High-adhesion weather-resistant glass sign heat transfer material and preparation method thereof

Abstract

The application belongs to the technical field of new heat transfer printing materials and glass surface marking printing, and discloses a high-adhesion weather-resistant glass marking heat transfer printing material and a preparation method thereof, which is sequentially and complexly provided with a PET carrier base film, a low-residual release layer, a nano-hardening wear-resistant protective layer, a weather-resistant graphic ink layer and a silane-modified epoxy adhesive layer from bottom to top; the silane-modified epoxy adhesive layer is composed of the following raw materials in parts by mass: alicyclic epoxy resin 20-25 parts, epoxy-silicone prepolymer 15-20 parts, silane coupling agent modified nano-titanium dioxide 5-10 parts, microcapsule latent curing agent 3-5 parts and acrylic tackifying resin 45-55 parts. The application has the advantages of simple process, high transfer efficiency, 5B-grade adhesion of finished products, strong weather resistance, cold and hot cycle stability, batch automatic production and replacement of traditional high-pollution and low-efficiency glass printing process.

Description

Technical Field

[0001] This invention belongs to the field of new heat transfer materials and glass surface marking printing technology, specifically relating to a high-adhesion weather-resistant glass marking heat transfer material and its preparation method. Background Technology

[0002] Glass, with its excellent light transmittance, high hardness, corrosion resistance, and superior texture, is widely used in building curtain walls, doors and windows, bathroom fixtures, photovoltaic modules, laboratory instruments, rail transit vehicle windows, and decorative mirrors. To meet the needs of product labeling, safety warnings, parameter markings, and brand logo decoration, fixed markings and text need to be printed on the glass surface.

[0003] Currently, the main glass sign processing techniques in the industry include screen printing, spray coating, laser etching, high-temperature glaze printing, and sandblasting. These existing techniques have several inherent defects: 1. Screen printing requires customized screens, which are costly and time-consuming to make. It is only suitable for large-scale standardized production and cannot meet the needs of small-batch, personalized, and customized labeling processing. In addition, the printing ink has high VOC emissions, which causes serious environmental pollution. 2. The coating process results in uneven thickness of the printed graphics, obvious burrs at the edges, and weak coating adhesion, making it prone to fading and peeling during daily wiping and rain washing. 3. Laser etching can only achieve monochrome shallow and medium depth engraving, and cannot achieve color marking. It will also damage the dense layer on the glass surface, reducing the glass's impact resistance and weather resistance. 4. Traditional high-temperature glaze printing process is extremely energy-intensive, complex, and has a high scrap rate, making it unsuitable for rapid processing of small and medium-sized glass products.

[0004] In addition, conventional general-purpose heat transfer materials are a new technology that has replaced traditional printing in recent years. However, glass is a substrate with extremely low surface energy and a smooth, non-porous surface. Ordinary heat transfer film bonding systems cannot achieve effective wetting and bonding, resulting in the following fatal defects: 1. Poor adhesion of text and images, generally below 3B in cross-cut adhesion test, and ink can be easily removed by light wiping with alcohol or a damp cloth; 2. Glass and ordinary resin materials have vastly different coefficients of thermal expansion. Under alternating high and low outdoor conditions, the graphics are prone to cracking, warping, and complete detachment. 3. Conventional inks have poor resistance to UV aging and acid and alkali, and will fade and turn white severely after 1 to 2 years of outdoor use, which cannot meet the requirements for long-term outdoor use of curtain walls and photovoltaic glass.

[0005] In summary, current technologies lack a dedicated heat transfer material for glass substrates that offers high adhesion, high wear resistance, high weather resistance, and stability under thermal cycling. Furthermore, it is unsuitable for dual-system products combining room-temperature rapid transfer and high-temperature tempering sintering. Therefore, developing a glass signage heat transfer material that is compatible with all types of glass, offers stable performance, and utilizes an efficient and environmentally friendly process is an urgent need in the industry. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention aims to provide a high-adhesion, weather-resistant glass signage heat transfer material and its preparation method, thereby solving the industry pain points of high plate-making costs, significant pollution, and lack of customization in traditional processes, as well as the poor adhesion, easy cracking, easy fading, and poor weather resistance of ordinary heat transfer materials on glass surfaces. At the same time, it achieves the goal of fast, high-definition, firm, and long-lasting printing of glass signs.

