Self-repairing scratch-resistant coating, pvc decorative film and preparation method thereof

Abstract

The application provides a self-repairing scratch-resistant coating, a PVC decorative film and a preparation method thereof, and relates to the technical field of decorative films.The self-repairing scratch-resistant coating provided by the application comprises flexible polyurethane acrylate, modified epoxy acrylate, active diluent, photoinitiator, silicone microcapsule repair agent, dynamic crosslinking agent, leveling agent, anti-fingerprint agent and butyl acetate; through the dual self-repairing mechanism of chemical repair of dynamic chemical bonds and physical repair of microcapsules, efficient repair of the coating can be realized; meanwhile, the flexible polyurethane acrylate can improve the toughness of the coating, avoid secondary damage after repair, and achieve the purpose of synergistic scratch resistance and self-repairing.The PVC decorative film provided by the application adopts the self-repairing scratch-resistant coating, so that the surface hardness is improved, the scratch resistance is enhanced, and the scratch self-repairing technology is added, so that the scratch is reversible and the service life is prolonged.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of decorative film, in particular to a self-repairing scratch-resistant coating, a PVC decorative film and a preparation method thereof. BACKGROUND

[0002] A single-layer PVC film is mainly produced by calendering or extrusion process. The preparation method uses polyvinyl chloride (PVC) resin as a base material, and adds plasticizers, stabilizers, colorants and other additives to prepare it. The single-layer PVC film is then prepared into a decorative film with diversified patterns by printing patterns, multi-layer hot sticking, embossing and the like. At present, this process is mature. With the improvement of production technology and the demand for product individualization and functionalization in the market, the existing production technology mainly focuses on the development of base material modification, surface treatment and functionalization while meeting the aesthetic requirements. Environmentally friendly and functional materials are used for the base material, and surface treatment technologies such as thermal curing, photocuring and electron beam curing are used. The functionalization of PVC decorative film includes properties such as wear resistance, weather resistance, scratch resistance and easy cleaning.

[0003] Ordinary scratch-resistant film uses photocured coating to improve hardness through surface treatment technology, but the coating cannot be repaired after damage. SUMMARY

[0004] The present application aims to provide a self-repairing scratch-resistant coating, a PVC decorative film and a preparation method thereof, and to solve the problem that the coating of the existing ordinary scratch-resistant film cannot be repaired after damage.

[0005] To achieve the above purpose, the present application provides a self-repairing scratch-resistant coating, the raw materials of which include, in mass parts:

[0006] 60-70 parts of flexible polyurethane acrylate, 5-10 parts of modified epoxy acrylate, 15-20 parts of active diluent, 3-5 parts of photoinitiator, 3-5 parts of silicone microcapsule repair agent, 3-5 parts of dynamic crosslinking agent, 0.2-0.3 parts of leveling agent, 0.5-1.0 parts of anti-fingerprint agent and 5-8 parts of butyl acetate.

[0007] The dynamic crosslinking agent includes a multifunctional acrylated polyether oligomer and a thioctic acid polyethylene glycol acrylate in a mass ratio of (2.5-3):1.

[0008] In some embodiments, the active diluent includes isobornyl acrylate and tripropylene glycol diacrylate in a mass ratio of (3-4):1.

[0009] In some embodiments, the photoinitiator includes 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide in a mass ratio of (1-2):1.

[0010] In some embodiments, the leveling agent is selected from at least one of polyether modified polysiloxane, perfluoropolyether acrylate.

[0011] In some embodiments, the anti-fingerprint agent is selected from at least one of perfluoropolyether, silicofluoride copolymer, nanosilica.

[0012] The application also provides a PVC decorative film, which comprises, from top to bottom, the self-repairing scratch-resistant coating, a weather-resistant PVC layer, a water-based ink layer, and a printed PVC base film.

[0013] The weather-resistant PVC layer comprises, in mass fraction, 100 parts of PVC resin, 20-25 parts of environmentally friendly plasticizer, and 1.0-1.5 parts of light stabilizer.

[0014] In some embodiments, the environmentally friendly plasticizer comprises dioctyl terephthalate (DOTP) and sebacic acid polyester in a mass ratio of (8-10):1.

