Outdoor high-weather-resistant OC protective carbon tape and preparation method

Abstract

The application relates to the technical field of carbon tape protection, in particular to an outdoor high-weather-resistance OC protective carbon tape and a preparation method thereof. The composition of a release layer comprises a release layer resin and a metal ion complexing agent; the release layer resin comprises a polyacrylic acid resin or a polymethyl methacrylate resin, and further comprises a polysiloxane modified resin; the metal ion complexing agent is at least one of an aluminum ion complexing agent, a zinc ion complexing agent, an iron ion complexing agent and a copper ion complexing agent. The OC protective carbon tape can enhance the chemical stability of dyes, has good foil holding property under high-speed printing, has high alcohol rubbing resistance, high gloss, anti-fouling self-cleaning and waterproof functions, and has good adaptability to different printing substrates; the preparation method is simple, low in cost and good in effect.

Description

Technical Field

[0001] This invention relates to the field of protective carbon ribbon technology, and more specifically, to an outdoor high weather-resistant OC protective carbon ribbon and its preparation method. Background Technology

[0002] Dye-sublimation technology is in high demand in outdoor advertising, automotive decoration and other fields due to its high color fidelity (ΔE < 5). However, the poor weather resistance of small molecule dyes (fading rate > 30% after 3 months of outdoor exposure) limits the expansion of outdoor applications. In outdoor environments, light sources (especially the 290-315nm ultraviolet band), temperature and humidity, rain erosion, contaminant adhesion and substrate compatibility can all accelerate the aging of printed materials.

[0003] Existing outdoor weather-resistant technologies mainly include: surface coating (achieving UV resistance by adding UV absorbers to PVC / PMMA-based protective films, but the process is complex, costly, and limited for large-format applications), traditional OC film (simply adding light stabilizers, with limited weather resistance and no waterproof or stain-resistant functions), re-transfer film (thick coating but lacking waterproof design, allowing dyes to easily diffuse in rainy environments), and nano-composite protective film (good weather resistance but requiring large equipment investment and complex processes). Among these, OC film is the preferred solution for high-speed printing of flexible labels due to its low cost and strong process adaptability.

[0004] However, existing OC films mostly improve weather resistance only through a single light stabilizer, without systematically optimizing for dye stability and coating environmental protection, making it difficult to meet the requirements for long-term outdoor use. Specifically, the following problems exist: (1) Insufficient dye stability: Existing OC films have not modified the dye molecular structure. Small molecule dyes are easily excited by ultraviolet light and undergo photo-oxidation / reduction reactions. There are no effective means to inhibit the photodepolymerization of dye aggregates, resulting in a fast fading rate. (2) Single weather protection: It relies solely on UV absorbers, without coordinating the control of multiple factors such as temperature, humidity, and rain erosion, and lacks targeted blocking of the sensitive 290-315nm wavelength band; (3) Lack of coating function: No anti-fouling and waterproof design. Outdoor pollutants and rainwater immersion will accelerate coating damage and dye loss; (4) The contradiction between high-speed printing adaptability and weather resistance: single-layer coating or simple multi-layer structure cannot balance foil retention, demolding and long-term weather resistance under high-speed printing, and the coating is prone to defects. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide an outdoor high weather resistance OC protective carbon ribbon and its preparation method.

[0006] The technical solution of the present invention to solve the above-mentioned technical problems is as follows: Based on the above technical solution, the present invention can be further improved as follows.

[0007] This invention provides an outdoor high weather resistance OC protective carbon ribbon, comprising a substrate, a back coating on one side of the substrate, a release layer on the other side, an adhesive layer on the release layer, and the release layer comprising a release layer resin and a metal ion complexing agent. The release layer resin includes polyacrylic acid resin or polymethyl methacrylate resin, and also includes polysiloxane modified resin; The metal ion complexing agent is at least one of aluminum ion complexing agents, zinc ion complexing agents, iron ion complexing agents, and copper ion complexing agents.

[0008] Furthermore, the Tg values ​​of the polyacrylic acid resin and the polymethyl methacrylate resin are both 80-130℃, and the molecular weights are both 30,000-200,000; the mass ratio of the polyacrylic acid resin or polymethyl methacrylate resin to the polysiloxane modified resin is 8-12:1.

