A wear-resistant PVC decorative film and its preparation method

Abstract

This invention proposes a wear-resistant PVC decorative film and its preparation method, relating to the field of composite films. It comprises a PVC substrate layer, an adhesive layer, and a coating layer arranged sequentially. The PVC substrate layer, by weight, includes the following raw materials: 90-100 parts PVC resin, 10-20 parts chlorinated polyethylene resin, 1-5 parts plasticizer, 1-5 parts lubricant, 5-10 parts montmorillonite / nano-silica composite, and 1-5 parts calcium-zinc composite stabilizer. The coating layer, by weight, includes the following raw materials: 90-100 parts PET resin, 10-20 parts polyisocyanate, 5-10 parts acrylate copolymer, 1-5 parts modified flake alumina, 1-5 parts modified glass flakes, and 0.1-0.2 parts dibutyltin dilaurate. The adhesive layer is a silicone adhesive. It exhibits good wear resistance, high bonding strength between layers, and a long service life.

Description

Technical Field

[0001] This invention relates to the field of composite films, and more specifically, to a wear-resistant PVC decorative film and its preparation method. Background Technology

[0002] Polyvinyl chloride (PVC) decorative film is a new type of decorative material made from PVC resin as the base material, with the addition of additives and using calendering, lamination, or printing processes. It has advantages such as lightweight, durability, design flexibility, and environmental friendliness, and is widely used in construction, furniture, transportation, and consumer electronics.

[0003] Physical or chemical modification can improve the abrasion resistance of PVC decorative films, enabling their application in furniture, flooring, automotive interiors, and electronics. Examples include high-wear scenarios such as furniture veneers, interior decoration, commercial flooring, and elevator interiors, thus extending the lifespan of the PVC decorative film. Currently, there are several ways to improve the abrasion resistance of PVC decorative films.

[0004] Surface coating technology: UV-cured coatings, nano-alumina, or silicone coatings are used to improve the surface hardness of PVC decorative films. However, this increases production costs, and the coating thickness and uniformity must be strictly controlled to ensure consistent wear resistance, meaning that strict requirements are placed on the coating application.

[0005] Blending modification: Abrasion-resistant fillers (such as silica and silicon carbide microparticles) are mixed into the PVC substrate to enhance scratch resistance. However, the dispersibility and compatibility of the fillers need to be strictly controlled to ensure the improvement of abrasion resistance. In addition, the addition of fillers will also affect the processing performance of PVC decorative film, such as melt flowability and formability.

[0006] Composite Structure: Composites are formed with materials such as PET and TPU to create a multi-layered structure that balances wear resistance and flexibility. The composite process increases production costs, and the interlayer bonding strength needs strict control to ensure the stability and consistent wear resistance of the composite structure. For example, patent 202410084124.6 discloses a PVC-PET composite sheet film and its preparation method, which adds polysiloxane / polyester diol composite, polyisocyanate, and modified nano-silica to polyethylene terephthalate (PET) to improve the wear resistance of PET; however, the bonding strength between layers still needs improvement. Summary of the Invention

[0007] The purpose of this invention is to provide a wear-resistant PVC decorative film with good wear resistance, high bonding strength between layers, and long service life.

[0008] Another objective of this invention is to provide a method for preparing a wear-resistant PVC decorative film, wherein the PVC film and the coating are first surface-treated, and then hot-pressed together to form a chemical bond between the PVC film and the coating, thereby improving the bonding strength between the two layers.

[0009] The technical problem solved by this invention is achieved by the following technical solution.

[0010] On one hand, embodiments of the present invention provide a wear-resistant PVC decorative film, comprising a PVC substrate layer, an adhesive layer, and a coating layer arranged sequentially;

[0011] The PVC substrate layer comprises, by weight, the following raw materials: 90-100 parts of PVC resin, 10-20 parts of chlorinated polyethylene resin, 1-5 parts of plasticizer, 1-5 parts of lubricant, 5-10 parts of montmorillonite / nano silica composite, and 1-5 parts of calcium-zinc composite stabilizer.

[0012] The coating layer comprises, by weight, the following raw materials: 90-100 parts PET resin; 10-20 parts polyisocyanate; 5-10 parts acrylate copolymer; 1-5 parts modified flake alumina; 1-5 parts modified glass flakes; and 0.1-0.2 parts dibutyltin dilaurate.

[0013] The adhesive layer is a silicone adhesive.

[0014] In some embodiments of the present invention, the montmorillonite / nano silica composite is prepared by the following method:

[0015] Nano-silica was calcined at 1200℃ for 1-2 hours in a mixed atmosphere of H2 and inert gas, and then rapidly cooled to room temperature at a rate of 30-50℃ / min to obtain hydrophobic nano-silica. Montmorillonite, hexadecyltrimethylammonium bromide, and ethanol solution were mixed and ultrasonically dispersed at 60-70℃ for 1-2 hours. Then, silane coupling agent and the hydrophobic nano-silica were added, ultrasonically dispersed for 10-20 minutes, centrifuged, vacuum dried at 50-60℃, and ground to obtain the montmorillonite / nano-silica composite.

