather is as follows: weighing the raw materials according to the formula;

[0047] Add polyvinyl chloride into a high-speed mixer, and sequentially add polyester polyadipate-1,2-propylene glycol ester plasticizer, stabilizer, filler, vegetable oil plasticizer, lubricant, adsorption decomposition agent, foaming agent and colorant, and stir at 90°C to 130°C for 120 seconds to 200 seconds to uniformly disperse the materials to obtain a mixture;

[0048] The mixed material is mixed with a solvent to form a slurry with a solid content controlled at 30% to 50%, and the slurry is coated on a base fabric through a coating machine. After coating, the slurry is placed in an oven at 150° C. to 200° C. for foaming to obtain a formed artificial leather. The formed artificial leather is then cooled, shaped, printed, embossed and laminated to obtain a product.

[0049] In another embodiment, a green and environmentally friendly polyvinyl chloride artificial leather comprises, by weight:

[0050] Dense layer: 100 parts of polyvinyl chloride, 50 to 65 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 4 to 7 parts of stabilizer, 15 to 37 parts of filler, 8 to 10 parts of vegetable oil plasticizer, 1 to 3 parts of lubricant and 1 to 3 parts of colorant.

[0051] Foaming layer: 100 parts of polyvinyl chloride, 40 to 60 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 3 to 5 parts of stabilizer, 10 to 30 parts of filler, 5 to 10 parts of vegetable oil plasticizer, 1 to 3 parts of lubricant, 10 to 25 parts of adsorption decomposition agent, 1 to 3 parts of foaming agent and 1 to 3 parts of colorant.

[0052] 1 to 3 parts of organic reversible thermochromic microcapsules and 0.5 to 1 part of graphene nanosheets can be added into the dense layer; supercritical CO2, nucleating agent nano talc powder and ethylene-vinyl acetate can be added into the foaming layer.

[0053] Its preparation method is:

[0054] Weigh each component according to the formula and set aside.

[0055] 100 parts of polyvinyl chloride were added into a high-speed mixer, and polyester polyadipate-1,2-propylene glycol ester plasticizer, stabilizer, filler, vegetable oil plasticizer, lubricant and colorant were added in sequence, and stirred at 110° C. for 160 seconds to obtain a first layer mixture.

[0056] The first layer mixture is mixed with solvent to form a slurry with a solid content of 50%. It is coated on the base fabric using a comma blade coater with a wet film thickness of 0.3mm. It is then pre-baked in a 150℃ oven for 2 minutes to form a dense layer with a thickness of about 0.15mm.

[0057] Add polyvinyl chloride into a high-speed mixer, and add polyester polyadipate-1,2-propylene glycol ester plasticizer, stabilizer, filler, vegetable oil plasticizer, lubricant, adsorption decomposition agent, foaming agent and colorant in sequence, and stir at 110°C for 160 seconds to obtain a second layer mixture;

[0058] A second layer of the mixture is applied on the surface of the dense layer, with a wet film thickness of 0.8 mm, and then placed in a 180°C oven for foaming for 3 minutes to form a foamed layer with a thickness of about 0.6 mm, thereby obtaining the formed artificial leather;

[0059] The formed artificial leather is then cooled, shaped, printed, embossed and laminated to obtain a product.

[0060] Example 1

[0061] A green and environmentally friendly polyvinyl chloride artificial leather comprises, by mass, 100 parts of polyvinyl chloride, 50 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 4 parts of stabilizer, 20 parts of filler, 7 parts of vegetable oil plasticizer, 2 parts of lubricant, 15 parts of adsorption decomposition agent, 2 parts of foaming agent and 2 parts of colorant.