[0009] Furthermore, the release layer also includes an ultraviolet absorber and a light stabilizer; the ultraviolet absorber is a solid benzotriazole ultraviolet absorber or a triazine solid ultraviolet absorber, and the light stabilizer is a hindered amine light stabilizer.

[0010] Furthermore, the release layer also includes an antioxidant and an anti-fouling and waterproofing agent; the mass fractions of each component are as follows: 20-25 parts of the release layer resin, 1.5-2 parts of the metal ion complexing agent, 2-3 parts of the ultraviolet absorber, 0.5-1 part of the light stabilizer, 0.3-0.4 parts of the antioxidant, and 1-1.5 parts of the anti-fouling and waterproofing agent.

[0011] Furthermore, the adhesive layer comprises an adhesive resin and reinforcing additives; The adhesive layer resin comprises vinyl chloride-vinyl acetate resin and polyester-modified acrylic resin, wherein the Tg value of the vinyl chloride-vinyl acetate resin is 60-80℃, and the mass percentage of vinyl acetate is 10-20%; the mass ratio of the vinyl chloride-vinyl acetate resin to the polyester-modified acrylic resin is 3-5:1. The reinforcing agent is fine talc powder with a mesh size of 5000-12000 and a specific surface area of ​​5-10 g / m². 2 .

[0012] Furthermore, the coating solution of the adhesive layer also includes a polymeric superdispersant, a silane coupling agent, and a solvent; the mass fractions of each component in the coating solution of the adhesive layer are: 8-12 parts of the adhesive layer resin, 0.5-3 parts of the reinforcing agent, 0.5-3 parts of the polymeric superdispersant, and 0.3-0.5 parts of the silane coupling agent.

[0013] Furthermore, the back coating comprises polyvinyl butyral resin and aromatic isocyanate curing agent, wherein the mass ratio of polyvinyl butyral resin to aromatic isocyanate curing agent is 8-12:3.

[0014] Furthermore, the back coating also includes inorganic fillers and a release agent; the inorganic filler is talc and / or kaolin, and the release agent is a mixture of phosphate ester and silicone oil.

[0015] The present invention also provides a method for preparing an outdoor high weather-resistant OC protective carbon ribbon as described above, comprising the step of preparing a release layer coating liquid containing each component of the release layer using an organic solvent; the viscosity of the release layer coating liquid is 100-500 mPa·s.

[0016] Furthermore, it also includes the following steps: A back coating liquid is applied to one side of the substrate after corona treatment, with a coating thickness of 0.4-0.6 μm, and the back coating is obtained after drying. The release layer coating liquid is applied to the other side of the substrate, with a coating thickness of 1-3 μm, and the release layer is obtained after drying. An adhesive coating liquid is applied to the release layer with a coating thickness of 0.1-0.5 μm, and the adhesive layer is obtained after drying.