[0016] Under a reducing atmosphere, elemental silicon can be formed on the surface of nano-silica through high-temperature calcination. Subsequently, under rapid cooling, a crack network is formed on the surface of nano-silica. The microcracks increase the surface roughness, reduce the density of hydroxyl groups (Si-OH), and improve hydrophobicity.

[0017] Under ultrasonic treatment, hexadecyltrimethylammonium bromide is used to exchange ions with the montmorillonite interlayer, allowing hexadecyltrimethylammonium bromide to embed into the montmorillonite interlayer and increase the interlayer spacing of montmorillonite. Subsequently, under the action of a coupling agent, hydrophobic nano-silica enters the montmorillonite interlayer. The two have a strong binding force, which can also reduce the aggregation of nano-silica and improve its dispersion uniformity in PVC.

[0018] During the preparation of PVC film, the layered montmorillonite is oriented through melt extrusion molding, and the nano-silica embedded in the layers can act as reinforcing particles to improve the tensile strength of the PVC film. The hexadecyltrimethylammonium bromide embedded in the layers has a long molecular chain and can be embedded into the PVC molecular chain, thereby enhancing the bonding force between montmorillonite and PVC.

[0019] In some embodiments of the present invention, the mass ratio of montmorillonite, hydrophobic nano-silica, hexadecyltrimethylammonium bromide, and ethanol is 1:(0.8-1):(0.3-0.5):(0.3-0.5).

[0020] In some embodiments of the present invention, the modified flake alumina is prepared by the following method:

[0021] Nanoscale γ-Al₂O₃ was mixed with toluene, heated and stirred until homogeneous under an inert atmosphere; then, a toluene solution of oleylamine was added dropwise, and the mixture was refluxed at 100-120°C for 2-3 hours; after cooling, filtration, washing, vacuum drying, and grinding, the modified flaky alumina was obtained. The amount of oleylamine added was 2-3 wt% of γ-Al₂O₃. Surface modification of alumina with oleylamine involves the condensation of oleylamine with hydroxyl groups on the alumina surface to form Al-ON bonds. The C18 long chain provides steric hindrance to inhibit agglomeration and promotes uniform dispersion of the flaky alumina in the coating.

[0022] In some embodiments of the present invention, the modified glass flakes are prepared by the following method:

[0023] Immerse glass flakes in hydrofluoric acid solution for 1-2 minutes, wash them clean, and obtain pretreated glass flakes. Mix silane coupling agent, water, and acetic acid, stir evenly, let stand for 20-30 minutes, then add pretreated glass flakes, octamercapto-POSS, and benzoyl peroxide. React at 80-100℃ under an inert atmosphere for 2-3 hours, quench the reaction, filter and collect the solid, wash it, and obtain the modified glass flakes. Through pretreatment, pits are formed on the surface of glass flakes. Subsequently, under the action of silane coupling agent, water, and acetic acid, covalent bonds are formed on the surface of the glass flakes, grafting groups of the silane coupling agent (such as methoxy and ethoxy) onto the surface of the glass flakes, providing active sites for subsequent reactions with the glass flake surface. Then, octamercapto-PSS and benzoyl peroxide are added, and the mercapto groups (-SH) form covalent bonds with metal oxides, enhancing the interfacial bonding. During melt extrusion molding, unreacted mercapto groups are incorporated into the molecular chain of PET resin, forming a three-dimensional network structure, thereby enhancing the bonding strength between the modified glass flakes and PET.

[0024] In some embodiments of the present invention, the mass ratio of pretreated glass flakes to octamercapto-POSS is 1:(1-1.2). This ratio ensures that unreacted sulfhydryl groups are present on the modified glass flakes. The volume ratio of silane coupling agent, water, and acetic acid is 1:(0.8-1):(0.8-1).

[0025] On the other hand, embodiments of the present invention provide a method for preparing a wear-resistant PVC decorative film, which includes: S1, mixing the raw materials of the PVC substrate layer, melting and extruding to obtain a PVC film;

[0026] S2, the raw materials for the coating layer are mixed, melt-extruded, and a coating is obtained;

[0027] S3. In an atmosphere of oxygen and inert gas, the surfaces of the PVC film and the laminate to be bonded are subjected to plasma treatment, and then silane coupling agent and silicone adhesive are sequentially coated on the surfaces of the PVC film and the laminate to be bonded.

[0028] S4. Hot-press lamination at 110-120℃, followed by cooling, yields the wear-resistant PVC decorative film.

