PVC-based film, decorative film and preparation method and application thereof

Abstract

The present application relates to the technical field of PVC decorative film, and discloses a PVC base film, a decorative film and a preparation method and application thereof, wherein the raw materials of the PVC base film, calculated by weight fraction, include: 100 parts of PVC, 2-5 parts of a stabilizer, 0.1-10 parts of dry oil, 0-50 parts of a filler, 0.5-5 parts of epoxy soybean oil and 0.1-2 parts of a peroxide.The peroxide in the present application opens the double bond of the dry oil, so that a part of the dry oil is self-crosslinked, a part of the dry oil and the epoxy soybean oil are partially crosslinked, a layered composite structure is formed, which can act as a reinforcing framework to improve the wear resistance and mechanical strength of the PVC base film, and the epoxy soybean oil acts as a plasticizer to synergistically optimize the toughness and processing stability.

Description

Technical Field

[0001] This invention relates to the field of PVC decorative film technology, specifically to a PVC base film, a decorative film, its preparation method, and its application. Background Technology

[0002] With the rapid development of my country's decorative materials industry and the deepening trend of consumption upgrading, the market demand for high-performance functional membrane materials has increased significantly. While pursuing aesthetic design, consumers have also placed higher demands on the durability, environmental friendliness, and functionality of materials. However, traditional decorative membrane materials, due to their poor wear resistance, stiff feel, and the emission of volatile organic compounds (VOCs) during the production process, are no longer able to meet these demands.

[0003] In the prior art, the main production methods of wear-resistant coating decorative film materials are: (1) using a resin system containing wear-resistant fillers to coat the surface of the substrate: first, wear-resistant particles (such as alumina, silicon carbide, etc.) are added to the resin (such as polyurethane, epoxy resin, etc.) to form a composite coating, and then applied to the surface of the substrate through solvent-based or water-based coating process. A large amount of VOCs will be released during the production process, causing serious environmental pollution; and, due to the difference in characteristics between the resin and the wear-resistant filler, the coating and the substrate have poor bonding strength, and the wear resistance is also limited; (2) physical vapor deposition (PVD) wear-resistant coating: a hard coating with a thickness of 200nm-500nm is deposited on the surface of the substrate through vacuum deposition, which has both wear resistance and metal decoration effect. However, due to the high deposition temperature (usually >150℃), many heat-sensitive polymer substrates cannot withstand it, resulting in a limited range of applications. In addition, the polymer material is soft and the hard coating is hard and brittle. The mechanical properties of the two are very different, which reduces the softness of the film material; in addition, the coating is too thick, which affects the aesthetic appearance of the surface color of the decorative material.

[0004] Therefore, optimizing and improving the preparation process of decorative membrane materials to reduce VOC emissions and enhance their wear resistance and flexibility is one of the technical problems that urgently need to be solved in this field. Summary of the Invention

[0005] In view of this, the present invention provides a decorative film with good wear resistance and good flexibility.

[0006] In a first aspect, the present invention provides a PVC base film, wherein the raw materials of the PVC base film, by weight, include: 100 parts of PVC, 2-5 parts of stabilizer, 0.1-10 parts of drying oil, 0-50 parts of filler, 0.5-5 parts of epoxidized soybean oil, and 0.1-2 parts of peroxide.

[0007] In some optional embodiments, the raw materials of the PVC base film include: 100 parts PVC, 2-3 parts stabilizer, 2-8 parts drying oil, 5-15 parts filler, 0.5-2 parts epoxidized soybean oil, and 0.2-0.5 parts peroxide.

[0008] In some alternative embodiments, the drying oil includes at least one of triα-tungstate glyceryl ester, linseed oil, and perilla seed oil.

[0009] In some alternative embodiments, the stabilizer includes at least one of methyltin thiolate, zinc stearate, and barium stearate.

[0010] In some alternative embodiments, the filler includes at least one of calcium carbonate, talc, and mica.

[0011] In some alternative embodiments, the peroxide includes at least one of benzoyl peroxide and dicumyl peroxide.