[0017] The beneficial effects of this invention are as follows: (1) The outdoor high weather-resistant OC protective carbon ribbon of the present invention adds aluminum, zinc, iron and copper ion complexing agents to the release layer to form stable coordination bonds with thermal sublimation dye molecules, inhibit the photodepolymerization behavior of dye aggregates, and reduce the sensitivity of dyes to ultraviolet light. (2) The outdoor high weather resistance OC protective carbon ribbon of the present invention adopts a solid benzotriazole or triazine UV absorber and hindered amine light stabilizer synergistic protection system in the release layer, which specifically blocks the sensitive wavelength band of 290-410nm, is embedded in the resin and is not easy to migrate, and works with the hindered amine free radical capture mechanism to inhibit the photodegradation chain reaction of the coating. (3) The outdoor high weather-resistant OC protective carbon ribbon of the present invention has a dense structure by adjusting the ratio of vinyl chloride-vinyl acetate resin and polyester modified acrylic resin in the adhesive layer, which can limit the depolymerization of dye molecules after being heated or exposed to light, so that the fading rate of outdoor for two years is ≤30%, which significantly enhances the chemical stability of the dye itself and is suitable for a variety of outdoor printing substrates such as inkjet cloth, light box film, and vehicle wrap. (4) The outdoor high weather-resistant OC protective carbon ribbon of the present invention can achieve the standard of two years of outdoor use. It has more than three times the weather resistance of traditional OC film. After 1000 hours of xenon lamp aging, the color density ratio is ≥72% and the ultraviolet blocking rate is ≥95%. After 168 hours of artificial accelerated aging, the color density ratio is ≥78%. It effectively solves the problem that small molecule dyes are prone to photo-oxidation / reduction reaction in the 290-315nm ultraviolet band, resulting in a fast fading rate. (5) The outdoor high weather resistance OC protective carbon ribbon of the present invention has foil retention under high speed printing (6m / min), and also has high alcohol friction resistance, high gloss, anti-fouling self-cleaning and waterproof functions. At the same time, the coating does not peel off or powder fall off, and it has good compatibility with different substrates (printing cloth, light box film, vehicle wrap, etc.). (6) The preparation method of the outdoor high weather resistance OC protective carbon ribbon of the present invention has a coating and drying temperature of 60-120℃, which can be directly used in existing thermal sublimation soft label printing machines. The production cost is low and the process is simple. At the same time, the multi-layer structure and auxiliary agent synergistic design ensure that the coating does not fall off or powder, and the yield and production efficiency are significantly improved. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the layer structure of the outdoor high weather-resistant OC protective carbon ribbon of the present invention.

[0019] The attached diagram lists the components represented by each number as follows: 1. Substrate; 2. Release layer; 3. Release layer; 4. Adhesive layer. Detailed Implementation

[0020] The principles and features of the present invention are described below. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0021] The outdoor high weather-resistant OC protective carbon ribbon of the present invention includes a substrate 1, a back coating 2 on one side of the substrate 1, a release layer 3 on the other side, an adhesive layer 4 on the release layer 3, and the release layer 3 comprises a release layer resin and a metal ion complexing agent; the release layer resin includes polyacrylic resin or polymethyl methacrylate resin, and also includes polysiloxane modified resin; the metal ion complexing agent is at least one of aluminum ion complexing agent, zinc ion complexing agent, iron ion complexing agent, and copper ion complexing agent.

[0022] The outdoor high weather-resistant OC protective ribbon of this invention, with its release layer 3 containing polyacrylic acid resin or polymethyl methacrylate resin, imparts excellent gloss and UV protection to printed materials. Combined with the use of polysiloxane-modified resin, it significantly improves coating density, thereby enhancing waterproof performance. The metal ion complexing agent forms stable complexes with sublimated dye molecules, effectively inhibiting photo-oxidation / reduction reactions and preventing dye aggregate depolymerization, reducing the fading rate to no more than 30% after two years of outdoor use, while achieving a UV blocking rate of over 95%. It also possesses anti-fouling and self-cleaning functions, abrasion resistance, and alcohol resistance, maintaining the low-cost process advantages of OC film and directly adapting to existing high-speed printing equipment for flexible labels. Compared to traditional single-layer ribbons, it achieves significant performance breakthroughs in weather resistance, comprehensive functionality, and structural stability.

[0023] Preferably, the Tg values ​​of both polyacrylic acid resin and polymethyl methacrylate resin are 80-130℃, and the molecular weights are both 30,000-200,000; the mass ratio of polyacrylic acid resin or polymethyl methacrylate resin to polysiloxane modified resin is 8-12:1.

[0024] The aforementioned polyacrylic acid resin or polymethyl methacrylate resin, as the resin body of release layer 3, exhibits moderate fluidity and film-forming properties at the transfer temperature during the thermal sublimation printing process. While ensuring the gloss of the printed surface, it can also ensure the smooth transfer of dye molecules, taking into account both the mechanical strength and coating processing performance of the coating, and avoiding the film brittleness and insufficient alcohol friction resistance caused by excessively low molecular weight. The specific mass ratio can significantly improve the coating density and waterproof penetration ability while maintaining the basic performance of the main resin. This ratio will not affect the adhesion between release layer 3 and adhesive layer 4 or the carbon ribbon foil retention due to excessive polysiloxane content, and can effectively enhance the anti-fouling and self-cleaning function. It can also effectively synergize with the metal ion complexing agent to enable the thermal sublimation dye molecules to obtain a stable protective structure.