[0015] In some embodiments, the light stabilizer comprises benzotriazole ultraviolet absorber and polymeric HALS in a mass ratio of (1.25-3):1.

[0016] The application also provides a preparation method of the PVC decorative film, comprising:

[0017] The self-repairing scratch-resistant coating is coated on the surface of the weather-resistant PVC layer to obtain a scratch-resistant layer.

[0018] The water-based ink layer is printed on the surface of the printed PVC base film to obtain a printed layer.

[0019] The scratch-resistant layer and the printed layer are laminated to obtain the PVC decorative film.

[0020] Compared with the prior art, the application has the following beneficial effects:

[0021] The self-repairing scratch-resistant coating provided by the application comprises flexible polyurethane acrylate, modified epoxy acrylate, active diluent, photoinitiator, silicone microcapsule repair agent, dynamic crosslinking agent, leveling agent, anti-fingerprint agent, and butyl acetate. Through the dual self-repairing mechanism of chemical repair by dynamic chemical bonds and physical repair by microcapsules, efficient repair of the coating can be achieved. Meanwhile, the flexible polyurethane acrylate can improve the toughness of the coating, avoid secondary damage after repair, and achieve the purpose of scratch resistance and self-repairing synergy.

[0022] The PVC decorative film provided by the application adopts the self-repairing scratch-resistant coating provided by the application, so that the surface hardness is improved and the scratch resistance is enhanced. Moreover, the scratch self-repairing technology is added, so that the scratches are reversible and the service life is prolonged. The environmentally friendly raw materials, environmentally friendly plasticizer, and water-based / mild solvent process meet the standards such as RoHS and REACH. Attached Figure Description

[0023] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation on the scope of this application.

[0024] Figure 1 This is a schematic diagram of the structure of the PVC decorative film of this application.

[0025] Figure label:

[0026] 1- Self-healing scratch-resistant coating; 2- Weather-resistant PVC layer; 3- Water-based ink layer; 4- Printable PVC base film. Detailed Implementation

[0027] As used in this article:

[0028] "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0029] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1–5” is disclosed, the described range should be interpreted as including ranges “1–4”, “1–3”, “1–2”, “1–2 and 4–5”, “1–3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0030] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0031] "Mass parts" refers to the basic unit of measurement indicating the mass ratio relationship of multiple components, 1 part can represent any unit mass, such as 1g, 2.689g, etc. If we say that the mass parts of component A is a parts, and the mass parts of component B is b parts, it means that the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it means that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number, indicating a multiple factor). It should not be misunderstood that unlike mass parts, the sum of the mass parts of all components is not limited to 100 parts.

[0032] "and / or" is used to indicate that one or both of the described cases can occur, for example, A and / or B includes (A and B) and (A or B).

[0033] The application provides a self-repairing scratch-resistant coating, which comprises, in mass parts:

[0034] 60-70 parts of flexible polyurethane acrylate, 5-10 parts of modified epoxy acrylate, 15-20 parts of reactive diluent, 3-5 parts of photoinitiator, 3-5 parts of silicone microcapsule repair agent, 3-5 parts of dynamic crosslinking agent, 0.2-0.3 parts of leveling agent, 0.5-1.0 parts of anti-fingerprint agent and 5-8 parts of butyl acetate;

[0035] The dynamic crosslinking agent comprises a multifunctional acrylated polyether oligomer and a lipoic acid polyethylene glycol acrylate in a mass ratio of (2.5-3):1.

[0036] The self-repairing scratch-resistant coating provided by the application comprises flexible polyurethane acrylate, modified epoxy acrylate, reactive diluent, photoinitiator, silicone microcapsule repair agent, dynamic crosslinking agent, leveling agent, anti-fingerprint agent and butyl acetate. Through the dual self-repairing mechanism of chemical repair by dynamic chemical bonds and physical repair by microcapsules, efficient repair of the coating can be achieved. At the same time, the flexible polyurethane acrylate can improve the toughness of the coating, avoid secondary damage after repair, and achieve the purpose of scratch resistance and self-repairing synergy.

