Imitation stone photovoltaic patch decorative material and preparation process thereof

Abstract

The invention discloses a stone-like photovoltaic patch decorative material and a preparation process thereof, and relates to the technical field of building decorative materials, the stone-like photovoltaic patch decorative material comprises a surface composite coating, a stone-like layer, a photovoltaic patch and a base material layer, the surface composite coating is prepared from the following components in parts by weight: 0.1 to 0.5 part of super-hydrophobic zinc oxide nano particles, 0.1 to 0.5 part of modified cerium oxide nano particles, 8 to 10 parts of polydimethylsiloxane, 0.5 to 1 part of curing agent and 100 parts of normal hexane. The surface of the stone-like layer is coated with the surface composite coating with polydimethylsiloxane as the flexible substrate, so that self-cleaning of the decorative material is achieved, and the problem that the power generation efficiency of the photovoltaic patch is reduced due to continuous accumulation of pollutants on the surface of the decorative material is solved.

Description

Technical Field

[0001] This invention relates to the field of building decoration materials technology, specifically to a stone-like photovoltaic patch decorative material and its preparation process. Background Technology

[0002] As the global energy structure transitions towards low-carbon development, building-integrated photovoltaics (BIPV) is a key pathway to achieving carbon neutrality in the building sector. Traditional photovoltaic modules have a monotonous appearance and poor integration with architectural aesthetics, making it difficult to meet the visual requirements of high-end buildings. Stone-like photovoltaic patches, which combine power generation and decoration functions, mimic the texture and feel of natural stone, achieving a dual breakthrough in energy production and architectural aesthetics.

[0003] To mimic the texture of natural stone, imitation stone photovoltaic (PV) tiles typically employ matte or frosted surface treatments. At a microscopic scale, these tiles exhibit a highly porous structure with numerous uneven surfaces. While this enhances visual realism, it also provides adhesion points for contaminants. The continuous accumulation of contaminants reduces PV power generation efficiency and damages the decorative appearance and aesthetic value.

[0004] Patent CN110512812B discloses a flexible imitation stone veneer for architectural decoration and its preparation method. The above patent achieves continuous and stable production, and the pigment layer exhibits a good stone texture. The provided flexible imitation stone veneer for architectural decoration has the advantages of stable process, stable structure, easy construction and wide range of applications. It can be used for the decoration of the interior and exterior walls of buildings such as villas, commercial spaces, commercial real estate podiums and residences.

[0005] The aforementioned patent modifies colored sand by adding silicone powder to increase its fluidity and uses direct hot-pressing to composite pigment particles on the surface of resin extrusion sheets. This solves the problems of existing flexible stone-like veneer for buildings, which is difficult to control due to the layer-by-layer coating process and requires drying after coating with polymer emulsion. However, there is still room for improvement in the self-cleaning properties of decorative materials. This application applies a surface composite coating to the surface of the stone-like layer to give the decorative material a stable self-cleaning property, thus solving the problem of continuous accumulation of pollutants on the surface of decorative materials.

[0006] Therefore, this application proposes a stone-like photovoltaic patch decorative material that achieves self-cleaning of the surface of decorative materials and its preparation process. Summary of the Invention

[0007] The purpose of this invention is to provide a stone-like photovoltaic patch decorative material and its preparation process, so as to solve the technical problem of continuous accumulation of pollutants on the surface of decorative materials mentioned in the background art.

[0008] To achieve the above objectives, the present invention provides the following technical solution: a stone-like photovoltaic patch decorative material, comprising a surface composite coating, a stone-like layer, a photovoltaic patch, and a substrate layer, wherein the surface composite coating comprises, by weight, 0.1-0.5 parts of superhydrophobic zinc oxide nanoparticles, 0.1-0.5 parts of modified cerium oxide nanoparticles, 8-10 parts of polydimethylsiloxane, 0.5-1 parts of curing agent, and 100 parts of n-hexane; the preparation method of the surface composite coating comprises the following steps: Polydimethylsiloxane and curing agent were poured into n-hexane and stirred for 1.5 h using a magnetic stirrer. Modified cerium oxide nanoparticles were added and stirred for 1.5 h. Superhydrophobic zinc oxide nanoparticles were added and stirred for 1.5 h. The mixture was then transferred to an ultrasonic cleaner and ultrasonically treated for 1 h to obtain a surface composite coating.

[0009] Preferably, the preparation method of the superhydrophobic zinc oxide nanoparticles includes the following steps: Nano zinc oxide particles and tetraethyl orthosilicate were poured into anhydrous ethanol and stirred with a magnetic stirrer for 1.5 hours. Ammonia and purified water were added in sequence, and stirring was continued for 1.5 hours. The mixture was then centrifuged, washed, and dried to obtain a composite powder. The composite powder and trimethylchlorosilane were poured into n-hexane and stirred with a magnetic stirrer for 1.5 h. After washing and drying, superhydrophobic zinc oxide nanoparticles were obtained.