[0007] Based on one aspect of the present invention, this application proposes a high-adhesion weather-resistant glass marking heat transfer material, which is composed of, from bottom to top, a PET carrier base film, a low-residue release layer, a nano-hardened wear-resistant protective layer, a weather-resistant graphic ink layer, and a silane-modified epoxy adhesive layer. The silane-modified epoxy adhesive layer is composed of the following raw materials in parts by weight: 20-25 parts alicyclic epoxy resin, 15-20 parts epoxy siloxane prepolymer, 5-10 parts silane coupling agent modified nano titanium dioxide, 3-5 parts microcapsule latent curing agent, and 45-55 parts acrylic tackifying resin.

[0008] Preferably, the PET carrier base film is a biaxially oriented PET film with a thickness of 25-75 μm, a temperature resistance of ≥250℃, a longitudinal heat shrinkage rate of ≤1.5%, and an organosilicon anti-slip back coating is applied to the back of the PET carrier base film.

[0009] Preferably, the low-residue release layer is composed of the following raw materials in parts by weight: 30-35 parts amino silicone oil, 25-35 parts methyl methacrylate, 25-30 parts PTFE micro powder, 5-8 parts crosslinking agent, and 3-5 parts leveling agent; the thickness of the low-residue release layer is 1-3 μm, and after high-temperature transfer, the carrier peels off without residual wax or haze.

[0010] Preferably, the thickness of the nano-hardened wear-resistant protective layer is 6-12 μm, and it is mainly composed of silane-modified polyurethane resin, doped with nano-silica and nano-alumina wear-resistant powders, with the powder addition amount being 8%-15% of the total resin mass.

[0011] Preferably, the weather-resistant graphic ink layer includes a room-temperature organic ink system and a high-temperature inorganic ink system. The room-temperature organic ink system is suitable for room-temperature heat transfer printing on ordinary glass, and the high-temperature inorganic ink system is suitable for high-temperature sintering printing on tempered glass.

[0012] Preferably, the room temperature organic ink system is composed of the following raw materials in parts by weight: 25-35 parts of chloroacetic acid resin, 10-15 parts of thermoplastic polyurethane, 45-55 parts of inorganic weather-resistant pigment, 2-4 parts of silane coupling agent, 4-6 parts of polyethylene wax, and 1-3 parts of antioxidant.

[0013] Preferably, the process parameters for the ordinary glass room temperature heat transfer printing are: temperature 210~230℃, pressure 0.3~0.6MPa, holding time 3~8s, and the PET carrier film is peeled off after cooling to room temperature.

[0014] Preferably, the high-temperature inorganic ink system is composed of the following raw materials in parts by weight: 35-45 parts of low-melting-point glass powder, 40-50 parts of high-temperature resistant metal oxide pigment, 10-15 parts of epoxy siloxane binder, and 2-4 parts of dispersant; after heat transfer at room temperature, it can be chemically bonded to the glass substrate and integrated with it under high-temperature sintering at 680-850℃ during glass tempering.

[0015] Preferably, after the high-adhesion weather-resistant glass marking heat transfer material is transferred, the adhesion test reaches level 5B, the RCA paper tape abrasion resistance is ≥55 revolutions, the graphics and text do not peel off or fade after 120 consecutive wipings with 95% alcohol, and the color difference ΔE is ≤3 after 5000h of UV aging.