[0025] Preferably, the polyacrylic resin is BR-52.

[0026] Preferably, the release layer 3 further includes an ultraviolet absorber and a light stabilizer; the ultraviolet absorber is a solid benzotriazole ultraviolet absorber or a triazine solid ultraviolet absorber, and the light stabilizer is a hindered amine light stabilizer.

[0027] The aforementioned UV absorbers and light stabilizers can form a synergistic protection system. Solid benzotriazole UV absorbers or triazine solid UV absorbers can specifically block the 290-315nm UV-sensitive band, achieving a UV blocking rate of over 95%. They effectively absorb the 290-410nm band while preventing the migration and precipitation of liquid additives. Together with metal ion complexing agents, they inhibit the photo-oxidation / reduction reaction of sublimated dyes and the depolymerization of aggregates, keeping the outdoor fading rate below 30% for two years.

[0028] Preferably, the solid benzotriazole ultraviolet absorber is UV-460. Hindered amine light stabilizers act as free radical scavengers to further inhibit the photodegradation chain reaction of the coating. Together with the main release layer resin and polysiloxane-modified resin, they form a multi-dimensional weather-resistant protective barrier.

[0029] Preferably, the hindered amine light stabilizer is HALS.

[0030] Preferably, the release layer 3 also includes an antioxidant and an anti-fouling and waterproofing agent; the antioxidant is a hindered phenol (B-225), which can prevent the coating from oxidizing and aging; the anti-fouling and waterproofing agent is a hydrophilic release agent, specifically polyethylene glycol modified silicone oil, which can improve the hydrophilicity of the coating surface, achieve self-cleaning, and enhance the anti-fouling performance.

[0031] Preferably, the mass fractions of each component are: 20-25 parts release layer resin, 1.5-2 parts metal ion complexing agent, 2-3 parts ultraviolet absorber, 0.5-1 part light stabilizer, 0.3-0.4 parts antioxidant, and 1-1.5 parts anti-fouling and waterproofing additive.

[0032] The adhesive layer 4 of the present invention comprises an adhesive layer resin and a reinforcing agent; the adhesive layer resin comprises vinyl chloride-vinyl acetate resin and polyester-modified acrylic resin, wherein the Tg value of the vinyl chloride-vinyl acetate resin is 60-80℃, and the mass percentage of vinyl acetate is 10-20%; the mass ratio of vinyl chloride-vinyl acetate resin to polyester-modified acrylic resin is 3-5:1; the reinforcing agent is fine talc powder with a mesh size of 5000-12000 and a specific surface area of ​​5-10 g / m². 2 .

[0033] The aforementioned adhesive resin imparts moderate flexibility and excellent adhesion to the adhesive layer 4, ensuring a strong bond with the release layer 3 and the substrate, preventing powder shedding and peeling during high-speed printing. Furthermore, the polyester-modified acrylic resin enhances weather resistance and interlayer compatibility. The reinforcing agent, fine talc powder, effectively improves abrasion resistance. The adhesive layer 4 of this invention has a dense structure, giving the ribbon excellent weather resistance, preventing powder shedding, and ensuring good compatibility with various substrates such as inkjet printing cloth, lightbox film, and vehicle wraps.

[0034] Preferably, the coating liquid of the next layer 4 also includes a polymeric superdispersant, a silane coupling agent, and a solvent; the polymeric superdispersant can ensure uniform dispersion of talc powder and improve the density of the coating, while the silane coupling agent, as a waterproofing aid, can improve the waterproofness of the coating, prevent rainwater penetration, and inhibit dye sublimation at high temperatures and the generation of hydrogen peroxide in high humidity environments.

[0035] Preferably, the mass fractions of each component in the coating liquid of the adhesive layer 4 are: 8-12 parts adhesive layer resin, 0.5-3 parts reinforcing agent, 0.5-3 parts high molecular weight superdispersant, and 0.3-0.5 parts silane coupling agent.

