Polyvinyl chloride knife-coated film for construction and industry and method for producing the same

Abstract

The application discloses a building and industrial polyvinyl chloride knife-coating film material and a preparation method thereof, and relates to the technical field of coated fabric film materials.The film material comprises a fabric reinforcing layer, a polyvinyl chloride structural knife-coating layer L1, a near-surface reservoir knife-coating layer L2 containing a reactive plasticizer B2 and core-shell microgel D3, an interface anchoring base coating layer E1, and an ultra-easy-to-clean top coating layer E2; B2 is a double-acrylate end group polyester, D3 is a microgel containing a polymerizable unsaturated group and a polydimethylsiloxane brush layer; E2 is an ultraviolet-cured acrylic system containing a bifunctional polydimethylsiloxane dipropylene glycol and an aromatic disulfide bond dipropylene glycol monomer; the method comprises knife-coating and plasticizing L1 and L2 on a base fabric, and then sequentially coating E1, drying, coating E2, and ultraviolet curing; wherein the plasticizing temperature of L2 is not higher than 190 DEG C, and the particle size of D3 is 80-180 nm, so that the adhesion of oil stains and dust and the rain mark residue are reduced, and the maintenance burden is reduced, and the film material is suitable for station sheds and tarpaulins.

Description

Technical Field

[0001] This invention relates to the field of coated fabric membrane technology, specifically to polyvinyl chloride blade-coated membrane materials for construction and industry and their preparation methods. Background Technology

[0002] Polyester-based reinforced PVC blade-coated membranes are suitable for long-term exposed or semi-exposed scenarios in construction and industry due to their advantages such as continuous coating, ease of hot air or high-frequency welding, flame retardancy, and weather resistance that can be controlled through formulation and structural design. These advantages include continuous coating, ease of hot air or high-frequency welding, and controllable flame and weather resistance through formulation and structural design. However, the membrane surface is subject to alternating effects of road dust and fine particulate matter deposition, oil fume aerosol adhesion, rain streaks from rainwater erosion, and highly adhesive substances such as bird droppings. It may also accumulate fingerprints and localized residues from human touch. To maintain cleanliness, reliable light transmission or reflection performance, and public environmental hygiene, maintenance often involves periodic cleaning using detergents, soft brushes, and high-pressure water rinsing. Stubborn stains may require localized cleaning with solvent-based cleaning agents. The adhesion of contaminants and the improvement of cleanability are usually achieved by applying a protective layer or topcoat to the surface of the polyvinyl chloride coating. The material system can be acrylic, fluoropolymer or silicone modified resin, or surface treatment or coating methods can be used.

[0003] However, after repeated scrubbing and friction abrasion during outdoor heat and humidity aging, the easy-to-clean and anti-fouling ability of the membrane surface will still decline with service: sand and dust and brushing will cause micro-scratches and local wear, increasing surface roughness and creating micro-depressions where pollutants can be retained; some components used to form low surface energy and improve leveling will migrate, be extracted or depleted under the action of washing, solvents and rainwater, resulting in increased surface energy and weakened low adhesion interfaces; in addition, the migration of components such as plasticizers in the PVC system under temperature gradients and mechanical action will change the surface adhesion state, making it easier for dust and oily contaminants to remain after cleaning. Especially in the membrane surface areas with high temperature rise due to summer sunlight, condensation at night, and wind vibration friction, the wear and migration effects are more likely to be superimposed; the surface layer at the weld overlap edge and stress fold line is more easily worn by repeated bending and scrubbing. If the attenuation is uncontrollable, it will lead to increased cleaning frequency and water and agent usage, long-term existence of local dirt accumulation, changes in appearance and optical properties, and premature maintenance needs for weld edges and high friction areas.

[0004] Therefore, under existing pollution loads and cleaning and maintenance conditions, how can the surface cleaning and anti-fouling capabilities of the membrane material be prevented from being damaged by repeated wiping and friction wear, resulting in surface micro-damage, surface energy recovery, and the accumulation and decay of pollutants? Summary of the Invention

[0005] (a) Technical problems to be solved To address the shortcomings of existing technologies, this invention provides a polyvinyl chloride (PVC) blade-coated membrane material for building and industrial applications and its preparation method, comprising a fabric reinforcement layer, a PVC structural blade-coated layer L1, a near-surface reservoir blade-coated layer L2 containing a reactive plasticizer B2 and a core-shell microgel D3, an interface anchoring undercoat E1, and an ultra-easy-clean topcoat E2; B2 is a diacrylate-terminated polyester, D3 is a microgel containing polymerizable unsaturated groups and a polydimethylsiloxane brush layer; E2 is a UV-curable acrylic system containing bifunctional polydimethylsiloxane diacrylate and aromatic disulfide diacrylate monomers; thereby reducing oil and dust adhesion and rain streak residue and reducing maintenance burden, solving the technical problems described in the background art.

[0006] (II) Technical Solution To achieve the above objectives, the present invention provides the following technical solution: The PVC blade-coated membrane material for building and industrial applications includes a fabric reinforcement layer, a PVC structural blade-coated layer L1, a PVC near-surface storage blade-coated layer L2, an interface anchoring undercoat E1, and a renewable, easy-clean topcoat E2. The plasticizing system of L2 includes a diacrylate-terminated polyester reactive plasticizer B2, with a number average molecular weight of 800 to 1800 and an acrylate functionality of 1.8 to 2.2. L2 contains core-shell microgel particles D3, with an average particle size of 80 to 180 nanometers and a gel content of not less than 85%. The shell of D3 contains polymerizable unsaturated groups with a content of 0.05 to 0.30 mmol / g. E2 is a UV-curable acrylic system containing bifunctional polydimethylsiloxane diacrylate, aromatic disulfide diacrylate monomers, and core-shell microgel particles D3.