[0016] Based on another aspect of the present invention, this application also proposes a method for preparing the above-mentioned high-adhesion weather-resistant glass marking heat transfer material, comprising the following steps: S1. Pretreatment of PET carrier film: Select biaxially oriented PET carrier film, perform surface corona treatment to improve surface adhesion, and remove dust for later use; S2. Coating a low-residue release layer: A low-residue release layer is coated on the front side of the PET carrier base film using a gravure coating method, and then dried and cured in sections at a gradient temperature of 80-110℃. S3. Coating a nano-hardened wear-resistant protective layer: Coating a nano-hardened wear-resistant protective layer onto the surface of the low-residue release layer, drying at 100-120℃, and naturally cooling to set; S4. Printing weather-resistant graphic ink layer: Using multi-color gravure printing process, room temperature organic ink or high temperature inorganic ink is printed on the surface of the coated nano-hardening wear-resistant protective layer, and then dried and cured. S5. Apply silane-modified epoxy adhesive layer: Apply silane-modified epoxy adhesive layer to the surface of the printed weather-resistant graphic ink layer, and dry slowly at a low temperature of 60-80℃ to avoid premature curing. S6. Curing and winding: The finished product is cured at a constant temperature of 25℃ for 24 hours, then cut, inspected, and wound up to obtain the special heat transfer material for glass marking.

[0017] The working principle of this invention is as follows: through a five-layer composite structure design, each layer is matched to the printing requirements of the glass substrate. The core innovation lies in the use of an epoxy-silane compound bonding system, which can be directly bonded to the smooth glass surface without the need for a primer or plasma pretreatment, thus solving the problem of low surface energy bonding. The surface hardness and wear resistance are greatly improved through a nano-hardened wear-resistant protective layer. The thermal expansion coefficient of the formulation system is highly matched with that of the glass, which improves the stability of thermal cycling. The dual ink system of room temperature organic and high temperature inorganic helps to realize glass applications in all scenarios.

[0018] Compared with the prior art, the beneficial effects of the present invention are: 1. Ultra-high adhesion: The adhesion of the 100-grid adhesive reaches 5B level. 3M strong adhesive tape can be torn without ink smudging or exposing the substrate, completely solving the problem of difficult bonding to glass substrates. 2. Excellent weather and wear resistance: resistant to alcohol, acids and alkalis, and oil stains; minimal color change after 5000 hours of UV aging; outdoor service life of over 8 years. 3. Stable thermal cycling: No cracking, warping, or peeling after 50 cycles of high and low temperatures from -40℃ to 180℃, suitable for extreme outdoor environments; 4. Full-scene adaptation: The normal temperature version is suitable for quick marking of bathroom fixtures, instruments, and indoor glass, while the high temperature version can be integrated with glass tempering and sintering, and is suitable for curtain walls, photovoltaic outdoor high-end glass; 5. Highly efficient and environmentally friendly process: No need for plate making, no wastewater or exhaust gas pollution, supports single sheet, small batch, and personalized customization, and is compatible with automated roll-to-roll continuous production and flat and small curved glass transfer. 6. Excellent finished product quality: The transferred images and text are high-definition and delicate, with smooth edges, no burrs, uniform light transmission, and do not damage the original transparent texture of the glass.

[0019] In summary, the present invention features a simple process, requires no pre-treatment of the base coating, has high transfer efficiency, achieves 5B-level adhesion of the finished product, maintains a stable overall structure, has tight interlayer bonding, and eliminates the risk of delamination or peeling. It also exhibits strong weather resistance, is stable under thermal cycling, and can be mass-produced automatically. After transfer, the graphics and text adhere firmly to the glass substrate, making it suitable for all types of glass, including soda-lime glass, borosilicate glass, tempered glass, coated Low-E glass, and mirror glass. It can be used to replace traditional high-pollution and low-efficiency glass printing processes. Attached Figure Description

[0020] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0021] Figure 1 This is a schematic diagram of the membrane structure of the present invention in an embodiment. Detailed Implementation

[0022] The present invention will now be clearly described with reference to the accompanying drawings and specific embodiments. This description is merely illustrative and is not intended to limit the scope of the invention. Any modifications, equivalent substitutions, or improvements made by those skilled in the art based on the embodiments of the present invention without inventive effort to obtain all other embodiments should be included within the scope of protection of the present invention.

[0023] Example 1 like Figure 1 As shown, this embodiment proposes a high-adhesion weather-resistant glass marking heat transfer material, which is composed of the following layers from bottom to top: PET carrier base film, low-residue release layer, nano-hardened wear-resistant protective layer, weather-resistant graphic ink layer and silane-modified epoxy adhesive layer; The PET carrier base film is a 50μm thick biaxially oriented PET film with a temperature resistance of ≥250℃ and a longitudinal heat shrinkage rate of ≤1.5%. The back of the PET carrier base film is coated with an organosilicon anti-slip back coating.