[0037] The mass parts of the flexible polyurethane acrylate may be, for example, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts or any value between 60-70 parts.

[0038] The flexible polyurethane acrylate has high elongation, matches the flexibility of the substrate PVC film, and disperses stress through elastic deformation when subjected to external force by virtue of its flexible properties. The flexible polyurethane acrylate can improve the toughness of the coating, avoid secondary damage after repair, and achieve the purpose of scratch resistance and self-repairing synergy.

[0039] The mass fraction of the modified epoxy acrylate may be, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or any value between 5 and 10 parts.

[0040] The silicone segment of the modified epoxy acrylate can enhance surface slipperiness and alcohol and stain resistance. The modified epoxy acrylate does not directly participate in the repair process, and its role is to improve the hardness of the coating and optimize the surface performance to support the repair effect.

[0041] The mass fraction of the active diluent may be, for example, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, or any value between 15 and 20 parts.

[0042] The active diluent can balance the viscosity and curing speed, improve the adhesion to the PVC substrate, and avoid plasticizer migration.

[0043] In some embodiments, the active diluent includes isobornyl acrylate and tripropylene glycol diacrylate in a mass ratio of (3-4): 1, for example, 3:1, 3.5:1, 4:1, or any ratio between 3 and 4:1.

[0044] Isobornyl acrylate (IBOA) is an important organic compound with low shrinkage, high adhesion, high hardness, low irritation, and other advantages, which can improve the hardness of the coating while maintaining and improving its elasticity, and enhance the gloss and adhesion of the coating.

[0045] Tripropylene glycol diacrylate (TPGDA) is widely used as a photocuring resin monomer in fields such as coatings, inks, adhesives, and electronic materials. It has the advantages of improving curing speed, wear resistance, excellent dilution capacity, low viscosity, and low cost. The combination of isobornyl acrylate and tripropylene glycol diacrylate has complementary and synergistic benefits, providing excellent adhesion and fast curing speed for the coating.

[0046] The mass fraction of the photoinitiator may be, for example, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or any value between 3 and 5 parts.

[0047] The photoinitiator is cured with a matching LED light source and has yellowing resistance.

[0048] In some embodiments, the photoinitiator includes 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide in a mass ratio of (1-2): 1, for example, 1:1, 1.5:1, 2:1, or any ratio between 1 and 2:1.

[0049] 1-hydroxycyclohexyl phenyl ketone is a high-efficiency, yellowing-resistant, free radical type solid photoinitiator, which has the advantages of long storage time, high initiation efficiency, and wide ultraviolet absorption range.

[0050] 2,4,6-trimethylbenzoyl diphenylphosphine oxide (TPO) is an important organic compound, which is widely used in photocuring materials. TPO is a high-efficiency free radical type photoinitiator, which is particularly suitable for colored systems and thick film curing fields. It can produce free radicals after absorbing ultraviolet light, which can initiate resin crosslinking reaction, and is often used in white coating systems.

[0051] The mass fraction of the siloxane microcapsule repair agent may be, for example, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or any value between 3 and 5 parts.

[0052] The siloxane microcapsule repair agent is a special repair agent for self-repairing materials, and the core material is usually an organosiloxane compound, such as active siloxane, polydimethylsiloxane (PDMS), vinyl polydimethylsiloxane, etc. The capsule wall material (shell material) is usually a polymer, such as polyurea, polyurea-formaldehyde, calcium alginate, etc., and the particle size is between 10-30 microns.

[0053] The repair mechanism includes exogenous repair and endogenous repair. Exogenous repair: when the coating is damaged by external force and scratches appear, the microcapsule wall breaks, releasing the internal core material (repair agent), which fills the scratch gap through flowability; Endogenous repair: part of the siloxane material realizes multiple repairs through dynamic bonds (such as hydrogen bonds and disulfide bonds) without the need for additional repair agents. In the coating material, the siloxane microcapsule repair agent can be used to repair scratches and damage on the surface of the coating, and improve the durability and protective performance of the coating.

[0054] The mass fraction of the dynamic crosslinking agent may be, for example, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or any value between 3 and 5 parts.