[0012] In some alternative embodiments, the thickness of the PVC base film is 0.05mm-1.0mm.

[0013] Secondly, the present invention provides a method for preparing the PVC-based film described in the first aspect, wherein the raw materials of the PVC-based film described in the first aspect are mixed and pressed to obtain the film.

[0014] Thirdly, the present invention provides a decorative film, the decorative film comprising a PVC base film and N stacked aluminum-plated film substrates;

[0015] Each of the aluminized film substrates sequentially includes an aluminum film layer, an aluminum oxide film layer, and a dry oil film layer. The aluminum film layer of the i-th aluminized film substrate is in contact with the dry oil film layer of the (i-1)-th aluminized film substrate, and 3≤i≤N.

[0016] The PVC base film includes the PVC base film described in the first aspect or is prepared by the preparation method described in the second aspect.

[0017] In some alternative embodiments, the thickness of the aluminum film layer is 50nm-200nm.

[0018] In some alternative embodiments, the thickness of the alumina film is 40 nm to 90 nm.

[0019] In some alternative embodiments, the thickness of the dry oil film layer is 50 nm to 200 nm.

[0020] In some alternative embodiments, the drying oil film includes at least one of triα-tungstate glyceryl ester, linseed oil, and perilla seed oil.

[0021] Fourthly, the present invention provides a method for preparing the decorative film described in the third aspect, wherein N layers of aluminized film substrates are formed on the surface of a PVC base film, the i-th aluminized film substrate comprising, in sequence, an i-th aluminum film layer, an i-th alumina film layer, and an i-th dry oil film layer, and N ≥ 3, wherein the method for preparing the first aluminized film substrate comprises the following steps:

[0022] (1) A coating is applied to the surface of the PVC base film to obtain an aluminum film layer;

[0023] (2) The surface of the aluminum film layer is subjected to a first oxidation treatment to form an aluminum oxide film layer grown in situ on the surface of the aluminum film layer, thereby obtaining an aluminum-plated film.

[0024] (3) Polish the surface of the aluminum oxide film layer of the aluminum-plated film in sequence and perform a second oxidation treatment to form a dry oil film layer, thereby obtaining the first aluminum-plated film substrate.

[0025] When i ≥ 2, the preparation method of the i-th aluminum-coated film substrate includes the following steps:

[0026] (a) A coating is applied to the surface of the dry oil film layer of the i-1th aluminum film substrate to form the ith aluminum film layer;

[0027] (b) A first oxidation treatment is performed on the surface of the i-th aluminum film layer to form an i-th aluminum oxide film layer grown in situ on the surface of the aluminum film layer, thereby obtaining the i-th aluminum-plated film.

[0028] (c) The surface of the i-th aluminum oxide film layer of the i-th aluminum-plated film is polished and subjected to a second oxidation treatment in sequence to form the i-th dry oil film layer, thereby obtaining the i-th aluminum-plated film substrate.

[0029] The polishing step also includes the addition of drying oil.

[0030] In some alternative implementations, 4 ≤ N ≤ 5;

[0031] In some optional embodiments, the coating method includes at least one of vacuum evaporation and vacuum sputtering.

[0032] In some alternative embodiments, the coating temperature during the vacuum evaporation is 15°C-35°C.

[0033] In some alternative embodiments, the working pressure during the vacuum sputtering is 0.3 Pa to 3 Pa.

[0034] In some alternative embodiments, the first oxidation method includes at least one of low-temperature plasma oxidation and ozone oxidation.

[0035] In some alternative embodiments, the oxygen flow rate in the low-temperature plasma oxidation is 20 sccm-50 sccm, and the time is 5 min-30 min.

[0036] Fifthly, the decorative film prepared by the method described in the third aspect or the fourth aspect is used in furniture and automobiles.