[0024] The low-residue release layer is composed of the following raw materials in parts by weight: 32 parts amino silicone oil, 30 parts methyl methacrylate, 28 parts PTFE micro powder, 6 parts crosslinking agent, and 4 parts leveling agent; the thickness of the low-residue release layer is 2 μm, and after high-temperature transfer, the carrier is peeled off without residual wax or haze.

[0025] The thickness of the nano-hardened wear-resistant protective layer is 8μm. It is mainly composed of silane-modified polyurethane resin, doped with nano-silica and nano-alumina wear-resistant powders, with the powder addition amount being 10% of the total resin mass.

[0026] The weather-resistant graphic ink layer adopts a room-temperature organic ink system, which is composed of the following raw materials in parts by weight: 30 parts of chloroacetic acid resin, 12 parts of thermoplastic polyurethane, 50 parts of inorganic weather-resistant pigment, 3 parts of silane coupling agent, 4 parts of polyethylene wax, and 1 part of antioxidant.

[0027] The silane-modified epoxy adhesive layer is composed of the following raw materials in parts by weight: 22 parts alicyclic epoxy resin, 18 parts epoxy siloxane prepolymer, 7 parts silane coupling agent modified nano titanium dioxide, 4 parts microcapsule latent curing agent, and 49 parts acrylic tackifying resin.

[0028] In this application, the epoxy siloxane binder, epoxy siloxane prepolymer, microencapsulated latent curing agent, crosslinking agent, leveling agent, antioxidant, and silane coupling agent are all conventional materials in the art or commercially available varieties. In this embodiment, the epoxy siloxane binder is Shin-Etsu KR-470 epoxy tetrafunctional oligomeric silicone resin, the epoxy siloxane prepolymer is a dimethyl siloxane with a molecular weight of 1000–5000, the microencapsulated latent curing agent is the ultrafine latent curing accelerator SH-A100, the crosslinking agent is 1,2-cyclohexene-4,5-dione, the leveling agent is L88, the antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and the silane coupling agent is γ-aminopropyltriethoxysilane. The preparation method of the above-mentioned high-adhesion weather-resistant glass marking heat transfer material includes the following steps: S1. Pretreatment of PET carrier film: Select biaxially oriented PET carrier film, perform surface corona treatment to improve surface adhesion, and remove dust for later use; S2. Coating a low-residue release layer: A low-residue release layer is coated on the front side of the PET carrier base film using a gravure coating method, and then dried and cured in sections at a gradient temperature of 80-110℃. S3. Coating a nano-hardened wear-resistant protective layer: Coating a nano-hardened wear-resistant protective layer onto the surface of the low-residue release layer, drying at 100-120℃, and naturally cooling to set; S4. Printing weather-resistant graphic ink layer: Using multi-color gravure printing process, room temperature organic ink or high temperature inorganic ink is printed on the surface of the coated nano-hardening wear-resistant protective layer, and then dried and cured. S5. Apply silane-modified epoxy adhesive layer: Apply silane-modified epoxy adhesive layer to the surface of the printed weather-resistant graphic ink layer, and dry slowly at a low temperature of 60-80℃ to avoid premature curing. S6. Curing and winding: The finished product is cured at a constant temperature of 25℃ for 24 hours, then cut, inspected, and wound up to obtain the special heat transfer material for glass marking.

[0029] The prepared high-adhesion weather-resistant glass marking heat transfer material was heat transferred at room temperature according to the following process parameters: temperature 220℃, pressure 0.4MPa, holding time 5s, and the PET carrier film was peeled off after cooling to room temperature.

[0030] After the above-mentioned high-adhesion weather-resistant glass marking heat transfer material was transferred, the performance test results were as follows: the adhesion test reached level 5B, the RCA paper tape was abrasion resistant for 60 revolutions without scratches, the graphics and text did not peel off or fade after 120 consecutive wipings with 95% alcohol, and there was no cracking after 50 cycles of cold and hot cycling from -40 to 180℃; the color difference ΔE=2.1 after 5000h of UV aging.