[0036] The back coating 2 of the present invention comprises polyvinyl butyral resin and aromatic isocyanate curing agent, wherein the mass ratio of polyvinyl butyral resin and aromatic isocyanate curing agent is 8-12:3.

[0037] Using an isocyanate curing agent in the composition of the back coating 2 can improve heat resistance and adhesion to the substrate 1.

[0038] Preferably, the back coating 2 also includes inorganic fillers and a release agent; the inorganic filler is talc and / or kaolin, which can effectively improve slipperiness, and the release agent is a mixture of phosphate ester and silicone oil. The silicone oil can optimize the release properties at high temperatures, and the talc, phosphate ester, and silicone oil have a synergistic effect, which can ensure that the ribbon does not wrinkle or become sticky at a printing speed of 6m / min.

[0039] Preferably, the composition of the back coating 2 comprises the following components by mass: 10 parts polyvinyl butyral resin, 3 parts aromatic isocyanate curing agent, 0.3-0.5 parts inorganic filler, 0.3-0.5 parts phosphate ester, and 0.5 parts silicone oil.

[0040] Preferably, the polyvinyl butyral resin is S-LEC BH-6, the aromatic isocyanate curing agent is 2,4-toluene diisocyanate, and the silicone oil is KF-965-100cs.

[0041] The substrate 1 of the present invention can be a transparent flexible plastic film, preferably PET or PEN, which has better weather resistance than PP or PE; the thickness of the substrate 1 is 4-6 μm, which can take into account both mechanical strength and adaptability to high-speed printing traction.

[0042] The preparation method of the outdoor high weather-resistant OC protective carbon ribbon of the present invention includes the step of preparing a release layer coating liquid containing each component of the release layer 3 using an organic solvent; the viscosity of the release layer coating liquid is 100-500 mPa·s; this viscosity range can ensure that the coating liquid has suitable fluidity and leveling properties during the coating process, and can be evenly spread under gravure coating or slot coating processes. It avoids defects such as sagging, uneven thickness and pinhole bubbles caused by excessively low viscosity, as well as problems such as coating difficulties, orange peel phenomenon on the coating surface and poor wetting with the substrate caused by excessively high viscosity.

[0043] The specific steps of the preparation method of this invention are as follows: S1. Apply a back coating liquid to one side of the substrate 1 after corona treatment. The coating thickness is 0.4-0.6μm. After drying, the back coating 2 is obtained.

[0044] Preferably, corona treatment of the substrate 1 surface can effectively improve the adhesion of the coating. If used in extreme outdoor environments, an additional 0.1-0.2μm silane coupling agent pretreatment layer can be applied to the substrate 1 surface to enhance the bonding stability with the back coating and improve the resistance to damp heat.

[0045] Preferably, the back coating liquid is prepared using a mixed organic solvent, which is a mixture of 2-butanone and toluene in a mass ratio of 8:2 to 1:1. The mass of the mixed organic solvent is 50% to 80% of the total mass of the release layer coating liquid. The viscosity of the back coating liquid is 100-500 mPa·s at 25°C, which also provides suitable flowability and leveling properties.

[0046] Preferably, the specific preparation steps of the back coating 2 are as follows: dissolve the resin in a mixed organic solvent, add each component, stir evenly, and then apply it to the back of the substrate by gravure coating or slit coating, and dry at 60-120℃ for 60-120s, with a coating thickness of 0.4-0.6μm.

[0047] S2. Apply a release layer coating liquid to the other side of the substrate 1 with a coating thickness of 1-3 μm, and obtain the release layer 3 after drying.

[0048] Preferably, the organic solvent used to prepare the release coating solution is a mixture of 2-butanone and toluene, with a mass ratio of 8:2 to 1:1, and the mass of the mixed organic solvent is 50% to 80% of the total mass of the release coating solution.

[0049] Preferably, the specific preparation steps of release layer 3 are as follows: dissolve resin in organic solvent, add metal ion complexing agent, weather-resistant agent, and anti-fouling and waterproof agent in sequence, ultrasonically disperse for 30 minutes to ensure uniformity, coat by gravure coating or slit coating, dry at 60-120℃ for 0.5-2 hours, and the coating thickness is 1-3μm. This thickness can ensure the thickness of the ultraviolet blocking and anti-fouling layer.