[0007] Furthermore, the total thickness of the PVC structural scraped layer L1 and the PVC near-surface storage scraped layer L2 is 420 to 520 micrometers, the thickness of L2 is 25 to 45 micrometers, the dry coating amount of the interface anchoring primer E1 is 2.0 to 3.5 g / m², and the dry coating amount of the renewable easy-clean topcoat E2 is 7 to 11 g / m².

[0008] Furthermore, L2 is based on 100 parts by mass of total polyvinyl chloride resin, including 175 parts by mass of polyvinyl chloride paste resin A1 and 225 parts by mass of vinyl chloride-vinyl acetate copolymer paste resin A2; B2 is used in an amount of 5 to 14 parts by mass; and D3 is used in L2 in an amount of 0.3 to 1.8 parts by mass, on a solids basis.

[0009] Furthermore, the core of D3 is a cross-linked flexible acrylate microgel, the shell of D3 is an acrylate shell containing polar groups and polymerizable unsaturated groups, and the surface brush layer of D3 is a methacrylate-terminated polydimethylsiloxane grafted segment. The interface anchoring primer E1, based on 100 parts by weight of solid components, includes 30 to 60 parts by weight of hydroxyl-containing vinyl chloride-vinyl acetate-vinyl alcohol terpolymer resin, 10 to 30 parts by weight of hydroxyl acrylic resin, 15 to 35 parts by weight of reactive diluent monomer, 2 to 10 parts by weight of epoxy-containing acrylate monomer, 0.3 to 1.5 parts by weight of silane coupling agent with methacrylate groups, 1.0 to 3.5 parts by weight of UV photoinitiator, and 0.1 to 0.8 parts by weight of reactive leveling agent; E2 includes 0.2 to 1.2 parts by weight of surface-treated organosilane silica nanoparticles and 0.3 to 2.5 parts by weight of core-shell microgel particles D3, all based on solids, and the primary particle size of the silica nanoparticles is 15 to 30 nanometers and the aggregate size is controlled to be no greater than 200 nanometers.

[0010] A method for preparing polyvinyl chloride (PVC) blade-coated films for building and industrial applications includes: The L1 structural layer PVC blade-coated paste was applied to the fabric reinforcement layer and plasticized to form the PVC structural blade-coated layer L1; the L2 near-surface reservoir PVC blade-coated paste was prepared, the paste containing diacrylate end-group polyester reactive plasticizer B2 and core-shell microgel particles D3 with an average particle size of 80 to 180 nanometers, the paste was applied to L1 by blade coating and plasticized at a temperature not exceeding 190 degrees Celsius to form the PVC near-surface reservoir blade-coated layer L2. Subsequently, an interface anchoring undercoat E1 was applied to L2 and dried, followed by a UV-curable regenerable easy-clean topcoat E2 of an acrylic system and UV-cured. E2 contains bifunctional polydimethylsiloxane diacrylate, aromatic disulfide diacrylate monomers, and core-shell microgel particles D3.

[0011] Furthermore, B2 has a number average molecular weight of 800 to 1800 and an acrylate functionality of 1.8 to 2.2, D3 has a gel content of not less than 85% and a shell polymerizable unsaturated group content of 0.05 to 0.30 mmol / g, and when preparing L2 near-surface reservoir PVC scraping paste, based on 100 parts by weight of total PVC resin, the amount of B2 is 5 to 14 parts by weight and the amount of D3 is 0.3 to 1.8 parts by weight, on a solids basis.

[0012] Furthermore, the gelation temperature of L1 is 150 to 170 degrees Celsius and the time is 30 to 60 seconds; the plasticizing temperature of L1 is 180 to 210 degrees Celsius and the time is 60 to 120 seconds; the plasticizing temperature of L2 is 160 to 185 degrees Celsius and the total residence time is 60 to 120 seconds, and the maximum oven temperature of L2 does not exceed 190 degrees Celsius. After L2 is taken out of the oven, it is cooled to a surface temperature not exceeding 35 to 40 degrees Celsius before being coated with E1.

[0013] Furthermore, when preparing L2 near-surface storage PVC scraping paste, B2 is added together with polyester-type polymer plasticizer B1, non-phthalate monomer plasticizer B1' and epoxidized vegetable oil auxiliary plasticizer / acid-absorbing synergist B3 in the first step to complete resin wetting and pigment dispersion, and then D3 is added with low shear and stirred for 10 to 15 minutes.

[0014] Furthermore, E1 is prepared with a construction solids content of 20 to 40% and then applied, resulting in a dry coating weight of 2.0 to 3.5 g / m². It is then dried in two stages: at 50 to 60 degrees Celsius for 30 to 60 seconds and at 70 to 85 degrees Celsius for 60 to 120 seconds. E2 is then applied with a dry coating weight of 7 to 11 g / m² and UV-cured. During UV curing, the surface temperature of the film is kept below 60 degrees Celsius. After UV curing, post-curing is performed, which involves holding the film at 50 to 70 degrees Celsius for 10 to 30 minutes or placing it at room temperature for 24 hours. A nitrogen curtain is used in the UV curing zone to reduce surface oxygen inhibition.

[0015] (III) Beneficial Effects This invention provides a polyvinyl chloride (PVC) blade-coated film for building and industrial applications and its preparation method, which has the following beneficial effects: Polyester-based reinforced PVC blade-coated films for construction and industrial applications can be used in long-term exposed environments requiring periodic cleaning, such as station sheds, parking sheds, connecting corridors for sunshade, and logistics vehicle tarpaulins. The outer coating of the PVC structural blade-coated layer contains a near-surface reservoir layer with reactive plasticizers and core-shell microgels. Low surface energy components can enter the reservoir for replenishment after surface wear or avoid washing and extraction. After drying, the interface anchoring base coating forms a controllable penetration anchoring zone, creating a stable interface with the subsequent UV-cured top coating, allowing for long-term adhesion even under repeated cleaning and bending conditions.