[0010] Preferably, the surface composite coating is applied to the imitation stone layer, which comprises, by weight: 60 parts fine stone powder, 8 parts unsaturated polyester resin, 0.1 parts polycarboxylate superplasticizer, 30 parts inorganic filler, 0.1 parts pigment, 0.05 parts cobalt naphthenate styrene solution, and 0.1 parts methyl ethyl ketone peroxide.

[0011] Preferably, the photovoltaic patch surface is coated with a polyurethane composite coating, and the method for preparing the polyurethane composite coating includes the following steps: Polytetrahydrofuran ether diol and polycarbonate diol were heated to 60°C and mixed. Isophorone diisocyanate was added, and the temperature was raised to 75°C. The reaction was carried out for 3 hours to obtain a polyurethane prepolymer. The polyurethane prepolymer was cooled to 70°C, and 1,3-butanediol and dibutyltin dilaurate were added. The mixture was stirred for 10 min, and hydroxyl acrylic resin preheated to 60°C was added. The mixture was reacted at 80°C for 1 h, cooled to 45°C, and carbodiimide was added. The mixture was stirred for 20 min, and modified cerium oxide nanoparticles were added. The mixture was ultrasonically dispersed for 45 min to obtain the polyurethane composite coating.

[0012] Preferably, the method for preparing the modified cerium oxide nanoparticles includes the following steps: Concentrated hydrochloric acid solution was added to the nano-cerium oxide dispersion to adjust the pH to 4-5. Under stirring conditions, γ-glycidyl ether propyltrimethoxysilane was added dropwise and the mixture was refluxed for 8 hours to obtain the modified nano-cerium oxide dispersion. The modified cerium oxide nano-dispersion was allowed to stand for 30 minutes, then centrifuged, washed, and dried to obtain modified cerium oxide nanoparticles.

[0013] Preferably, the substrate layer is selected from one of polycarbonate, glass fiber reinforced plastic, aluminum alloy, and wood-plastic composite materials.

[0014] Preferably, the fine stone powder is selected from one or more of the following: quartz powder, marble powder, granite powder, and calcite powder.

[0015] Preferably, the inorganic filler is one or more of talc, aluminum hydroxide, barium sulfate, and kaolin.

[0016] Preferably, the preparation process includes the following steps: S1. After weighing the unsaturated polyester resin, polycarboxylate superplasticizer, pigment, fine stone powder, inorganic filler, cobalt naphthenate styrene solution, and methyl ethyl ketone peroxide, a slurry is obtained. S2. Using epoxy adhesive, the photovoltaic patch coated with polyurethane composite coating is attached to the substrate layer to bring out the positive and negative electrodes; S3. Apply the slurry to the photovoltaic patch with the polyurethane composite coating, cure it on the photovoltaic patch to form a stone-like layer, and then apply a surface composite coating on the stone-like layer.

[0017] Preferably, the preparation process further includes the following steps: S11. Add unsaturated polyester resin, polycarboxylate superplasticizer, and pigment to a planetary mixer and stir for 5 minutes. Add fine stone powder and inorganic filler and stir for 10 minutes. Add cobalt naphthenate styrene solution and stir for 3 minutes. Then add methyl ethyl ketone peroxide and stir for 2 minutes to obtain the slurry.

[0018] Compared with the prior art, the beneficial effects of the present invention are: 1. This invention achieves self-cleaning of decorative materials by coating the surface of the imitation stone layer with a surface composite coating based on polydimethylsiloxane as a flexible substrate, thus solving the problem of reduced photovoltaic power generation efficiency caused by the continuous accumulation of pollutants on the surface of decorative materials. 2. This invention introduces superhydrophobic zinc oxide nanoparticles into the surface composite coating to form a lotus leaf-like micro-nano protrusion structure on the coating surface. This structure works synergistically with the low surface energy characteristics of polydimethylsiloxane to achieve superhydrophobicity and improve self-cleaning performance. 3. This invention protects the photovoltaic patch by coating the surface of the photovoltaic patch with a polyurethane composite coating. The excellent elasticity buffers mechanical stress, thereby improving the long-term working stability and service life of the photovoltaic patch. 4. This invention achieves efficient UV shielding by introducing modified cerium oxide nanoparticles into the surface composite coating and polyurethane composite coating, thereby improving the overall performance of the coating and solving the problem of coating yellowing caused by UV aging. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the decorative material preparation process of the present invention; Figure 2 This is a schematic diagram of the surface composite coating preparation process of the present invention; Figure 3 This is a schematic diagram of the preparation process of the superhydrophobic zinc oxide nanoparticles of the present invention; Figure 4 This is a schematic diagram of the polyurethane prepolymer preparation process of the present invention; Figure 5 This is a schematic diagram of the polyurethane composite coating preparation process of the present invention; Figure 6 This is a schematic diagram of the preparation process of the modified cerium oxide nanoparticles of the present invention; Figure 7 This is a schematic diagram of the preparation process of the stone-like layer slurry of the present invention; Figure 8 This is a schematic diagram of the substrate layer of the present invention. Detailed Implementation