[0050] S3. Apply an adhesive coating liquid to the release layer 3 with a coating thickness of 0.1-0.5 μm, and dry it to obtain the adhesive layer 4.

[0051] Preferably, the organic solvent used to prepare the adhesive coating solution is a mixture of 2-butanone and toluene in a ratio of 8:2 to 1:1, with a total content of 50% to 80% and a viscosity of 100 to 500 mPa·s. Preferably, the specific preparation method of the next layer 4 is as follows: dissolve the resin in an organic solvent, add talc, a high molecular weight superdispersant and a silane coupling agent, grind and disperse, and then coat it on the surface of the release layer 3 by gravure coating or slit coating, and dry it at 60-120℃ for 0.5-2h, with a coating thickness of 0.1-0.5μm.

[0052] In the above preparation method, the multi-layer thin coating method can avoid the traction tension defects caused by single-layer thick coating, and take into account both foil retention and demolding properties.

[0053] The effects of the present invention will be illustrated below through specific embodiments and comparative examples.

[0054] Example 1 The outdoor high weather-resistant OC protective carbon ribbon of this embodiment has the following specific details regarding the composition, thickness, and preparation method of each layer: Substrate 1 is a 4.5μm PET film, which is subjected to corona treatment before preparation.

[0055] The back coating layer 2 consists of: 10 parts polyvinyl butyral resin, 3 parts 2,4-toluene diisocyanate, 0.5 parts talc, 0.5 parts phosphate ester, and 0.5 parts silicone oil. The coating solution is prepared using a mixed solvent, which is a mixture of 2-butanone and toluene, wherein 2-butanone comprises 60 parts by mass and toluene comprises 30 parts by mass. After mixing and stirring, the back coating solution is obtained, with a viscosity of 300 mPa·s at 25°C. Gravure coating or slot coating is used for coating, with a coating thickness of 0.5 μm. After coating, it is dried at 100°C for 100 s.

[0056] The release layer 3 consists of: 20 parts polyacrylic acid resin (BR-52), 2 parts polysiloxane modified resin, 1.5 parts aluminum ion complexing agent, 2.5 parts UV-460, 0.8 parts HALS, 0.4 parts B-225, and 1.2 parts polyethylene glycol modified silicone oil. The coating solution is prepared using a mixed solvent, specifically a mixture of 2-butanone and toluene, with 38 parts by mass of 2-butanone and 38 parts by mass of toluene. After mixing, the components are ultrasonically dispersed for 30 minutes to ensure uniform mixing, resulting in a coating solution with a viscosity of 350 mPa·s. Gravure coating or slot coating is used for coating, achieving a coating thickness of 1.5 μm. After coating, the coating is dried at 80°C for 2 hours.

[0057] The composition of the fourth adhesive layer is as follows: 8 parts vinyl chloride-vinyl acetate resin, 2 parts polyester-modified acrylic resin, 2 parts fine talc powder, 1 part polymeric dispersant, and 0.4 parts silane coupling agent. The coating solution is prepared using a mixed solvent, which is a mixture of 2-butanone and toluene, with 43 parts by mass of 2-butanone and 43 parts by mass of toluene. The components are mixed and dispersed to obtain an adhesive layer coating solution with a viscosity of 450 mPa·s. Gravure coating or slot coating is used for coating, with a coating thickness of 0.3 μm. After coating, it is dried at 60℃ for 1.5 h.

[0058] Example 2 Compared with Example 1, this embodiment uses a different ratio of metal ion complexing agents in the composition of release layer 3.

[0059] Specifically, the metal ion complexing agent in this embodiment is 1 part aluminum ion complexing agent and 0.8 parts zinc ion complexing agent, and the remaining components, proportions, and preparation process are completely consistent with those in Example 1.

[0060] Example 3 In this embodiment, different antifouling additives are used in the composition of the release layer 3 compared to embodiment 1.