[0031] Example 2 The only difference between this embodiment and Embodiment 1 is that: The weather-resistant graphic ink layer adopts a high-temperature inorganic ink system, which is composed of the following raw materials in parts by weight: 40 parts of low melting point glass powder, 45 parts of high-temperature resistant metal oxide pigment, 12 parts of epoxy siloxane binder, and 3 parts of dispersant. The dispersant used is a commercially available variety; in this embodiment, BYK-164 dispersant was specifically used. After transfer printing at room temperature, the sample was sent to a tempering furnace for sintering at 720°C.

[0032] After sintering, the graphics and text are tested and found to be integrated with the glass, making it scratch-resistant, resistant to strong acids and alkalis, and theoretically weather-resistant for more than 10 years outdoors, with permanent adhesion that will not peel off.

[0033] Example 3 The only difference between this embodiment and Embodiment 1 is that: The PET carrier base film is 25 μm thick. The low-residue release layer contains 30 parts amino silicone oil, 25 parts methyl methacrylate, 25 parts PTFE micropowder, 5 parts crosslinking agent, and 3 parts leveling agent, with a low-residue release layer thickness of 1 μm. The nano-cured wear-resistant protective layer is 6 μm thick, and the powder addition is 8% of the total resin mass. The room-temperature organic ink system contains 25 parts chloroacetic acid resin, 10 parts thermoplastic polyurethane, 45 parts inorganic weather-resistant pigment, 2 parts silane coupling agent, 4 parts polyethylene wax, and 1 part antioxidant. The silane-modified epoxy adhesive layer contains 20 parts alicyclic epoxy resin, 15 parts epoxy-based siloxane prepolymer, 5 parts modified nano-titanium dioxide, 3 parts microcapsule latent curing agent, and 45 parts acrylic tackifying resin.

[0034] The amino silicone oil is an amino-modified polysiloxane with a molecular weight between 3800 and 4500; the TG point of methyl methacrylate is 105℃-110℃; the melting point of PTFE micronized wax is 130-135℃; the crosslinking agent is TDI; the leveling agent is BYK-333; the vinyl chloride resin is Shin-Etsu TA3; the thermoplastic polyurethane is Lubrizol TPU5715; and the inorganic weather-resistant pigment is iron oxide black with an oil absorption value of 30g / 100ml.

[0035] The process parameters for room temperature heat transfer printing are: temperature 210℃, pressure 0.3MPa, and holding time 3s.

[0036] The performance test results after transfer are as follows: the adhesion test reaches level 5B, the RCA paper tape has abrasion resistance of 55 revolutions without exposing the base material, the graphics and text do not peel off or fade after 120 consecutive wipings with 95% alcohol, and there is no cracking or curling after 50 cycles of cold and heat cycling from -40 to 180℃; the color difference ΔE=2.7 after 5000h of UV aging.

[0037] Example 4 The only difference between this embodiment and Embodiment 1 is that: The PET carrier base film has a thickness of 75 μm. The low-residue release layer contains 35 parts amino silicone oil, 35 parts methyl methacrylate, 30 parts PTFE micropowder, 8 parts crosslinking agent, and 5 parts leveling agent, with a thickness of 3 μm. The nano-cured wear-resistant protective layer has a thickness of 12 μm, and the powder addition amount is 15% of the total resin mass. The room-temperature organic ink system contains 35 parts chloroacetic acid resin, 15 parts thermoplastic polyurethane, 55 parts inorganic weather-resistant pigment, 4 parts silane coupling agent, 6 parts polyethylene wax, and 3 parts antioxidant. The silane-modified epoxy adhesive layer contains 25 parts alicyclic epoxy resin, 20 parts epoxy-based siloxane prepolymer, 10 parts modified nano-titanium dioxide, 5 parts microcapsule latent curing agent, and 55 parts acrylic tackifying resin.

[0038] The alicyclic epoxy resin has a softening point of 80-90℃, the modified nano-titanium dioxide has a D50 particle size of 200nm, and the acrylic tackifying resin is a copolymer of ethyl acrylate and terpene resin.

[0039] The process parameters for room temperature heat transfer printing are: temperature 230℃, pressure 0.6MPa, and holding time 8s.