[0055] The dynamic crosslinking agent has self-repairing performance. After the coating surface is damaged, the broken disulfide bonds reconnect within a certain time, realizing self-healing of the microstructure of the coating, and can cooperate with the siloxane microcapsule repair agent to repair scratches of different degrees.

[0056] In some embodiments, the dynamic crosslinking agent includes a multifunctional acrylated polyether oligomer and a lipoic acid polyethylene glycol acrylate in a mass ratio of (2.5-3):1, such as 2.5:1, 2.8:1, 3:1, or any ratio between 2.5 and 3:1.

[0057] The multifunctional acrylated polyether oligomer is generated by condensation reaction of acrylic acid or methacrylic acid with polyether polyols, contains dynamic disulfide bonds, and provides good crosslinking performance. The combination of multifunctional acrylated polyether oligomer and ubiquinol polyethylene glycol acrylate builds a repair network, which can enhance the self-repair efficiency.

[0058] In some embodiments, the mass fraction of the leveling agent may, for example, be 0.2 parts, 0.25 parts, 0.3 parts, or any value between 0.2-0.3 parts.

[0059] The leveling agent functions to optimize leveling, avoid reaction with PVC surface plasticizer, and ensure smooth coating surface.

[0060] In some embodiments, the leveling agent is selected from at least one of polyether-modified polysiloxane, perfluoropolyether acrylate. Polyether-modified polysiloxane is an organosilicon compound modified by introducing polyether segments into the polysiloxane chain. This structure makes it have both the low surface tension of polysiloxane and the hydrophilicity of polyether. As a leveling agent, polyether-modified polysiloxane can reduce surface tension, improve the wettability of the coating to the substrate, promote the flow of the coating film, eliminate orange peel and crater phenomenon, and make the coating film smooth and flat. Perfluoropolyether acrylate leveling agent can significantly reduce the surface tension of the coating, improve the leveling performance, and reduce the defects on the surface of the coating film.

[0061] In some embodiments, the mass fraction of the anti-fingerprint agent may, for example, be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, or any value between 0.5-1.0 parts.

[0062] The anti-fingerprint agent can improve stain resistance and touch, meeting the cleaning needs of furniture surfaces.

[0063] In some embodiments, the anti-fingerprint agent is selected from at least one of perfluoropolyether, silicon-fluorine copolymer, and nano-silicon dioxide. Perfluoropolyether (PFPE for short) is a class of synthetic polymers with unique properties, whose molecular chain is composed of fluorine atoms, carbon atoms, and oxygen atoms, exhibiting extremely low surface tension, excellent chemical stability, low volatility, and a wide temperature range of use. Silicon-fluorine copolymer is a high molecular material copolymerized from silicon-containing monomers and fluorine-containing monomers, combining the properties of organic silicon and organic fluorine, and having unique physical and chemical properties, which is used to manufacture high-performance coatings with excellent water resistance, stain resistance, and weather resistance.

[0064] In some embodiments, the mass fraction of butyl acetate may, for example, be 5 parts, 6 parts, 7 parts, 8 parts, or any value between 5-8 parts.

[0065] Butyl acetate is used to adjust the viscosity and belongs to a mild solvent, avoiding dissolving the PVC film.

[0066] The application also provides a PVC decorative film, please refer to Figure 1 From top to bottom, in turn, include: the above-mentioned self-repairing scratch-resistant coating 1, weather-resistant PVC layer 2, water-based ink layer 3, printed PVC base film 4;

[0067] The weather-resistant PVC layer comprises, in mass fraction: 100 parts of PVC resin, 20-25 parts of environmentally friendly plasticizer and 1.0-1.5 parts of light stabilizer.

[0068] The PVC decorative film provided by the application adopts the self-repairing scratch-resistant coating of the application, so that the surface hardness is improved, the scratch resistance is enhanced, and the scratch self-repairing technology is added, so that the scratch is reversible and the service life is prolonged. The use of environmentally friendly raw materials, environmentally friendly plasticizers, water-based / mild solvent process, conforms to the standards such as RoHS and REACH.