[0016] The renewable, ultra-easy-clean topcoat uses chemically anchored bifunctional polydimethylsiloxane diacrylate to provide durable low surface energy, while aromatic disulfide acrylates provide exchangeable rearrangement capabilities. Together, they drive surface temperature rise or a low-adhesion state after cleaning. A siloxane-side-chain-containing acrylic copolymer leveling and self-stratification regulator, along with organosilane-treated silica, work together to reduce pinholes and micro-scratches, maintaining a dense, smooth surface, reducing oil and dust adhesion and rain streaks, and lowering maintenance costs. Attached Figure Description

[0017] Figure 1 This is a schematic diagram illustrating the preparation method of the polyvinyl chloride blade-coated film material for building and industrial applications according to the present invention. Detailed Implementation

[0018] 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.

[0019] Please see Figure 1 This invention provides a polyvinyl chloride (PVC) blade-coated film for building and industrial applications and its preparation method, specifically including the following: Membrane layer structure (from inside to outside) and thickness setting This embodiment uses a polyester-based fabric-reinforced knife-coated film material, with the following structure: Fabric reinforcement layer: high-strength polyester filament base fabric; PVC structural scraped layer (L1): mainly bears the mechanical and weather-resistant skeleton; PVC near-surface reservoir scraped layer (L2): embeds a renewable and easy-to-clean functional reservoir and provides an interface reaction window; interface anchoring base coating (E1): thin-layer penetration anchoring, constructing an interpenetrating / co-curing zone; renewable ultra-easy-to-clean top coating (E2): a dense and smooth layer with self-layering + dynamic network + chemical anchoring of low surface energy chain segments; Recommended thickness / coating amount (median value used in this example): Total PVC coating thickness (L1+L2): approximately 420–520 micrometers (adjustable according to design weight); L2 near-surface reservoir layer thickness: approximately 25–45 micrometers; E1 primer dry coating weight: approximately 2.0–3.5 g / m²; E2 topcoat dry coating weight: approximately 7–11 g / m² (dry film approximately 7–11 micrometers).

[0020] III. Raw Materials and Key Characteristic Parameters This embodiment divides the formulation into four independently implementable formulation units: Formulation Unit 1: L1 Structural Layer PVC Blade-Coated Paste; Formulation Unit 2: L2 Near-Surface Storage Layer PVC Blade-Coated Paste; Formulation Unit 3: E1 Interface Anchoring Primer; Formulation Unit 4: E2 Renewable Ultra-Easy-Clean Topcoat; wherein, the formulations of L1 and L2 are based on 100 parts by mass of total PVC resin; E1 / E2 are based on 100 parts by mass of total solid resin and reactive components.

[0021] Formulation Unit 1: L1 structural layer PVC blade-coated paste (mainly components A+B+C) 1) Component A: Polyvinyl chloride resin system (L1) A1: Polyvinyl chloride paste resin (main resin): Key parameter range: K value: 68–72; median particle size (D50): 0.8–1.2 micrometers; Dosage range: 70–90 parts by weight (as a percentage of total A). A2: Vinyl chloride-vinyl acetate copolymer paste resin (compatibility / interface assistance): Key parameter ranges: K value: 60–66; vinyl acetate mass fraction: 2–8%; dosage range: 10–30 parts by mass (as a percentage of total A). In this embodiment, the amount of component A in L1 (total A = 100 parts by mass) is: A1: 80 parts by mass; A2: 20 parts by mass; 2) Component B: Plasticizing system (L1): B1: Polyester-type polymeric plasticizer (low migration primary plasticizer); Key parameter ranges: Number average molecular weight: 2500–4500, viscosity at 25 degrees Celsius: 2000–6000 mPa·s, dosage range: 28–45 parts by weight; B1': Non-phthalate monomer plasticizer used for rheology and processing window adjustment (e.g., di(2-ethylhexyl) terephthalate or similar systems); Key parameter ranges: Viscosity at 25°C: 30–120 mPa·s; Volatile matter: ≤0.2%; Dosage range: 8–20 parts by weight; B3: Epoxidized vegetable oil-based auxiliary plasticizer / acid absorber Key parameter range: epoxy value: ≥6.0% (or epoxy equivalent 150–220 g / equivalent), dosage range: 4–12 parts by mass; Note: reactive plasticizer may not be required for the L1 structural layer, but if it is desired to enhance the overall interlayer reaction window, a small amount (0–4 parts by mass) of reactive plasticizer may be added; In this embodiment, the reactive plasticizer is concentrated in the L2 storage layer.

[0022] The amount of component B in L1 of this embodiment (based on 100 parts of resin): B1: 38 parts by weight; B1': 14 parts by weight; B3: 8 parts by weight; Component C: Stabilizer / Weather resistant / Lubricant and pigment (L1). C1: Calcium-zinc composite stabilizer, key parameter range: metal soap content (based on solids): 30–60%; dosage range: 2.0–3.8 parts by weight; C2: Hydrotalcite acid absorber (layered double hydroxide); key parameter range: D50: 0.8–1.8 micrometers; specific surface area: 10–25 square meters / gram; dosage range: 0.8–2.5 parts by weight; C3: High molecular weight hindered amine light stabilizer (migration resistant); key parameter range: number average molecular weight: ≥2000; dosage range: 0.25–0.85 parts by weight; C4: Benzotriazole or triazine UV absorber, dosage range: 0.15–0.60 parts by weight.