[0040] The performance test results after transfer are as follows: the adhesion test reaches level 5B, the RCA paper tape has no scratches after 72 abrasions, the graphics do not peel off or fade after 150 consecutive wipings with 95% alcohol, and there is no delamination after 50 cycles of cold and hot cycling from -40 to 180℃; the color difference ΔE=1.6 after 5000h of UV aging.

[0041] Example 5 The only difference between this embodiment and Embodiment 2 is that: The high-temperature inorganic ink system is composed of the following raw materials in parts by weight: 35 parts low-melting-point glass powder, 40 parts high-temperature resistant metal oxide pigment, 10 parts epoxy siloxane binder, and 2 parts dispersant. After being transferred at room temperature, it is sent to a tempering furnace for sintering at 680℃.

[0042] After sintering, the images and text are chemically bonded to the glass substrate; they can withstand immersion in 5% acid and alkali for 72 hours without corrosion or peeling; after 5000 hours of UV aging, the color difference ΔE is 2.4; and the theoretical outdoor weather resistance is ≥8 years.

[0043] Example 6 The only difference between this embodiment and Embodiment 2 is that: The high-temperature inorganic ink system is composed of the following raw materials in parts by weight: 45 parts of low-melting-point glass powder, 50 parts of high-temperature resistant metal oxide pigment, 15 parts of epoxy siloxane binder, and 4 parts of dispersant. After being transferred at room temperature, it is sent to a tempering furnace for sintering at 850℃.

[0044] After sintering, the coating is found to be dense and free of pinholes; after being rubbed with a steel wool ball 100 times, the base layer remains intact; after being soaked in strong acid and alkali for 120 hours, it remains intact; and the theoretical outdoor weather resistance is ≥11 years.

[0045] Comparative Example 1 The performance of commercially available glass heat transfer film was tested under the same process conditions as in Example 1. The results were as follows: adhesion rating of 3B, ink loss after 30 alcohol wipes, cracking after 20 cycles of hot and cold cycling from -40 to 180°C, and severe fading after 2000 hours of UV aging.

[0046] The comparison shows that the material of this invention has far superior performance compared to existing ordinary products, with a significant performance improvement.

[0047] Comparative Example 2 The only difference between this comparative example and Example 1 is that: The silane-modified epoxy adhesive layer is composed of the following raw materials in parts by weight: 22 parts alicyclic epoxy resin, 0 parts epoxy siloxane prepolymer, 7 parts silane coupling agent modified nano titanium dioxide, 4 parts microcapsule latent curing agent, and 67 parts acrylic tackifying resin.

[0048] The performance test results are as follows: cross-cut adhesion grade 2B; RCA paper tape abrasion resistance after 18 turns resulted in bare metal exposure; large-area ink loss after 42 alcohol wipes; edge curling and cracking after 22 cycles of -40~180℃ thermal cycling; and color difference ΔE=8.6 after 2000h UV aging. It is evident that the silane-free epoxy composite system cannot form chemical bonds with the hydroxyl groups on the glass surface, leading to low surface energy interfacial adhesion failure and overall deterioration in weather resistance and abrasion resistance.

[0049] Comparative Example 3 The only difference between this comparative example and Example 1 is that: In the nano-hardened wear-resistant protective layer, the amount of powder added is 5% of the total mass of the resin.

[0050] Its performance test results are as follows: cross-cut adhesion grade 4B; RCA paper tape abrasion resistance 26 revolutions with scratches and ink exposure; 75 alcohol wipes with color fading and discoloration; 3000h UV aging with surface loss of gloss and whitening, insufficient abrasion-resistant powder, insufficient surface hardness of the hardened layer, and a significant decrease in abrasion resistance and UV aging resistance.

[0051] Comparative Example 4 The only difference between this comparative example and Example 1 is that: The room-temperature organic ink system, which removes the silane coupling agent, is composed of the following raw materials in parts by weight: 30 parts chloroacetic acid resin, 12 parts thermoplastic polyurethane, 53 parts inorganic weather-resistant pigment, 4 parts polyethylene wax, and 1 part antioxidant.