[0020] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] Example 1, please refer to Figure 1 , Figure 2 and Figure 8A stone-like photovoltaic panel decorative material includes a surface composite coating, a stone-like layer, a photovoltaic panel, and a substrate layer. The surface composite coating comprises, by weight, 0.5 parts superhydrophobic zinc oxide nanoparticles, 0.5 parts modified cerium oxide nanoparticles, 10 parts polydimethylsiloxane, 1 part curing agent, and 100 parts n-hexane. The stone-like layer comprises, by weight, 60 parts fine stone powder, 8 parts unsaturated polyester resin, 0.1 parts polycarboxylate-based water-reducing agent, 30 parts inorganic filler, 0.1 parts pigment, 0.05 parts cobalt naphthenate styrene solution, and 0.1 parts methyl ethyl ketone peroxide. The preparation method of the decorative material includes the following steps: Polydimethylsiloxane and curing agent were poured into n-hexane and stirred for 1.5 h using a magnetic stirrer. Modified cerium oxide nanoparticles were added and stirred for 1.5 h. Superhydrophobic zinc oxide nanoparticles were added and stirred for 1.5 h. The mixture was then transferred to an ultrasonic cleaner and ultrasonically treated for 1 h to obtain a surface composite coating. The weighed unsaturated polyester resin, polycarboxylate superplasticizer, pigment, fine stone powder, inorganic filler, cobalt naphthenate styrene solution, and methyl ethyl ketone peroxide are mixed to obtain a slurry. Using epoxy adhesive, photovoltaic patches coated with polyurethane composite coating are mounted onto the substrate layer to bring out the positive and negative electrodes; The slurry is applied to a photovoltaic panel with a polyurethane composite coating, cured on the photovoltaic panel to form a stone-like layer, and then a surface composite coating is applied to the stone-like layer to obtain a decorative material.

[0022] Furthermore, after reacting with its specialized curing agent, polydimethylsiloxane crosslinks to form a three-dimensional network structure of elastic film, firmly bonding the superhydrophobic zinc oxide nanoparticles and modified cerium oxide nanoparticles, and tightly adhering them to the surface of the stone-like layer, forming a continuous and dense protective layer. The polydimethylsiloxane molecular chain, with Si-O-Si as the main chain and nonpolar methyl groups as side groups, endows it with extremely low surface free energy, giving the coating superhydrophobic properties. The low surface energy characteristics of polydimethylsiloxane and the rough structure constructed by the nanoparticles produce a synergistic effect, forming a superhydrophobic system of micro-nano rough structure and low-energy substrate, jointly achieving a stable and efficient superhydrophobic effect, causing water droplets to roll spherically on the coating surface, achieving a self-cleaning function. The Si-O bond energy of polydimethylsiloxane is as high as 443. With a strength of kJ / mol, far exceeding the C / C bond energy of traditional organic polymers such as acrylic resins and polyurethanes, polydimethylsiloxane possesses excellent thermal stability, oxidation resistance, and UV aging resistance, ensuring that the coating maintains its performance in harsh outdoor environments for a long time. This effectively protects the internal stone-like layer and photovoltaic panels, extending the service life of the decorative materials. Compared to hydrophobic materials such as fluorinated compounds, polydimethylsiloxane has low toxicity and is more environmentally friendly, meeting the requirements of green building materials. In addition, polydimethylsiloxane itself has high transparency, and the film formed after curing has low absorption of visible light, thus ensuring that sufficient sunlight penetrates the coating and is absorbed by the photovoltaic panels in the middle, ensuring the impact on power generation efficiency.