[0023] C5: Lubrication / release system (mainly internal lubrication to prevent surface migration and contamination), options include: ethylene bis-stearamide, polyethylene wax, etc.; dosage range: 0.15–0.60 parts by weight; C6: Titanium dioxide pigment (outdoor weather-resistant type), key parameters range: rutile type, surface coating treatment, median particle size: 0.20–0.35 microns; dosage range: 4–12 parts by weight; C7: Calcium carbonate filler (for cost and dimensional stability), key parameters range: median particle size: 0.8–1.5 microns; surface treatment: optional stearic acid treatment to reduce oil absorption, dosage range: 5–25 parts by weight; The amounts of component C in L1 of this embodiment are as follows: C1: 3.0 parts by mass, C2: 1.5 parts by mass, C3: 0.5 parts by mass, C4: 0.3 parts by mass, C5: 0.3 parts by mass, C6: 7.0 parts by mass, and C7: 12.0 parts by mass.

[0024] Formulation Unit 2: L2 near-surface storage PVC scraper paste (introducing key components of renewable storage) L2's design goals are: to pre-embed renewable and easy-to-clean components (reservoirs) near the surface; to construct interpenetrating / co-curing zones with E1 / E2 through reactive components; and to control roughness and migration to prevent the reservoir from becoming a source of contamination.

[0025] 1) Component A: Polyvinyl chloride resin system (L2), with a range similar to L1, but the proportion of copolymer resin can be increased to enhance near-surface polarity and interfacial compatibility.

[0026] In this embodiment, component A of L2 (total A = 100 parts by mass) is: A1 (polyvinyl chloride paste resin, K value 68–72): 75 parts by mass; A2 (vinyl chloride-vinyl acetate copolymer paste resin, K value 60–66): 25 parts by mass.

[0027] 2) Component B: Plasticizing system (L2, with added reactive plasticizer B2): B1: Polyester-type polymeric plasticizer, dosage range: 22–40 parts by weight; B2: Reactive plasticizer (in this example, a diacrylate-terminated polyester reactive plasticizer is used). Key parameter ranges: Number average molecular weight: 800–1800; Acrylate functionality: 1.8–2.2 (close to bifunctional); Viscosity at 25°C: 800–6000 mPa·s; Self-polymerization inhibitor content: 200–600 mg / kg (e.g., p-methoxyphenol); Dosage range: 5–14 parts by weight. The content of polymerization inhibitors in B2 should be 300–1000 mg / kg; and the peroxide content in B2 should be controlled at a low level (subject to supplier specifications); the maximum temperature of the L2 oven should not exceed 190 degrees Celsius, and the residence time in this temperature range should be controlled; strong ultraviolet radiation should be avoided during the preparation and storage of L2 paste; if zinc-containing stabilizers are used, acid scavengers / compatibility control should be used to avoid promoting the side reactions of acrylates.

[0028] B1': Non-phthalate monomer plasticizer: Dosage range: 6–16 parts by weight; B3: Epoxidized vegetable oil auxiliary plasticizer / acid scavenger: Dosage range: 4–10 parts by weight.

[0029] The amounts of component B in L2 of this embodiment are as follows: B1: 30 parts by mass; B2: 10 parts by mass; B1': 10 parts by mass; B3: 6 parts by mass.

[0030] 3) Component C: Stabilizer / Weather-resistant / Pigment / Filler (L2): L2 requires a denser and smoother texture, and the filler and lubricant should be used more sparingly. C1: Calcium-zinc composite stabilizer: 2.0–3.6 parts by weight (Example 3.0), C2: Hydrotalcite acid absorber: 0.8–2.0 parts by weight (Example 1.2), C3: High molecular weight hindered amine light stabilizer: 0.25–0.85 parts by weight (Example 0.5), C4: Ultraviolet absorber: 0.15–0.60 parts by weight (Example 0.3), C5: Internal lubricant: 0.10–0.40 parts by weight (Example 0.2), C6: Titanium dioxide: 3–10 parts by weight (Example 6.0), C7: Calcium carbonate: 0–8 parts by weight (Example 3.0).

[0031] 4) Component D: Near-surface renewable reservoir functional package: Component D of L2 is a combination of core-shell microgel particles and a small amount of surface energy-regulated copolymer.

[0032] D3: Core-shell microgel particles with a regenerable low surface energy brush layer on the surface and reactive groups on the shell. The core-shell microgel forms dispersed microdomains in the near-surface layer of polyvinyl chloride and is compatible with the top coating layer to provide a source of replenishment of low surface energy components after wear. Structural characteristics: Core: Flexible acrylate microgel (crosslinked); Shell: Acrylate shell containing epoxy or hydroxyl groups, such as polar groups (one of hydroxyl / epoxy / carboxyl) and polymerizable unsaturated groups; Content of polymerizable unsaturated groups in the shell: 0.05–0.30 mmol / g (solids). Surface brush layer: methacrylate-terminated polydimethylsiloxane grafted segments (low surface energy output) Key parameter ranges: average particle size (dynamic light scattering): 80–180 nm; gel content: ≥85%; content of reactive groups in the shell: 0.2–0.8 mmol / g (as solids); Supply form: as a dispersion in monomeric plasticizers or reactive diluents, with a solid content of 40–60% (to avoid water from being introduced into the PVC paste); the dispersion medium is preferably a high-boiling-point liquid compatible with PVC (e.g., non-phthalic plasticizers or polyester plasticizers), to avoid introducing easily migrating low-molecular-weight reactive diluent monomers into L2.

[0033] Dosage range in L2: 0.3–1.8 parts by weight (as solids); Dosage in this embodiment: 0.9 parts by weight (as solids). If the solid content of the microgel dispersion is 50%, then add 1.8 parts by weight of the dispersion directly. During the drying process, the interfacial anchoring primer layer undergoes limited swelling and penetration into the near-surface layer of PVC, forming an anchoring zone. It is then laminated with a recyclable, easy-clean topcoat layer and UV-cured, resulting in an interpenetrating network and segment entanglement at the interface. This improves the adhesion stability of the topcoat and reduces the risk of peeling after scrubbing. Epoxy-containing acrylate monomers enhance the polarity and wettability of the primer system, aiding in the formation of a continuous and dense anchoring layer. Core-shell microgels form dispersed microdomains within the near-surface layer of PVC, providing a source of replenishment for low surface energy components after abrasion.