[0052] Its performance test results are as follows: interlayer adhesion grade 3B, slight delamination between ink layer and wear-resistant layer; cracking at the edges of graphics after 30 cycles of hot and cold cycling from -40 to 180℃; color fading after 60 alcohol wipes, poor interface compatibility between ink and upper wear-resistant layer and lower adhesive layer, and insufficient interlayer bonding force.

[0053] Comparative Example 5 Commercially available PET heat transfer film (general plastic heat transfer film) with an adhesive layer of ordinary acrylic resin, no silane-modified epoxy system, and no independent nano wear-resistant layer is transferred onto tempered glass at 220℃, 0.4MPa, and 5s.

[0054] Its performance test results are as follows: cross-cut adhesion grade 1B; RCA paper tape abrasion resistance less than 10 revolutions completely exposes the substrate; after 20 alcohol wipes, the entire piece falls off; after 10 cycles of -40~180℃ hot and cold cycling, large area cracks occur; after 1000 hours of UV aging, it severely fades and chalks.

[0055] Comparative Example 6 It uses industry-standard glass screen printing ink (traditional glass screen printing process), with a special screen printing plate, and is dried at 150℃ for 30 minutes.

[0056] Its performance test results are as follows: adhesion grade 3B; color fade after 50 alcohol wipes; color difference ΔE=7.2 after 2500h UV aging; fine cracks appear after 35 cycles of -40~180℃ hot and cold cycling; plate making cycle is 3 days, the cost of opening a single plate is 800 yuan, it cannot be customized for single pieces, and the VOC emissions from production exceed the standard.

[0057] Comparing the performance test results of Examples 1-6 with those of Comparative Examples 1-6, it can be seen that the product of this application has superior performance, mainly in the following aspects: 1. Stable compliance across all parameter ranges: The raw materials, thickness, powder addition, transfer / sintering temperature and pressure of each layer are limited by this invention. Regardless of whether the lower limit, middle value or upper limit of the range is taken, the adhesion of the finished product is stable at 5B level. The indicators such as wear resistance, solvent resistance, high and low temperature resistance, and UV aging resistance all meet the industry's high-end outdoor glass use standards. 2. Key formulations are indispensable: As long as the formulation protected by this application is removed (removing the silane-epoxy adhesive body, reducing the wear-resistant powder, and deleting the ink silane coupling agent), the adhesion, wear resistance, and weather resistance drop sharply, proving that the silane-modified epoxy adhesive system, nano-hardened wear-resistant layer, and silane-modified ink of this application are the core innovations for solving the problem of low surface energy adhesion and long-term weather resistance of glass. 3. Significant advantages compared to existing traditional processes: Compared to ordinary heat transfer films and traditional glass screen printing on the market, the adhesion of the material of this invention is improved by 2 to 4 levels, the wear resistance and wiping resistance are increased by 2 to 8 times, the color difference under ultraviolet aging is greatly reduced, and the stability of cold and heat cycles is greatly improved. At the same time, it can take into account small-batch personalized customization, low pollution, and automated and efficient production, which can solve all the pain points of the existing industry and has outstanding technological progress.

[0058] The embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A high-adhesion, weather-resistant glass marking heat transfer material, characterized in that, The following components are sequentially arranged from bottom to top: PET carrier base film, low-residue release layer, nano-hardened wear-resistant protective layer, weather-resistant graphic ink layer, and silane-modified epoxy adhesive layer; The silane-modified epoxy adhesive layer is composed of the following raw materials in parts by weight: 20-25 parts alicyclic epoxy resin, 15-20 parts epoxy siloxane prepolymer, 5-10 parts silane coupling agent modified nano titanium dioxide, 3-5 parts microcapsule latent curing agent, and 45-55 parts acrylic tackifying resin.

2. The high-adhesion weather-resistant glass marking heat transfer material according to claim 1, characterized in that: The PET carrier base film is a biaxially oriented PET film with a thickness of 25-75 μm, a temperature resistance of ≥250℃, and a longitudinal heat shrinkage rate of ≤1.5%. The back of the PET carrier base film is coated with an organosilicon anti-slip back coating.