[0037] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0038] 1. The PVC base film provided by this invention, by weight, comprises the following raw materials: 100 parts PVC, 2-5 parts stabilizer, 0.1-10 parts drying oil, 0-50 parts filler, 0.5-5 parts epoxidized soybean oil, and 0.1-2 parts peroxide. In this invention, the peroxide opens the double bonds of the drying oil, causing some of the drying oil to undergo self-crosslinking, and some of the drying oil and epoxidized soybean oil to partially crosslink, forming a layered composite structure. This structure acts as a reinforcing skeleton, improving the wear resistance and mechanical strength of the PVC base film. Furthermore, the epoxidized soybean oil acts as a plasticizer, synergistically optimizing toughness and processing stability. Additionally, the addition of the stabilizer enhances the weather resistance of the PVC base film and improves its initial color; the addition of the filler improves the hardness of the PVC base film, forming a physical support structure, enhancing dimensional stability, and reducing molding shrinkage.

[0039] 2. The decorative film provided by the present invention comprises a PVC base film and N stacked aluminized film substrates; each aluminized film substrate sequentially comprises an aluminum film layer, an aluminum oxide film layer, and a dry oil film layer, wherein the aluminum film layer of the i-th aluminized film substrate is in contact with the dry oil film layer of the (i-1)-th aluminized film substrate, and 3≤i≤N; the present invention oxidizes the aluminum film layer into a dense aluminum oxide film layer, improving the wear resistance of the decorative film surface, and then uses the dry oil film to fill and cover the aluminum oxide film layer, and oxidizes and crosslinks with the remaining dry oil in the PVC base film to form an integrated composite film material, thereby improving the adhesion of the aluminized film substrate; at the same time, the dry oil film layer has flexibility, improving the folding and crack resistance of the decorative film; in addition, the unoxidized aluminum film layer is combined with the PVC base film, improving the flexibility of the decorative film.

[0040] 3. The method for preparing the decorative film provided by the present invention further includes adding drying oil in the polishing step. The drying oil added during polishing and the remaining drying grease of the PVC base film are combined with the self-crosslinking properties and wear-resistant layer in the presence of oxygen to form an integrated composite film material, which provides high adhesion and increases the folding and crack resistance of the decorative film. The production process of the present invention is completely solvent-free, truly achieving zero VOC emissions. Detailed Implementation

[0041] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0042] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0043] To address the problems existing in the aforementioned related technologies, according to a first aspect of the present invention, the present invention provides a PVC base film, wherein, by weight, the raw materials of the PVC base film include: 100 parts PVC, 2-5 parts stabilizer, 0.1-10 parts drying oil, 0-50 parts filler, 0.5-5 parts epoxidized soybean oil, and 0.1-2 parts peroxide; preferably: 100 parts PVC, 2-3 parts stabilizer, 2-8 parts drying oil, 5-15 parts filler, 0.5-2 parts epoxidized soybean oil, and 0.2-0.5 parts peroxide.

[0044] In some alternative embodiments, the drying oil includes at least one of triα-tungstate glyceryl ester, linseed oil, and perilla seed oil.

[0045] In some alternative embodiments, the stabilizer includes at least one of methyltin thiolate, zinc stearate, and barium stearate.

[0046] In some alternative embodiments, the filler includes at least one of calcium carbonate, talc, and mica.

[0047] In some alternative embodiments, the peroxide includes at least one of benzoyl peroxide and dicumyl peroxide.

[0048] In some alternative embodiments, the thickness of the PVC base film is 0.05mm-1.0mm.

[0049] Secondly, the present invention provides a method for preparing the PVC-based film described in the first aspect, wherein the raw materials of the PVC-based film described in the first aspect are mixed and pressed to obtain the film.

[0050] Thirdly, the present invention provides a decorative film, the decorative film comprising a PVC base film and N stacked aluminum-plated film substrates;

[0051] Each of the aluminized film substrates includes an aluminum film layer, an aluminum oxide film layer, and a dry oil film layer. The aluminum film layer of the i-th aluminized film substrate is in contact with the dry oil film layer of the (i-1)-th aluminized film substrate, and 3≤i≤N.