[0034] D2 (optional): Acrylic copolymer containing siloxane side chains (surface energy modifier): Key parameter ranges: siloxane content: 10–25%, acid value: 2–12 mg potassium hydroxide / g; number average molecular weight: 4000–12000; dosage range: 0.1–0.8 parts by weight (0.3 in this example).

[0035] The significance of L2 arranging D3 is that when the E2 surface layer is worn thin or locally damaged, the newly exposed near-surface layer still contains low surface energy regenerable microdomains, which can be re-enriched on the surface during subsequent temperature rise / cleaning processes.

[0036] Formulation Unit 3: E1 Interface Anchoring Primer (Thin-Layer Penetration Anchoring + Co-Cure Window) The design objectives of E1 are: to form a micro-swelling penetration (with controllable depth) into L2, bringing reactive sites near B2 (reactive plasticizer) and D3 microgel into the interface region; and to form an interpenetrating / co-cured anchoring layer through UV curing, reducing the risk of peeling off the topcoat after scrubbing. During the drying process, E1 undergoes limited swelling penetration into L2 and forms an anchoring zone, subsequently undergoing layer-by-layer curing with the UV-cured layer of E2. The interface forms an interpenetrating network and chain segment entanglement, thereby improving the adhesion stability of the topcoat to the PVC layer.

[0037] The composition range of E1 (based on 100 parts by mass of total solid components): E1-1: A terpolymer resin containing hydroxyl groups of vinyl chloride-vinyl acetate-vinyl alcohol (a vinyl chloride-based resin compatible with polyvinyl chloride and containing a small amount of hydroxyl groups). Key parameter ranges: hydroxyl content (mass fraction): 1.0–3.0%; solution viscosity at 25°C (20% ethyl acetate): 100–400 mPa·s; dosage range: 30–60 parts by mass; in this example: 45 parts by mass. E1-2: Hydroxyl acrylic resin (improves adhesion and toughness): Key parameter ranges: Hydroxyl value: 40–120 mg / g potassium hydroxide; Number average molecular weight: 4000–12000; Dosage range: 10–30 parts by weight; This example: 15 parts by weight; E1-3: Reactive diluent monomers (for UV curing and penetration conditioning), one or more or a mixture: isoborneol acrylate, hydroxyethyl acrylate, etc.; Dosage range: 15–35 parts by weight; In this example: Total reactive dilution monomers: 31.8g isoborneol acrylate, 20.0g hydroxyethyl acrylate, 11.8g hydroxyethyl acrylate; E1-4: Epoxy-containing acrylate monomers (e.g., glycidyl methacrylate). E1-4 epoxy-containing acrylate monomers are used to improve the polarity and interfacial wetting of the primer layer, and to assist in the formation of a dense anchoring layer. Dosage range: 2–10 parts by weight; in this example: 5 parts by weight. E1-5: Silane coupling agent with methacrylate group (e.g., 3-methacryloyloxypropyltrimethoxysilane), dosage range: 0.3–1.5 parts by weight; in this example: 0.8 parts by weight; E1-6: UV photoinitiator; recommended as a combination of α-hydroxy ketone and phosphine oxide; dosage range: 1.0–3.5 parts by weight; in this example: 2.0 parts by weight; E1-7: Reactive leveling agent (avoids staining caused by migrating surfactants), dosage range: 0.1–0.8 parts by weight, in this example: 0.4 parts by weight; Solvent and construction solids content of E1 (excluding the above 100 parts by weight): Solvent: a mixed solvent of ethyl acetate / butyl acetate / isopropanol (mass ratio can be 60 / 30 / 10); Construction solids content range: 20–40%; This embodiment has a solid content of 30% and a formulation unit 4: E2 renewable ultra-easy-clean topcoat (self-layering + dynamic network + chemically anchored low surface energy segments).

[0038] E2's design goals are: a dense and smooth surface (reducing contamination); low surface energy segments that can float and accumulate but are not easily extracted; and a network with exchange / relaxation capabilities, allowing for rearrangement and enrichment after wear (demonstrating renewability).

[0039] Composition range of E2 (based on 100 parts by mass of total solid reactive components): E2-1: aliphatic polyurethane diacrylate oligomer (main resin); key parameter range: viscosity at 25 degrees Celsius: 3000–12000 mPa·s; acrylate functionality: about 2; dosage range: 30–55 parts by mass; this example: 38 parts by mass.

[0040] E2-2: Polyester acrylate oligomer (improves the balance between abrasion resistance and toughness), key parameter range: hydroxyl value: 10–60 mg potassium hydroxide / g (for certain polarity and intra-network hydrogen bonding); viscosity at 25 degrees Celsius: 2000–8000 mPa·s; dosage range: 5–20 parts by weight; in this example: 12 parts by weight.

[0041] E2-3: Bifunctional polydimethylsiloxane diacrylate (chemically anchored low surface energy segments, key): Key parameter range: Number average molecular weight: 6000–12000, viscosity at 25°C: 5000–15000 mPa·s, acrylate functionality: approx. 2, dosage range: 6–18 parts by weight, in this example: 10 parts by weight.

[0042] E2-4: Diacrylate monomer containing disulfide bonds, source of dynamic exchange bonds. E2-4 is an aromatic disulfide type diacrylate or equivalent structure, and the disulfide monomer is an aromatic disulfide structure; dosage range 4–10 parts by weight (based on E2 solids). Key parameter ranges: Purity: ≥95%, Dosage range: 3–12 parts by weight, in this example: 6 parts by weight.