[0029] By plasma treatment of PVC film and coating, oxygen-containing functional groups are grafted onto the surface of the film. During hot-pressing lamination, the long carbon molecular chains of hexadecyltrimethylammonium bromide on the surface of the PVC film, the silicone adhesive, and the octamercapto-POSS and oleylamine on the surface of the coating can form chemical bonds. Alternatively, the molecular chains of PET resin can be embedded into the montmorillonite layers to form anchoring points. The PVC resin molecules and the octamercapto-POSS molecular chains can intertwine to improve the bonding strength between the PVC film and the coating.

[0030] In some embodiments of the present invention, the power of the plasma treatment is 200-275 W·min / m, and the treatment time is 30-60 s.

[0031] In some embodiments of the present invention, in step S4, the pressure of hot pressing is 0.5-1.0 MPa and the time is 10-30 s.

[0032] In some embodiments of the present invention, in step S3, the coated silane coupling agent is 0.5-1 wt% of the silicone adhesive.

[0033] Compared with the prior art, the embodiments of the present invention have at least the following advantages or beneficial effects:

[0034] The wear-resistant PVC membrane provided by this invention is composed of a PVC substrate layer and a coating layer, exhibiting good wear resistance and strong interlayer bonding. The addition of a montmorillonite / nano-silica composite to the PVC base material enhances the mechanical properties of the PVC membrane. The layered structure of montmorillonite allows it to form intercalation or peeling structures within the PVC matrix, effectively transferring stress and strengthening mechanical properties. The composite of montmorillonite and nano-silica avoids the aggregation of nano-silica, improving its dispersion within the PVC substrate. Furthermore, the insertion of nano-silica between the montmorillonite layers results in a high bonding strength, increasing the bond strength between the nano-silica and the substrate, reducing nano-silica leakage during stress, and improving the tensile strength of the PVC membrane.

[0035] Flake alumina and glass flakes are added to the coating layer. The flake-structured microparticles are stacked and arranged on the surface of the membrane, which can provide the membrane with barrier properties and wear resistance. The glass flakes and flake alumina are used together to enhance the wear resistance of the PVC membrane.

[0036] The preparation method provided by the present invention first performs plasma treatment on the surfaces of the PVC film and the coating, grafts oxygen-containing functional groups such as -OH and -COOH onto the surfaces of the PVC film and the coating, and then coats them with a silane coupling agent and a silicone adhesive. Under the action of the silane coupling agent and hot pressing, the adhesive and the PVC film and the coating can form chemical bonds, thereby improving the interlayer bonding strength of the PVC film and the coating. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0038] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other. The present invention will now be described in detail with reference to specific embodiments.

[0039] Example 1

[0040] 1. Prepare the montmorillonite / nano silica composite as follows:

[0041] Nano-silica was calcined at 1200℃ for 2 hours in a mixed atmosphere of H2 and inert gas, and then rapidly cooled to room temperature at a rate of 50℃ / min to obtain hydrophobic nano-silica.

[0042] Montmorillonite, hexadecyltrimethylammonium bromide, and an ethanol solution were mixed and ultrasonically dispersed at 70°C for 1 hour. Then, a silane coupling agent and the hydrophobic nano-silica were added, and the mixture was ultrasonically dispersed for 20 minutes. After centrifugation, the mixture was vacuum dried at 60°C and then ground to obtain the montmorillonite / nano-silica composite. The mass ratio of montmorillonite, hydrophobic nano-silica, hexadecyltrimethylammonium bromide, and ethanol was 1:0.8:0.3:0.5.

[0043] 2. Prepare modified sheet-like alumina using the following method:

[0044] Nanosheet γ-Al₂O₃ was mixed with toluene, heated and stirred until homogeneous under an inert atmosphere; then, a toluene solution of oleylamine was added dropwise, and the mixture was refluxed at 100°C for 3 hours; after cooling, filtration, washing, vacuum drying, and grinding, the modified sheet alumina was obtained. The amount of oleylamine added was 3 wt% of the nanosheet γ-Al₂O₃.

[0045] 3. Prepare modified glass flakes using the following method:

[0046] Glass flakes were immersed in hydrofluoric acid solution for 2 minutes and washed clean to obtain pretreated glass flakes. A silane coupling agent, water, and acetic acid were mixed, stirred thoroughly, and allowed to stand for 20 minutes. Then, the pretreated glass flakes, octamercaptoPOSS, and benzoyl peroxide were added. The reaction was carried out at 100°C under an inert atmosphere for 3 hours. The reaction was then quenched, the solid was collected by filtration, and washed to obtain the modified glass flakes. The mass ratio of pretreated glass flakes to octamercaptoPOSS was 1:1.2. The volume ratio of silane coupling agent, water, and acetic acid was 1:0.8:0.8.