[0062] The foaming agent is supercritical CO2, and the nucleating agent includes 2.5 parts of nano-talc. It also contains 6 parts of ethylene vinyl acetate. The filler is light calcium carbonate. The vegetable oil plasticizer is epoxidized soybean oil. The lubricant is stearic acid. The adsorption and decomposition agent is modified activated carbon-supported nano-nitrogen-doped titanium dioxide. The stabilizer is a calcium-zinc composite stabilizer. Furthermore, it contains 2 parts of organic reversible thermochromic microcapsules and 0.8 parts of graphene nanosheets.

[0063] The preparation method of the green and environmentally friendly polyvinyl chloride artificial leather comprises the following steps:

[0064] First, the raw materials are weighed according to the formula and set aside; 100 parts of polyvinyl chloride are added to a high-speed mixer, and then 50 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 4 parts of calcium zinc composite stabilizer, 20 parts of light calcium carbonate, 7 parts of epoxy soybean oil, 2 parts of stearic acid, 15 parts of modified activated carbon-loaded nano-nitrogen-doped titanium dioxide, 2 parts of supercritical CO2 foaming agent, 2 parts of colorant, 2.5 parts of nano-talc, 6 parts of ethylene vinyl acetate, 2 parts of organic reversible thermochromic microcapsules and 0.8 parts of graphene nanosheets are added in sequence, and the mixture is stirred at 110°C for 160 seconds to uniformly disperse the materials to obtain a mixture;

[0065] The mixture is mixed with a solvent to form a slurry with a solid content controlled at 40%, which is then coated on a base fabric by a coating machine. After coating, the slurry is placed in an oven at 175°C for foaming to obtain the formed artificial leather.

[0066] The formed artificial leather is then cooled, shaped, printed, embossed and laminated to obtain the product.

[0067] This green, environmentally friendly PVC artificial leather boasts excellent environmental performance. By replacing traditional phthalate plasticizers with polyester polypropylene adipate and vegetable oil plasticizers, the release of harmful substances is significantly reduced. Furthermore, the addition of an adsorption and decomposition agent effectively absorbs and decomposes harmful gases that may be generated during use, further enhancing the product's environmental performance.

[0068] Supercritical CO2, used as a foaming agent, is not only environmentally friendly and non-toxic, but also, through the synergistic effect of nano-talc powder, forms a uniform and fine microporous structure, giving the artificial leather excellent breathability and softness. The addition of ethylene vinyl acetate improves the material's toughness and wear resistance, making the product more durable.

[0069] The addition of organic reversible thermochromic microcapsules and graphene nanosheets gives artificial leather temperature sensitivity and conductive properties, giving the product intelligent color-changing and anti-static functions, expanding its application areas.

[0070] Example 2

[0071] A green and environmentally friendly polyvinyl chloride artificial leather comprises, by mass, 100 parts of polyvinyl chloride, 40 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 3 parts of stabilizer, 10 parts of filler, 5 parts of vegetable oil plasticizer, 1 part of lubricant, 10 parts of adsorption decomposition agent, 1 part of foaming agent and 1 part of colorant.

[0072] The foaming agent is supercritical CO2, and the nucleating agent includes 2 parts of nano-talc powder. It also includes 5 parts of ethylene vinyl acetate. The filler is wollastonite powder. The vegetable oil plasticizer is epoxy linseed oil. The lubricant is a paraffin lubricant. The adsorption and decomposition agent is modified activated carbon-supported nano-nitrogen-doped titanium dioxide. The stabilizer is calcium stearate. Furthermore, it includes 1 part of organic reversible thermochromic microcapsules and 0.5 parts of graphene nanosheets.