[0069] The thickness of the self-repairing scratch-resistant coating 1 is 5-15 microns. The weather-resistant PVC layer 2 is a transparent PVC surface layer with weather-resistant performance, with a thickness of 0.04mm-0.08mm, without phthalate and heavy metals, and passes the EU REACH regulation. The water-based ink layer 3 is printed by water-based ink, with a thickness range of 10-20 microns, and the thickness is determined by the depth of the intaglio pits. It has rich patterns and the advantages of environmental protection and non-toxicity. The printed PVC base film 4 is a printable PVC colored base film, which is produced by calendering process with environmentally friendly plasticizer, with a thickness of 0.06mm-0.10mm, without phthalate and heavy metals, and passes the EU REACH regulation.

[0070] In some embodiments, the mass fraction of the environmentally friendly plasticizer may be, for example, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, or any value between 20-25 parts.

[0071] In some embodiments, the environmentally friendly plasticizer comprises di-2-ethylhexyl terephthalate and sebacic acid polyester in a mass ratio of (8-10):1, for example, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, or any ratio between (8-10):1.

[0072] Di-2-ethylhexyl terephthalate (DOTP) is a commonly used plasticizer, which has excellent heat resistance, cold resistance, low volatility and electrical insulation, etc.

[0073] Sebacic acid polyester is a polyester compound synthesized by sebacic acid (Sebacic Acid) and polyols (such as ethylene glycol, butanediol, etc.) through polycondensation reaction, which is used as a plasticizer for PVC and other plastics to improve the flexibility and processability of the material.

[0074] The combination of dioctyl terephthalate and sebacic acid-based polyester has the advantages of enhanced migration resistance, low-temperature toughness, processing stability, extended service life, etc. than when used alone.

[0075] In some embodiments, the light stabilizer comprises a benzotriazole-based ultraviolet absorber and a polymeric HALS in a mass ratio of (1.25-3): 1, for example, 1.25:1, 1.5:1, 2:1, 2.5:1, 3:1, or any ratio between (1.25-3): 1.

[0076] Benzotriazole-based ultraviolet absorbers (UVAs) are a class of compounds that can effectively absorb ultraviolet light and convert it into heat energy, widely used in various materials to improve their light resistance and stability. Benzotriazole UVA prevents photodegradation of materials by absorbing ultraviolet light and converting it into heat energy.

[0077] Polymeric HALS (hindered amine light stabilizer) is usually connected to the polymer backbone by a hindered amine functional group, forming a high molecular weight structure. By forming a nitroxyl radical (TEMPO), it captures harmful free radicals generated during the photooxidation of the polymer, preventing the breakage and degradation of the polymer chain.

[0078] The application also provides a preparation method of the PVC decorative film as described above, comprising:

[0079] The self-repairing scratch-resistant coating is coated on the surface of the weather-resistant PVC layer to obtain a scratch-resistant layer;

[0080] The water-based ink layer is printed on the surface of the printed PVC base film to obtain a printed layer;

[0081] The scratch-resistant layer and the printed layer are laminated to obtain the PVC decorative film.

[0082] Using UV curing technology, the self-repairing scratch-resistant coating uniformly coated on the surface of the weather-resistant PVC layer is cured into a thin film by ultraviolet irradiation, i.e. a self-repairing scratch-resistant coating, to obtain a scratch-resistant layer comprising the self-repairing scratch-resistant coating and the weather-resistant PVC layer, so that the surface has the properties of stain resistance, scratch resistance, weather resistance, etc., especially the surface scratches can be self-repaired, protecting the decorative surface and prolonging the service life.

[0083] The water-based ink layer is printed on the surface of the printed PVC base film to obtain a printed layer.

[0084] Finally, the scratch-resistant layer and the printed layer are hot-stuck by lamination embossing technology to form a PVC decorative film with scratch self-repairing function.

[0085] The embodiments of the present application will be described in detail below with specific examples, but those skilled in the art will understand that the following examples are only for illustration of the present application and should not be regarded as limiting the scope of the present application. The specific conditions are not specified in the examples, and the conventional conditions or the conditions recommended by the manufacturer are used. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be purchased on the market.