[0047] 4. Prepare a wear-resistant PVC decorative film using the following method:

[0048] S1, 100 parts of PVC resin, 20 parts of chlorinated polyethylene resin, 5 parts of plasticizer, 5 parts of lubricant, 10 parts of montmorillonite / nano silica composite, and 5 parts of calcium-zinc composite stabilizer; the raw materials of the PVC substrate layer are mixed and melt-extruded to obtain a PVC film.

[0049] S2, 100 parts of PET resin; 20 parts of polyisocyanate; 10 parts of acrylate copolymer; 5 parts of modified flake alumina; 5 parts of modified glass flakes; 0.2 parts of dibutyltin dilaurate. The raw materials of the coating layer are mixed and melt-extruded to obtain the coating.

[0050] S3. In an atmosphere of oxygen and inert gas (N2), the surfaces of the PVC film and the laminate to be bonded are subjected to plasma treatment at a power of 200 W·min / m for 60 s. Subsequently, a silane coupling agent and a silicone adhesive are sequentially coated onto the surfaces of the PVC film and the laminate to be bonded. The amount of silane coupling agent applied is 1 wt% of the silicone adhesive, and the amount of silicone adhesive applied is 1.5 g / cm³. 2 .

[0051] S4. Hot-press lamination at 110-120℃ (pressure 1.0MPa, time 20s), followed by cooling, yields the wear-resistant PVC decorative film.

[0052] Example 2

[0053] 1. Prepare the montmorillonite / nano silica composite as follows:

[0054] Nano-silica was calcined at 1200℃ for 1.5h in a mixed atmosphere of H2 and inert gas, and then rapidly cooled to room temperature at a rate of 50℃ / min to obtain hydrophobic nano-silica.

[0055] Montmorillonite, hexadecyltrimethylammonium bromide, and an ethanol solution were mixed and ultrasonically dispersed at 70°C for 2 hours. Then, a silane coupling agent and the hydrophobic nano-silica were added, and the mixture was ultrasonically dispersed for 20 minutes. After centrifugation, the mixture was vacuum dried at 60°C and then ground to obtain the montmorillonite / nano-silica composite. The mass ratio of montmorillonite, hydrophobic nano-silica, hexadecyltrimethylammonium bromide, and ethanol was 1:0.8:0.3:0.5.

[0056] 2. Prepare modified sheet-like alumina using the following method:

[0057] Nanosheet γ-Al₂O₃ was mixed with toluene, heated and stirred until homogeneous under an inert atmosphere; then, a toluene solution of oleylamine was added dropwise, and the mixture was refluxed at 100°C for 3 hours; after cooling, filtration, washing, vacuum drying, and grinding, the modified sheet alumina was obtained. The amount of oleylamine added was 1 wt% of the nanosheet γ-Al₂O₃.

[0058] 3. Prepare modified glass flakes using the following method:

[0059] Glass flakes were immersed in hydrofluoric acid solution for 1.5 min, washed clean, and pretreated glass flakes were obtained. Silane coupling agent, water, and acetic acid were mixed, stirred evenly, and allowed to stand for 30 min. Then, pretreated glass flakes, octamercaptoPOSS, and benzoyl peroxide were added. The reaction was carried out at 80°C under an inert atmosphere for 3 h. The reaction was quenched, the solid was collected by filtration, and washed to obtain the modified glass flakes. The mass ratio of pretreated glass flakes to octamercaptoPOSS was 1:1.2. The volume ratio of silane coupling agent, water, and acetic acid was 1:1:1.

[0060] 4. Prepare a wear-resistant PVC decorative film using the following method:

[0061] S1, 90 parts of PVC resin, 10 parts of chlorinated polyethylene resin, 1 part of plasticizer, 1 part of lubricant, 5 parts of montmorillonite / nano silica composite, and 1 part of calcium-zinc composite stabilizer; the raw materials of the PVC substrate layer are mixed and melt-extruded to obtain a PVC film.

[0062] S2, 90 parts of PET resin; 10 parts of polyisocyanate; 5 parts of acrylate copolymer; 1 part of modified flake alumina; 1 part of modified glass flakes; 0.1 parts of dibutyltin dilaurate. The raw materials of the coating layer are mixed and melt-extruded to obtain the coating.

[0063] S3. In an atmosphere of oxygen and inert gas (N2), the surfaces of the PVC film and the laminate to be bonded are subjected to plasma treatment. The plasma treatment power is 200 W·min / m and the treatment time is 30 s. Subsequently, silane coupling agent and silicone adhesive are sequentially coated on the surfaces of the PVC film and the laminate to be bonded. The amount of silane coupling agent coated is 1 wt% of the silicone adhesive, and the amount of silicone adhesive coated is 1.5 g / cm2.

[0064] S4. Hot-press lamination at 110-120℃ (pressure 1.0MPa, time 30s), followed by cooling, yields the wear-resistant PVC decorative film.