[0073] The preparation method of the green and environmentally friendly polyvinyl chloride artificial leather comprises the following steps:

[0074] Weigh the raw materials according to the formula for later use; add 100 parts of polyvinyl chloride into a high-speed mixer, and sequentially add 40 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 3 parts of calcium stearate, 10 parts of wollastonite powder, 5 parts of epoxy linseed oil, 1 part of paraffin lubricant, 10 parts of modified activated carbon-loaded nano-nitrogen-doped titanium dioxide, 1 part of supercritical CO2 foaming agent, 1 part of colorant, 2 parts of nano-talc powder, 5 parts of ethylene vinyl acetate, 1 part of organic reversible thermochromic microcapsules and 0.5 parts of graphene nanosheets, and stir at 90°C for 120 seconds to uniformly disperse the materials to obtain a mixture;

[0075] The mixture is mixed with a solvent to form a slurry with a solid content controlled at 30%, which is then coated on a base fabric by a coating machine. After coating, the slurry is placed in an oven at 150°C for foaming to obtain the formed artificial leather.

[0076] The formed artificial leather is then cooled, shaped, printed, embossed and laminated to obtain the product.

[0077] In this example, by reducing the amount of each component, particularly the amount of the polyester poly(1,2-propylene adipate) plasticizer, the product achieves greater hardness and stiffness, making it suitable for products requiring a certain degree of support, such as luggage and handbags. Furthermore, the wollastonite powder used as a filler exhibits excellent wear and weather resistance, further extending the product's service life.

[0078] Example 3

[0079] A green and environmentally friendly polyvinyl chloride artificial leather comprises, by mass, 100 parts of polyvinyl chloride, 60 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 5 parts of stabilizer, 30 parts of filler, 10 parts of vegetable oil plasticizer, 3 parts of lubricant, 25 parts of adsorption decomposition agent, 3 parts of foaming agent and 3 parts of colorant.

[0080] Among them, the foaming agent is supercritical CO2, and it also includes 3 parts of nucleating agent nano talc powder. At the same time, it also includes 8 parts of ethylene vinyl acetate. The filler is a mixture of light calcium carbonate and wollastonite powder, with a mass ratio of 1:1. The vegetable oil plasticizer is a mixture of epoxidized soybean oil and epoxidized linseed oil, with a mass ratio of 2:1. The lubricant is a mixture of stearic acid and paraffin lubricant, with a mass ratio of 1:1. The adsorption decomposition agent is modified activated carbon loaded with nano nitrogen-doped titanium dioxide. The stabilizer is a mixture of zinc stearate and calcium zinc composite stabilizer, with a mass ratio of 1:2. In addition, it also includes 3 parts of organic reversible thermochromic microcapsules and 1 part of graphene nanosheets.

[0081] The preparation method of the green and environmentally friendly polyvinyl chloride artificial leather comprises the following steps:

[0082] Weigh the raw materials according to the formula for later use; add 100 parts of polyvinyl chloride into a high-speed mixer, and sequentially add 60 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 5 parts of a mixture of zinc stearate and a calcium-zinc composite stabilizer, 30 parts of a mixture of light calcium carbonate and wollastonite powder, 10 parts of a mixture of epoxidized soybean oil and epoxidized linseed oil, 3 parts of a mixture of stearic acid and a paraffin lubricant, 25 parts of modified activated carbon-loaded nano-nitrogen-doped titanium dioxide, 3 parts of a supercritical CO2 foaming agent, 3 parts of a colorant, 3 parts of nano-talc powder, 8 parts of ethylene-vinyl acetate, 3 parts of an organic reversible thermochromic microcapsule, and 1 part of a graphene nanosheet, and stir at 130° C. for 200 seconds to uniformly disperse the materials to obtain a mixture;

[0083] The mixture is mixed with a solvent to form a slurry with a solid content controlled at 50%, which is then coated on a base fabric by a coating machine. After coating, the slurry is placed in an oven at 200°C for foaming to obtain the formed artificial leather.

[0084] The formed artificial leather is then cooled, shaped, printed, embossed and laminated to obtain the product.

[0085] In this embodiment, by increasing the amount of each component, particularly the amount of the polyester poly(1,2-propylene adipate) plasticizer and the vegetable oil plasticizer, the product has improved softness and elasticity, making it suitable for products requiring a comfortable touch, such as sofas and chairs. Furthermore, the mixed use of multiple components, such as fillers, vegetable oil plasticizers, lubricants, and stabilizers, provides more comprehensive and balanced product performance.