[0052] The PVC base film includes the PVC base film described in the first aspect or is prepared by the preparation method described in the second aspect.

[0053] In some alternative embodiments, the thickness of the aluminum film layer is 50nm-200nm.

[0054] In some alternative embodiments, the thickness of the alumina film is 40 nm to 90 nm.

[0055] In some alternative embodiments, the thickness of the dry oil film layer is 50 nm to 200 nm.

[0056] In some alternative embodiments, the drying oil film includes at least one of triα-tungstate glyceryl ester, linseed oil, and perilla seed oil.

[0057] Fourthly, the present invention provides a method for preparing the decorative film described in the third aspect, wherein N layers of aluminized film substrates are formed on the surface of a PVC base film, the i-th aluminized film substrate comprising, in sequence, an i-th aluminum film layer, an i-th alumina film layer, and an i-th dry oil film layer, and N ≥ 3, wherein the method for preparing the first aluminized film substrate comprises the following steps:

[0058] (1) A coating is applied to the surface of the PVC base film to obtain an aluminum film layer;

[0059] (2) The surface of the aluminum film layer is subjected to a first oxidation treatment to form an aluminum oxide film layer grown in situ on the surface of the aluminum film layer, thereby obtaining an aluminum-plated film.

[0060] (3) Polish the surface of the aluminum oxide film layer of the aluminum-plated film in sequence and perform a second oxidation treatment to form a dry oil film layer, thereby obtaining the first aluminum-plated film substrate.

[0061] When i ≥ 2, the preparation method of the i-th aluminum-coated film substrate includes the following steps:

[0062] (a) A coating is applied to the surface of the dry oil film layer of the i-1th aluminum film substrate to form the ith aluminum film layer;

[0063] (b) A first oxidation treatment is performed on the surface of the i-th aluminum film layer to form an i-th aluminum oxide film layer grown in situ on the surface of the aluminum film layer, thereby obtaining the i-th aluminum-plated film.

[0064] (c) The surface of the i-th aluminum oxide film layer of the i-th aluminum-plated film is polished and subjected to a second oxidation treatment in sequence to form the i-th dry oil film layer, thereby obtaining the i-th aluminum-plated film substrate.

[0065] The polishing step also includes the addition of drying oil.

[0066] It should be noted that the polishing machine of this application consists of multiple sets of microfiber cloth wheels, wherein there are no fewer than two sets of polishing wheels. The first set of fiber cloth is impregnated with drying oil. Through multiple sets of polishing, a uniform thin layer of drying oil is formed on the surface.

[0067] In some optional embodiments, the coating method includes at least one of vacuum evaporation and vacuum sputtering.

[0068] In some alternative embodiments, the coating temperature during the vacuum evaporation is 15°C-35°C.

[0069] In some alternative embodiments, the working pressure during the vacuum sputtering is 0.3 Pa to 3 Pa.

[0070] It should be noted that the aluminum wire used for coating in this application has a purity of ≥99.99% and a pressure of <5×10. -2 Pa, the evaporation source is tungsten filament and electron beam.

[0071] In some alternative embodiments, the first oxidation method includes at least one of low-temperature plasma oxidation and ozone oxidation.

[0072] In some alternative embodiments, the oxygen flow rate in the low-temperature plasma oxidation is 20 sccm-50 sccm, and the time is 5 min-30 min.

[0073] It should be noted that low-temperature plasma oxidation uses a radio frequency / microwave plasma oxidation system, with argon and oxygen as auxiliary gases, and an electrode spacing of 50mm-100mm.

[0074] Fifthly, the present invention provides an application of the decorative film described in the third aspect or the decorative film prepared by the preparation method described in the fourth aspect in furniture and automobiles.

[0075] The present invention will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed by the present invention.