[0065] Example 3

[0066] 1. Prepare the montmorillonite / nano silica composite as follows:

[0067] Nano-silica was calcined at 1200℃ for 2 hours in a mixed atmosphere of H2 and inert gas, and then rapidly cooled to room temperature at a rate of 50℃ / min to obtain hydrophobic nano-silica.

[0068] Montmorillonite, hexadecyltrimethylammonium bromide, and an ethanol solution were mixed and ultrasonically dispersed at 70°C for 1 hour. Then, a silane coupling agent and the hydrophobic nano-silica were added, and the mixture was ultrasonically dispersed for 20 minutes. After centrifugation, the mixture was vacuum dried at 60°C and then ground to obtain the montmorillonite / nano-silica composite. The mass ratio of montmorillonite, hydrophobic nano-silica, hexadecyltrimethylammonium bromide, and ethanol was 1:0.8:0.3:0.5.

[0069] 2. Prepare modified sheet-like alumina using the following method:

[0070] Nanosheet γ-Al₂O₃ was mixed with toluene, heated and stirred until homogeneous under an inert atmosphere; then, a toluene solution of oleylamine was added dropwise, and the mixture was refluxed at 100°C for 3 hours; after cooling, filtration, washing, vacuum drying, and grinding, the modified sheet alumina was obtained. The amount of oleylamine added was 1 wt% of the nanosheet γ-Al₂O₃.

[0071] 3. Prepare modified glass flakes using the following method:

[0072] Glass flakes were immersed in hydrofluoric acid solution for 2 minutes and washed clean to obtain pretreated glass flakes. A silane coupling agent, water, and acetic acid were mixed, stirred thoroughly, and allowed to stand for 20 minutes. Then, the pretreated glass flakes, octamercaptoPOSS, and benzoyl peroxide were added. The reaction was carried out at 100°C under an inert atmosphere for 3 hours. The reaction was then quenched, the solid was collected by filtration, and washed to obtain the modified glass flakes. The mass ratio of pretreated glass flakes to octamercaptoPOSS was 1:1. The volume ratio of silane coupling agent, water, and acetic acid was 1:0.8:1.

[0073] 4. Prepare a wear-resistant PVC decorative film using the following method:

[0074] S1, 100 parts of PVC resin, 20 parts of chlorinated polyethylene resin, 5 parts of plasticizer, 5 parts of lubricant, 10 parts of montmorillonite / nano silica composite, and 5 parts of calcium-zinc composite stabilizer; the raw materials of the PVC substrate layer are mixed and melt-extruded to obtain a PVC film.

[0075] S2, 90 parts of PET resin; 10 parts of polyisocyanate; 5 parts of acrylate copolymer; 1 part of modified flake alumina; 1 part of modified glass flakes; 0.1 parts of dibutyltin dilaurate. The raw materials of the coating layer are mixed and melt-extruded to obtain the coating.

[0076] S3. In an atmosphere of oxygen and inert gas (N2), the surfaces of the PVC film and the laminate to be bonded are subjected to plasma treatment. The plasma treatment power is 200 W·min / m and the treatment time is 30 s. Subsequently, silane coupling agent and silicone adhesive are sequentially coated on the surfaces of the PVC film and the laminate to be bonded. The amount of silane coupling agent coated is 1 wt% of the silicone adhesive, and the amount of silicone adhesive coated is 1.5 g / cm2.

[0077] S4. Hot-press lamination at 110-120℃ (pressure 1.0MPa, time 30s), followed by cooling, yields the wear-resistant PVC decorative film.

[0078] Example 4

[0079] 1. Prepare the montmorillonite / nano silica composite as follows:

[0080] Nano-silica was calcined at 1200℃ for 1-2 hours in a mixed atmosphere of H2 and inert gas, and then rapidly cooled to room temperature at a rate of 30-50℃ / min to obtain hydrophobic nano-silica.

[0081] Montmorillonite, hexadecyltrimethylammonium bromide, and ethanol solution were mixed and ultrasonically dispersed at 60-70℃ for 1-2 hours. Then, a silane coupling agent and the hydrophobic nano-silica were added, and the mixture was ultrasonically dispersed for 10-20 minutes. After centrifugation, the mixture was vacuum dried at 50-60℃ and then ground to obtain the montmorillonite / nano-silica composite. The mass ratio of montmorillonite, hydrophobic nano-silica, hexadecyltrimethylammonium bromide, and ethanol was 1:0.8:0.3:0.5.

[0082] 2. Prepare modified sheet-like alumina using the following method:

[0083] Nanosheet γ-Al₂O₃ was mixed with toluene, heated and stirred until homogeneous under an inert atmosphere; then, an oilamine solution in toluene was added dropwise, and the mixture was refluxed at 100°C for 3 hours; after cooling, filtration, washing, vacuum drying, and grinding, the modified sheet alumina was obtained. The amount of oilamine added was 2.5 wt% of the nanosheet γ-Al₂O₃.