[0023] Example 2, please refer to Figure 1 , Figure 2 , Figure 3 and Figure 8 A stone-like photovoltaic panel decorative material includes a surface composite coating, a stone-like layer, a photovoltaic panel, and a substrate layer. The surface composite coating comprises, by weight, 0.4 parts superhydrophobic zinc oxide nanoparticles, 0.4 parts modified cerium oxide nanoparticles, 10 parts polydimethylsiloxane, 1 part curing agent, and 100 parts n-hexane. The stone-like layer comprises, by weight, 60 parts fine stone powder, 8 parts unsaturated polyester resin, 0.1 parts polycarboxylate-based water-reducing agent, 30 parts inorganic filler, 0.1 parts pigment, 0.05 parts cobalt naphthenate styrene solution, and 0.1 parts methyl ethyl ketone peroxide. The preparation method of the decorative material includes the following steps: Nano-zinc oxide particles and tetraethyl orthosilicate were added to anhydrous ethanol and stirred with a magnetic stirrer for 1.5 h. Ammonia and purified water were added sequentially, and stirring was continued for 1.5 h. The mixture was then centrifuged, washed, and dried to obtain a composite powder. The composite powder and trimethylchlorosilane were added to n-hexane and stirred with a magnetic stirrer for 1.5 h. The mixture was then washed and dried to obtain superhydrophobic zinc oxide nanoparticles. Polydimethylsiloxane and a curing agent were added to n-hexane and stirred with a magnetic stirrer for 1.5 h. Modified cerium oxide nanoparticles were added and stirred for 1.5 h. Then, superhydrophobic zinc oxide nanoparticles were added and stirred for 1.5 h. The mixture was then transferred to an ultrasonic cleaner and ultrasonically treated for 1 h to obtain a surface composite coating. The weighed unsaturated polyester resin, polycarboxylate superplasticizer, pigment, fine stone powder, inorganic filler, cobalt naphthenate styrene solution, and methyl ethyl ketone peroxide are mixed to obtain a slurry. Using epoxy adhesive, photovoltaic patches coated with polyurethane composite coating are mounted onto the substrate layer to bring out the positive and negative electrodes; The slurry is applied to a photovoltaic panel with a polyurethane composite coating, cured on the photovoltaic panel to form a stone-like layer, and then a surface composite coating is applied to the stone-like layer to obtain a decorative material.

[0024] Furthermore, nano-zinc oxide is mixed with tetraethyl orthosilicate in anhydrous ethanol and hydrolyzed using ammonia catalysis to coat the zinc oxide surface with a silica shell, forming core-shell structured nanoparticles. This provides chemical modification sites for the silica shell, preventing excessively high photocatalytic activity caused by direct exposure of zinc oxide. The core-shell nanoparticles are then reacted with trimethylchlorosilane in hexane, and methyl groups are grafted onto the particle surface through silanization, forming superhydrophobic zinc oxide nanoparticles. The particles form a rough structure on the coating surface, increasing the solid-liquid contact angle, causing water droplets to roll spherically on the surface, achieving superhydrophobic self-cleaning. The silica shell isolates zinc oxide from contact with polydimethylsiloxane, preventing photocatalytic degradation and the potential decomposition of the Si-C bonds of tetraethyl orthosilicate under ultraviolet light, significantly improving the anti-photoaging performance of the composite coating and extending its service life. In addition, silica is translucent or transparent to ultraviolet light; therefore, ultraviolet photons used to excite zinc oxide to generate photogenerated electrons and holes can effectively penetrate the silica shell. Absorbed by the core zinc oxide, oxygen and water molecules in the air diffuse through the pores of the silica shell to the core-shell interface, reacting with photogenerated electrons and holes generated on the zinc oxide surface. The resulting reactive oxygen species diffuse through the pores to the outside of the shell, effectively degrading organic pollutants attached to the material surface. The trimethylchlorosilane grafted onto the surface of the superhydrophobic zinc oxide nanoparticles provides nonpolar methyl functional groups. The main chain of polydimethylsiloxane contains a large number of methyl groups. This similar chemical structure improves the compatibility between the superhydrophobic zinc oxide nanoparticles and the polydimethylsiloxane matrix, reducing the interfacial energy and ensuring that the nanoparticles can be uniformly dispersed in the polydimethylsiloxane, avoiding agglomeration. This allows the surface composite coating to maintain its complete hydrophobic structure under external forces such as rain erosion, improving the stability of the material. It can effectively resist the adhesion of moisture and stains under various environmental conditions, keeping the surface clean and reducing the frequency and cost of manual cleaning. This allows the decorative material to maintain its original aesthetics and functionality during long-term use.