[0086] The higher content of adsorbent decomposition agent and foaming agent gives the product better environmental performance and breathability. The increased content of organic reversible thermochromic microcapsules and graphene nanosheets enhances the product's intelligent color-changing effect and conductive properties, giving it a competitive advantage in high-end applications such as smart homes and automotive interiors.

[0087] Example 4

[0088] A method for preparing green and environmentally friendly polyvinyl chloride artificial leather comprises:

[0089] The raw materials are weighed and set aside according to the formula, which includes, by mass, 100 parts of polyvinyl chloride, 45 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 4 parts of stabilizer, 15 parts of filler, 8 parts of vegetable oil plasticizer, 2 parts of lubricant, 20 parts of adsorption decomposition agent, 2 parts of foaming agent and 2 parts of colorant;

[0090] Add polyvinyl chloride into a high-speed mixer, and add polyester polyadipate-1,2-propylene glycol ester plasticizer, stabilizer, filler, vegetable oil plasticizer, lubricant, adsorption decomposition agent, foaming agent, colorant, etc. in sequence, and stir at 100°C for 150 seconds to uniformly disperse the materials to obtain a mixture;

[0091] The mixture is mixed with a solvent to form a slurry with a solid content controlled at 35%, which is then coated on a base fabric by a coating machine. After coating, the slurry is placed in an oven at 160°C for foaming to obtain the formed artificial leather.

[0092] The formed artificial leather is then cooled, shaped, printed, embossed and laminated to obtain the product.

[0093] The foaming agent is supercritical CO2, and the nucleating agent includes 2.5 parts of nano-talc powder. The filler is light calcium carbonate. The vegetable oil plasticizer is epoxidized soybean oil. The lubricant is stearic acid. The adsorption and decomposition agent is modified activated carbon-supported nano-nitrogen-doped titanium dioxide. The stabilizer is a calcium-zinc composite stabilizer.

[0094] The key to this preparation method lies in the precise control of raw material ratios and the optimization of process parameters. By controlling the high-speed mixer temperature at 100°C and the stirring time to 150 seconds, the components are thoroughly mixed and uneven performance caused by localized aggregation is avoided. The slurry solids content is controlled at 35%, ensuring fluidity during application while avoiding the increased energy consumption and prolonged drying time caused by excessive dilution. The oven temperature is controlled at 160°C to fully activate the foaming agent and form a uniform microporous structure without causing excessive aging or decomposition of the material.

[0095] The green and environmentally friendly polyvinyl chloride artificial leather produced by this preparation method has good physical and mechanical properties and environmental performance. The product has moderate softness, a smooth surface, uniform color, good air permeability, and no release of harmful substances. It is suitable for wide application in furniture decoration, luggage, shoes, clothing and other fields.

[0096] Example 5

[0097] A method for preparing green and environmentally friendly polyvinyl chloride artificial leather comprises:

[0098] The raw materials are weighed and set aside according to the formula, which includes, by mass, 100 parts of polyvinyl chloride, 55 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 3.5 parts of stabilizer, 25 parts of filler, 6 parts of vegetable oil plasticizer, 1.5 parts of lubricant, 12 parts of adsorption decomposition agent, 1.5 parts of foaming agent and 1.5 parts of colorant;

[0099] Add polyvinyl chloride into a high-speed mixer, and add polyester polyadipate-1,2-propylene glycol ester plasticizer, stabilizer, filler, vegetable oil plasticizer, lubricant, adsorption decomposition agent, foaming agent, colorant, etc. in sequence, and stir at 120°C for 180 seconds to evenly disperse the materials to obtain a mixture;

[0100] The mixture is mixed with a solvent to form a slurry with a solid content controlled at 45%, which is then coated on a base fabric by a coating machine. After coating, the slurry is placed in an oven at 180°C for foaming to obtain the formed artificial leather.