[0084] 3. Prepare modified glass flakes using the following method:

[0085] Glass flakes were immersed in hydrofluoric acid solution for 1.5 min, washed clean, and pretreated glass flakes were obtained. Silane coupling agent, water, and acetic acid were mixed, stirred evenly, and allowed to stand for 30 min. Then, pretreated glass flakes, octamercaptoPOSS, and benzoyl peroxide were added. The reaction was carried out at 80°C under an inert atmosphere for 3 h. The reaction was quenched, the solid was collected by filtration, and washed to obtain the modified glass flakes. The mass ratio of pretreated glass flakes to octamercaptoPOSS was 1:1.2. The volume ratio of silane coupling agent, water, and acetic acid was 1:1:1.

[0086] 4. Prepare a wear-resistant PVC decorative film using the following method:

[0087] S1, 90 parts of PVC resin, 10 parts of chlorinated polyethylene resin, 1 part of plasticizer, 1 part of lubricant, 5 parts of montmorillonite / nano silica composite, and 1 part of calcium-zinc composite stabilizer; the raw materials of the PVC substrate layer are mixed and melt-extruded to obtain a PVC film.

[0088] S2, 100 parts of PET resin; 20 parts of polyisocyanate; 10 parts of acrylate copolymer; 5 parts of modified flake alumina; 5 parts of modified glass flakes; 0.2 parts of dibutyltin dilaurate. The raw materials of the coating layer are mixed and melt-extruded to obtain the coating.

[0089] S3. In an atmosphere of oxygen and inert gas (N2), the surfaces of the PVC film and the laminate to be bonded are subjected to plasma treatment. The plasma treatment power is 200 W·min / m and the treatment time is 30-60 s. Subsequently, silane coupling agent and silicone adhesive are sequentially coated on the surfaces of the PVC film and the laminate to be bonded. The amount of silane coupling agent coated is 1 wt% of the silicone adhesive, and the amount of silicone adhesive coated is 1.5 g / cm2.

[0090] S4. Hot-press lamination at 110-120℃ (pressure 1.0MPa, time 30s), followed by cooling, yields the wear-resistant PVC decorative film.

[0091] Example 5

[0092] 1. Prepare the montmorillonite / nano silica composite as follows:

[0093] Nano-silica was calcined at 1200℃ for 2 hours in a mixed atmosphere of H2 and inert gas, and then rapidly cooled to room temperature at a rate of 30℃ / min to obtain hydrophobic nano-silica.

[0094] Montmorillonite, hexadecyltrimethylammonium bromide, and ethanol solution were mixed and ultrasonically dispersed at 60°C for 1.5 h. Then, a silane coupling agent and the hydrophobic nano-silica were added, and the mixture was ultrasonically dispersed for 15 min. After centrifugation, the mixture was vacuum dried at 50°C and then ground to obtain the montmorillonite / nano-silica composite. The mass ratio of montmorillonite, hydrophobic nano-silica, hexadecyltrimethylammonium bromide, and ethanol was 1:1:0.5:0.5.

[0095] 2. Prepare modified sheet-like alumina using the following method:

[0096] γ-Al₂O₃ was mixed with toluene, heated and stirred until homogeneous under an inert atmosphere; then, a toluene solution of oleylamine was added dropwise, and the mixture was refluxed at 120°C for 3 hours; after cooling, filtration, washing, vacuum drying, and grinding, the modified flake alumina was obtained. The amount of oleylamine added was 2 wt% of γ-Al₂O₃.

[0097] 3. Prepare modified glass flakes using the following method:

[0098] Glass flakes were immersed in hydrofluoric acid solution for 2 minutes and washed clean to obtain pretreated glass flakes. A silane coupling agent, water, and acetic acid were mixed, stirred thoroughly, and allowed to stand for 30 minutes. Then, the pretreated glass flakes, octamercaptoPOSS, and benzoyl peroxide were added. The reaction was carried out at 100°C under an inert atmosphere for 3 hours. The reaction was then quenched, the solid was collected by filtration, and washed to obtain the modified glass flakes. The mass ratio of pretreated glass flakes to octamercaptoPOSS was 1:1. The volume ratio of silane coupling agent, water, and acetic acid was 1:0.8:0.8.

[0099] 4. Prepare a wear-resistant PVC decorative film using the following method:

[0100] S1, 100 parts of PVC resin, 15 parts of chlorinated polyethylene resin, 3 parts of plasticizer, 3 parts of lubricant, 8 parts of montmorillonite / nano silica composite, and 3 parts of calcium-zinc composite stabilizer; the raw materials of the PVC substrate layer are mixed and melt-extruded to obtain a PVC film.

[0101] S2, 100 parts of PET resin; 15 parts of polyisocyanate; 8 parts of acrylate copolymer; 3 parts of modified flake alumina; 3 parts of modified glass flakes; 0.2 parts of dibutyltin dilaurate. The raw materials of the coating layer are mixed and melt-extruded to obtain the coating.