[0086] The sources of raw materials used in each example and comparative example are as follows:

[0087] Flexible polyurethane acrylate, purchased from Shanghai Guangyi Chemical Co., Ltd.;

[0088] Modified epoxy acrylate, purchased from Jining Tangyi Chemical Co., Ltd.;

[0089] Isobornyl acrylate and tripropylene glycol diacrylate, purchased from Sinoreagent Co., Ltd.;

[0090] 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, purchased from Sinoreagent Co., Ltd.;

[0091] Silicone microcapsule repair agent, customized by Hefei Zhongkechuang Microtechnology Co., Ltd., with polyurea as shell material and active silicone as core material, particle size 15 microns;

[0092] Polyfunctional acrylated polyether oligomer, purchased from Shandong Tunan New Material Co., Ltd.;

[0093] Thioctic acid polyethylene glycol acrylate, purchased from Xi'an Qiyue Biological;

[0094] Polyether modified polysiloxane, purchased from Guangdong Fangxin Biological Technology Co., Ltd.;

[0095] Perfluoropolyether, purchased from Dongguan Jialuode Lubricating Material Co., Ltd.;

[0096] Dioctyl terephthalate, purchased from Zhuhai Liancheng Chemical Industry Co., Ltd.;

[0097] Sebacic acid-based polyester, purchased from Sinoreagent Co., Ltd.;

[0098] Benzotriazole ultraviolet absorber, purchased from Dongguan Yingsheng Plastic Chemical Co., Ltd.;

[0099] Polymeric HALS, purchased from Dongguan Kangjin New Material Technology Co., Ltd.

[0100] Example 1

[0101] Example 1 first provides a self-repairing scratch-resistant coating, raw materials of which include: 65 g of flexible polyurethane acrylate, 8 g of modified epoxy acrylate, 18 g of reactive diluent (a combination of isobornyl acrylate and tripropylene glycol diacrylate in a mass ratio of 3:1), 4 g of photoinitiator (a combination of 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide in a mass ratio of 1:1), 4 g of silicone microcapsule repair agent, 4 g of dynamic crosslinking agent (a combination of multifunctional acrylated polyether oligomer and thioctic acid polyethylene glycol acrylate in a mass ratio of 2.5:1), 0.2 g of leveling agent polyether modified polysiloxane, 0.7 g of anti-fingerprint agent perfluoropolyether, and 6 g of butyl acetate.

[0102] Example 1 also provides a PVC decorative film, which sequentially includes, from top to bottom, the self-repairing scratch-resistant coating of Example 1 (thickness of 10 microns), a weather-resistant PVC layer (thickness of 0.06 mm), a water-based ink layer (thickness of 15 microns), and a printed PVC base film (thickness of 0.08 mm). The raw materials of the weather-resistant PVC layer include, in mass fractions, 100 parts of PVC resin, 22 parts of environmentally friendly plasticizer (a combination of dioctyl terephthalate and sebacic acid polyester in a mass ratio of 10:1), and 1.3 parts of light stabilizer (a combination of benzotriazole ultraviolet absorber and polymeric HALS in a mass ratio of 3:1).

[0103] Example 1 also provides a method for preparing a PVC decorative film, which includes the following steps:

[0104] (1) Preparation of self-repairing scratch-resistant coating: First, mix the flexible polyurethane acrylate and the dynamic crosslinking agent at 60°C to form a polymer, then mix all the materials thoroughly until the resin is completely dissolved, the whole slurry has a certain viscosity (10-20 seconds in a 3# Caien cup test) and is a slightly yellow transparent solution, and then seal and store.

[0105] (2) Production of the weather-resistant PVC layer by calendering process. The weather-resistant PVC layer is preheated at 60°C for 2 min, the self-repairing scratch-resistant coating is uniformly coated on the surface of the weather-resistant PVC layer by printing, and the coating is cured by UV curing technology with mercury lamp irradiation for 2-5 seconds to form a self-repairing scratch-resistant coating on the surface of the weather-resistant PVC layer, thereby preparing a scratch-resistant layer with self-repairing function.

[0106] (3) Using multi-plate printing coating technology, the water-based ink is printed layer by layer on the surface of the printed PVC base film through the coordinated work of multiple printing plates (such as intaglio plate, screen plate or flexographic plate), the color patterns of each plate are combined into a complete pattern to realize the sequential coating of multiple layers of ink, thereby forming a water-based ink layer on the surface of the printed PVC base film and preparing a printed layer with rich patterns.