[0043] E2-5: Trifunctional acrylate crosslinking monomer (to control network density), such as trimethylolpropane triacrylate, dosage range: 2–8 parts by weight; in this example: 4 parts by weight.

[0044] E2-6: Reactive diluent monomers (adjust viscosity and flexibility), in combination of: isoborneol acrylate (to improve hardness and abrasion resistance), dodecyl acrylate or similar long-chain acrylates (to improve flexibility and crack resistance), dosage range: 15–35 parts by weight; in this example: total reactive diluent monomers: 22.4 (e.g., isoborneol acrylate 13.0, long-chain acrylate 9.4).

[0045] E2-7: Acrylic copolymer leveling / self-stratification regulator containing siloxane side chains (representation of component D2 in the topcoat): Key parameter ranges: siloxane content: 10–25%, acid value: 2–12 mg potassium hydroxide / g, dosage range: 1–5 parts by weight, in this example: 3 parts by weight.

[0046] E2-8: Core-shell microgel particles (representation of component D3 in the topcoat, used for regenerating microdomains), key parameter range: particle size: 80–180 nm, supply form: dispersion in reactive diluent monomer (30–60% solids), dosage range: 0.3–2.5 parts by weight (based on solids), in this example: 1.0 part by weight based on solids; if the dispersion has a solids content of 40%, then add 2.5 parts by weight of the dispersion.

[0047] E2-9: Surface-treated silica nanoparticles with organosilane (enhanced scrub resistance, roughness control), key parameter range: primary particle size: 15–30 nm, aggregate control: ≤200 nm, supply form: dispersion in reactive diluent monomers (20–40% solids content), dosage range: 0.2–1.2 parts by weight (based on solids); silica is added as a pre-dispersion; aggregate control ≤200 nm; E2 mixture must be filtered through a 100–200 mesh to avoid pinholes and particle protrusions caused by gel particles. In this example: 0.5 parts by weight based on solids; if the dispersion has a solids content of 30%, then approximately 1.7 parts by weight of dispersion are added.

[0048] E2-10: Ultraviolet photoinitiator, dosage range: 1.0–4.0 parts by weight, in this example: 2.45 parts by weight.

[0049] E2-11: Polymerization inhibitor (to prevent self-polymerization during storage) (e.g., p-methoxyphenol), dosage range: 0.01–0.10 parts by weight, in this example: 0.05 parts by weight; hindered amine light stabilizer: 0.30; UV absorber: 0.30.

[0050] V. Detailed preparation method of Example 1

[0051] Step 1: Preparation of the fabric reinforcement layer: Polyester filament base fabric is selected: warp and weft linear density: 900–1100 dtex, warp and weft density: 9–12 threads / cm. The base fabric is heat-set and degreased (conventional process is sufficient). After drying, the moisture content is controlled below 0.5%.

[0052] Step 2: Preparation of L1 structural layer PVC scraping paste: Equipment: Planetary vacuum mixer or equivalent dispersion equipment; temperature control in the mixing vessel jacket: 20–35 degrees Celsius. Addition sequence: Add B1, B1', and B3 (plasticizing system) and stir for 5–10 minutes; add C1, C2, and C5 (stabilizer / lubricant) and stir for 5 minutes; slowly add A1 and A2 (resin) and maintain medium-speed stirring for 20–30 minutes until no obvious lumps remain; add C6 (titanium dioxide) and C7 (calcium carbonate) and disperse for 15–25 minutes; finally, add C3 and C4 (weather-resistant additives) and stir for another 10 minutes; Degassing: Degas under negative pressure for 10–20 minutes. Curing: Let stand at room temperature for 2–8 hours to stabilize the paste rheology (helping to achieve a smoother coating surface).

[0053] Step 3: L1 blade coating and gelation / plasticization: Blade coating method: Multiple blade coatings can be used to gradually achieve the required basis weight and thickness. After each coating, the material enters a multi-stage hot air oven for gelation / plasticization: initial gelation: 150–170 degrees Celsius, 30–60 seconds; middle and later plasticization: 180–210 degrees Celsius, 60–120 seconds. The number of coatings and the wet film amount per coating are adjusted according to the target total thickness. After L1 is completed, a smooth, pinhole-free, and bubble-free structural layer should be formed.

[0054] Step 4: Prepare and coat the L2 near-surface storage PVC paste: Prepare L2 paste according to formulation unit 2, with a stirring sequence similar to L1, but with two key points: the reactive plasticizer B2 is added in the first step along with B1 / B1' / B3 to facilitate subsequent resin wetting; the core-shell microgel D3 is added after the resin is fully wetted and the pigments and fillers are dispersed, using low-shear stirring for 10–15 minutes to avoid particle breakage and agglomeration. L2 coating: as the final PVC layer, the thickness is controlled at approximately 25–45 micrometers. The heat treatment of L2 is gentler to reduce undesirable reactions of B2 at high temperatures: gelation / plasticization: 160–185 degrees Celsius, total residence time 60–120 seconds (adjusted according to equipment and thickness). After exiting the furnace, cool to a surface temperature not exceeding 35–40 degrees Celsius before proceeding to the surface coating process.

[0055] Step 5: Apply E1 interface anchoring primer: Prepare the E1 formulation as a 30% solids content application solution and filter (100–200 mesh) to remove gel particles. Apply using gravure or roller coating, controlling the wet weight to achieve a dry coating weight of approximately 2.0–3.5 g / m². Drying: Two-stage drying promotes controlled penetration and anchoring: First stage: 50–60°C, 30–60 seconds (allowing slow solvent evaporation and limited E1 penetration into L2); Second stage: 70–85°C, 60–120 seconds (completely removing solvent). After drying, allow to stand for 1–5 minutes to stabilize the interface before applying the top coat.