[0061] Specifically, the hydrophilic release agent in this embodiment is 1.5 parts of polyethylene glycol modified phosphate, and the remaining components, proportions, and preparation process are completely consistent with those in Example 1.

[0062] Comparative Example This comparative example uses a traditional OC membrane, and the specific layer structure and parameters of each layer are as follows: Substrate 1: 4.5μm PET film.

[0063] Back coating 2: completely consistent with Example 1.

[0064] Release layer 3: 20 parts polyacrylic acid resin, 2 parts UV-1130 (liquid), 0.4 parts B-225, 0.6 parts erucamide, 40 parts 2-butanone, 40 parts toluene, coating thickness 1.5μm.

[0065] Next, layer 4: 10 parts vinyl chloride-vinyl acetate resin, 45 parts 2-butanone, and 45 parts toluene, with a coating thickness of 0.3 μm.

[0066] Performance tests were conducted on the above embodiments and comparative examples. The specific test plan is as follows: Test equipment: DTP330 dye-sublimation label printing machine (6m / min), Sanenshi NHG268 gloss meter, X-Rite i1-PRO3 colorimeter, DZ-204 alcohol abrasion tester, xenon lamp aging test chamber (simulating outdoor environment, blackboard temperature 40℃±3℃, relative humidity 50%±5%, irradiance 340nm); Test items and standards: (1) Gloss: 20° gloss, A (55-80), B (35-55), C (below 35). (2) Alcohol resistance to friction: 500g weight, 60 times / min, 1200 times of friction, color density ratio ≥95% is A, 80%-95% is B, 60%-80% is C, <60% is D.

[0067] (3) Weather resistance: After 1000 hours of xenon lamp aging (simulating 2 years of outdoor use), a color density ratio of ≥70% is acceptable; after 168 hours of artificial accelerated aging, a color density ratio of ≥70% is acceptable.

[0068] (4) Water resistance: After immersion in water for 24 hours, the coating does not peel off and the color density change is ≤5%.

[0069] (5) Stain resistance: After oil and dust adhere to it, rainwater can clean it without leaving any residue.

[0070] (6) Foil retention: After high-speed printing for 100m, the coating does not shed powder or peel off.

[0071] The test results are shown in Table 1: Table 1 Test results of the examples and comparative examples The test results above show that the three embodiments are superior to the comparative examples in all aspects, including gloss, alcohol abrasion resistance, artificial accelerated aging and xenon lamp aging performance, water and stain resistance, and foil retention.

[0072] In Example 1, an aluminum ion complexing agent and polyethylene glycol modified silicone oil were used, achieving a color density ratio of 97% after alcohol rubbing, 78% after 168 hours of artificial aging, and 72% after 1000 hours of xenon lamp aging, with all performance indicators meeting Grade A standards. In Example 2, an aluminum-zinc composite complexing agent was used, with color density ratios of 79% and 73% after artificial and xenon lamp aging, respectively, showing slightly better aging performance than Example 1. In Example 3, a polyethylene glycol modified phosphate release agent was used, achieving an optimal color density ratio of 98% after alcohol rubbing, while maintaining excellent levels of 77% and 71% after artificial and xenon lamp aging, respectively.

[0073] In contrast, the comparison sample used traditional liquid UV absorbers and erucamide release agents without metal ion complexing agents. The gloss level only reached grade B, the alcohol rubbing resistance color density ratio was significantly reduced to 82%, the artificial and xenon lamp aging color density ratios were only 62% and 45% respectively, the waterproofing showed slight whitening of the coating, the stain resistance showed obvious residue, and the foil retention showed slight powdering.

[0074] The above test results effectively verify that the present invention achieves a performance breakthrough of more than three times in terms of weather resistance, chemical resistance, gloss and high-speed printing adaptability through multi-layer structure synergistic design, dye stabilization and strengthening system and functional auxiliary agent compounding.

[0075] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. An outdoor high weather-resistant OC protective carbon ribbon, comprising a substrate (1), wherein a back coating (2) is provided on one side of the substrate (1), and a release layer (3) is provided on the other side, wherein an adhesive layer (4) is provided on the release layer (3), characterized in that, The release layer (3) comprises a release layer resin and a metal ion complexing agent. The release layer resin includes polyacrylic acid resin or polymethyl methacrylate resin, and also includes polysiloxane modified resin; The metal ion complexing agent is at least one of aluminum ion complexing agents, zinc ion complexing agents, iron ion complexing agents, and copper ion complexing agents.