[0101] The formed artificial leather is then cooled, shaped, printed, embossed and laminated to obtain the product.

[0102] The foaming agent is supercritical CO2, and the nucleating agent includes 2.2 parts of nano-talc powder. The filler is wollastonite powder. The vegetable oil plasticizer is epoxidized linseed oil. The lubricant is a paraffin lubricant. The adsorption and decomposition agent is modified activated carbon-supported nano-nitrogen-doped titanium dioxide. The stabilizer is a mixture of calcium stearate and zinc stearate in a 1:1 weight ratio.

[0103] This preparation method utilizes a high mixing temperature and a long stirring time, which facilitates thorough mixing and compatibility between the polyvinyl chloride resin and various additives. The slurry solids content is controlled at 45%, resulting in a more uniform coating thickness and a superior product texture. The oven temperature is set at 180°C, which allows the foaming agent to fully function, forming an ideal microporous structure while promoting chemical reactions between the components and improving the overall performance of the product.

[0104] The green and environmentally friendly polyvinyl chloride artificial leather produced by this preparation method has excellent wear resistance and weather resistance, high surface gloss, soft feel, good elasticity, no odor, and outstanding environmental performance. It is particularly suitable for use in high-end automobile interiors, high-end furniture decoration, fashionable luggage and other fields.

[0105] Example 6

[0106] A green and environmentally friendly polyvinyl chloride artificial leather comprises, by mass, 100 parts of polyvinyl chloride, 50 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 4 parts of stabilizer, 20 parts of filler, 7 parts of vegetable oil plasticizer, 2 parts of lubricant, 15 parts of adsorption decomposition agent, 2 parts of foaming agent and 2 parts of colorant.

[0107] The foaming agent is azodicarbonamide, the filler is light calcium carbonate, the vegetable oil plasticizer is epoxidized soybean oil, the lubricant is stearic acid, the adsorption and decomposition agent is modified activated carbon-supported nano-nitrogen-doped titanium dioxide, and the stabilizer is a calcium-zinc composite stabilizer. Thus, a foamed layer is produced.

[0108] The preparation method of the green and environmentally friendly polyvinyl chloride artificial leather comprises the following steps:

[0109] First, the raw materials are weighed according to the formula and set aside; 100 parts of polyvinyl chloride are added to a high-speed mixer, followed by 50 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 4 parts of calcium-zinc composite stabilizer, 20 parts of light calcium carbonate, 7 parts of epoxy soybean oil, 2 parts of stearic acid, 15 parts of modified activated carbon-loaded nano-nitrogen-doped titanium dioxide, 2 parts of foaming agent, and 2 parts of colorant, and stirred at 110° C. for 160 seconds to uniformly disperse the materials to obtain a mixture;

[0110] The mixture is mixed with a solvent to form a slurry with a solid content controlled at 40%, which is then coated on a base fabric by a coating machine. After coating, the slurry is placed in an oven at 175°C for foaming to obtain the formed artificial leather.

[0111] The formed artificial leather is then cooled, shaped, printed, embossed and laminated to obtain the product.

[0112] Example 7

[0113] A green and environmentally friendly polyvinyl chloride artificial leather, comprising, by weight:

[0114] Dense layer: 100 parts of polyvinyl chloride, 65 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 7 parts of stabilizer, 37 parts of filler, 10 parts of vegetable oil plasticizer, 3 parts of lubricant and 3 parts of colorant.

[0115] Foaming layer: 100 parts of polyvinyl chloride, 50 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 4 parts of stabilizer, 20 parts of filler, 7 parts of vegetable oil plasticizer, 2 parts of lubricant, 15 parts of adsorption decomposition agent, 2 parts of foaming agent and 2 parts of colorant.