[0056] Step 6: Apply E2 renewable easy-clean topcoat and cure with UV: Prepare E2 according to formulation unit 4: First, mix the oligomers (polyurethane diacrylate, polyester acrylate) with reactive diluent monomers; then add bifunctional polydimethylsiloxane diacrylate and diacrylate containing disulfide bonds; add a leveling / self-stratification regulator containing siloxane side chains; finally, add the microgel dispersion, silica nanodispersion, and UV photoinitiator, and disperse under low shear until uniform; filter (100–200 mesh) to remove occasional gels. Coating: Roller coating or gravure coating, controlling the dry coating amount to approximately 7–11 g / m².

[0057] UV Curing: Use a medium-pressure mercury lamp or LED UV light source (adjusted according to the formulation to ensure complete surface curing after one or two irradiations). Key Controls: During the curing process, keep the surface temperature of the film material below 60 degrees Celsius to avoid stress and ripples caused by secondary thermal history of the PVC layer.

[0058] Post-curing: Hold at 50–70°C for 10–30 minutes, or leave at room temperature for 24 hours. Purpose: To allow chemically anchored low surface energy segments to fully oriented and enrich within the network relaxation window, forming a stable low surface energy outer layer, while remaining independent of extractable migration. For UV curing, use a nitrogen curtain or reduce local oxygen content; or use a phosphorus oxide + α-hydroxy ketone composite photoinitiator system with sufficient energy dose; or add a short-wavelength supplementary irradiation / secondary curing to improve surface conversion efficiency.

[0059] I. Key Differences Among the Five Groups of Experiments Common process conditions for all experimental groups: Total thickness of L1+L2 PVC coating: approximately 470±30 micrometers; L2 thickness: approximately 35±10 micrometers; E1 dry coating weight: approximately 2.8±0.5 g / m²; E2 dry coating weight: approximately 9.0±2.0 g / m² (dry film approximately 9±2 micrometers); UV curing: same lamp type / same line speed, ensuring consistent surface dryness and hard dryness; test again after 24 hours of curing (or aging at 50–70 degrees Celsius for 20 minutes); Table 0: Summary of formulation differences (key features) across the five experimental groups

[0060] II. Brief Description of Test Conditions Static contact angle of water droplets: 23±2 degrees Celsius, 5 microliters of deionized water, averaged at 5 points.

[0061] Water droplet rolling angle: For a 10 microliter water droplet, the inclined stage is raised at a constant speed, and the starting rolling angle is recorded (average of 3 times).

[0062] Artificial composite dirt removal rate: A slurry of carbon black / mineral oil (mass ratio 1:4) was prepared, quantitatively coated and dried; a microfiber cloth moistened with 0.5% neutral detergent solution was used to wipe the dirt 20 times under a 1 kg load, rinsed and dried, and the removal rate was evaluated (equivalently evaluated by color difference / image grayscale method).

[0063] Wear resistance: Taber wear, CS-10 grinding wheel, 500g load, 5000 cycles.

[0064] Washing and scrubbing cycle resistance: 0.5% neutral detergent, microfiber cloth, 1 kg load, 100 cycles of reciprocating wiping (replenishing the solution every 10 cycles), tested after rinsing and drying.

[0065] Top coating peel strength: After forming a peel strip with high-strength adhesive sheet, perform a 180° peel (25 mm wide, 100 mm / min) and take the average value.

[0066] Plasticizer migration: 70 degrees Celsius × 7 days, filter paper contact method, record the weight gain per unit area of ​​filter paper (mg / m²).

[0067] Surface roughness: The average value of Ra is taken by contact or white light interferometry.

[0068] III. Performance Test Data Table 1 Initial Performance

[0069] Table 2 Abrasion resistance and self-compensation performance Note: Self-compensation capability is reflected by the decrease in contact angle after wear and the degree of recovery after heat / time. The recovery condition is uniformly placed at 50 degrees Celsius for 3 hours (simulating the heat history after sun exposure or warm water washing).

[0070]

[0071] Table 3 Washability and Interface Reliability

[0072] IV. Data Interpretation Experimental Example 2 (Migration-type Easy-Clean): Initial performance was not bad, but it failed rapidly after wear and washing (contact angle decreased significantly, decontamination rate decreased significantly, peel strength and anti-adhesion deteriorated), which is consistent with the typical engineering law of "migration-type low surface energy additives being extracted / depleted".

[0073] Experimental Example 3 (without dynamic bonds): The initial and wear-resistant performance was acceptable, but the recovery was "significantly insufficient". The stain removal rate decreased more significantly after washing, reflecting the contribution of dynamic exchange bonds in "reorientation and enrichment after scrubbing / wearing".

[0074] Experimental Example 4 (without reservoir): It can still recover, but the decline after wear is greater, indicating that the reservoir micro-domain has direct value for "replenishment when the surface is worn thin".

[0075] Experimental Example 5 (Non-reactive plasticized bridge): Dynamic bonds and low surface energy segments can still bring some recovery, but the interface reliability and migration control are significantly worse (decrease in peeling, increase in migration), ultimately resulting in inferior washability and durability compared to the target solution.

[0076] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A polyvinyl chloride (PVC) knife-coated film material for construction and industry, characterized in that: include, The product consists of a fabric reinforcement layer, a PVC structural scraped layer L1, a PVC near-surface storage scraped layer L2, an interface anchoring undercoat E1, and a renewable, easy-clean topcoat E2; the plasticizing system of L2 includes a diacrylate-terminated polyester reactive plasticizer B2, which has a number average molecular weight of 800 to 1800 and an acrylate functionality of 1.8 to 2.