[0107] (4) The scratch-resistant layer with self-repairing function and the printed layer with rich patterns are combined together by using the lamination and hot pressing technology to produce a PVC decorative film with self-repairing function for scratches.

[0108] Example 2

[0109] Example 2 first provides a self-repairing scratch-resistant coating, the difference between the raw materials of which and those of Example 1 is that the mass of the silicone microcapsule repairing agent is 3 g and the mass of the dynamic crosslinking agent is 3 g, and the rest of the amounts are the same as those of Example 1.

[0110] Example 2 also provides a PVC decorative film, the difference between which and that of Example 1 is that the amount of the environmentally friendly plasticizer in the raw materials of the weather-resistant PVC layer is 20 parts and the amount of the light stabilizer is 1.0 part, and the rest of the amounts and the preparation method are the same as those of Example 1.

[0111] Example 3

[0112] Example 3 first provides a self-repairing scratch-resistant coating, the difference between the raw materials of which and those of Example 1 is that the mass of the silicone microcapsule repairing agent is 5 g and the mass of the dynamic crosslinking agent is 5 g, and the rest of the amounts are the same as those of Example 1.

[0113] Example 3 also provides a PVC decorative film, the difference between which and that of Example 1 is that the amount of the environmentally friendly plasticizer in the raw materials of the weather-resistant PVC layer is 25 parts and the amount of the light stabilizer is 1.5 parts, and the rest of the amounts and the preparation method are the same as those of Example 1.

[0114] Comparative Example 1

[0115] Comparative Example 1 first provides a self-repairing scratch-resistant coating, the difference between the raw materials of which and those of Example 1 is that no silicone microcapsule repairing agent and no dynamic crosslinking agent are added, and the rest of the amounts are the same as those of Example 1.

[0116] Comparative Example 1 also provides a PVC decorative film, the preparation method of which is the same as that of Example 1.

[0117] Comparative Example 2

[0118] Comparative Example 2 first provides a self-repairing scratch-resistant coating, the difference between the raw materials of which and those of Example 1 is that no dynamic crosslinking agent is added, and the rest of the amounts are the same as those of Example 1.

[0119] Comparative Example 2 also provides a PVC decorative film, the preparation method of which is the same as that of Example 1.

[0120] Comparative Example 3

[0121] Comparative Example 3 first provides a self-repairing scratch-resistant coating, the difference between the raw materials of which and those of Example 1 is that no silicone microcapsule repairing agent is added, and the rest of the amounts are the same as those of Example 1.

[0122] Comparative Example 3 also provides a PVC decorative film, which is prepared in the same way as Example 1.

[0123] Comparative Example 4

[0124] Comparative Example 4 first provides a self-repairing scratch-resistant coating, which is prepared in the same way as Example 1, except that the dynamic crosslinker is a combination of multifunctional acrylated polyether oligomer and lipoic acid polyethylene glycol acrylate in a mass ratio of 1:1, and the rest of the amount is the same as Example 1.

[0125] Comparative Example 4 also provides a PVC decorative film, which is prepared in the same way as Example 1.

[0126] Comparative Example 5

[0127] Comparative Example 5 first provides a self-repairing scratch-resistant coating, which is prepared in the same way as Example 1, except that the dynamic crosslinker is a combination of multifunctional acrylated polyether oligomer and lipoic acid polyethylene glycol acrylate in a mass ratio of 4:1, and the rest of the amount is the same as Example 1.

[0128] Comparative Example 5 also provides a PVC decorative film, which is prepared in the same way as Example 1.

[0129] Comparative Example 6

[0130] Comparative Example 6 first provides a self-repairing scratch-resistant coating, which is prepared in the same way as Example 1, except that the dynamic crosslinker is urea-based pyrimidinone, and the rest of the amount is the same as Example 1.

[0131] Comparative Example 6 also provides a PVC decorative film, which is prepared in the same way as Example 1.

[0132] Comparative Example 7

[0133] Comparative Example 7 first provides a self-repairing scratch-resistant coating, which is prepared in the same way as Example 1.