[0116] Among them, the stabilizer is a calcium-zinc composite stabilizer, the filler is light calcium carbonate, the vegetable oil plasticizer is epoxidized soybean oil, the lubricant is stearic acid, the foaming agent of the foaming layer is azodicarbonamide, and the adsorption decomposition agent of the foaming layer is modified activated carbon loaded nano-nitrogen-doped titanium dioxide.

[0117] The preparation method of the green and environmentally friendly polyvinyl chloride artificial leather comprises the following steps:

[0118] Weigh each component according to the formula and set aside.

[0119] 100 parts of polyvinyl chloride were added into a high-speed mixer, and 65 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 7 parts of calcium zinc composite stabilizer, 37 parts of light calcium carbonate, 10 parts of epoxy soybean oil, 3 parts of stearic acid, and 3 parts of colorant were added in sequence, and the mixture was stirred at 110° C. for 160 seconds to obtain a mixture.

[0120] The mixture was mixed with solvent to form a slurry with a solid content of 50%, which was then coated on the base fabric using a comma blade coater with a wet film thickness of 0.3 mm. The mixture was then pre-baked in a 150°C oven for 2 minutes to form a dense layer with a thickness of about 0.15 mm.

[0121] Add 100 parts of polyvinyl chloride into a high-speed mixer, and add 50 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 4 parts of calcium zinc composite stabilizer, 20 parts of light calcium carbonate, 7 parts of epoxy soybean oil, 2 parts of stearic acid, 15 parts of modified activated carbon-loaded nano-nitrogen-doped titanium dioxide, 2 parts of foaming agent, and 2 parts of colorant in sequence, and stir at 110°C for 160 seconds to obtain a second layer of mixture.

[0122] The second layer of mixture is applied on the surface of the dense layer with a wet film thickness of 0.8 mm. The mixture is then placed in an oven at 180°C for foaming for 3 minutes to form a foaming layer with a thickness of about 0.6 mm.

[0123] After cooling and shaping, embossing is performed with the embossing parameters being 150°C and 3MPa, followed by printing and coating with a water-based polyurethane surface layer with the coating parameters being dried and cured at 80°C to obtain the final product.

[0124] Among them, the solvent solid content is: 50% for dense layer and 45% for foaming layer; coating thickness: 0.3mm wet film for dense layer → 0.15mm dry film for foaming layer, 0.8mm wet film for foaming layer → 0.6mm dry film; temperature control: pre-baking of dense layer at 150℃ → foaming of foaming layer at 180℃.

[0125] It can be understood that the present application improves the formaldehyde purification efficiency by 40%, the elongation at break ≥350%, the interface bonding strength ≥2N / mm, and the migration resistance by 30% through a layered structure. That is, this solution, while maintaining the main body of Example 6 unchanged, realizes a double-layer structure through step-by-step coating and temperature gradient control, meeting the dual requirements of environmental protection and performance.

[0126] Example 8

[0127] A green and environmentally friendly polyvinyl chloride artificial leather comprises, by mass, 100 parts of polyvinyl chloride, 50 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 4 parts of stabilizer, 20 parts of filler, 7 parts of vegetable oil plasticizer, 2 parts of lubricant, 15 parts of adsorption decomposition agent, 2 parts of foaming agent, 2 parts of colorant, 12 parts of dynamic disulfide bond modified PVC and 6 parts of liquid crystal elastomer.

[0128] The foaming agent is azodicarbonamide, the filler is light calcium carbonate, the vegetable oil plasticizer is epoxidized soybean oil, the lubricant is stearic acid, the adsorption and decomposition agent is modified activated carbon-supported nano-nitrogen-doped titanium dioxide, and the stabilizer is a calcium-zinc composite stabilizer. Thus, a foamed layer is produced.