[0076] Example 1

[0077] This embodiment provides a method for preparing a PVC decorative film, including the following steps:

[0078] (1) Mix 100 parts PVC, 2 parts methyl tin mercaptan, 5 parts triα-tungstate glycerol, 8 parts calcium carbonate, 1.5 parts epoxidized soybean oil and 0.3 parts benzoyl peroxide, and process them sequentially through a kneader, a rolling mill and a calender to press them into a PVC base film with a thickness of 0.30 mm.

[0079] (2) A high-vacuum suspension roll coating machine was used to vapor-deposit aluminum film on the surface of PVC base film at a coating temperature of 25℃ to obtain an aluminum film with a thickness of 50nm.

[0080] (3) The aluminum-coated substrate is placed in a low-temperature plasma chamber and an RF / microwave plasma oxidation system is used. The oxygen flow rate is 35 sccm and the time is 20 min to form an Al2O3 wear-resistant layer with a thickness of 40 nm grown in situ on the surface of the aluminum film, thus obtaining an aluminum-coated film.

[0081] (4) The aluminum-coated film is placed in a polishing machine for polishing. There are 3 polishing wheel sets. The first set of fiber cloth is impregnated with triα-tungsten glycerol to form a uniform dry oil thin layer on the surface. Then it is placed in an ozone box for oxidation cross-linking to form a dry oil film layer with a thickness of 150nm.

[0082] (5) Repeat steps (2) to (4) three times to form a composite film layer and prepare a PVC decorative film.

[0083] Example 2

[0084] This embodiment provides a method for preparing a PVC decorative film, including the following steps:

[0085] (1) Mix 100 parts of PVC, 3 parts of methyl tin mercaptan, 8 parts of triα-tungsten glycerol, 15 parts of calcium carbonate, 2 parts of epoxidized soybean oil and 0.5 parts of benzoyl peroxide, and process them sequentially through a kneader, a rolling mill and a calender to press them into a PVC base film with a thickness of 0.50 mm.

[0086] (2) A high-vacuum suspension roll coating machine was used to vapor-deposit aluminum film on the surface of PVC base film at a coating temperature of 25℃ to obtain an aluminum film with a thickness of 50nm.

[0087] (3) The aluminum-coated substrate is placed in an ozone chamber for oxidation for 2 hours to form an Al2O3 wear-resistant layer with a thickness of 40nm grown in situ on the surface of the aluminum film, thus obtaining an aluminum-coated film.

[0088] (4) The aluminum-coated film is placed in a polishing machine for polishing. There are 4 polishing wheel sets. Tri-α-tung oil glycerol is impregnated on the first set of fiber cloth to form a uniform dry oil film on the surface. Then it is placed in an ozone box for oxidation cross-linking to form a dry oil film layer with a thickness of 200nm.

[0089] (5) Repeat steps (2) to (4) three times to form a composite film layer and prepare a PVC decorative film.

[0090] Example 3

[0091] This embodiment provides a method for preparing a PVC decorative film, including the following steps:

[0092] (1) Mix 100 parts of PVC, 2.5 parts of thiol methyltin, 4 parts of triα-tungsten glycerol, 15 parts of calcium carbonate, 1 part of epoxidized soybean oil and 0.2 parts of benzoyl peroxide, and process them sequentially through a kneader, a rolling mill and a calender to press them into a PVC base film with a thickness of 0.10 mm.

[0093] (2) Aluminum film with a thickness of 100 nm was obtained by vacuum sputtering on the surface of PVC base film at a working pressure of 1.5 Pa.

[0094] (3) The aluminum-coated substrate is placed in an ozone chamber for oxidation for 2 hours to form an Al2O3 wear-resistant layer with a thickness of 80nm grown in situ on the surface of the aluminum film, thus obtaining the aluminum-coated film.

[0095] (4) The aluminum-coated film is placed in a polishing machine for polishing. There are 5 polishing wheel groups. Tri-α-tung oil glycerol is impregnated on the first group of fiber cloth to form a uniform dry oil thin layer on the surface. Then it is placed in an ozone box for oxidation cross-linking to form a dry oil film layer with a thickness of 150nm.