3. The high-adhesion weather-resistant glass marking heat transfer material according to claim 1, characterized in that: The low-residue release layer is composed of the following raw materials in parts by weight: 30-35 parts amino silicone oil, 25-35 parts methyl methacrylate, 25-30 parts PTFE micro powder, 5-8 parts crosslinking agent, and 3-5 parts leveling agent; the thickness of the low-residue release layer is 1-3 μm, and after high-temperature transfer, the carrier peels off without residual wax or haze.

4. The high-adhesion weather-resistant glass marking heat transfer material according to claim 1, characterized in that: The thickness of the nano-hardened wear-resistant protective layer is 6-12 μm. It is mainly composed of silane-modified polyurethane resin, doped with nano-silica and nano-alumina wear-resistant powders, with the powder addition amount being 8%-15% of the total resin mass.

5. The high-adhesion weather-resistant glass marking heat transfer material according to claim 1, characterized in that: The weather-resistant graphic ink layer includes a room-temperature organic ink system and a high-temperature inorganic ink system. The room-temperature organic ink system is suitable for room-temperature heat transfer printing on ordinary glass, and the high-temperature inorganic ink system is suitable for high-temperature sintering printing on tempered glass.

6. The high-adhesion weather-resistant glass marking heat transfer material according to claim 5, characterized in that: The room-temperature organic ink system is composed of the following raw materials in parts by weight: 25-35 parts of chloroacetic acid resin, 10-15 parts of thermoplastic polyurethane, 45-55 parts of inorganic weather-resistant pigment, 2-4 parts of silane coupling agent, 4-6 parts of polyethylene wax, and 1-3 parts of antioxidant.

7. The high-adhesion weather-resistant glass marking heat transfer material according to claim 6, characterized in that: The process parameters for ordinary glass room temperature heat transfer printing are: temperature 210~230℃, pressure 0.3~0.6MPa, holding time 3~8s, and after cooling to room temperature, the PET carrier film is peeled off.

8. The high-adhesion weather-resistant glass marking heat transfer material according to claim 5, characterized in that: The high-temperature inorganic ink system is composed of the following raw materials in parts by weight: 35-45 parts of low-melting-point glass powder, 40-50 parts of high-temperature resistant metal oxide pigment, 10-15 parts of epoxy siloxane binder, and 2-4 parts of dispersant. After heat transfer at room temperature, it can be chemically bonded to the glass substrate and integrated with it under high-temperature sintering at 680-850℃ during glass tempering.

9. A high-adhesion weather-resistant glass marking heat transfer material according to any one of claims 1 to 8, characterized in that: After the high-adhesion weather-resistant glass marking heat transfer material is transferred, the adhesion test reaches level 5B, the RCA paper tape abrasion resistance is ≥55 revolutions, the graphics and text do not peel off or fade after 120 consecutive wipings with 95% alcohol, and the color difference ΔE is ≤3 after 5000h of UV aging.

10. A method for preparing a high-adhesion weather-resistant glass marking heat transfer material according to claim 9, characterized in that, Includes the following steps: S1. Pretreatment of PET carrier film: Select biaxially oriented PET carrier film, perform surface corona treatment to improve surface adhesion, and remove dust for later use; S2. Coating a low-residue release layer: A low-residue release layer is coated on the front side of the PET carrier base film using a gravure coating method, and then dried and cured in sections at a gradient temperature of 80-110℃. S3. Coating a nano-hardened wear-resistant protective layer: Coating a nano-hardened wear-resistant protective layer onto the surface of the low-residue release layer, drying at 100-120℃, and naturally cooling to set; S4. Printing weather-resistant graphic ink layer: Using multi-color gravure printing process, room temperature organic ink or high temperature inorganic ink is printed on the surface of the coated nano-hardening wear-resistant protective layer, and then dried and cured. S5. Apply silane-modified epoxy adhesive layer: Apply silane-modified epoxy adhesive layer to the surface of the printed weather-resistant graphic ink layer, and dry slowly at a low temperature of 60-80℃ to avoid premature curing. S6. Curing and winding: The finished product is cured at a constant temperature of 25℃ for 24 hours, then cut, inspected, and wound up to obtain the special heat transfer material for glass marking.

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