[0102] S3. In an atmosphere of oxygen and inert gas (N2), the surfaces of the PVC film and the laminate to be bonded are subjected to plasma treatment. The plasma treatment power is 200 W·min / m and the treatment time is 50 s. Subsequently, silane coupling agent and silicone adhesive are sequentially coated on the surfaces of the PVC film and the laminate to be bonded. The amount of silane coupling agent coated is 1 wt% of the silicone adhesive, and the amount of silicone adhesive coated is 1.5 g / cm2.

[0103] S4. Hot-press lamination at 110-120℃ (pressure 1.0MPa, time 10s), followed by cooling, yields the wear-resistant PVC decorative film.

[0104] Comparative Example 1

[0105] The difference from Example 1 is that montmorillonite and nano-silica are used instead of the montmorillonite / nano-silica composite in Example 1, and the mass ratio of montmorillonite to nano-silica is 1:0.8. The remaining raw material ratios and preparation methods are the same as in Example 1.

[0106] Comparative Example 2

[0107] The difference from Example 1 is that flake alumina is used instead of the modified flake alumina in Example 1, and glass flakes are used instead of the modified glass flakes in Example 1. The remaining raw material ratios and preparation methods are the same as in Example 1.

[0108] Comparative Example 3

[0109] The difference from Example 1 is that montmorillonite and nano-silica were used instead of the montmorillonite / nano-silica composite in Example 1, and the mass ratio of montmorillonite to nano-silica was 1:0.8. Flake alumina was used instead of the modified flake alumina in Example 1, and glass flakes were used instead of the modified glass flakes in Example 1. The remaining raw material ratios and preparation methods were the same as in Example 1.

[0110] Comparative Example 4

[0111] The difference from Example 1 is that in the preparation of the wear-resistant PVC decorative film, in step S3, plasma treatment is not performed, and hot pressing is performed directly. The remaining raw material ratios and preparation methods are the same as in Example 1.

[0112] It should be noted that in the above embodiments and comparative examples, the plasticizer used was dioctyl phthalate, the lubricant was calcium stearate, the calcium-zinc composite stabilizer was PVC calcium-zinc type stabilizer from Fujian Ruide Chemical Technology Co., Ltd., and the other raw materials, unless otherwise specified, were all purchased directly from the market.

[0113] Experimental Example

[0114] 1. Combined strength test

[0115] The tear strength of the films in Examples 1-5 and Comparative Examples 1-4 was tested according to the method in GB / T529-2008. Each group was tested 3 times and the average value was taken. The results are shown in Table 1.

[0116] 2. Peel strength test

[0117] According to the standard ASTM D903, the peel strength of each film at 90° was tested. Each group was tested 3 times and the average value was taken. The results are shown in Table 1.

[0118] 3. Abrasion resistance test

[0119] Referring to GB1768-79(89), the grinding disc diameter is 200mm and the center hole diameter is 9mm. After drying, the grinding disc rotates 100 times to test the weight loss of the film and calculate the wear resistance. Each group is tested 3 times and the average value is taken. The results are shown in Table 1.

[0120] Table 1

[0121]

[0122] Table 1 shows that the PVC composite films of Examples 1-5 have better tear resistance, glass strength, and abrasion resistance.

[0123] In Comparative Example 1, without the addition of the montmorillonite / nano-silica composite, the tear strength, peel strength, and abrasion resistance of the membrane decreased. In Comparative Example 2, without the addition of modified lamellar alumina and modified glass flakes, the mechanical properties of the membrane decreased accordingly. In Comparative Example 3, without the addition of the montmorillonite / nano-silica composite, modified lamellar alumina, and modified glass flakes, the composite membrane in Comparative Example 3 exhibited the worst mechanical properties compared to Comparative Examples 1 and 2. This indicates that the montmorillonite / nano-silica composite, modified lamellar alumina, and modified glass flakes have a synergistic effect, working together to improve the mechanical properties of the membrane. In Comparative Example 4, without plasma treatment, the tear strength and abrasion resistance of the membrane decreased slightly, and the peel strength also decreased to some extent, but it was still higher than the peel strength of Comparative Examples 1-3.

[0124] In summary, the wear-resistant PVC membrane provided in this embodiment of the invention is composed of a PVC substrate layer and a coating layer, exhibiting good wear resistance and strong interlayer bonding. The addition of a montmorillonite / nano-silica composite to the PVC base material enhances the mechanical properties of the PVC membrane. The layered structure of montmorillonite allows it to form intercalation or peeling structures within the PVC matrix, effectively transferring stress and strengthening mechanical properties. The composite of montmorillonite and nano-silica avoids the aggregation of nano-silica, improving its dispersion within the PVC substrate. Furthermore, the insertion of nano-silica between the montmorillonite layers results in a high bonding strength, increasing the bond strength between the nano-silica and the substrate, reducing nano-silica leakage during stress, and improving the tensile strength of the PVC membrane.