[0096] (5) Repeat steps (2) to (4) above 4 times to form a composite film layer and prepare PVC decorative film.

[0097] Example 4

[0098] This embodiment provides a method for preparing PVC decorative film, which is basically the same as the steps in Embodiment 1, except that in step (5), steps (2) to (4) are repeated twice.

[0099] Example 5

[0100] This embodiment provides a method for preparing a PVC decorative film, including the following steps:

[0101] (1) Mix 100 parts PVC, 2 parts barium stearate, 1 part zinc stearate, 6 parts perilla seed oil, 20 parts talc powder, 4 parts epoxidized soybean oil and 1 part dicumyl peroxide, and process them sequentially through a kneader, a rolling mill and a calender to press them into a PVC base film with a thickness of 0.10 mm.

[0102] (2) A high-vacuum suspension roll coating machine was used to vapor-deposit aluminum film on the surface of PVC base film at a coating temperature of 23℃ to obtain an aluminum film with a thickness of 100nm.

[0103] (3) The aluminum-coated substrate is placed in a low-temperature plasma chamber and an RF / microwave plasma oxidation system is used. The oxygen flow rate is 20 sccm and the time is 30 min to form an Al2O3 wear-resistant layer with a thickness of 70 nm grown in situ on the surface of the aluminum film, thus obtaining an aluminum-coated film.

[0104] (4) The aluminum-coated film is placed in a polishing machine for polishing. There are 3 polishing wheel sets. The first set of fiber cloth is soaked with perilla seed oil to form a uniform dry oil thin layer on the surface. Then it is placed in an ozone box for oxidation cross-linking to form a dry oil film layer with a thickness of 200nm.

[0105] (5) Repeat steps (2) to (4) three times to form a composite film layer and prepare a PVC decorative film.

[0106] Example 6

[0107] This embodiment provides a method for preparing a PVC decorative film, including the following steps:

[0108] (1) Mix 100 parts of PVC, 4 parts of mercaptan methyltin, 0.1 parts of linseed oil, 4 parts of mica, 3 parts of epoxidized soybean oil and 0.1 parts of benzoyl peroxide, and process them sequentially through a kneader, a rolling mill and a calender to press them into a PVC base film with a thickness of 0.07 mm.

[0109] (2) A high-vacuum suspension roll coating machine was used to vapor-deposit aluminum film on the surface of PVC base film at a coating temperature of 35℃ to obtain an aluminum film with a thickness of 100nm.

[0110] (3) The aluminum-coated substrate is placed in an ozone chamber for oxidation for 2 hours to form an Al2O3 wear-resistant layer with a thickness of 70nm grown in situ on the surface of the aluminum film, thus obtaining an aluminum-coated film.

[0111] (4) The aluminum-coated film is placed in a polishing machine for polishing. There are 3 polishing wheel sets. The first set of fiber cloth is soaked with linseed oil to form a uniform dry oil thin layer on the surface. Then it is placed in an ozone box for oxidation cross-linking to form a dry oil film layer with a thickness of 50nm.

[0112] (5) Repeat steps (2) to (4) three times to form a composite film layer and prepare a PVC decorative film.

[0113] Comparative Example 1

[0114] This comparative example provides a method for preparing a PVC decorative film, which is basically the same as the steps in Example 1, except that step (5) is omitted.

[0115] Comparative Example 2

[0116] This comparative example provides a method for preparing a PVC decorative film, which is basically the same as the steps in Example 1, except that triα-tungstate glyceryl ester is replaced with 0.05 parts.

[0117] Comparative Example 3

[0118] This comparative example provides a method for preparing a PVC decorative film, which is basically the same as the steps in Example 1, except that triα-tungstate glycerol ester is replaced with 12 parts.

[0119] Experimental Example

[0120] The PVC decorative films prepared in Examples 1-6 and Comparative Examples 1-3 were tested for surface scratch resistance and surface abrasion resistance according to GB / T17657-2013, and for peel resistance according to GB / T9286-2021. The results are shown in Table 1.