2. L2 contains core-shell microgel particles D3, with an average particle size of 80 to 180 nanometers and a gel content of not less than 85%. The shell of D3 contains polymerizable unsaturated groups with a content of 0.05 to 0.30 mmol / g. E2 is a UV-curable acrylic system containing bifunctional polydimethylsiloxane diacrylate, aromatic disulfide diacrylate monomers, and core-shell microgel particles D3.

2. The polyvinyl chloride blade-coated film material for building and industrial applications according to claim 1, characterized in that: The total thickness of the PVC structural scraped layer L1 and the PVC near-surface storage scraped layer L2 is 420 to 520 micrometers, the thickness of L2 is 25 to 45 micrometers, the dry coating weight of the interface anchoring primer E1 is 2.0 to 3.5 g / m², and the dry coating weight of the renewable easy-clean topcoat E2 is 7 to 11 g / m².

3. The polyvinyl chloride blade-coated membrane material for building and industrial applications according to claim 1, characterized in that: L2 is based on 100 parts by weight of total polyvinyl chloride resin, including 175 parts by weight of polyvinyl chloride paste resin A1 and 225 parts by weight of vinyl chloride-vinyl acetate copolymer paste resin A2; B2 is used in amounts of 5 to 14 parts by weight. The amount of D3 in L2 is 0.3 to 1.8 parts by mass, on a solid basis.

4. The polyvinyl chloride blade-coated membrane material for building and industrial applications according to claim 1, characterized in that: The core of D3 is a cross-linked flexible acrylate microgel, the shell of D3 is an acrylate shell containing polar groups and polymerizable unsaturated groups, and the surface brush layer of D3 is a methacrylate-terminated polydimethylsiloxane grafted segment.

5. The polyvinyl chloride blade-coated film material for building and industrial applications according to claim 1, characterized in that: The interface anchoring primer E1, based on 100 parts by weight of solid components, includes 30 to 60 parts by weight of hydroxyl-containing vinyl chloride-vinyl acetate-vinyl alcohol terpolymer resin, 10 to 30 parts by weight of hydroxyl acrylic resin, 15 to 35 parts by weight of reactive diluent monomer, 2 to 10 parts by weight of epoxy-containing acrylate monomer, 0.3 to 1.5 parts by weight of silane coupling agent with methacrylate groups, 1.0 to 3.5 parts by weight of UV photoinitiator, and 0.1 to 0.8 parts by weight of reactive leveling agent; E2 includes 0.2 to 1.2 parts by weight of surface-treated organosilane silica nanoparticles and 0.3 to 2.5 parts by weight of core-shell microgel particles D3, all based on solids, and the primary particle size of the silica nanoparticles is 15 to 30 nanometers and the aggregate size is controlled to be no greater than 200 nanometers.

6. A method for preparing polyvinyl chloride (PVC) blade-coated film for building and industrial applications, characterized in that: include: The L1 structural layer PVC blade-coated paste is applied to the fabric reinforcement layer by blade coating and plasticized to form the PVC structural blade-coated layer L1; Prepare L2 near-surface storage PVC scraping paste. The paste contains diacrylate-terminated polyester reactive plasticizer B2 and core-shell microgel particles D3 with an average particle size of 80 to 180 nanometers. The paste is scraped onto L1 and plasticized at a temperature not exceeding 190 degrees Celsius to form PVC near-surface storage scraping layer L2. Subsequently, an interface anchoring undercoat E1 was applied to L2 and dried, followed by a UV-curable regenerable easy-clean topcoat E2 of an acrylic system and UV-cured. E2 contains bifunctional polydimethylsiloxane diacrylate, aromatic disulfide diacrylate monomers, and core-shell microgel particles D3.

7. The membrane preparation method according to claim 6, characterized in that: B2 has a number average molecular weight of 800 to 1800 and an acrylate functionality of 1.8 to 2.

2. D3 has a gel content of not less than 85% and a shell polymerizable unsaturated group content of 0.05 to 0.30 mmol / g. When preparing L2 near-surface reservoir PVC scraping paste, based on 100 parts by weight of total PVC resin, the amount of B2 is 5 to 14 parts by weight and the amount of D3 is 0.3 to 1.8 parts by weight, on a solids basis.

8. The membrane preparation method according to claim 6, characterized in that: The gelation temperature of L1 is 150 to 170 degrees Celsius and the time is 30 to 60 seconds. The plasticizing temperature of L1 is 180 to 210 degrees Celsius and the time is 60 to 120 seconds. The plasticizing temperature of L2 is 160 to 185 degrees Celsius and the total residence time is 60 to 120 seconds. The maximum oven temperature of L2 is not higher than 190 degrees Celsius. After L2 is taken out of the oven, it is cooled to a surface temperature not higher than 35 to 40 degrees Celsius before coating with E1.

9. The membrane preparation method according to claim 6, characterized in that: When preparing L2 near-surface storage PVC scraping paste, B2 is added together with polyester-type polymer plasticizer B1, non-phthalate monomer plasticizer B1' and epoxidized vegetable oil auxiliary plasticizer / acid saturator B3 in the first step to complete resin wetting and pigment dispersion. Then, D3 is added with low shear and stirred for 10 to 15 minutes.

10. The membrane preparation method according to claim 6, characterized in that: E1 is prepared with a construction solids content of 20 to 40% and then applied, resulting in a dry coating weight of 2.0 to 3.5 g / m². It is then dried in two stages: 50 to 60 degrees Celsius for 30 to 60 seconds and 70 to 85 degrees Celsius for 60 to 120 seconds. E2 is applied with a dry coating weight of 7 to 11 g / m² and then UV cured. During UV curing, the surface temperature of the film is kept below 60 degrees Celsius. After UV curing, post-curing is performed, which involves holding the film at 50 to 70 degrees Celsius for 10 to 30 minutes or placing it at room temperature for 24 hours. A nitrogen curtain is used in the UV curing zone to reduce surface oxygen inhibition.

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