[0129] The preparation method of the green and environmentally friendly polyvinyl chloride artificial leather comprises the following steps:

[0130] First, the raw materials are weighed according to the formula and set aside; 100 parts of polyvinyl chloride are added to a high-speed mixer, followed by 50 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 4 parts of calcium-zinc composite stabilizer, 20 parts of light calcium carbonate, 7 parts of epoxy soybean oil, 2 parts of stearic acid, 15 parts of modified activated carbon-loaded nano-nitrogen-doped titanium dioxide, 2 parts of foaming agent, and 2 parts of colorant, and stirred at 110° C. for 160 seconds to uniformly disperse the materials to obtain a mixture;

[0131] The mixture is mixed with a solvent to form a slurry with a solid content controlled at 40%, which is then coated on a base fabric by a coating machine. After coating, the slurry is placed in an oven at 175°C for foaming to obtain the formed artificial leather.

[0132] The formed artificial leather is then cooled, shaped, printed, embossed and laminated to obtain the product.

[0133] Wherein, the dynamic disulfide bond modified PVC is prepared as follows:

[0134] 10 parts of PVC resin, 1.5 parts of 3,3'-dithiodipropionic acid, 0.08 parts of dibenzoyl peroxide and 30 parts of tetrahydrofuran (solvent).

[0135] Step-by-step modification process

[0136] 10 parts of PVC resin were added to a reactor, tetrahydrofuran was injected, and the temperature was raised to 55°C with stirring to dissolve to form a transparent solution; 1.5 parts of 3,3'-dithiodipropionic acid and 0.08 parts of dibenzoyl peroxide were added, and the mixture was reacted at 65°C under nitrogen protection for 4 hours to achieve thiol grafting through the addition of thiol groups to PVC chain free radicals (the grafting rate was controlled at 1.2-1.5 mol%).

[0137] The reaction system was heated to 85° C. and oxidized by air for 2.5 hours to couple the thiol groups to form disulfide bonds. The product was precipitated with methanol, filtered, and dried under vacuum at 55° C. to constant weight to obtain 12 parts of dynamically disulfide-modified PVC (yield of approximately 95%).

[0138] The preparation of liquid crystal elastomer is as follows:

[0139] Monomer composition: 70 parts of methyl methacrylate, 30 parts of phenyl 4-acryloyloxybenzoate, 5 parts of 2-methacryloyloxyethyl cinnamate, 0.05 parts of azobisisobutyronitrile, and 0.5 parts of Irgacure 819.

[0140] Polymerization process:

[0141] 70 parts of methyl methacrylate, 30 parts of phenyl 4-acryloyloxybenzoate, 5 parts of 2-methacryloyloxyethyl cinnamate, 0.05 parts of azobisisobutyronitrile, and 0.5 parts of Irgacure 819 were reacted in toluene at 60° C. under nitrogen protection for 3 hours, wherein the double bond retention rate monitored by infrared spectroscopy was ≥30%.

[0142] The prepolymer solution was injected into a glass mold and heated to 100°C, the liquid crystal phase temperature. A 1T magnetic field was applied for 30 minutes to achieve elementary alignment. 365nm UV light was then irradiated for 10 minutes to achieve crosslinking and fixation. The product was then vacuum-dried at 60°C for 48 hours to remove the toluene. Uniaxial textured parallel stripes were observed using POM, and the phase transition temperature was measured using DSC.

[0143] The leather obtained in this embodiment was tested, and the test results are as follows:

[0144] Self-repair performance test: A 0.5mm deep scratch was made on the surface of artificial leather at 80°C. After standing for 30 minutes, the scratch width was reduced by 92% under optical microscope observation. Tensile testing showed that the breaking strength after repair recovered to 91% of the original value.

[0145] Shape memory cycle test: initial shape: flat plate; temporary shape: folded into a 90° angle;

[0146] After heating to 60°C and holding for 5 minutes, the shape recovery rate reaches 98% after the external force is removed, and the recovery rate decays by less than 5% after 50 cycles.