[0025] Example 3, please refer to Figure 1 , Figure 2 , Figure 4 and Figure 5 A stone-like photovoltaic panel decorative material includes a surface composite coating, a stone-like layer, a photovoltaic panel, and a substrate layer. The surface composite coating comprises, by weight, 0.3 parts superhydrophobic zinc oxide nanoparticles, 0.3 parts modified cerium oxide nanoparticles, 10 parts polydimethylsiloxane, 1 part curing agent, and 100 parts n-hexane. The stone-like layer comprises, by weight, 60 parts fine stone powder, 8 parts unsaturated polyester resin, 0.1 parts polycarboxylate-based water-reducing agent, 30 parts inorganic filler, 0.1 parts pigment, 0.05 parts cobalt naphthenate styrene solution, and 0.1 parts methyl ethyl ketone peroxide. The preparation method of the decorative material includes the following steps: Polydimethylsiloxane and curing agent were poured into n-hexane and stirred for 1.5 h using a magnetic stirrer. Modified cerium oxide nanoparticles were added and stirred for 1.5 h. Superhydrophobic zinc oxide nanoparticles were added and stirred for 1.5 h. The mixture was then transferred to an ultrasonic cleaner and ultrasonically treated for 1 h to obtain a surface composite coating. The weighed unsaturated polyester resin, polycarboxylate superplasticizer, pigment, fine stone powder, inorganic filler, cobalt naphthenate styrene solution, and methyl ethyl ketone peroxide are mixed to obtain a slurry. Polytetrahydrofuran ether glycol and polycarbonate glycol were heated to 60°C and mixed. Isophorone diisocyanate was added, and the mixture was heated to 75°C and reacted for 3 hours to obtain a polyurethane prepolymer. The polyurethane prepolymer was cooled to 70°C, and 1,3-butanediol and dibutyltin dilaurate were added. The mixture was stirred for 10 minutes, and hydroxyl acrylic resin preheated to 60°C was added. The mixture was reacted at 80°C for 1 hour, cooled to 45°C, and carbodiimide was added. The mixture was stirred for 20 minutes, and modified cerium oxide nanoparticles were added. The mixture was ultrasonically dispersed for 45 minutes to obtain a polyurethane composite coating. Using epoxy adhesive, a photovoltaic patch coated with the polyurethane composite coating was mounted on a substrate layer to bring out the positive and negative electrodes. The slurry is applied to a photovoltaic panel with a polyurethane composite coating, cured on the photovoltaic panel to form a stone-like layer, and then a surface composite coating is applied to the stone-like layer to obtain a decorative material.

[0026] Furthermore, polytetrahydrofuran ether glycol and polycarbonate glycol, as soft segments, help form a polyurethane prepolymer with a regular structure and flexible molecular chains, providing excellent optical transparency for the polyurethane composite coating. This maximizes the transmission of sunlight, ensuring that the photovoltaic patch maintains high photoelectric conversion efficiency. The polyurethane prepolymer crosslinks with hydroxyl acrylic resin to form a three-dimensional network. The introduction of modified cerium oxide and carbodiimide forms a composite structure of hard particles and a flexible matrix, enhancing UV resistance and hydrolysis resistance. The polyurethane composite coating forms a dense film on the surface of the photovoltaic patch, effectively blocking environmental corrosive agents from directly contacting the electrodes and semiconductor materials of the photovoltaic patch. This provides protection for the stone-like layer slurry applied to the photovoltaic patch and effectively buffers the external mechanical stress transmitted from the stone-like layer, preventing microcracks or even breakage of the photovoltaic patch. In addition, the introduction of the same modified cerium oxide nanoparticles as the surface composite coating into the polyurethane composite coating enhances the UV aging resistance of the surface composite coating and prevents powdering of the surface composite coating, thereby protecting the stability of the coating's optical and mechanical properties.

[0027] Example 4, please refer to Figure 1 , Figure 2 and Figure 6A stone-like photovoltaic panel decorative material includes a surface composite coating, a stone-like layer, a photovoltaic panel, and a substrate layer. The surface composite coating comprises, by weight, 0.2 parts superhydrophobic zinc oxide nanoparticles, 0.2 parts modified cerium oxide nanoparticles, 8 parts polydimethylsiloxane, 0.8 parts curing agent, and 100 parts n-hexane. The stone-like layer comprises, by weight, 60 parts fine stone powder, 8 parts unsaturated polyester resin, 0.1 parts polycarboxylate-based water-reducing agent, 30 parts inorganic filler, 0.1 parts pigment, 0.05 parts cobalt naphthenate styrene solution, and 0.1 parts methyl ethyl ketone peroxide. The preparation method of the decorative material includes the following steps: Concentrated hydrochloric acid solution was added to the nano-cerium oxide dispersion to adjust the pH to 4-5. Under stirring, γ-glycidyl ether propyltrimethoxysilane was added dropwise and refluxed for 8 hours to obtain the modified nano-cerium oxide dispersion. The modified nano-cerium oxide dispersion was allowed to stand for 30 minutes, then centrifuged, washed, and dried to obtain modified cerium oxide nanoparticles. Polydimethylsiloxane and curing agent were poured into n-hexane and stirred with a magnetic stirrer for 1.5 hours. The modified cerium oxide nanoparticles were added and stirred for 1.5 hours. Superhydrophobic zinc oxide nanoparticles were added and stirred for 1.5 hours. The mixture was then transferred to an ultrasonic cleaner and ultrasonically treated for 1 hour to obtain a surface composite coating. The weighed unsaturated polyester resin, polycarboxylate superplasticizer, pigment, fine stone powder, inorganic filler, cobalt naphthenate styrene solution, and methyl ethyl ketone peroxide are mixed to obtain a slurry. Using epoxy adhesive, photovoltaic patches coated with polyurethane composite coating are mounted onto the substrate layer to bring out the positive and negative electrodes; The slurry is applied to a photovoltaic panel with a polyurethane composite coating, cured on the photovoltaic panel to form a stone-like layer, and then a surface composite coating is applied to the stone-like layer to obtain a decorative material.