[0121] Among them, peel resistance grade 0 indicates that the cut edge is completely smooth and there is no peeling within the grid; grade 1 indicates that there is a small amount of coating peeling at the cut intersection, but the affected cross-cut area is no more than 5%; grade 2 indicates that there is coating peeling at the cut intersection and / or along the cut edge, but the affected cross-cut area is greater than 5% but not more than 15%.

[0122] Flexibility Test: Due to poor material flexibility or high rigidity of the aluminum coating, cracks easily appear in the aluminum coating when bent. The presence and extent of cracks can be observed to determine the flexibility of the aluminum-coated film. Therefore, a 90-degree right-angle adsorption molding method was designed to test its flexibility. Specifically, the sample is bent at 90 degrees using a right-angle adsorption device at 120℃ and left for 2 hours. After removal, a magnifying glass is used to observe whether cracks appear in the film. If cracks appear, it is considered unqualified; if no cracks appear, it is considered qualified.

[0123] Table 1. Performance test results of PVC decorative films in each embodiment and comparative example.

[0124]

[0125] As shown in Table 1, the decorative films prepared in Examples 1-6 did not show visible scratches under loads of 4.5-5N, and the wear values ​​fluctuated very little. Within the range of 0.04mg / 100r-0.08mg / 100r, the peel resistance results were all grade 0, indicating good peel resistance, and the flexibility all met the qualified standard. Compared with Example 1, Example 4, with fewer aluminum plating layers (only repeating steps (2)-(4) twice), showed a decrease in scratch resistance (4.5N) and surface abrasion resistance (wear value 0.07mg / 100r). This indicates that the number of composite film layers affects the surface mechanical properties of the decorative film, and appropriately increasing the number of composite film layers can improve its abrasion resistance. Example 3 had the lowest wear value (0.04 mg / 100r). This was because in Example 3, steps (2)-(4) were repeated four times, and there were five polishing wheel sets, which resulted in more complete coating adhesion and the formation of a thicker and more uniform composite film. The thickened Al2O3 wear-resistant layer effectively reduced surface wear. Example 6 had a wear value of 0.08 mg / 100r. This was because the proportion of dry oil (0.1 parts linseed oil) in the PVC film substrate was low, and the thinner dry oil layer resulted in a higher wear value. In Examples 5 and 6, the ratio of dry oil and epoxidized soybean oil resulted in a lower proportion of Al2O3 wear-resistant layer thickness in the aluminized film, leading to a decrease in scratch resistance compared to Examples 1-3.

[0126] Comparative Example 1 exhibited a scratch resistance of only 3N, a peel resistance grade of 1, and failed to meet flexibility standards. This was because the repeated operation of step (5) was omitted, resulting in only a single layer of aluminum film and Al2O3 layer. The film structure was thin and could not form effective superimposed protection, leading to a significant decrease in overall mechanical properties. Comparative Example 2 showed a scratch resistance of 3.5N and a peel resistance grade of 2, which was weaker than the example. This was because the weight of triα-tungstate glycerol ester was 0.05 parts, which was too little. Triα-tungstate glycerol ester can play a role in film formation during raw material mixing and polishing. Insufficient amount will lead to a decrease in film adhesion and a weakening of surface wear resistance. Comparative Example 3 showed a scratch resistance of 4N and a peel resistance grade of 1. This was because the weight of triα-tungstate glycerol ester was 12 parts. Excessive triα-tungstate glycerol ester will leave unreacted components in the film layer, reducing the density of the film layer and leading to a decrease in peel resistance.

[0127] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A decorative film, characterized in that, The decorative film includes a PVC base film and N stacked aluminum-plated film substrates; Each of the aluminized film substrates sequentially includes an aluminum film layer, an aluminum oxide film layer, and a dry oil film layer. The aluminum film layer of the i-th aluminized film substrate is in contact with the dry oil film layer of the (i-1)-th aluminized film substrate, and 3≤N≤5. By weight, the raw materials of the PVC base film include: 100 parts PVC, 2-5 parts stabilizer, 0.1-10 parts drying oil, 5-15 parts filler, 0.5-5 parts epoxidized soybean oil, and 0.1-2 parts peroxide. The drying oils include at least one of triα-tungstate glyceryl ester, linseed oil, and perilla seed oil; The dry oil film layer includes at least one of triα-tungsten glycerol, linseed oil, and perilla seed oil.