[0147] Therefore, it can be seen that this embodiment uses a liquid crystal elastomer as a shape memory fixed phase with a phase transition temperature of 60°C, and introduces -SS- bonds into the PVC molecular chain as a shape memory switching phase. After heating at 80°C, scratches can be repaired, and the repair rate is ≥90%. That is, the liquid crystal elastomer and the dynamic disulfide bond PVC form an interpenetrating network, which makes the shape recovery rate reach 98%. Therefore, it can be seen that the introduction of disulfide bonds changes the cross-linking mechanism of the PVC molecular chain, giving it a functional coupling of self-repair and shape memory. In this way, the application scenarios of leather are wider and can be repeatedly deformed. However, the existing shape memory materials only have a single function and cannot achieve the technical effects of this application.

[0148] In any of the above embodiments, the colorant is selected according to actual production requirements. For example, the colorant can be set to any one or more of iron oxide red, iron oxide yellow, carbon black, titanium dioxide and phthalocyanine blue.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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 green and environmentally friendly polyvinyl chloride artificial leather, characterized in that: Included by mass: 100 parts of polyvinyl chloride, 40 to 60 parts of polyester polyadipate-1,2-propylene glycol ester plasticizer, 3 to 5 parts of stabilizer, 10 to 30 parts of filler, 5 to 10 parts of vegetable oil plasticizer, 1 to 3 parts of lubricant, 10 to 25 parts of adsorption decomposition agent, 1 to 3 parts of foaming agent and 1 to 3 parts of colorant.

2. The green and environmentally friendly polyvinyl chloride artificial leather according to claim 1, characterized in that: The foaming agent is set to be supercritical CO2, and also includes 2 to 3 parts of nano talc powder as a nucleating agent.

3. The green and environmentally friendly polyvinyl chloride artificial leather according to claim 2, characterized in that: It also includes 5 to 8 parts of ethylene vinyl acetate.

4. The green and environmentally friendly polyvinyl chloride artificial leather according to claim 1, characterized in that: The stabilizer is any one or more of calcium stearate, calcium zinc composite stabilizer, and zinc stearate.

5. The green and environmentally friendly polyvinyl chloride artificial leather according to claim 1, characterized in that: The filler is configured as light calcium carbonate or wollastonite powder.

6. The green and environmentally friendly polyvinyl chloride artificial leather according to claim 1, characterized in that: The vegetable oil plasticizer is any one or more of epoxidized soybean oil and epoxidized linseed oil.

7. The green and environmentally friendly polyvinyl chloride artificial leather according to claim 1, characterized in that: The lubricant is configured as stearic acid or paraffin lubricant.

8. The green and environmentally friendly polyvinyl chloride artificial leather according to claim 1, characterized in that: The adsorption decomposition agent is configured as modified activated carbon loaded with nano nitrogen-doped titanium dioxide.

9. The green and environmentally friendly polyvinyl chloride artificial leather according to claim 1, characterized in that: It also includes 1 to 3 parts of organic reversible thermochromic microcapsules and 0.5 to 1 part of graphene nanosheets.

10. A method for preparing green and environmentally friendly polyvinyl chloride artificial leather, characterized in that: include: Weigh the raw materials according to the formula; Add polyvinyl chloride into a high-speed mixer, and sequentially add polyester polyadipate-1,2-propylene glycol ester plasticizer, stabilizer, filler, vegetable oil plasticizer, lubricant, adsorption decomposition agent, foaming agent and colorant, and stir at 90°C to 130°C for 120 seconds to 200 seconds to uniformly disperse the materials to obtain a mixture; The mixture is mixed with a solvent to form a slurry with a solid content controlled at 30% to 50%, and the slurry is coated on a base fabric by a coating machine. After coating, the slurry is placed in an oven at 150° C. to 200° C. for foaming to obtain a formed artificial leather; The formed artificial leather is then cooled, shaped, printed, embossed and laminated to obtain a product.

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