[0028] Furthermore, in the surface composite coating, modified cerium oxide nanoparticles and superhydrophobic zinc oxide nanoparticles jointly construct a dual protective network. Cerium oxide and zinc oxide exhibit a synergistic enhancement effect in ultraviolet shielding. Their energy levels match, forming a more efficient ultraviolet absorption system and jointly building a robust light barrier. In addition, the superhydrophobic zinc oxide nanoparticles are mainly responsible for constructing micro-nano rough structures on the coating surface, which is the physical basis for achieving superhydrophobicity. Modified cerium oxide further consolidates the physical barrier by enhancing the density of the coating. The two work synergistically to construct a dual protective system that possesses both surface superhydrophobicity and internal high shielding performance, thereby significantly improving the decorative material's resistance to ultraviolet rays, effectively preventing material aging and discoloration caused by long-term ultraviolet radiation, and extending the service life of the decorative material. Moreover, the surface superhydrophobicity makes the material surface less prone to dust and stains, and it can be restored to cleanliness by rain or simple wiping, greatly reducing the difficulty and cost of daily cleaning and maintenance, and providing a reliable guarantee for the long-term stable use of decorative materials in various complex environments.

[0029] Example 5, please refer to Figure 1 , Figure 7 and Figure 8 A stone-like photovoltaic panel decorative material includes a surface composite coating, a stone-like layer, a photovoltaic panel, and a substrate layer. The surface composite coating comprises, by weight, 0.1 parts superhydrophobic zinc oxide nanoparticles, 0.1 parts modified cerium oxide nanoparticles, 8 parts polydimethylsiloxane, 0.8 parts curing agent, and 100 parts n-hexane. The stone-like layer comprises, by weight, 60 parts fine stone powder, 8 parts unsaturated polyester resin, 0.1 parts polycarboxylate-based water-reducing agent, 30 parts inorganic filler, 0.1 parts pigment, 0.05 parts cobalt naphthenate styrene solution, and 0.1 parts methyl ethyl ketone peroxide. The preparation method of the decorative material includes the following steps: Polydimethylsiloxane and curing agent were poured into n-hexane and stirred for 1.5 h using a magnetic stirrer. Modified cerium oxide nanoparticles were added and stirred for 1.5 h. Superhydrophobic zinc oxide nanoparticles were added and stirred for 1.5 h. The mixture was then transferred to an ultrasonic cleaner and ultrasonically treated for 1 h to obtain a surface composite coating. Unsaturated polyester resin, polycarboxylate superplasticizer, and pigment are added to a planetary mixer and stirred for 5 minutes. Then, fine stone powder and inorganic filler are added and stirred for 10 minutes. Finally, cobalt naphthenate styrene solution is added and stirred for 3 minutes. Then, methyl ethyl ketone peroxide is added and stirred for 2 minutes to obtain the slurry. Using epoxy adhesive, photovoltaic patches coated with polyurethane composite coating are mounted onto the substrate layer to bring out the positive and negative electrodes; The slurry is applied to a photovoltaic panel with a polyurethane composite coating, cured on the photovoltaic panel to form a stone-like layer, and then a surface composite coating is applied to the stone-like layer to obtain a decorative material.

[0030] Furthermore, through the above design, this imitation stone photovoltaic patch decorative material not only performs excellently in photovoltaic performance, but its surface coating of imitation stone slurry also gives the product a realistic stone texture, meeting the aesthetic requirements of architectural decoration; it can effectively utilize solar energy to generate electricity, and can also be perfectly integrated with the building's appearance, enhancing the overall quality and value of the building; at the same time, its excellent resistance to ultraviolet rays, hydrolysis, and mechanical stress greatly extends the material's service life and reduces maintenance costs.