[0125] Flake alumina and glass flakes are added to the coating layer. The flake-structured microparticles are stacked and arranged on the surface of the membrane, which can provide the membrane with barrier properties and wear resistance. The glass flakes and flake alumina are used together to enhance the wear resistance of the PVC membrane.

[0126] The preparation method provided by the present invention first performs plasma treatment on the surfaces of the PVC film and the coating, grafts oxygen-containing functional groups such as -OH and -COOH onto the surfaces of the PVC film and the coating, and then coats them with a silane coupling agent and a silicone adhesive. Under the action of the silane coupling agent and hot pressing, the adhesive and the PVC film and the coating can form chemical bonds, thereby improving the interlayer bonding strength of the PVC film and the coating.

[0127] The embodiments described above are some, but not all, embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. A wear resistant PVC decorative film, characterized in that, The PVC substrate layer, the adhesive layer and the film layer are sequentially arranged. The PVC substrate layer comprises the following raw materials in parts by weight: 90-100 parts of PVC resin, 10-20 parts of chlorinated polyethylene resin, 1-5 parts of plasticizer, 1-5 parts of lubricant, 5-10 parts of montmorillonite / nano-silica composite, and 1-5 parts of calcium-zinc composite stabilizer. The film layer comprises the following raw materials in parts by weight: 90-100 parts of PET resin, 10-20 parts of polyisocyanate, 5-10 parts of acrylic ester copolymer, 1-5 parts of modified flaky alumina, 1-5 parts of modified glass flake, and 0.1-0.2 parts of dibutyltin dilaurate. The adhesive layer is a silicone adhesive. The montmorillonite / nano-silica composite is prepared by the following method: The nano-silica is calcined at 1200℃ under H2 and inert mixed gas atmosphere for 1-2h, and then rapidly cooled to room temperature to obtain hydrophobic nano-silica. The montmorillonite, cetyltrimethylammonium bromide and ethanol solution are mixed, ultrasonically dispersed at 60-70℃ for 1-2h, and then the silane coupling agent and the hydrophobic nano-silica are added and ultrasonically dispersed for 10-20min, centrifuged, vacuum dried at 50-60℃, and ground to obtain the montmorillonite / nano-silica composite. The modified flaky alumina is prepared by the following method: The nano-flaky γ-Al2O3 is mixed with toluene, heated and stirred uniformly under inert gas atmosphere, and then the oleylamine toluene solution is added dropwise and refluxed at 100-120℃ for 2-3h, cooled, filtered, washed, vacuum dried, and ground to obtain the modified flaky alumina. The modified glass flake is prepared by the following method: The glass flake is soaked in a hydrofluoric acid solution for 1-2min, washed clean to obtain pretreated glass flake. The silane coupling agent, water and acetic acid are mixed, stirred uniformly, and then left to stand for 20-30min, and then the pretreated glass flake, octamercapto POSS and dibenzoyl peroxide are added, reacted at 80-100℃ under inert gas atmosphere for 2-3h, quenched, and then the solid is collected by suction filtration and washed to obtain the modified glass flake.

2. The wear resistant PVC decorative film according to claim 1, characterized in that, The amount of oleylamine added dropwise is 2-3wt% of the nano-flaky γ-Al2O3.

3. The wear resistant PVC decorative film according to claim 2, characterized in that, The mass ratio of the pretreated glass flake to octamercapto POSS is 1: (1-1.2).

4. A process for the production of a wear resistant PVC decorative film as claimed in any one of claims 1 to 3, characterized in that, The method comprises the following steps: S1, the raw materials of the PVC substrate layer are mixed and melt extruded to obtain a PVC film; S2, the raw materials of the film layer are mixed and melt extruded to obtain a film; S3, the surfaces to be bonded of the PVC film and the film are subjected to plasma treatment under the atmosphere of oxygen and inert gas, and then the surfaces to be bonded of the PVC film and the film are coated with silane coupling agent and silicone adhesive in sequence; S4, hot pressing is performed at 110-120℃, and then cooling is performed to obtain the wear-resistant PVC decorative film.

5. The method for preparing the wear-resistant PVC decorative film according to claim 4, characterized in that, The power of the plasma treatment is 200-275 W·min / m 2 , the treatment time is 30-60 s.

6. The method for preparing the wear-resistant PVC decorative film according to claim 4, characterized in that, In the step S4, the pressure of hot pressing is 0.5-1.0MPa, and the time is 10-30s.

7. The method for preparing the wear-resistant PVC decorative film according to claim 4, characterized in that, In the step S3, the amount of silane coupling agent coated is 0.5-1wt% of the silicone adhesive.

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