2. The outdoor high weather-resistant OC protective carbon ribbon according to claim 1, characterized in that, The Tg values ​​of both the polyacrylic acid resin and the polymethyl methacrylate resin are 80-130℃, and the molecular weights are both 30,000-200,000; the mass ratio of the polyacrylic acid resin or the polymethyl methacrylate resin to the polysiloxane modified resin is 8-12:

1.

3. The outdoor high weather-resistant OC protective carbon ribbon according to claim 1, characterized in that, The release layer (3) also includes an ultraviolet absorber and a light stabilizer; the ultraviolet absorber is a solid benzotriazole ultraviolet absorber or a triazine solid ultraviolet absorber, and the light stabilizer is a hindered amine light stabilizer.

4. The outdoor high weather-resistant OC protective carbon ribbon according to claim 3, characterized in that, The release layer (3) also includes an antioxidant and an anti-fouling and waterproofing agent; the mass fractions of each component are: 20-25 parts of the release layer resin, 1.5-2 parts of the metal ion complexing agent, 2-3 parts of the ultraviolet absorber, 0.5-1 part of the light stabilizer, 0.3-0.4 parts of the antioxidant, and 1-1.5 parts of the anti-fouling and waterproofing agent.

5. An outdoor high weather-resistant OC protective carbon ribbon according to any one of claims 1-4, characterized in that, The adhesive layer (4) comprises an adhesive resin and reinforcing additives; The adhesive layer resin comprises vinyl chloride-vinyl acetate resin and polyester-modified acrylic resin, wherein the Tg value of the vinyl chloride-vinyl acetate resin is 60-80℃, and the mass percentage of vinyl acetate is 10-20%; the mass ratio of the vinyl chloride-vinyl acetate resin to the polyester-modified acrylic resin is 3-5:

1. The reinforcing agent is fine talc powder with a mesh size of 5000-12000 and a specific surface area of ​​5-10 g / m². 2 .

6. The outdoor high weather-resistant OC protective carbon ribbon according to claim 5, characterized in that, The adhesive layer (4) also includes a polymeric superdispersant, a silane coupling agent and a solvent; the mass fractions of each component in the adhesive layer (4) are 8-12 parts of the adhesive layer resin, 0.5-3 parts of the reinforcing agent, 0.5-3 parts of the polymeric superdispersant, and 0.3-0.5 parts of the silane coupling agent.

7. An outdoor high weather-resistant OC protective carbon ribbon according to any one of claims 1-4, characterized in that, The back coating (2) comprises polyvinyl butyral resin and aromatic isocyanate curing agent, wherein the mass ratio of polyvinyl butyral resin to aromatic isocyanate curing agent is 8-12:

3.

8. The outdoor high weather-resistant OC protective carbon ribbon according to claim 7, characterized in that, The back coating (2) also includes inorganic fillers and release agents; the inorganic fillers are talc and / or kaolin, and the release agents are a mixture of phosphate esters and silicone oils.

9. A method for preparing an outdoor high weather-resistant OC protective carbon ribbon as described in any one of claims 1-8, characterized in that, The process includes the step of preparing a release layer coating liquid containing each component of the release layer (3) using an organic solvent; the viscosity of the release layer coating liquid is 100-500 mPa·s.

10. The method for preparing an outdoor high weather-resistant OC protective carbon ribbon according to claim 9, characterized in that, It also includes the following steps: A back coating liquid is applied to one side of the substrate (1) after corona treatment, with a coating thickness of 0.4-0.6 μm, and the back coating (2) is obtained after drying. The release layer coating liquid is coated on the other side of the substrate (1) with a coating thickness of 1-3 μm, and the release layer (3) is obtained after drying. An adhesive coating liquid is applied to the release layer (3) with a coating thickness of 0.1-0.5 μm, and the adhesive layer (4) is obtained after drying.

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