[0031] Comparative Example 1: A stone-like photovoltaic panel decorative material, comprising a surface composite coating, a stone-like layer, a photovoltaic panel, and a substrate layer. The surface composite coating, by weight, comprises: 0.5 parts superhydrophobic zinc oxide nanoparticles, 10 parts polydimethylsiloxane, 1 part curing agent, and 100 parts n-hexane. The stone-like layer, by weight, comprises: 60 parts fine stone powder, 8 parts unsaturated polyester resin, 0.1 parts polycarboxylate-based water-reducing agent, 30 parts inorganic filler, 0.1 parts pigment, 0.05 parts cobalt naphthenate styrene solution, and 0.1 parts methyl ethyl ketone peroxide. The preparation method of the decorative material includes the following steps: Polydimethylsiloxane and curing agent were poured into n-hexane and stirred for 1.5 hours using a magnetic stirrer. Superhydrophobic zinc oxide nanoparticles were added and stirred for 1.5 hours. The mixture was then transferred to an ultrasonic cleaner and ultrasonically treated for 1 hour to obtain a surface composite coating.

[0032] Comparative Example 2: A stone-like photovoltaic panel decorative material, comprising a surface composite coating, a stone-like layer, a photovoltaic panel, and a substrate layer. The surface composite coating, by weight, comprises: 0.5 parts modified cerium oxide nanoparticles, 10 parts polydimethylsiloxane, 1 part curing agent, and 100 parts n-hexane. The stone-like layer, by weight, comprises: 60 parts fine stone powder, 8 parts unsaturated polyester resin, 0.1 parts polycarboxylate-based water-reducing agent, 30 parts inorganic filler, 0.1 parts pigment, 0.05 parts cobalt naphthenate styrene solution, and 0.1 parts methyl ethyl ketone peroxide. The preparation method of the decorative material includes the following steps: Polydimethylsiloxane and curing agent were poured into n-hexane and stirred for 1.5 h using a magnetic stirrer. Modified cerium oxide nanoparticles were added and stirred for 1.5 h. The mixture was then transferred to an ultrasonic cleaner and ultrasonically treated for 1 h to obtain a surface composite coating.

[0033] Performance testing Test 1 Self-cleaning test: The surface composite coatings prepared in Examples 1-5 and Comparative Examples 1-2 were coated on a glass slide to obtain a sample. Graphite powder, silicon powder or standard red clay dust was evenly sprinkled on the surface of the sample. The sample was tilted at 15°. Using a micro-syringe or a standard dropper, deionized water droplets were dropped onto the contaminated area from about 1-2 cm above the sample. The effect of the water droplets carrying away the dust was observed.

[0034] Test 2: Durability test. The surface composite coatings prepared in Examples 1-5 and Comparative Examples 1-2 were coated on glass slides to obtain samples. The samples were placed under the light source of a triple ultraviolet analyzer, and the contact angles were measured after 5 days without light exposure and after light exposure.

[0035] In summary, the UV shielding effect of modified cerium oxide nanoparticles can effectively protect the surface composite coating from aging, thereby maintaining the long-term stability of the micro-rough structure of superhydrophobic zinc oxide nanoparticles. In addition, the superhydrophobicity provided by the superhydrophobic zinc oxide nanoparticles constructs a superhydrophobic physical structure, realizing a self-cleaning function.

[0036] Working principle: Hydrophobic zinc oxide nanoparticles reduce the residence time of moisture on the surface of the composite coating, reduce the risk of moisture penetration and corrosion, and create a dry environment for the modified cerium oxide nanoparticles to exert long-term protection, together forming a protective barrier. After polydimethylsiloxane crosslinks with the curing agent, a transparent film is formed, which bonds superhydrophobic zinc oxide nanoparticles and modified cerium oxide nanoparticles to the surface of the stone-like layer to form a protective layer, thus protecting the stone-like layer. The self-cleaning properties of the surface composite coating reduce the frequency of manual cleaning. The polyurethane composite coating applied to the photovoltaic patch creates a multi-functional protective system on the surface of the photovoltaic patch that resists mechanical damage, resists ultraviolet aging, and has high light transmittance, ensuring the long-term stability of the photovoltaic patch in harsh environments.

[0037] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

Claims

1. A stone-like photovoltaic panel decorative material, characterized in that: The material includes a surface composite coating, a stone-like layer, a photovoltaic patch, and a substrate layer. The surface composite coating comprises, by weight, 0.1-0.5 parts of superhydrophobic zinc oxide nanoparticles, 0.1-0.5 parts of modified cerium oxide nanoparticles, 8-10 parts of polydimethylsiloxane, 0.5-1 parts of curing agent, and 100 parts of n-hexane. The preparation method of the surface composite coating includes the following steps: Polydimethylsiloxane and curing agent were poured into n-hexane and stirred for 1.5 h using a magnetic stirrer. Modified cerium oxide nanoparticles were added and stirred for 1.5 h. Superhydrophobic zinc oxide nanoparticles were added and stirred for 1.5 h. The mixture was then transferred to an ultrasonic cleaner and ultrasonically treated for 1 h to obtain a surface composite coating.