[0134] Comparative Example 7 also provides a PVC decorative film, which is prepared in the same way as Example 1, except that no light stabilizer is added to the raw materials of the weather-resistant PVC layer, and the rest of the amount and preparation method are the same as Example 1.

[0135] The technical solutions of the PVC decorative films of each example and comparative example are shown in Table 1, and the technical effects are shown in Table 2.

[0136] Table 1 Technical solutions of PVC decorative films of each example and comparative example (unit: g)

[0137]

[0138] Table 2 Technical effects of PVC decorative films of each example and comparative example

[0139]

[0140] Finally, it should be noted that the above embodiments are merely used to illustrate the technical solutions of the present application, rather than limit the technical solutions of the present application; although the present application has been described in detail with reference to the above embodiments, those skilled in the art should understand that the technical solutions recorded in the above embodiments can still be modified, or some or all of the technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

[0141] In addition, those skilled in the art can understand that although some of the embodiments herein include certain features rather than other features included in other embodiments, the combination of features of different embodiments means to be within the scope of the present application and form different embodiments. For example, in the above claims, any one of the claimed embodiments can be used in any combination. The information disclosed in the BACKGROUND section is merely intended to deepen the understanding of the overall background of the present application, and should not be regarded as acknowledging or implying in any form that the information constitutes the prior art known to those skilled in the art.

Claims

1. A self-repairing scratch resistant coating, characterized in that, The raw materials include, by mass fraction: 60-70 parts of flexible polyurethane acrylate, 5-10 parts of modified epoxy acrylate, 15-20 parts of active diluent, 3-5 parts of photoinitiator, 3-5 parts of silicone microcapsule repair agent, 3-5 parts of dynamic crosslinking agent, 0.2-0.3 parts of leveling agent, 0.5-1.0 parts of anti-fingerprint agent, and 5-8 parts of butyl acetate; The dynamic crosslinking agent includes a multifunctional acrylated polyether oligomer and a lipoic acid polyethylene glycol acrylate in a mass ratio of (2.5-3):1; the multifunctional acrylated polyether oligomer is generated by condensation reaction of acrylic acid or methacrylic acid with a polyether polyol, and contains a dynamic disulfide bond.

2. The self-repairing scratch resistant coating according to claim 1, wherein, The active diluent includes isobornyl acrylate and tripropylene glycol diacrylate in a mass ratio of (3-4):

1.

3. The self-repairing scratch resistant coating according to claim 1, wherein, The photoinitiator includes 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide in a mass ratio of (1-2):

1.

4. The self-repairing scratch resistant coating of claim 1, wherein, The leveling agent is selected from at least one of polyether modified polysiloxane and perfluoropolyether acrylate.

5. The self-repairing scratch resistant coating of claim 1, wherein, The anti-fingerprint agent is selected from at least one of perfluoropolyether, silicofluorocopolymer, and nanosilica.

6. A PVC decorative film, characterized in that, From top to bottom, in order, include: the self-repairing scratch-resistant coating layer according to any one of claims 1-5, the weather-resistant PVC layer, the water-based ink layer, and the printed PVC base film; The weather-resistant PVC layer includes, by mass fraction: 100 parts of PVC resin, 20-25 parts of environmentally friendly plasticizer, and 1.0-1.5 parts of light stabilizer.

7. The PVC trim film according to claim 6, characterized in that, The environmentally friendly plasticizer includes dioctyl terephthalate and sebacic acid-based polyester in a mass ratio of (8-10):

1.

8. The PVC trim film of claim 6, wherein, The light stabilizer includes benzotriazole ultraviolet absorber and polymeric HALS in a mass ratio of (1.25-3):

1.

9. A method of producing a PVC decorative film as claimed in any one of claims 6 to 8, characterized in that, Including: The self-repairing scratch-resistant coating layer is coated on the surface of the weather-resistant PVC layer to obtain a scratch-resistant layer; The water-based ink layer is printed on the surface of the printed PVC base film to obtain a printed layer; The scratch-resistant layer and the printed layer are laminated to obtain the PVC decorative film.

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