2. The decorative film according to claim 1, characterized in that, The raw materials of the PVC base film include: 100 parts PVC, 2-3 parts stabilizer, 2-8 parts drying oil, 5-15 parts filler, 0.5-2 parts epoxidized soybean oil, and 0.2-0.5 parts peroxide.

3. The decorative film according to claim 2, characterized in that, The stabilizer includes at least one of methyltin thiolate, zinc stearate, and barium stearate; And / or, the filler includes at least one of calcium carbonate, talc, and mica; And / or, the peroxide includes at least one of benzoyl peroxide and dicumyl peroxide.

4. The decorative film according to claim 1, characterized in that, The thickness of the PVC base film is 0.05mm-1.0mm.

5. The decorative film according to any one of claims 1-4, characterized in that, The method for preparing the PVC base film includes: mixing and pressing the raw materials of the PVC base film.

6. The decorative film according to claim 1, characterized in that, The thickness of the aluminum film layer is 50nm-200nm; And / or, the thickness of the alumina film is 40nm-90nm; And / or, the thickness of the dry oil film layer is 50nm-200nm.

7. The method for preparing the decorative film according to any one of claims 1-6, characterized in that, N layers of aluminized film substrate are formed on the surface of a PVC base film. The i-th layer of aluminized film substrate sequentially includes an i-th aluminum film layer, an i-th alumina film layer, and an i-th dry oil film layer, where 3 ≤ N ≤ 5. The preparation method of the first aluminized film substrate includes the following steps: (1) A coating is applied to the surface of the PVC base film to obtain an aluminum film layer; (2) The surface of the aluminum film layer is subjected to a first oxidation treatment to form an aluminum oxide film layer grown in situ on the surface of the aluminum film layer, thereby obtaining an aluminum-plated film; (3) Polish the surface of the aluminum oxide film layer of the aluminum-plated film in sequence and perform a second oxidation treatment to form a dry oil film layer, thereby obtaining the first aluminum-plated film substrate; When i ≥ 2, the method for preparing the i-th layer of aluminum-coated film substrate includes the following steps: (a) A coating is applied to the surface of the dry oil film layer of the i-1th aluminum film substrate to form the ith aluminum film layer; (b) A first oxidation treatment is performed on the surface of the i-th aluminum film layer to form an i-th aluminum oxide film layer grown in situ on the surface of the aluminum film layer, thereby obtaining the i-th aluminum-plated film; (c) The surface of the i-th aluminum oxide film layer of the i-th aluminum-plated film is polished and subjected to a second oxidation treatment in sequence to form the i-th dry oil film layer, thereby obtaining the i-th aluminum-plated film substrate. The polishing step also includes the addition of drying oil.

8. The method for preparing the decorative film according to claim 7, characterized in that, The coating method includes at least one of vacuum evaporation and vacuum sputtering.

9. The method for preparing the decorative film according to claim 8, characterized in that, In the vacuum evaporation process, the coating temperature is 15℃-35℃.

10. The method for preparing the decorative film according to claim 8, characterized in that, In the vacuum sputtering process, the working gas pressure is 0.3 Pa to 3 Pa.

11. The method for preparing the decorative film according to claim 7, characterized in that, The first oxidation method includes at least one of low-temperature plasma oxidation and ozone oxidation.

12. The method for preparing the decorative film according to claim 11, characterized in that, In the aforementioned low-temperature plasma oxidation, the oxygen flow rate is 20 sccm-50 sccm, and the time is 5 min-30 min.

13. The application of the decorative film prepared by the preparation method according to any one of claims 7-12 in furniture and automobiles.

Images