2. The stone-like photovoltaic panel decorative material according to claim 1, characterized in that: The preparation method of the superhydrophobic zinc oxide nanoparticles includes the following steps: Nano zinc oxide particles and tetraethyl orthosilicate were poured into anhydrous ethanol and stirred with a magnetic stirrer for 1.5 hours. Ammonia and purified water were added in sequence, and stirring was continued for 1.5 hours. The mixture was then centrifuged, washed, and dried to obtain a composite powder. The composite powder and trimethylchlorosilane were poured into n-hexane and stirred with a magnetic stirrer for 1.5 h. After washing and drying, superhydrophobic zinc oxide nanoparticles were obtained.

3. The stone-like photovoltaic panel decorative material according to claim 1, characterized in that: The surface composite coating is applied to the imitation stone layer, which comprises, by weight: 60 parts fine stone powder, 8 parts unsaturated polyester resin, 0.1 parts polycarboxylate superplasticizer, 30 parts inorganic filler, 0.1 parts pigment, 0.05 parts cobalt naphthenate styrene solution, and 0.1 parts methyl ethyl ketone peroxide.

4. The stone-like photovoltaic panel decorative material according to claim 1, characterized in that: The photovoltaic patch surface is coated with a polyurethane composite coating, and the preparation method of the polyurethane composite coating includes the following steps: Polytetrahydrofuran ether diol and polycarbonate diol were heated to 60°C and mixed. Isophorone diisocyanate was added, and the temperature was raised to 75°C. The reaction was carried out for 3 hours to obtain a polyurethane prepolymer. The polyurethane prepolymer was cooled to 70°C, and 1,3-butanediol and dibutyltin dilaurate were added. The mixture was stirred for 10 min, and hydroxyl acrylic resin preheated to 60°C was added. The mixture was reacted at 80°C for 1 h, cooled to 45°C, and carbodiimide was added. The mixture was stirred for 20 min, and modified cerium oxide nanoparticles were added. The mixture was ultrasonically dispersed for 45 min to obtain the polyurethane composite coating.

5. The stone-like photovoltaic panel decorative material according to claim 1, characterized in that: The preparation method of the modified cerium oxide nanoparticles includes the following steps: Concentrated hydrochloric acid solution was added to the nano-cerium oxide dispersion to adjust the pH to 4-5. Under stirring conditions, γ-glycidyl ether propyltrimethoxysilane was added dropwise and the mixture was refluxed for 8 hours to obtain the modified nano-cerium oxide dispersion. The modified cerium oxide nano-dispersion was allowed to stand for 30 minutes, then centrifuged, washed, and dried to obtain modified cerium oxide nanoparticles.

6. The stone-like photovoltaic panel decorative material according to claim 1, characterized in that: The substrate layer is selected from one of polycarbonate, glass fiber reinforced plastic, aluminum alloy, and wood-plastic composite materials.

7. The stone-like photovoltaic panel decorative material according to claim 3, characterized in that: The fine stone powder is selected from one or more of the following: quartz powder, marble powder, granite powder, and calcite powder.

8. The stone-like photovoltaic panel decorative material according to claim 3, characterized in that: The inorganic filler is selected from one or more of the following: talc, aluminum hydroxide, barium sulfate, and kaolin.

9. A preparation process for a stone-like photovoltaic panel decorative material, applicable to the stone-like photovoltaic panel decorative material according to any one of claims 1-8, characterized in that: The preparation process includes the following steps: S1. After weighing the unsaturated polyester resin, polycarboxylate superplasticizer, pigment, fine stone powder, inorganic filler, cobalt naphthenate styrene solution, and methyl ethyl ketone peroxide, a slurry is obtained. S2. Using epoxy adhesive, the photovoltaic patch coated with polyurethane composite coating is attached to the substrate layer to bring out the positive and negative electrodes; S3. Apply the slurry to the photovoltaic patch with the polyurethane composite coating, cure it on the photovoltaic patch to form a stone-like layer, and then apply a surface composite coating on the stone-like layer.

10. The preparation process of a stone-like photovoltaic patch decorative material according to claim 9, characterized in that: The preparation process further includes the following steps: S11. Add unsaturated polyester resin, polycarboxylate superplasticizer, and pigment to a planetary mixer and stir for 5 minutes. Add fine stone powder and inorganic filler and stir for 10 minutes. Add cobalt naphthenate styrene solution and stir for 3 minutes. Then add methyl ethyl ketone peroxide and stir for 2 minutes to obtain a slurry.

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